931 resultados para change-point detection


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This thesis looks at how non-experts develop an opinion on climate change, and how those opinions could be changed by public discourse. I use Hubert Dreyfus’ account of skill acquisition to distinguish between experts and non-experts. I then use a combination of Walter Fisher’s narrative paradigm and the hermeneutics of Paul Ricœur to explore how non-experts form opinions, and how public narratives can provide a point of critique. In order to develop robust narratives, they must be financially realistic. I therefore consider the burgeoning field of environmental, social, and corporate governance (ESG) analysis as a way of informing realistic public narratives. I identify a potential problem with this approach: the Western assumptions of ESG analysis might make for public narratives that are not convincing to a non-Western audience. I then demonstrate how elements of the Chinese tradition, the Confucian, Neo-Confucian, and Daoist schools, as presented by David Hall and Roger Ames, can provide alternative assumptions to ESG analysis so that the public narratives will be more culturally adaptable. This research contributes to the discipline by bringing disparate traditions together in a unique way, into a practical project with a view towards applications. I conclude by considering avenues for further research.

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This study aims at exploring the potential impact of forest protection intervention on rural households’ private fuel tree planting in Chiro district of eastern Ethiopia. The study results revealed a robust and significant positive impact of the intervention on farmers’ decisions to produce private household energy by growing fuel trees on their farm. As participation in private fuel tree planting is not random, the study confronts a methodological issue in investigating the causal effect of forest protection intervention on rural farm households’ private fuel tree planting through non-parametric propensity score matching (PSM) method. The protection intervention on average has increased fuel tree planting by 503 (580.6%) compared to open access areas and indirectly contributed to slowing down the loss of biodiversity in the area. Land cover/use is a dynamic phenomenon that changes with time and space due to anthropogenic pressure and development. Forest cover and land use changes in Chiro District, Ethiopia over a period of 40 years was studied using remotely sensed data. Multi temporal satellite data of Landsat was used to map and monitor forest cover and land use changes occurred during three point of time of 1972,1986 and 2012. A pixel base supervised image classification was used to map land use land cover classes for maps of both time set. The result of change detection analysis revealed that the area has shown a remarkable land cover/land use changes in general and forest cover change in particular. Specifically, the dense forest cover land declined from 235 ha in 1972 to 51 ha in 1986. However, government interventions in forest protection in 1989 have slowed down the drastic change of dense forest cover loss around the protected area through reclaiming 1,300 hectares of deforested land through reforestation program up to 2012.

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The problem of decentralized sequential detection is studied in this thesis, where local sensors are memoryless, receive independent observations, and no feedback from the fusion center. In addition to traditional criteria of detection delay and error probability, we introduce a new constraint: the number of communications between local sensors and the fusion center. This metric is able to reflect both the cost of establishing communication links as well as overall energy consumption over time. A new formulation for communication-efficient decentralized sequential detection is proposed where the overall detection delay is minimized with constraints on both error probabilities and the communication cost. Two types of problems are investigated based on the communication-efficient formulation: decentralized hypothesis testing and decentralized change detection. In the former case, an asymptotically person-by-person optimum detection framework is developed, where the fusion center performs a sequential probability ratio test based on dependent observations. The proposed algorithm utilizes not only reported statistics from local sensors, but also the reporting times. The asymptotically relative efficiency of proposed algorithm with respect to the centralized strategy is expressed in closed form. When the probabilities of false alarm and missed detection are close to one another, a reduced-complexity algorithm is proposed based on a Poisson arrival approximation. In addition, decentralized change detection with a communication cost constraint is also investigated. A person-by-person optimum change detection algorithm is proposed, where transmissions of sensing reports are modeled as a Poisson process. The optimum threshold value is obtained through dynamic programming. An alternative method with a simpler fusion rule is also proposed, where the threshold values in the algorithm are determined by a combination of sequential detection analysis and constrained optimization. In both decentralized hypothesis testing and change detection problems, tradeoffs in parameter choices are investigated through Monte Carlo simulations.

