The objective of this study is to develop a robust portable nano-calorimeter sensor for detection of energetic materials, primarily explosives, combustible materials and propellants. A micro-cantilever sensor array is actuated thermally using bi-morph structure consisting of gold (Au: 400 nm) and silicon nitride (Si3N4: 600 nm) thin film layers of sub-micron thickness. An array of micro-heaters is integrated with the microcantilevers at their base. On electrically activating the micro-heaters at different actuation currents the microcantilevers undergo thermo-mechanical deformation, due to differential coefficient of thermal expansion. This deformation is tracked by monitoring the reflected ray from a laser illuminating the individual microcantilevers (i.e., using the optical lever principle). In the presence of explosive vapors, the change in bending response of microcantilever is affected by the induced thermal stresses arising from temperature changes due to adsorption and combustion reactions (catalyzed by the gold surface). A parametric study was performed for investigating the optimum values by varying the thickness and length in parallel with the heater power since the sensor sensitivity is enhanced by the optimum geometry as well as operating conditions for the sensor (e.g., temperature distribution within the microcantilever, power supply, concentration of the analyte, etc.). Also, for the geometry present in this study the nano-coatings of high thermal conductivity materials (e.g., Carbon Nanotubes: CNTs) over the microcantilever surface enables maximizing the thermally induced stress, which results in the enhancement of sensor sensitivity. For this purpose, CNTs are synthesized by post-growth method over the metal (e.g., Palladium Chloride: PdCl2) catalyst arrays pre-deposited by Dip-Pen Nanolithography (DPN) technique. The threshold current for differential actuation of the microcantilevers is correlated with the catalytic activity of a particular explosive (combustible vapor) over the metal (Au) catalysts and the corresponding vapor pressure. Numerical modeling is also explored to study the variation of temperature, species concentration and deflection of individual microcantilevers as a function of actuation current. Joule-heating in the resistive heating elements was coupled with the gaseous combustion at the heated surface to obtain the temperature profile and therefore the deflection of a microcantilever by calculating the thermally induced stress and strain relationship. The sensitivity of the threshold current of the sensor that is used for the specific detection and identification of individual explosives samples - is predicted to depend on the chemical kinetics and the vapor pressure. The simulation results showed similar trends with the experimental results for monitoring the bending response of the microcantilever sensors to explosive vapors (e.g., Acetone and 2-Propanol) as a function of the actuation current.

<p>The theme of this thesis is the reaction to fire performanceof wood and other building products, andparticularly thematerial fire properties time to ignition, rate of heat releaseand smoke production. These properties have been measured by asmall-scale fire test method, the Cone Calorimeter, andpresented for different types of building products.</p><p>Uncertainty analysis, included instrument and assumptionuncertainty, has been performed for the case that both O2 andCO2 are measured for calculation of the rate of heat release inthe Cone Calorimeter. The partial derivatives for theuncertainty analysis are given. The relative uncertainty forthe rate of heat release measurements in the Cone Calorimeteris between ±5% to ±10% for rate of heat releasevalues larger than about 50 kW/m2.</p><p>The time to ignition in the Cone Calorimeter is compatiblewith the time to ignition in the ISO Ignitability test, whichis the main test method for measuring time to ignition. Thetime to ignition is an increasing linear function of density.The rate of heat release in the Cone Calorimeter is dependentof material thickness and of use of retainer frame. Thematerial thickness gives the heat release curve duration andshape. Thin materials have short burning time and two maximumvalues. Thick materials have long burning time and when thematerial is thicker than about 35 mm no second maximum appears.When the retainer frame is used the actual exposed surface isreduced from 0.01 m2 to 0.0088 m2, the rate of heat release isreduced and the burning time is increased. A comparison ofresults with and without use of the retainer frame gives thenequal results when the exposed area is set to 0.0088 m2 in thecase of using the retainer frame.</p><p>The time to flashover in the full-scale room corner test waspredicted on the basis of Cone Calorimeter data at 50 kW/m2 bya power law of ignition time, the total heat release calculatedover 300 s after ignition and the density of the product. Therelation gives a simple relation to evaluate if a productreaches flashover in the room corner test.</p><p>The smoke production has also been measured in the ConeCalorimeter. The white light and the laser smoke measurementsystems have shown similar results. There is a correlationbetween Cone Calorimeter and room corner test smoke productionwhen the products are divided into groups: those that reachflashover in the room corner test in less than 10 min and thosethat have more than 10 min to flashover. Temperature profilesin wood have been measured in the Cone Calorimeter by a simpletechnique. The effect of fire protective gypsum plasterboardson the charring of wood frame members has been determined andcompared with fullscale furnace wall tests. The protectiveeffects of twenty different boards have been presented. ConeCalorimeter and furnace tests show similar charring of wooduntil the boards fall down in furnace tests. After that, thecharring of wood is higher in the furnace, because the wood isexposed directly to the fire.</p><p><b>Keywords:</b>building products, charring of wood, ConeCalorimeter, fire retardant treated wood, fire tests,ignitability, mass loss, rate of heat release, reaction tofire, smoke production, wood products</p>

