Extruded colour-based plastic film for the measurement of dissolved CO2

Dissolved CO2 measurements are usually made using a Severinghaus electrode, which is bulky and can suffer from electrical interference. In contrast, optical sensors for gaseous CO2, whilst not suffering these problems, are mainly used for making gaseous (not dissolved) CO2 measurements, due to dye leaching and protonation, especially at high ionic strengths (>0.01 M) and acidity (<pH 4). This is usually prevented by coating the sensor with a gas-permeable, but ion-impermeable, membrane (GPM). Herein, we introduce a highly sensitive, colourimetric-based, plastic film sensor for the measurement of both gaseous and dissolved CO2, in which a pH-sensitive dye, thymol blue (TB) is coated onto particles of hydrophilic silica to create a CO2-sensitive, TB-based pigment, which is then extruded into low density polyethylene (LDPE) to create a GPM-free, i.e. naked, TB plastic sensor film for gaseous and dissolved CO2 measurements. When used for making dissolved CO2 measurements, the hydrophobic nature of the LDPE renders the film: (i) indifferent to ionic strength, (ii) highly resistant to acid attack and (iii) stable when stored under ambient (dark) conditions for >8 months, with no loss of colour or function. Here, the performance of the TB plastic film is primarily assessed as a dissolved CO2 sensor in highly saline (3.5 wt%) water. The TB film is blue in the absence of CO2 and yellow in its presence, exhibiting 50% transition in its colour at ca. 0.18% CO2. This new type of CO2 sensor has great potential in the monitoring of CO2 levels in the hydrosphere, as well as elsewhere, e.g. food packaging and possibly patient monitoring.

Initiation of Orderly Spinning Detonation Waves via Phased Sparking

Thesis (Master's)--University of Washington, 2016-06

On the modelling of fire atmosphere/sprinkler spray interacting using an Euler-Lagrange framework

An Euler-Lagrange particle tracking model, developed for simulating fire atmosphere/sprinkler spray interactions, is described. Full details of the model along with the approximations made and restrictions applying are presented. Errors commonly found in previous formulations of the source terms used in this two-phase approach are described and corrected. In order to demonstrate the capabilities of the model it is applied to the simulation of a fire in a long corridor containing a sprinkler. The simulation presented is three-dimensional and transient and considers mass, momentum and energy transfer between the gaseous atmosphere and injected liquid droplets.

The FIREDASS (Fire Detection and Suppression Simulation) Model

The FIREDASS (FIRE Detection And Suppression Simulation) project is concerned with the development of fine water mist systems as a possible replacement for the halon fire suppression system currently used in aircraft cargo holds. The project is funded by the European Commission, under the BRITE EURAM programme. The FIREDASS consortium is made up of a combination of Industrial, Academic, Research and Regulatory partners. As part of this programme of work, a computational model has been developed to help engineers optimise the design of the water mist suppression system. This computational model is based on Computational Fluid Dynamics (CFD) and is composed of the following components: fire model; mist model; two-phase radiation model; suppression model and detector/activation model. The fire model - developed by the University of Greenwich - uses prescribed release rates for heat and gaseous combustion products to represent the fire load. Typical release rates have been determined through experimentation conducted by SINTEF. The mist model - developed by the University of Greenwich - is a Lagrangian particle tracking procedure that is fully coupled to both the gas phase and the radiation field. The radiation model - developed by the National Technical University of Athens - is described using a six-flux radiation model. The suppression model - developed by SINTEF and the University of Greenwich - is based on an extinguishment crietrion that relies on oxygen concentration and temperature. The detector/ activation model - developed by Cerberus - allows the configuration of many different detector and mist configurations to be tested within the computational model. These sub-models have been integrated by the University of Greenwich into the FIREDASS software package. The model has been validated using data from the SINTEF/GEC test campaigns and it has been found that the computational model gives good agreement with these experimental results. The best agreement is obtained at the ceiling which is where the detectors and misting nozzles would be located in a real system. In this paper the model is briefly described and some results from the validation of the fire and mist model are presented.

Monitoring pollutants in occupied spaces.