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We present air–sea fluxes of carbon dioxide (CO2), methane (CH4), momentum, and sensible heat measured by the eddy covariance method from the recently established Penlee Point Atmospheric Observatory (PPAO) on the south-west coast of the United Kingdom. Measurements from the south-westerly direction (open water sector) were made at three different sampling heights (approximately 15, 18, and 27m above mean sea level, a.m.s.l.), each from a different period during 2014–2015. At sampling heights ≥18ma.m.s.l., measured fluxes of momentum and sensible heat demonstrate reasonable (≤ ±20% in the mean) agreement with transfer rates over the open ocean. This confirms the suitability of PPAO for air–sea exchange measurements in shelf regions. Covariance air–sea CO2 fluxes demonstrate high temporal variability. Air-to-sea transport of CO2 declined from spring to summer in both years, coinciding with the breakdown of the spring phytoplankton bloom. We report, to the best of our knowledge, the first successful eddy covariance measurements of CH4 emissions from a marine environment. Higher sea-to-air CH4 fluxes were observed during rising tides (20±3; 38±3; 29±6 μmolem-2 d-1 at 15, 18, 27ma.m.s.l.) than during falling tides (14±2; 22±2; 21±5 μmolem-2 d-1), consistent with an elevated CH4 source from an estuarine outflow driven by local tidal circulation. These fluxes are a few times higher than the predicted CH4 emissions over the open ocean and are significantly lower than estimates from other aquatic CH4 hotspots (e.g. polar regions, freshwater). Finally, we found the detection limit of the air–sea CH4 flux by eddy covariance to be 20 μmolem-2 d-1 over hourly timescales (4 μmolem-2 d-1 over 24 h).

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We present air–sea fluxes of carbon dioxide (CO2), methane (CH4), momentum, and sensible heat measured by the eddy covariance method from the recently established Penlee Point Atmospheric Observatory (PPAO) on the south-west coast of the United Kingdom. Measurements from the south-westerly direction (open water sector) were made at three different sampling heights (approximately 15, 18, and 27m above mean sea level, a.m.s.l.), each from a different period during 2014–2015. At sampling heights ≥18ma.m.s.l., measured fluxes of momentum and sensible heat demonstrate reasonable (≤ ±20% in the mean) agreement with transfer rates over the open ocean. This confirms the suitability of PPAO for air–sea exchange measurements in shelf regions. Covariance air–sea CO2 fluxes demonstrate high temporal variability. Air-to-sea transport of CO2 declined from spring to summer in both years, coinciding with the breakdown of the spring phytoplankton bloom. We report, to the best of our knowledge, the first successful eddy covariance measurements of CH4 emissions from a marine environment. Higher sea-to-air CH4 fluxes were observed during rising tides (20±3; 38±3; 29±6 μmolem-2 d-1 at 15, 18, 27ma.m.s.l.) than during falling tides (14±2; 22±2; 21±5 μmolem-2 d-1), consistent with an elevated CH4 source from an estuarine outflow driven by local tidal circulation. These fluxes are a few times higher than the predicted CH4 emissions over the open ocean and are significantly lower than estimates from other aquatic CH4 hotspots (e.g. polar regions, freshwater). Finally, we found the detection limit of the air–sea CH4 flux by eddy covariance to be 20 μmolem-2 d-1 over hourly timescales (4 μmolem-2 d-1 over 24 h).

