Lors du déclenchement d’un incendie en milieu clos, la quantité d’oxygène du local décroît, entrainant une combustion incomplète. Des gaz chauds imbrûlés peuvent alors s’accumuler dans le local ou dans les gaines de ventilation et un accident thermique peut survenir suite à un apport d’air frais. Ce travail, réalisé pour AREVA, vise à quantifier et d’analyser ce risque, afin de pouvoir le prédire et le prévenir. Tout d’abord, une étude bibliographique a été réalisée afin de définir les paramètres d’auto-inflammation à partir du modèle de Frank-Kamenetskii. Celui-ci permet, après un bilan d’énergie, l’établissement d’un paramètre critique, δC, d’auto-inflammation du mélange. δC réunit la géométrie, la température (et la température ambiante) et la composition du mélange à l’auto-inflammation.Puis, la dégradation thermique du Polyéthylène Haute Densité en fonction de la densité surfacique de flux incident à la surface du matériau et de la sous-ventilation a été caractérisée (cinétique de dégradation, productions gazeuses). Le Cône Calorimètre à Atmosphère Contrôlée a été employé.Ce travail expérimental a permis d’obtenir plusieurs mélanges gazeux suivant les conditions. La dernière partie de l’étude a permis, à partir de δC, de poser le volume de mélange via le rayon comme critère d’auto-inflammabilité des mélanges. En imposant une température, en faisant varier la fraction volumique de chaque gaz combustible entre sa LII et LSI le risque d’accident thermique a été défini. / After the beginning of a fire in a closed room, the oxygen rate in the atmosphere decreases. This implies an incomplete combustion and unburnt gases production. These ones may accumulate in the room or in ventilation pipes, and, after mixing with fresh air, auto-ignite. This could trigger a thermal accident such as backdraft. This present work, conducted for AREVA, aims to analyse this hazard and provide some methods to predict and prevent it. First, a bibliographical research, was carried on to define a mixture’s auto-ignition parameters. This study was based on Frank-Kamenetskii’s model: after establishing the energetics balance between the heat produced by combustion, and the one consumed by conduction, an auto-ignition critical parameter, δC, was defined. It reunites the system’s geometry, temperature (or the room temperature) and composition.Then, the High Density Polythene degradation in a Controlled Atmosphere Cone Calorimeter was studied. The effect on the material’s degradation of under-ventilation and of the energy brought has been tested through the oxygen concentration in the atmosphere and the incident heat flux.During this work many different gas mixtures were analyzed. On the ground of δC formula, the final step was to set the volume, through the radius (characteristic size of the system), as an auto-ignition parameter. Making the concentration of each combustible varying between the LFL and UFL and imposing the temperature allowed to predict this hazard.

Cíle této práce jsou: (i) vyhodnocení vlivu Y2O3 kelímku na kontaminaci indukčně tavené NiTi slitiny obohacené niklem, (ii) optimalizace podmínek, při kterých jsou tavby uskutečněny a (iii) získání nových DSC a 3D AP dat o vlivu vodíkové atmosféry na martenzitickou transformaci a na strukturu NiTi slitin obohacené niklem s tvarovou pamětí. Byly provedeny následující experimenty: – Pět taveb bylo navrženo a provedeno tak, aby byla snížena maximální tavící teplota. – Pět přetaveb bylo uskutečněno při teplotě 1500 C s dobou výdrže 2, 10 a 20 minut a při teplotách 1450 C a 1550 C s 20 minutovou dobou výdrže. Experiment byl navržen tak, aby byl vyšetřen vliv tavící teploty a doby výdrže na obsah kyslíku pocházejícího z kelímku Y2O3 v tavenině. – Tepelné zpracování NiTi slitiny obohacené niklem v režimu I (žíhání) a v režimu II (kombinace žíhání se stárnutím) pod atmosférou vodíku, směsi vodíku s héliem a pod referenční atmosférou čistého hélia. Získané výsledky jsou: – Navržené tavící postupy vedou ke snížení maximální tavící teploty a to z 1800 C na 1400 C. Přesto toto velké snížení maximální tavící teploty nevedlo k významnému poklesu obsahu kyslíku. – Během přetavby uskutečněné při teplotě 1500 C s dobou výdrže 2 minuty se obsah kyslíku navýšil o trojnásobek jeho počáteční hodnoty a příliš se nelišil od obsahu kyslíku naměřeného ve slitině, která byla přetavena při stejné teplotě s dobou výdrže 10 minut. K nárustu o čtyřnásobek počáteční hodnoty obsahu kyslíku došlo u přetavby vedené na teplotě 1450 C po dobu 20 minut a hodnota obsahu kyslíku se příliš nelišila od hodnoty naměřené ve slitině přetavené při teplotě 1550 C se stejnou dobou výdrže. – S rostoucím parciálním tlakem vodíku dochází k potlačení jednokrokové martenzitické transformace. Významný pokles výšky DSC píku nastává při parciálním tlaku 100 mbar. 3D AP analýza odhalila, že nedochází k žádné lokální změně koncentrace a nebo pozic niklových a titanových atomů ve vzorku, který byl žíhán v režimu I ve vodíku. Bylo objeveno, že vodík tvoří stabilní intersticiální tuhý roztok v NiTi B2 mřížce, kde vytváří systém nanodomén s obsahem vodíku vyšší než 10 at%.