There is increasing evidence of a causal link between airborne particles and ill health and this study monitored the exposure to both airborne particles and the gas phase contaminants of environmental tobacco smoke (ETS) in a nightclub. The present study followed a number of pilot studies in which the human exposure to airborne particles in a nightclub was assessed and the spatio-temporal distribution of gas phase pollutants was evaluated in restaurants and pubs. The work reported here re-examined the nightclub environment and utilized concurrent and continuous monitoring using optical scattering samplers to measure particulates (PM10) together with multi-gas analysers. The analysis illustrated the highly episodic nature of both gaseous and particulate concentrations in both the dance floor and in the bar area but levels were well below the maximum recommended exposure levels. Short-term exposure to high concentrations may however be relevant when considering the possible toxic effects on biological systems. The results give an indication of the problems associated with achieving acceptable indoor air quality (IAQ) in a complex space and identified some of the problems inherent in the design and operation of ventilation systems for such spaces.

Prediction of Upward Flame Spread over Polymers

In this work, the existing understanding of flame spread dynamics is enhanced through an extensive study of the heat transfer from flames spreading vertically upwards across 5 cm wide, 20 cm tall samples of extruded Poly (Methyl Methacrylate) (PMMA). These experiments have provided highly spatially resolved measurements of flame to surface heat flux and material burning rate at the critical length scale of interest, with a level of accuracy and detail unmatched by previous empirical or computational studies. Using these measurements, a wall flame model was developed that describes a flame’s heat feedback profile (both in the continuous flame region and the thermal plume above) solely as a function of material burning rate. Additional experiments were conducted to measure flame heat flux and sample mass loss rate as flames spread vertically upwards over the surface of seven other commonly used polymers, two of which are glass reinforced composite materials. Using these measurements, our wall flame model has been generalized such that it can predict heat feedback from flames supported by a wide range of materials. For the seven materials tested here – which present a varied range of burning behaviors including dripping, polymer melt flow, sample burnout, and heavy soot formation – model-predicted flame heat flux has been shown to match experimental measurements (taken across the full length of the flame) with an average accuracy of 3.9 kW m-2 (approximately 10 – 15 % of peak measured flame heat flux). This flame model has since been coupled with a powerful solid phase pyrolysis solver, ThermaKin2D, which computes the transient rate of gaseous fuel production of constituents of a pyrolyzing solid in response to an external heat flux, based on fundamental physical and chemical properties. Together, this unified model captures the two fundamental controlling mechanisms of upward flame spread – gas phase flame heat transfer and solid phase material degradation. This has enabled simulations of flame spread dynamics with a reasonable computational cost and accuracy beyond that of current models. This unified model of material degradation provides the framework to quantitatively study material burning behavior in response to a wide range of common fire scenarios.

Study and development of UV photodetectors envisaging COMPASS RICH-1 upgrade and applications

COMPASS is an experiment at CERN’s SPS whose goal is to study hadron structure and spectroscopy. The experiment includes a wide acceptance RICH detector, operating since 2001 and subject to a major upgrade of the central region of its photodetectors in 2006. The remaining 75% of the photodetection area are still using MWPCs from the original design, who suffer from limitations in gain due to aging of the photocathodes from ion bombardment and due to ion-induced instabilities. Besides the mentioned limitations, the increased luminosity conditions expected for the upcoming years of the experiment make an upgrade to the remaining detectors pertinent. This upgrade should be accomplished in 2016, using hybrid detectors composed of ThGEMs and MICROMEGAS. This work presents the study, development and characterization of gaseous photon detectors envisaging the foreseen upgrade, and the progress in production and evaluation techniques necessary to reach increasingly larger area detectors with the performances required. It includes reports on the studies performed under particle beam environment of such detectors. MPGD structures can also be used in a variety of other applications, of which nuclear medical imaging is a notorious example. This work includes, additionally, the initial steps in simulating, assembling and characterizing a prototype of a gaseous detector for application as a Compton Camera.