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Abstract How employees make sense of change is a very complex process. Recently, academics have neglected to research sense making activities in a micro culture implementation context, through the eyes of front line employees. In contrast to a macro view, a micro perspective limits researchers to only look at an individual, departmental or group level. By doing so, we can zoom in on the details of sense making processes that employees use in their daily work life. A macro (organisational) view is based on the notion that there is a general integrated culture that can be found in all organisational units and departments. It is assumed that culture can be researched by using the entire organisation as one single research entity. This thesis challenges this assumption. In case of planned change it is usually the management community who are in charge of the change intervention. Because of their formal hierarchical position, they have the power to abort or initiate change programs. It is perhaps therefore that researchers tend to be focused on the management community rather than on lower level organisational members, such as front line employees. Apart from the micro view, scholars also neglected to research culture change implementation through the eyes of front line employees. This thesis is an attempt to fill these two gaps that currently exists in academic change management publications. The main research question is therefore: From a micro point of view how do front-line employees make sense of the impact of culture change, during the implementation phase? This thesis starts with a literature review which exposes the two main gaps. The most important outcome of this review is that only 2% of the research articles dealt with culture implementation, through the eyes of front line employees. A conceptual research model is built on the integrated sense making theory of Weber and Manning (2001) and the micro variables of Raelin and Cataldo (2011). These theories emphasize elements of sense making in a daily working context. It is likely that front line employees can identify themselves with research elements such as tasks, skills practices, involvement and behaviour. Front line employees were selected, because as lower level organisational members they are usually the change recipients. They are further away from the change initiating scene (usually the management of an organisation) and form a potential sense making ‘hotspot’ that could provide new academic insights. In order to carry out the primary research, two case organisations were selected in the leisure industry. A participative case study research method was chosen. This meant that the researcher worked in the concerning departments of the case organisations. The goal was to observe and interview front line employees, while they were performing their jobs. The most important advantage of this approach is that the researcher temporarily becomes one with the organisation and is therefore able to acquire both formal and informal narratives that front line employees use during sense making activities. It was found that front line employees make sense of organisational change by using a practical approach. They make sense of the change program by carrying out new tasks, developing new skills and sharing best practices. The most noticeable conclusion was that sense making activities predominantly take place at an individual level in relation to change acceptance. Organisational members tend to create a mental equation in order to weigh the advantages against the disadvantages. They evaluate whether the concerning change program is beneficial to them or not. For future research a sense making scheme model is suggested that is based on two methods: an introspection and an action method.

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Large (10 × 10 cm) sheets of surface-enhanced Raman spectroscopy (SERS) active polymer have been prepared by stabilising metal nanoparticle aggregates within dry hydroxyethylcellulose (HEC) films. In these films the aggregates are protected by the polymer matrix during storage but in use they are released when aqueous analyte droplets cause the films to swell to their gel form. The fact that these "Poly-SERS" films can be prepared in bulk but then cut to size and stored in air before use means that they provide a cost effective and convenient method for routine SERS analysis. Here we have tested both Ag and Au Poly-SERS films for use in point-of-care monitoring of therapeutic drugs, using phenytoin as the test compound. Phenytoin in water could readily be detected using Ag Poly-SERS films but dissolving the compound in phosphate buffered saline (PBS) to mimic body fluid samples caused loss of the drug signal due to competition for metal surface sites from Cl- ions in the buffer solution. However, with Au Poly-SERS films there was no detectable interference from Cl- and these materials allowed phenytoin to be detected at 1.8 mg L-1, even in PBS. The target range of detection of phenytoin in therapeutic drug monitoring is 10-20 mg L-1. With the Au Poly-SERS films, the absolute signal generated by a given concentration of phenytoin was lower for the films than for the parent colloid but the SERS signals were still high enough to be used for therapeutic monitoring, so the cost in sensitivity for moving from simple aqueous colloids to films is not so large that it outweighs the advantages which the films bring for practical applications, in particular their ease of use and long shelf life.