Doctor of Philosophy (PhD) / The goal of this research was to investigate changes in the physiological properties including firmness, stiffness, weight, background colour, ethylene production and respiration of ‘Cripps Pink’ apple stored under different temperature and atmosphere conditions,. This research also seeks to establish mathematical models for the prediction of changes in firmness and stiffness of the apple during normal atmosphere (NA) storage. Experiments were conducted to determine the quality changes in ‘Cripps Pink’ apple under three sets of storage conditions. The first set of storage conditions consisted of NA storage at 0oC, 2.5oC, 5oC, 10oC, 20oC and 30oC. In the second set of conditions the apples were placed in NA cold storage at 0oC for 61 days, followed by NA storage at the aforementioned six temperatures. The third set of conditions consisted of controlled atmosphere (CA) (2 kPa O2 : 1 kPa CO2) at 0oC storage for 102 days followed by NA storage at the six temperatures mentioned previously. The firmness, stiffness, weight loss, skin colour, ethylene and carbon dioxide production of the apples were monitored at specific time intervals during storage. Firmness was measured using a HortPlus Quick Measure Penetrometer (HortPlus Ltd, Hawke Bat, New Zealand); stiffness was measured using a commercial acoustic firmness sensor-AFS (AWETA, Nootdorp, The Netherlands). Experimental data analysis was performed using the GraphPad Prism 4.03, 2005 software package. The Least-Squares method and iterative non-linear regression were used to model and simulate changes in firmness and stiffness in GraphPad Prism 4.03, 2005 and DataFit 8.1, 2005 softwares. The experimental results indicated that the firmness and stiffness of ‘Cripps Pink’ apple stored in NA decreased with increases in temperature and time. Under NA, the softening pattern was tri-phasic for apples stored at 0oC, 2.5oC and 5oC for firmness, and at 0oC and 2.5oC for stiffness. However, there were only two softening phases for apples stored at higher temperatures. NA at 0oC, 2.5oC and 5oC improved skin background colour and extended the storage ability of apples compared to higher temperatures. CA during the first stage of storage better maintained the firmness and stiffness of the apples. However, it reduced subsequent ethylene and carbon dioxide (CO2) production after removal from storage. Steep increases in ethylene and CO2 production coincided with rapid softening in the fruit flesh and yellowing of the skin background colour, under NA conditions. The exponential decay model was the best model for predicting changes in the firmness, stiffness and keeping quality of the apples. The exponential decay model satisfied the biochemical theory of softening in the apple, and had the highest fitness to the experimental data collected over the wide range of temperatures. The softening rate increased exponentially with storage temperature complying with the Arrhenius equation. Therefore a combination of the exponential decay model with the Arrhenius equation was found to best characterise the softening process and to predict changes in the firmness and stiffness of apples stored at different temperatures in NA conditions.