Design of experiments to optimized the determination of TDIs in agglomerated cork stoppers

Isocyanates are included into a class with an extreme commercial importance because their use in the manufacture of polyurethanes. Polyurethanes are used in several applications such as adhesives, coatings, foams, thermoplastics resins, printing inks, foundry moulds and rubbers. Agglomerated cork stoppers are currently used for still wines, semi-sparkle and gaseous wines, beer and cider. Methylene diphenyl diisocyanate (MDI) is presently the isocyanate used in the production of polyurethane based adhesive in use due to its lowest toxicity comparing with toluene diisocyanate (TDI) previously employed. However, free monomeric TDI or MDI, depending on the based polyurethane, can migrate from agglomerated cork stoppers to beverages therefore it needs to be under control. The presence of these compounds are usually investigated by HPLC with Fluorescence or UV-Vis detector depending on the derivatising agent. Ultra Performance Liquid Chromatography with Diode Array Detector (UPLC-DAD) method is replacing HPLC. The objective of this study is to determine which method is better to analyze isocyanates from agglomerated cork stoppers, essentially TDI to quantify its monomer. A Design of Experiments (DOE) with three factors, column temperature, flow and solvent, at two levels was done. Eight experiments with three replications and two repetitions were developed. Through an ANOVA the significance of the factors was evaluated and the best level’s factors were selected. As the TDI has two isomers and in this method these two isomers were not always separated an ANOVA with results of resolution between peaks was performed. The Design of Experiments reveals to be a suitable statistical tool to determine the best conditions to quantified free isocyanates from agglomerated cork stoppers to real foodstuff. The best level’s factors to maximize area was column temperature at 30ºC, flow to 0,3 mL/min and solvent 0,1% Ammonium Acetate, to maximize resolution was the same except the solvent that was 0,01% Ammonium Acetate.

A Generalized Methodology to Characterize Composite Materials for Pyrolysis Models

The predictive capabilities of computational fire models have improved in recent years such that models have become an integral part of many research efforts. Models improve the understanding of the fire risk of materials and may decrease the number of expensive experiments required to assess the fire hazard of a specific material or designed space. A critical component of a predictive fire model is the pyrolysis sub-model that provides a mathematical representation of the rate of gaseous fuel production from condensed phase fuels given a heat flux incident to the material surface. The modern, comprehensive pyrolysis sub-models that are common today require the definition of many model parameters to accurately represent the physical description of materials that are ubiquitous in the built environment. Coupled with the increase in the number of parameters required to accurately represent the pyrolysis of materials is the increasing prevalence in the built environment of engineered composite materials that have never been measured or modeled. The motivation behind this project is to develop a systematic, generalized methodology to determine the requisite parameters to generate pyrolysis models with predictive capabilities for layered composite materials that are common in industrial and commercial applications. This methodology has been applied to four common composites in this work that exhibit a range of material structures and component materials. The methodology utilizes a multi-scale experimental approach in which each test is designed to isolate and determine a specific subset of the parameters required to define a material in the model. Data collected in simultaneous thermogravimetry and differential scanning calorimetry experiments were analyzed to determine the reaction kinetics, thermodynamic properties, and energetics of decomposition for each component of the composite. Data collected in microscale combustion calorimetry experiments were analyzed to determine the heats of complete combustion of the volatiles produced in each reaction. Inverse analyses were conducted on sample temperature data collected in bench-scale tests to determine the thermal transport parameters of each component through degradation. Simulations of quasi-one-dimensional bench-scale gasification tests generated from the resultant models using the ThermaKin modeling environment were compared to experimental data to independently validate the models.

Características de cinzas e sua aplicação no tratamento de gases durante a gasificação de biomassa