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Climate change will exacerbate challenges facing food security in the UK. Increasing frequency and intensity of extreme weather events will further impact upon farm systems. At the heart of the impending challenges to UK agricultural production, farmers’ resilience will be tested to new limits. Research into farmers’ resilience to climate change in the UK is distinctly underdeveloped when compared to research in developing and other developed nations. This research gap is addressed through exploration of farmers’ resilience in the Welsh Marches, establishing the role of risk perceptions, local knowledge and adaptive capacity in farmers’ decision-making to limit climate shocks. Further contributions to agricultural geography are made through experimentation of a ‘cultural-behavioural approach’, seeking to revisit the behavioural approach in view of the cultural-turn. The Welsh Marches, situated on the English-Welsh border, has been selected as a focal point due to its agricultural diversity, and known experiences of extreme weather events. A phased mixed methodological approach is adopted. Phase one explores recorded and reported experiences of past extreme weather events in local meteorological records and local newspaper articles. Phase two consists of 115 survey-questionnaires, 15 in-depth semi-structured interviews, and a scenario based focus group with selected farmers from the Welsh Marches. This allows farmers’ resilience to climate change in the past, present and future to be explored. Original contributions to knowledge are made through demonstrating the value of focusing upon the culture of a specific farm community, applying a ‘bottom-up’ approach. The priority given to the weather in farmers’ decision-making is identified to be determined by individual relationships that farmers’ develop with the weather. Yet, a consensus of farmers’ observations has established recognition of considerable changes in the weather over the last 30 years, acknowledging more extremes and seasonal variations. In contrast, perceptions of future climate change are largely varied. Farmers are found to be disengaged with the communication of climate change science, as the global impacts portrayed are distant in time and place from probable impacts that may be experienced locally. Current communication of climate change information has been identified to alienate farmers from the local reality of probable future impacts. Adaptation options and responses to extreme weather and climate change are identified from measures found to be already implemented and considered for the future. A greater need to explore local knowledge and risk perception in relation to farmers’ understanding of future climate challenges is clear. There is a need to conduct comparable research in different farm communities across the UK. Progression into establishing the role of farmers’ resilience in responding effectively to future climate challenges has only just begun.

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Abstract : Images acquired from unmanned aerial vehicles (UAVs) can provide data with unprecedented spatial and temporal resolution for three-dimensional (3D) modeling. Solutions developed for this purpose are mainly operating based on photogrammetry concepts, namely UAV-Photogrammetry Systems (UAV-PS). Such systems are used in applications where both geospatial and visual information of the environment is required. These applications include, but are not limited to, natural resource management such as precision agriculture, military and police-related services such as traffic-law enforcement, precision engineering such as infrastructure inspection, and health services such as epidemic emergency management. UAV-photogrammetry systems can be differentiated based on their spatial characteristics in terms of accuracy and resolution. That is some applications, such as precision engineering, require high-resolution and high-accuracy information of the environment (e.g. 3D modeling with less than one centimeter accuracy and resolution). In other applications, lower levels of accuracy might be sufficient, (e.g. wildlife management needing few decimeters of resolution). However, even in those applications, the specific characteristics of UAV-PSs should be well considered in the steps of both system development and application in order to yield satisfying results. In this regard, this thesis presents a comprehensive review of the applications of unmanned aerial imagery, where the objective was to determine the challenges that remote-sensing applications of UAV systems currently face. This review also allowed recognizing the specific characteristics and requirements of UAV-PSs, which are mostly ignored or not thoroughly assessed in recent studies. Accordingly, the focus of the first part of this thesis is on exploring the methodological and experimental aspects of implementing a UAV-PS. The developed system was extensively evaluated for precise