<p>The latent-heat-storage capacity in Phase-Change Materials can be used for storing or releasing energy within a small temperature interval. Upon the phase transition taking place in a narrow temperature span, the material takes up or releases more energy compared to sensible heat storage. For an ideal phase-change material, the transition temperature is a single value, but for the most common phase-change materials on the market, used in building applications, the transition temperature is distributed within a temperature range of several degrees.</p><p>Integration of phase-change materials in building applications can be effected in several ways, for example by impregnating phase-change materials into porous building materials like concrete, wallboards, bricks or complements of the building structure. Integrating storages filled with phase-change materials makes other implementations, for instance accumulating tanks or envelopes as presented in this thesis, in an air heat exchanger. An appropriate phasetransition temperature of the supposed application is critical to the functionality of the material. For example, in cooling applications, the transition temperature of the material should be a few degrees lower than the requested comfort temperature in the building, and the opposite for heating applications.</p><p>In order to assess the thermal properties and the durability of the material, a watercalorimetric equipment was developed and employed in an accelerated testing programme. The heat capacity of the material and in particular possible change in the heat capacity over time, after thermal cycling of the material, were measured. In the thermal cycling of the material from solid to liquid phase, the temperature rise and required energy supply were recorded. The testing programme was undertaken according to control procedures and documents. In order to be able to utilize the heat-storage capacity in the best way, it is necessary to gain knowledge about thermal properties of the material, especially the long-term behaviour of the material and the deterioration rates of the thermal properties.</p><p>A semi-full-scale air heat exchanger based on phase-change material was developed and tested under real temperature conditions during the summer of 2004. The test results were used to compare and verify computer simulations made on a similar plant. The air heat exchanger utilises the ambient diurnal temperature swing to charge and discharge the phasechange material. The material tested in the calorimeter and in the air heat exchanger has an estimated phase-change temperature of about 24 °C.</p>

Due to their outstanding properties, poly(arylene ethers) are useful as toughness modifiers in epoxy resins (EP). Furthermore, these polymers show rather low intrinsic fire risks. According to recent research it has been incorporated that poly(arylene ether phosphine oxides) [PAEPO’s] can further improve the fire behavior. Increasing phosphorous content of the PAEPO can influence the fire behavior too. Fire retardants containing phosphorus – regardless of whether an additive or reactive approach is used – show different mechanisms in the condensed and gas phase. In the present study PSU Control (BPA based polysulfone) with four different PAEPO’s and their corresponding blends with an EP were investigated. All poly(arylene ether phosphine oxides) were synthesized by nucleophilic aromatic polycondensation. The polymers obtained covered a wide range of weight average molar masses (6,000 – 150,000 g/mol) as determined by size exclusion chromatography with multi-angle light scattering detection (MALLS). FTIR, NMR spectroscopy and MALDI-TOF revealed formation of the desired polymer structure of the linear poly(arylene ethers). All polymers were easily soluble in common organic solvents, thus enabling processing from solution.The pyrolysis and the fire retardancy mechanisms of the polymers and blends with epoxy resin (EP) were tackled by means of a comprehensive thermal analysis (thermogravimetry (TG), TG-evolved gas analysis) and fire tests [PCFC, limiting oxygen index (LOI), UL-94, cone calorimeter]. The Mitsunobu reaction of Dimethyl-5-hydroxyisophthalate and a long chain semifluorinated alcohol requires triphenyl phosphine as a reactant. Identical, in some case higher yield was obtained in the usual conditions, with triphenyl phosphine and with trivalent phosphorus containing polymers, which was prepared in solvent free bulk (melt) polymerization technique from trivalent phosphorus monomer and a silylated diphenol in presence of CsF. Purification and the recovery of the final product which is always a big challenge in case of Mitsunobu reaction, was far more easier using polymer compared to triphenyl phosphine. During polymerization there was a possibility to have polymer having repeating unit containing both trivalent phosphorus and phosphine oxide. The trivalent phosphorus content of the polymer can be varied using different molar concentration of CsF.