Na procura de melhores combustíveis para a produção de energia térmica e energia elétrica, a biomassa apresenta-se como uma das fontes de energia renováveis menos prejudiciais ao meio ambiente, esta é considerada como um recurso neutro do ponto de vista de emissões de dióxido de carbono. Atualmente, a tecnologia predominante no domínio da conversão energética de biomassa por via termoquímica é a combustão. Contudo, verifica-se a procura de combustíveis de melhor qualidade produzidos a partir de biomassa, como por exemplo na forma gasosa (gás de combustível). A produção deste tipo de combustíveis gasosos envolvendo processos de gasificação carece do desenvolvimento de tecnologia que permita obter um gás combustível com características adequadas às utilizações pretendidas. Os problemas mais relevantes relacionados com a conversão termoquímica da biomassa incluem a produção de cinzas e de alcatrões, estes podem levar a vários problemas operatórios. O presente trabalho teve dois objetivos, a caracterização das cinzas resultantes do processo de combustão de biomassa e o estudo do efeito da aplicação das cinzas para melhorar as propriedades do gás produzido durante o processo de gasificação de biomassa, principalmente na redução de compostos condensáveis (alcatrões). As cinzas volantes da combustão de biomassa analisadas apresentam na sua constituição elementos químicos característicos da biomassa, onde o cálcio apresenta-se em concentrações mais elevadas. Em menores concentrações encontram-se sódio, magnésio, fósforo, enxofre, cloro, potássio, manganês e ferro. As cinzas de fundo, pelo contributo que a areia do leito tem, são caracterizadas por conterem grandes concentrações de silício. Durante os processos de gasificação de biomassa a concentração de compostos condensáveis diminuiu com o aumento da razão de equivalência. As cinzas, colocadas no reator de leito fixo, apresentam um efeito positivo sobre a qualidade do gás, nomeadamente um aumento de 47,8% no teor de H2 e de 11% de CO, consequentemente obteve-se um gás combustível com PCI (poder calorífico inferior) mais elevado.

Nitrogen use efficiency in summer sorghum grown on clay soils

Nitrogen fertilizer inputs dominate the fertilizer budget of grain sorghum growers in northern Australia, so optimizing use efficiency and minimizing losses are a primary agronomic objective. We report results from three experiments in southern Queensland sown on contrasting soil types and with contrasting rotation histories in the 2012-2013 summer season. Experiments were designed to quantify the response of grain sorghum to rates of N fertilizer applied as urea. Labelled 15N fertilizer was applied in microplots to determine the fate of applied N, while nitrous oxide (N2O) emissions were continuously monitored at Kingaroy (grass or legume ley histories) and Kingsthorpe (continuous grain cropping). Nitrous oxide is a useful indicator of gaseous N losses. Crops at all sites responded strongly to fertilizer N applications, with yields of unfertilized treatments ranging from 17% to 52% of N-unlimited potential. Maximum yields ranged from 4500 (Kupunn) to 5450 (Kingaroy) and 8010 (Kingsthorpe) kg/ha. Agronomic efficiency (kg additional grain produced/kg fertilizer N applied) at the optimum N rate on the Vertosol sites was 23 (80 N, Kupunn) to 25 (160N, Kingsthorpe), but 40-42 on the Ferrosols at Kingaroy (70-100N). Cumulative N2O emissions ranged from 0.44% (Kingaroy legume) to 0.93% (Kingsthorpe) and 1.15% (Kingaroy grass) of the optimum fertilizer N rate at each site, with greatest emissions from the Vertosol at Kingsthorpe. The similarity in N2O emissions factors between Kingaroy and Kingsthorpe contrasted markedly with the recovery of applied fertilizer N in plant and soil. Apparent losses of fertilizer N ranged from 0-5% (Ferrosols at Kingaroy) to 40-48% (Vertosols at Kupunn and Kingsthorpe). The greater losses on the Vertosols were attributed to denitrification losses and illustrate the greater risks of N losses in these soils in wet seasonal conditions.

Valorização de resíduos provenientes da atividade no setor avícola: aplicação do processo de compostagem