modeling of an open-pit gravel mine and performing volumetric-change measurements. This application was selected for two main reasons. Firstly, this case study provided a challenging environment for 3D modeling, in terms of scale changes, terrain relief variations as well as structure and texture diversities. Secondly, open-pit-mine monitoring demands high levels of accuracy, which justifies our efforts to improve the developed UAV-PS to its maximum capacities. The hardware of the system consisted of an electric-powered helicopter, a high-resolution digital camera, and an inertial navigation system. The software of the system included the in-house programs specifically designed for camera calibration, platform calibration, system integration, onboard data acquisition, flight planning and ground control point (GCP) detection. The detailed features of the system are discussed in the thesis, and solutions are proposed in order to enhance the system and its photogrammetric outputs. The accuracy of the results was evaluated under various mapping conditions, including direct georeferencing and indirect georeferencing with different numbers, distributions and types of ground control points. Additionally, the effects of imaging configuration and network stability on modeling accuracy were assessed. The second part of this thesis concentrates on improving the techniques of sparse and dense reconstruction. The proposed solutions are alternatives to traditional aerial photogrammetry techniques, properly adapted to specific characteristics of unmanned, low-altitude imagery. Firstly, a method was developed for robust sparse matching and epipolar-geometry estimation. The main achievement of this method was its capacity to handle a very high percentage of outliers (errors among corresponding points) with remarkable computational efficiency (compared to the state-of-the-art techniques). Secondly, a block bundle adjustment (BBA) strategy was proposed based on the integration of intrinsic camera calibration parameters as pseudo-observations to Gauss-Helmert model. The principal advantage of this strategy was controlling the adverse effect of unstable imaging networks and noisy image observations on the accuracy of self-calibration. The sparse implementation of this strategy was also performed, which allowed its application to data sets containing a lot of tie points. Finally, the concepts of intrinsic curves were revisited for dense stereo matching. The proposed technique could achieve a high level of accuracy and efficiency by searching only through a small fraction of the whole disparity search space as well as internally handling occlusions and matching ambiguities. These photogrammetric solutions were extensively tested using synthetic data, close-range images and the images acquired from the gravel-pit mine. Achieving absolute 3D mapping accuracy of 11±7 mm illustrated the success of this system for high-precision modeling of the environment.

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Phase change problems arise in many practical applications such as air-conditioning and refrigeration, thermal energy storage systems and thermal management of electronic devices. The physical phenomenon in such applications are complex and are often difficult to be studied in detail with the help of only experimental techniques. The efforts to improve computational techniques for analyzing two-phase flow problems with phase change are therefore gaining momentum. The development of numerical methods for multiphase flow has been motivated generally by the need to account more accurately for (a) large topological changes such as phase breakup and merging, (b) sharp representation of the interface and its discontinuous properties and (c) accurate and mass conserving motion of the interface. In addition to these considerations, numerical simulation of multiphase flow with phase change introduces additional challenges related to discontinuities in the velocity and the temperature fields. Moreover, the velocity field is no longer divergence free. For phase change problems, the focus of developmental efforts has thus been on numerically attaining a proper conservation of energy across the interface in addition to the accurate treatment of fluxes of mass and momentum conservation as well as the associated interface advection. Among the initial efforts related to the simulation of bubble growth in film boiling applications the work in \cite{Welch1995} was based on the interface tracking method using a moving unstructured mesh. That study considered moderate interfacial deformations. A similar problem was subsequently studied using moving, boundary fitted grids \cite{Son1997}, again for regimes of relatively small topological changes. A hybrid interface tracking method with a moving interface grid overlapping a static Eulerian grid was developed \cite{Juric1998} for the computation of a range of phase change problems including, three-dimensional film boiling \cite{esmaeeli2004computations}, multimode