In preparation for the large backgrounds expected to be present in the Belle II detector from the SuperKEKB e+e- collider, the radiation hardness of several large (5 x 5 x 30 cm3) thallium doped cesium iodide (CsI(Tl)) scintillation crystals are studied. The crystal samples studied consist of 2 spare crystals from the Belle experiment using PIN diode readout and 7 spare crystals from the BaBar experiment using photomultiplier tube readout. The radiation hardness of the scintillation properties of the CsI(Tl) crystals was studied at accumulated 1 MeV photon doses of 2, 10 and 35 Gy. At each dose, the longitudinal uniformity of the crystals light yield, scintillation decay times, time resolution and energy resolution was measured. As the Belle II collaboration is considering an upgrade to pure CsI crystals if CsI(Tl) does not satisfy radiation hardness requirements, the scintillation properties of a pure CsI scintillation crystal were also measured and compared to the CsI(Tl) crystal measurements. In addition to experimental work, Monte Carlo simulations using GEANT4 were written to compare ideal pure CsI and CsI(Tl) crystals and to study the effects of radiation damage on the performance of the Belle II electromagnetic calorimeter. / Graduate

Le Spectromètre Magnétique Alpha (AMS) est un détecteur de particules installé à bord de la Station Spatiale Internationale ; il enregistre des données depuis mai 2011. L'expérience a pour objectif d'identifier la nature des rayons cosmiques chargés et des photons et de mesurer leur flux dans la gamme d'énergie du GeV au TeV. Ces mesures permettent d'affiner les modèles de propagation de rayons cosmiques, d'effectuer une recherche indirecte de matière noire, et de chercher l'antimatière primordiale (anti-hélium). Dans ce mémoire, les données des premières années ont été utilisées pour mesurer les flux d'électrons et de leptons (électrons + positons) dans la gamme d'énergie de 0.5 GeV à 700 GeV. L'identification d'électrons nécessite une séparation électrons/protons de l'ordre de 104, obtenue par l'utilisation conjointe des estimateurs de différents sous-détecteurs d'AMS, en particulier du calorimètre électromagnétique (ECAL), du trajectomètre et du détecteur à radiation de transition (TRD). Dans cette analyse, les nombres d'électrons et de leptons sont estimés par un ajustement des distributions de l'estimateur du calorimètre et vérifiés en utilisant l'estimateur du TRD : 11 millions leptons ont été sélectionnés et analysés. Les incertitudes systématiques sont déterminées en variant les coupures de sélection et la procédure d'ajustement. L'acceptance géométrique du détecteur et les efficacités de sélection sont estimées grâce aux données de simulation. Les différences observées sur les échantillons de contrôle issus des données permettent de corriger la simulation. Les incertitudes systématiques associées à ces corrections sont établies en variant les échantillons de contrôle. Au total, à 100 GeV (resp. 700 GeV), l'incertitude statistique du flux de leptons est 2% (30%) et l'incertitude systématique est 3% (40%). Comme les flux se comportent globalement en loi de puissance en fonction de l'énergie, il est important de maitriser la calibration en énergie. Nous avons contrôlé in situ la mesure en énergie du calorimètre en comparant les électrons des données de vol et les données de tests en faisceaux, en utilisant en particulier la variable E/p ou p est la quantité de mouvement mesurée par le trajectomètre. Une deuxième méthode de calibration absolue à basse énergie, indépendante du trajectomètre, basée sur l'effet de la coupure géomagnétique a été développée. Deux modèles de prédiction de la coupure géomagnétique, l'approximation Störmer et le modèle IGRF, ont été testés et comparés. Ces deux méthodes ont permis de contrôler la calibration en énergie à 2% et de vérifier la stabilité des performances du calorimètre dans le temps. / The Alpha Magnetic Spectrometer (AMS) is a particle detector installed on the International Space Station; it starts to record data since May 2011. The experiment aims to identify the nature of charged cosmic rays and photons and measure their fluxes in the