O setor avícola, como setor em constante crescimento está associado à produção de elevadas quantidades de resíduos sólidos orgânicos. A crescente taxa de produção de resíduos avícolas leva à necessidade de lhes dar um destino adequado podendo a valorização orgânica, nomeadamente a compostagem, ser uma opção. O presente estudo pretende dar um contributo para o projeto de uma unidade de compostagem numa empresa portuguesa do setor, com valorização dos resíduos produzidos pela mesma, avaliando o potencial de aplicação desta operação de tratamento de resíduos e a qualidade do produto final. Como primeiro passo foi realizada uma caracterização dos resíduos a utilizar de forma a perceber a sua possível influência no processo de degradação. Os ensaios de compostagem foram realizados à escala laboratorial, numa gama de temperatura de 50 a 55ᵒC, utilizando como substrato base uma mistura dos resíduos avícolas, de acordo com os seus quantitativos de produção. Vários potenciais agentes estruturantes foram também testados, como adição ao substrato. A monitorização do processo foi feita com base em análises das fases gasosa (gases de exaustão), sólida (substrato em decomposição) e líquida (lixiviado). A avaliação do processo foi ainda complementada com a caracterização dos produtos finais obtidos, os quais foram ainda sujeitos a testes de fitotoxicidade. Foram observados graus de conversão de matéria orgânica relativamente altos (40-50%), comprovando a aplicabilidade desta operação de tratamento de resíduos. Embora a diferença entre ensaios tenha sido pouco notória, a utilização de uma combinação de cama de aviário e mato destroçado e compostado aparenta ser ligeiramente mais eficiente, enquanto a utilização de casca de eucalipto produziu os piores resultados. Perdas de humidade e de azoto foram as duas situações mais críticas observadas para os vários ensaios, tendo influência tanto sobre o processo como sobre o produto final. Os compostos obtidos revelam baixa qualidade, exibindo valores elevados de pH e condutividade elétrica e elevadas concentrações de metais pesados, tais como cobre e zinco. Supõe-se que as características adversas verificadas estejam associadas à aplicação de quantidades demasiado elevadas de cinza nos substratos, levando à necessidade de redução deste material; estudos adicionais seriam necessários a fim de avaliar as possibilidades de ajuste das quantidades a utilizar, dos diferentes materiais, com o intuito de produzir um produto final com qualidade, respeitando os requisitos legais.

Monitorização das condições de operação de uma caldeira a biomassa

A reduzida informação e o pouco trabalho científico desenvolvido na área de sistemas de combustão de biomassa de média potência, faz dos objectivos propostos neste trabalho elementos importantes. O trabalho científico a seguir apresentado, vai permitir obter as bases para o desenvolvimento de condições apropriadas de operação de sistemas de combustão a biomassa, aumentando a eficiência e a rentabilidade económica deste tipo de sistema energético. O principal objetivo do presente trabalho consistiu na aplicação de metodologias de monitorização que permitam caracterizar e melhorar a eficiência do sistema de combustão, na implementação dos métodos escolhidos e na monitorização das condições de operação de uma caldeira industrial de combustão de biomassa, destacando-se: (i) monitorização dos caudais de alimentação de biomassa à caldeira realizada por sistemas de alimentação sem-fim; (ii) análise e monitorização de temperaturas e pressão; (iii) monitorização do caudal de ar de combustão; (iv) monitorização do caudal de gases de exaustão; (v) monitorização da potência térmica; (vi) monitorização da composição do efluente gasoso. A caracterização físicas de amostras de biomassa, o teste a diferentes tipos de biomassa com diferentes condições de operação e a recolha de amostras de cinzas de combustão para a caracterização físico-química são outros métodos de monitorização e caracterização aplicados. Também foi desenvolvido e aplicado um ensaio de controlo do sistema de alimentação em modo de operação manual e comparado com o sistema de controlo do sistema de alimentação em modo de operação automático. O estudo realizado permite concluir que deve ser desenvolvido e implementado um algoritmo de controlo e operação da fornalha que permita um doseamento mais adequado dos caudais de combustível e ar de combustão com vista a melhorar o desempenho do sistema combustão.

Close-in planets around giant stars: lack of hot-Jupiters and prevalence of multiplanetary systems

Extrasolar planets abound in almost any possible configuration. However, until five years ago, there was a lack of planets orbiting closer than 0.5 au to giant or subgiant stars. Since then, recent detections have started to populated this regime by confirming 13 planetary systems. We discuss the properties of these systems in terms of their formation and evolution off the main sequence. Interestingly, we find that 70.0 ± 6.6% of the planets in this regime are inner components of multiplanetary systems. This value is 4.2σ higher than for main-sequence hosts, which we find to be 42.4 ± 0.1%. The properties of the known planets seem to indicate that the closest-in planets (a< 0.06 au) to main-sequence stars are massive (i.e., hot Jupiters) and isolated and that they are subsequently engulfed by their host as it evolves to the red giant branch, leaving only the predominant population of multiplanetary systems in orbits 0.06