two-dimensional pool boiling \cite{Esmaeeli2004} and film boiling on horizontal cylinders \cite{Esmaeeli2004a}. The handling of interface merging and pinch off however remains a challenge with methods that explicitly track the interface. As large topological changes are crucial for phase change problems, attention has turned in recent years to front capturing methods utilizing implicit interfaces that are more effective in treating complex interface deformations. The VOF (Volume of Fluid) method was adopted in \cite{Welch2000} to simulate the one-dimensional Stefan problem and the two-dimensional film boiling problem. The approach employed a specific model for mass transfer across the interface involving a mass source term within cells containing the interface. This VOF based approach was further coupled with the level set method in \cite{Son1998}, employing a smeared-out Heaviside function to avoid the numerical instability related to the source term. The coupled level set, volume of fluid method and the diffused interface approach was used for film boiling with water and R134a at the near critical pressure condition \cite{Tomar2005}. The effect of superheat and saturation pressure on the frequency of bubble formation were analyzed with this approach. The work in \cite{Gibou2007} used the ghost fluid and the level set methods for phase change simulations. A similar approach was adopted in \cite{Son2008} to study various boiling problems including three-dimensional film boiling on a horizontal cylinder, nucleate boiling in microcavity \cite{lee2010numerical} and flow boiling in a finned microchannel \cite{lee2012direct}. The work in \cite{tanguy2007level} also used the ghost fluid method and proposed an improved algorithm based on enforcing continuity and divergence-free condition for the extended velocity field. The work in \cite{sato2013sharp} employed a multiphase model based on volume fraction with interface sharpening scheme and derived a phase change model based on local interface area and mass flux. Among the front capturing methods, sharp interface methods have been found to be particularly effective both for implementing sharp jumps and for resolving the interfacial velocity field. However, sharp velocity jumps render the solution susceptible to erroneous oscillations in pressure and also lead to spurious interface velocities. To implement phase change, the work in \cite{Hardt2008} employed point mass source terms derived from a physical basis for the evaporating mass flux. To avoid numerical instability, the authors smeared the mass source by solving a pseudo time-step diffusion equation. This measure however led to mass conservation issues due to non-symmetric integration over the distributed mass source region. The problem of spurious pressure oscillations related to point mass sources was also investigated by \cite{Schlottke2008}. Although their method is based on the VOF, the large pressure peaks associated with sharp mass source was observed to be similar to that for the interface tracking method. Such spurious fluctuation in pressure are essentially undesirable because the effect is globally transmitted in incompressible flow. Hence, the pressure field formation due to phase change need to be implemented with greater accuracy than is reported in current literature. The accuracy of interface advection in the presence of interfacial mass flux (mass flux conservation) has been discussed in \cite{tanguy2007level,tanguy2014benchmarks}. The authors found that the method of extending one phase velocity to entire domain suggested by Nguyen et al. in \cite{nguyen2001boundary} suffers from a lack of mass flux conservation when the density difference is high. To improve the solution, the authors impose a divergence-free condition for the extended velocity field by solving a constant coefficient Poisson equation. The approach has shown good results with enclosed bubble or droplet but is not general for more complex flow and requires additional solution of the linear system of equations. In current thesis, an improved approach that addresses both the numerical oscillation of pressure and the spurious interface velocity field is presented by featuring (i) continuous velocity and density fields within a thin interfacial region and (ii) temporal velocity correction steps to avoid unphysical pressure source term. Also I propose a general (iii) mass flux projection correction for improved mass flux conservation. The pressure and the temperature gradient jump condition are treated sharply. A series of one-dimensional and two-dimensional problems are solved to verify the performance of the new algorithm. Two-dimensional and cylindrical film boiling problems are also demonstrated and show good qualitative agreement with the experimental observations and heat transfer correlations. Finally, a study on Taylor bubble flow with heat transfer and phase change in a small vertical tube in axisymmetric coordinates is carried out using the new multiphase, phase change method.