energy range of GeV to TeV. These measurements enable us to refine the cosmic ray propagation models, to perform indirect research of dark matter and to search for primordial antimatter (anti-helium). In this context, the data of the first years have been utilized to measure the electron flux and lepton flux (electron + positron) in the energy range of 0.5 GeV to 700 GeV. Identification of electrons requires an electrons / protons separation power of the order of 104, which is acquired by combining the information from different sub-detectors of AMS, in particular the electromagnetic calorimeter (ECAL), the tracker and the transition radiation detector (TRD). In this analysis, the numbers of electrons and leptons are estimated by fitting the distribution of the ECAL estimator and are verified using the TRD estimator: 11 million leptons are selected and analyzed. The systematic uncertainties are determined by changing the selection cuts and the fit procedure. The geometric acceptance of the detector and the selection efficiency are estimated thanks to simulated data. The differences observed on the control samples from data allow to correct the simulation. The systematic uncertainty associated to this correction is estimated by varying the control samples. In total, at 100 GeV (resp. 700 GeV), the statistic uncertainty of the lepton flux is 2% (30%) and the systematic uncertainty is 3% (40%). As the flux generally follows a power law as a function of energy, it is important to control the energy calibration. We have controlled in-situ the measurement of energy in the ECAL by comparing the electrons from flight data and from test beams, using in particular the E/p variable where p is momentum measured by the tracker. A second method of absolute calibration at low energy, independent from the tracker, is developed based on the geomagnetic cutoff effect. Two models of geomagnetic cutoff prediction, the Störmer approximation and the IGRF model, have been tested and compared. These two methods allow to control the energy calibration to a precision of 2% and to verify the stability of the ECAL performance with time.

This thesis deals with two aspects of the International Linear Collider (ILC) which is a project of a linear electron-positron collider of up to at least 500 GeV center of mass energy.The first aspect is the development of a silicon-tungsten electromagnetic calorimeter (SiW-ECAL) for one of the detectors of the ILC. The concept of this detector is driven by the ILC beam specifications and by the Particle Flow Algorithm (PFA). This requires highly granular calorimeter and very compact one with integrated electronics. To prove the capability of the SiW- ECAL a technological prototype has been built and tested in test beam at DESY. The results are presented here, and show, after the calibration procedure a signal over noise ratio of 10, even in the power pulsing mode.The second aspect is the study of one of the important physics channels of the ILC, the top anti-top quark pairs production. The main goal of this study is to determine the precision that we can expect at the ILC on the top coupling with the W boson and the photon. To get this precision differents observables are used, the cross- section, the forward- backward asymmetry and the helicity distribution of the top anti-top quark pairs production. The analysis is based on the events with polarized beams and reconstructed with the full simulation of the ILD detector, which is the detector of the SIW- ECAL, for the Detector Baseline Design of the ILD. The final expected errors on the top coupling is of the order of 2%.

This document, prepared to obtain the "Habilitation à Diriger des Recherches", is a compendium of the photon-related analysis activities I carried on within ATLAS in the past four years and a half. The activities I will describe can be broadly classified into three categories: optimization and/or in situ measurement of photon-related performance, measurements of the cross sections of Standard Model processes producing prompt photons, and searches (leading to discovery!) of a Standard Model Higgs boson decaying to final states containing photons.