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Biochemical agents, including bacteria and toxins, are potentially dangerous and responsible for a wide variety of diseases. Reliable detection and characterization of small samples is necessary in order to reduce and eliminate their harmful consequences. Microcantilever sensors offer a potential alternative to the state of the art due to their small size, fast response time, and the ability to operate in air and liquid environments. At present, there are several technology limitations that inhibit application of microcantilever to biochemical detection and analysis, including difficulties in conducting temperature-sensitive experiments, material inadequacy resulting in insufficient cell capture, and poor selectivity of multiple analytes. This work aims to address several of these issues by introducing microcantilevers having integrated thermal functionality and by introducing nanocrystalline diamond as new material for microcantilevers. Microcantilevers are designed, fabricated, characterized, and used for capture and detection of cells and bacteria. The first microcantilever type described in this work is a silicon cantilever having highly uniform in-plane temperature distribution. The goal is to have 100 μm square uniformly heated area that can be used for thermal characterization of films as well as to conduct chemical reactions with small amounts of material. Fabricated cantilevers can reach above 300C while maintaining temperature uniformity of 2−4%. This is an improvement of over one order of magnitude over currently available cantilevers. The second microcantilever type is a doped single crystal silicon cantilever having a thin coating of ultrananocrystalline diamond (UNCD). The primary application of such a device is in biological testing, where diamond acts as a stable, electrically isolated reaction surface while silicon layer provides controlled heating with minimum variations in temperature. This work shows that composite cantilevers of this kind are an effective platform for temperature-sensitive biological experiments, such as heat lysing and polymerase chain reaction. The rapid heat-transfer of Si-UNCD cantilever compromised the membrane of NIH 3T3 fibroblast and lysed the cell nucleus within 30 seconds. Bacteria cells, Listeria monocytogenes V7, were shown to be captured with biotinylated heat-shock protein on UNCD surface and 90% of all viable cells exhibit membrane porosity due to high heat in 15 seconds. Lastly, a sensor made solely from UNCD diamond is fabricated with the intention of being used to detect the presence of biological species by means of an integrated piezoresistor or through frequency change monitoring. Since UNCD diamond has not been previously used in piezoresistive applications, temperature-denpendent piezoresistive coefficients and gage factors are determined first. The doped UNCD exhibits a significant piezoresistive effect with gauge factor of 7.53±0.32 and a piezoresistive coefficient of 8.12×10^−12 Pa^−1 at room temperature. The piezoresistive properties of UNCD are constant over the temperature range of 25−200C. 300 μm long cantilevers have the highest sensitivity of 0.186 m-Ohm/Ohm per μm of cantilever end deflection, which is approximately half that of similarly sized silicon cantilevers. UNCD cantilever arrays were fabricated consisting of four sixteen-cantilever arrays of length 20–90 μm in addition to an eight-cantilever array of length 120 μm. Laser doppler vibrometry (LDV) measured the cantilever resonant frequency, which ranged as 218 kHz−5.14 MHz in air and 73 kHz−3.68 MHz in water. The quality factor of the cantilever was 47−151 in air and 18−45 in water. The ability to measure frequencies of the cantilever arrays opens the possibility for detection of individual bacteria by monitoring frequency shift after cell capture.

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Esta Dissertação aborda a temática da eficiência energética em sistemas de iluminação fabris. Desde os primórdios da história da humanidade que a iluminação tem representado um papel importante. Não só garante condições de segurança, como começou por ser o intuito primordial das fogueiras pré-históricas, traduzindo-se num elemento de conforto. Atualmente seria impensável conceber as mais diversas atividades económicas e produtivas de um país sem iluminação. Nesse sentido a iluminação representa também um elemento fomentador de produtividade. Não é bem conhecido o impacto que a iluminação tem nos custos operacionais de uma unidade fabril. Principalmente por ser difícil de quantificar separadamente na fatura de eletricidade qual a percentagem correspondente à iluminação. Tipicamente estes custos podem ascender a 20% do orçamento global da autarquia em países desenvolvidos. Por esse motivo, o sector da iluminação tem investido esforço no sentido de promover melhores soluções de iluminação capazes de por um lado de satisfazer os requisitos do espaço a iluminar, e por outro propiciar soluções eficientes do ponto de vista energético. Estas soluções assentam essencialmente no uso de dispositivos mais eficientes (como por exemplo os LED´s ou as lâmpadas compactas fluorescentes) bem como em estratégias de controlo eficientes baseadas em dados sensoriais (como por exemplo deteção de movimento/presença). A combinação destas estratégias permite reduzir os consumos em cerca de 80% quando comparadas com soluções passivas. A empresa Amorim Cork Research Lda. é uma empresa prestadora de serviços ao universo das empresas da Corticeira Amorim, uma das maiores multinacionais de origem portuguesa. Teve origem no negócio da cortiça, em 1870, sendo hoje líder destacada no sector a nível mundial. Dada a dimensão da empresa e a sua subdivisão em várias Unidades Industriais com requisitos individuais, será expectável que a iluminação represente uma parte significativa da fatura de eletricidade. Atualmente, os vários setores encontram-se equipados com soluções de iluminação diferentes, na sua maioria empregando tecnologias passivas, noutros casos com dispositivos eficientes. Há algum interesse em migrar para soluções mais eficientes, em parte suportadas em DALI (com interface de comunicação PLC ou Zigbee).

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A micro gas sensor has been developed by our group for the detection of organo-phosphate vapors using an aqueous oxime solution. The analyte diffuses from the high flow rate gas stream through a porous membrane to the low flow rate aqueous phase. It reacts with the oxime PBO (1-Phenyl-1,2,3,-butanetrione 2-oxime) to produce cyanide ions, which are then detected electrochemically from the change in solution potential. Previous work on this oxime based electrochemistry indicated that the optimal buffer pH for the aqueous solution was approximately 10. A basic environment is needed for the oxime anion to form and the detection reaction to take place. At this specific pH, the potential response of the sensor to an analyte (such as acetic anhydride) is maximized. However, sensor response slowly decreases as the aqueous oxime solution ages, by as much as 80% in first 24 hours. The decrease in sensor response is due to cyanide which is produced during the oxime degradation process, as evidenced by the cyanide selective electrode. Solid phase micro-extraction carried out on the oxime solution found several other possible degradation products, including acetic acid, N-hydroxy benzamide, benzoic acid, benzoyl cyanide, 1-Phenyl 1,3-butadione, 2-isonitrosoacetophenone and an imine derived from the oxime. It was concluded that degradation occurred through nucleophilic attack by a hydroxide or oxime anion to produce cyanide, as well as a nitrogen atom rearrangement similar to Beckmann rearrangement. The stability of the oxime in organic solvents is most likely due to the lack of water, and specifically hydroxide ions. The reaction between oxime and organo-phosphate to produce cyanide ions requires hydroxide ions, and therefore pure organic solvents are not compatible with the current micro-sensor electrochemistry. By combining a concentrated organic oxime solution with the basic aqueous buffer just prior to being used in the detection process, oxime degradation can be avoided while preserving the original electrochemical detection scheme. Based on beaker cell experiments with selective cyanide sensitive electrodes, ethanol was chosen as the best organic solvent due to its stabilizing effect on the oxime, minimal interference with the aqueous electrochemistry, and compatibility with the current microsensor material (PMMA). Further studies showed that ethanol had a small effect on micro-sensor performance by reducing the rate of cyanide production and decreasing the overall response time. To avoid incomplete mixing of the aqueous and organic solutions, they were pre-mixed externally at a 10:1 ratio, respectively. To adapt the microsensor design to allow for mixing to take place within the device, a small serpentine channel component was fabricated with the same dimensions and material as the original sensor. This allowed for seamless integration of the microsensor with the serpentine mixing channel. Mixing in the serpentine microchannel takes place via diffusion. Both detector potential response and diffusional mixing improve with increased liquid residence time, and thus decreased liquid flowrate. Micromixer performance was studies at a 10:1 aqueous buffer to organic solution flow rate ratio, for a total rate of 5.5 μL/min. It was found that the sensor response utilizing the integrated micromixer was nearly identical to the response when the solutions were premixed and fed at the same rate.