A differential, membrane-based nanocalorimeter has been designed and constructed for thermal studies of mesoscopic samples at low temperatures. The calorimeter is intended for sample masses from mg to sub-μg and a broad temperature range from above room temperature down to the sub-K region. It allows concurrent use of ac steady state and relaxation methods. Effort was spent to achieve good absolute accuracy to enable investigations of the electronic contribution to the heat capacity of superconductors. The calorimeter consists of a pair of cells, each of which is a stack of heaters and thermometer in the center of a silicon nitride membrane, in total giving a background heat capacity less than 100 nJ/K at 300 K, decreasing to 10 pJ/K at 1 K. The device has several distinctive features: i) The resistive thermometer, made of a GeAu alloy, displays a high sensitivity, dlnR/dlnT ≈ −1 over the entire temperature range. ii) The sample is placed in direct contact with the thermometer, which is allowed to self-heat. The thermometer can thus be operated at high dc current to increase the resolution. iii) Data are acquired with a set of eight synchronized lock-in amplifiers measuring dc, 1st and 2nd harmonic signals of heaters and thermometer. iv) Absolute accuracy is achieved via a novel variable-frequency fixed-phase technique in which the measurement frequency is automatically adjusted during ac-calorimetry measurements to account for the temperature variation of the sample specific heat and the device thermal conductance. The properties of the empty cell and the effect of the thermal link between sample and cell were analytically studied. Practical expressions for describing the frequency dependence of heat capacity, thermal conductance, and temperature oscillation amplitude of the system were formulated. Comparisons with measurements and numerical simulations show excellent agreement. Calibration procedures are simple, but care should be taken to minimize thermal radiation effects. The experimental setup is operated with self-regulation of heater powers and thermometer bias, including compensation to zero the differential dc signal. As a result its high resolution and compact format, the calorimeter is well suited for studies of phase transitions and phase diagrams as well as electronic specific heat. The performance of the device is demonstrated by a study of the superconducting state of a small lead crystal. / En differentiell, membran-baserad nanocalorimeter har designats och tillverkats för termiska studier av mesoskopiska prover vid låg temperatur. Kalorimetern är avsedd för provmassor från mg till sub-μg och ett brett temperaturområde från över rumstemperatur till under 1 K. Den tillåter samtidig användning av både ac steady state och relaxations-metod. Fokus har lagts på att uppnå en god absolut noggrannhet för att möjliggöra studier av det elektroniska bidraget till värmekapaciteten hos supraledare. Kalorimetern består av två celler, var och en uppbyggd som en stack med värmeelement och termometer i mitten av ett kiselnitrid-membran, med en total bakgrundsvärmekapacitet på mindre än 100 nJ/K vid 300 K, minskande till 10 pJ/K vid 1 K. Kalorimetern har flera särdrag: i) Den resistiva termometern, gjord av en GeAu legering, visar en hög känslighet, dlnR/dlnT ≈ −1 över hela temperaturområdet. ii) Provet placeras i direkt kontakt med termometern, som tillåts att självvärma. Termometern kan alltså användas vid hög dc ström för att öka upplösningen. iii) Mätningarna genomförs med en uppsättning av åtta synkroniserade lock-in förstärkare, som mäter dc, grundfrekvens och 1:a övertonen hos värme-element och termometer. iv) Absolut noggrannhet uppnås genom en ny variabel-frekvens konstant-fas teknik där mätfrekvensen justeras automatiskt under ac-kalorimetrimätningar för att kompensera temperaturberoendet hos provets specifika värmekapacitet och kalorimetercellens värmeledningsförmåga. Egenskaperna hos den tomma cellen och inverkan av den termiska länken mellan prov och cell studerades analytiskt. Praktiska uttryck för att beskriva frekvens beroendet hos systemets värmekapacitet, värmeledningsförmåga, och temperaturoscillationer har formulerats. Jämförelser mellan mätningar och numeriska simuleringar visar mycket bra överensstämmelse. Kalibreringsförfarandet är enkelt, men försiktighet bör vidtas för att minimera värmestrålningseffekter. Experimentuppställningen drivs med självreglering av värmare och termometer, inklusive kompensation för att nollställa den differentiella dc signalen. Som en följd av dess höga upplösning och kompakta format är kalorimetern väl lämpad för studier av fasövergångar och fasdiagram såväl som det elektroniska specifika värmet. Kalorimeterns prestanda demonstreras genom en studie av det supraledande tillståndet hos en liten blykristall. / At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Accepted.

O presente trabalho objetiva estudar a eficiência térmica do arco elétrico e de fusão para o processo de soldagem MAG, do inglês Metal Active Gas, em diferentes geometrias de juntas soldadas. As soldas foram feitas inicialmente em um calorímetro de fluxo contínuo de água, seguidas de deposição de cordão sobre chapa e soldagem de juntas em ângulo “T”, sempre em aço carbono. A metodologia de projeto de experimentos Box-Behnken foi empregada para a avaliação da influência da variação dos parâmetros de soldagem (tensão, velocidade de alimentação do eletrodo e velocidade de soldagem) nas eficiências, dentro do modo de transferência metálica por curto circuito. Diferentes equações propostas na literatura para o cálculo da eficiência de fusão são comparadas. Para a adequada aquisição da eficiência térmica pelo calorímetro, preliminarmente é avaliada a influência da vazão de água e da geometria na entrada de um calorímetro de fluxo contínuo sobre a eficiência térmica do arco. O procedimento experimental consiste em testar diferentes vazões de água e três configurações geométricas na região de entrada de água no calorímetro: com rolha reta, com difusor cônico e com obstáculo. Os experimentos foram planejados e os resultados avaliados com base na análise de variância estatística de um único fator, no caso, a vazão de água na entrada do calorímetro. A maior eficiência térmica média de 80,5% foi obtida para a vazão de 4 l/min, com baixo erro estatístico, utilizando rolha de entrada com geometria de difusor cônico. O modelo em que o fluxo entra diretamente no tubo apresentou todos os valores de eficiência térmica do arco com pequeno decréscimo numérico se comparados com o difusor cônico, enquanto a rolha com obstáculo apresentou elevado erro estatístico. Com base nos resultados descritos, a eficiência térmica do arco elétrico foi avaliada com a vazão de 4 l/min para o projeto de experimentos Box-Behnken, os valores obtidos estão na faixa de 72 a 82% conforme a combinação dos parâmetros de soldagem. A velocidade de soldagem e a tensão do arco se mostraram como os parâmetros de maior influência na eficiência térmica do arco. Os resultados relativos à eficiência de fusão indicam maiores valores nas soldas realizadas no calorímetro e por simples deposição sobre chapa. A junta T apresentou os menores valores de eficiência de fusão e de diluição para todos os casos. O parâmetro de maior influência na eficiência de fusão foi a corrente de soldagem. / The main aim of the present work is to study arc thermal efficiency and fusion efficiency to Gas Metal Arc Welding – GMAW, using different joint geometries. At first, the welds were performed in a continuous water flow calorimeter, followed by bead on plate and T – joint deposits. The Box-Behken design of experiments methodology was used to analyze the effect of welding parameters (arc voltage, wire feed speed and welding speed) on the efficiencies, when using short circuit metal transfer. The results of the fusion efficiency calculation were compared using different equations found in the literature. To correctly evaluate the thermal efficiency, it was necessary to analyze the influence of water flow rate and calorimeter inlet geometry. The experimental procedure consists of varying water flow rate and testing three different calorimeter inlet seal geometries: straight seal, conical diffuser seal and seal with water flux obstacle. The experiments were designed and the results evaluated based in a one-factor statistical analysis of variance, in this case the inlet calorimeter water flow. The highest average thermal efficiency is 80.5% to water flow of 4 l/min, with a low statistical error, using the conical diffuser seal inlet geometry. The inlet with straight seal model shown all the arc thermal efficiency values with slightly lower numerical values compared with conical diffuser, while the seal with flux obstacle exhibited high statistical error. Based on these results, the arc thermal efficiency was evaluated using 4 l/min water flow to the Box-Behnken Design, resulting values in the 72 to 82% range, depending on the welding parameters. The welding speed and arc voltage were the parameters that significantly affect arc thermal efficiency. The fusion efficiency results of the welds performed on the calorimeter and bead on plate were. The welds performed in T joints exhibit lowest fusion efficiency and dilution to each welding parameters combination tested. The fusion efficiency is strongly affected by the welding current.