Doctor of Philosophy (PhD) / The goal of this research was to investigate changes in the physiological properties including firmness, stiffness, weight, background colour, ethylene production and respiration of ‘Cripps Pink’ apple stored under different temperature and atmosphere conditions,. This research also seeks to establish mathematical models for the prediction of changes in firmness and stiffness of the apple during normal atmosphere (NA) storage. Experiments were conducted to determine the quality changes in ‘Cripps Pink’ apple under three sets of storage conditions. The first set of storage conditions consisted of NA storage at 0oC, 2.5oC, 5oC, 10oC, 20oC and 30oC. In the second set of conditions the apples were placed in NA cold storage at 0oC for 61 days, followed by NA storage at the aforementioned six temperatures. The third set of conditions consisted of controlled atmosphere (CA) (2 kPa O2 : 1 kPa CO2) at 0oC storage for 102 days followed by NA storage at the six temperatures mentioned previously. The firmness, stiffness, weight loss, skin colour, ethylene and carbon dioxide production of the apples were monitored at specific time intervals during storage. Firmness was measured using a HortPlus Quick Measure Penetrometer (HortPlus Ltd, Hawke Bat, New Zealand); stiffness was measured using a commercial acoustic firmness sensor-AFS (AWETA, Nootdorp, The Netherlands). Experimental data analysis was performed using the GraphPad Prism 4.03, 2005 software package. The Least-Squares method and iterative non-linear regression were used to model and simulate changes in firmness and stiffness in GraphPad Prism 4.03, 2005 and DataFit 8.1, 2005 softwares. The experimental results indicated that the firmness and stiffness of ‘Cripps Pink’ apple stored in NA decreased with increases in temperature and time. Under NA, the softening pattern was tri-phasic for apples stored at 0oC, 2.5oC and 5oC for firmness, and at 0oC and 2.5oC for stiffness. However, there were only two softening phases for apples stored at higher temperatures. NA at 0oC, 2.5oC and 5oC improved skin background colour and extended the storage ability of apples compared to higher temperatures. CA during the first stage of storage better maintained the firmness and stiffness of the apples. However, it reduced subsequent ethylene and carbon dioxide (CO2) production after removal from storage. Steep increases in ethylene and CO2 production coincided with rapid softening in the fruit flesh and yellowing of the skin background colour, under NA conditions. The exponential decay model was the best model for predicting changes in the firmness, stiffness and keeping quality of the apples. The exponential decay model satisfied the biochemical theory of softening in the apple, and had the highest fitness to the experimental data collected over the wide range of temperatures. The softening rate increased exponentially with storage temperature complying with the Arrhenius equation. Therefore a combination of the exponential decay model with the Arrhenius equation was found to best characterise the softening process and to predict changes in the firmness and stiffness of apples stored at different temperatures in NA conditions.

[EN] Persimmon (Diospyros kaki L.) 'Rojo Brillante' is an astringent variety characterised by good growing conditions, excellent colour, size, sensory characteristics and good nutritional properties. In the last decade, its production has grown substantially in Spain given the application of high levels of CO2 to remove astringency while firmness is preserved. This technology has also increased its potential as a fresh-cut commodity. However, physical damage during processing result in degradation of the colour and firmness of the product and a higher susceptibility to microbial spoilage that significantly reduces the fruit's shelf life. The objective of the present thesis was to develop optimum procedures for processing and marketing 'Rojo Brillante' persimmon into a fresh-cut product with the maximum shelf life and best physicochemical, nutritional, sensory and microbiological quality. Firstly, the objective was to evaluate the effect of the maturity stage (MS) at harvest, storage time at 15 ºC before processing, and the application of different antioxidant treatments on enzymatic browning, sensory and nutritional quality of fresh-cut 'Rojo Brillante' persimmon during storage at 5 ºC. Concentrations of 10 g L-1 ascorbic acid (AA) or 10 g L-1 citric acid (CA) controlled tissue browning and maintained the visual quality of fresh-cut persimmon above the limit of marketability for 6-8 storage days at 5 ºC, depending on the MS. However, these acidic solutions reduced fruit firmness as compared to control samples. Further studies showed that the combination of these antioxidants with 10 g L-1 CaCl2 maintained firmness of the persimmon slices within the same range as the control samples. In another work, the application of 1-methylcyclopropene (1-MCP) allowed to process fruits after 45 days of storage at 1 ºC with commercial firmness and the antioxidant solution (10 g L-1 CA + 10 g L-1 CaCl2) extended the limit of marketability up to 9 days of storage at 5 ºC. Different controlled atmosphere conditions in combination with AA or CA dips were also evaluated as a first step to select optimum O2 and CO2 concentrations for modified atmosphere packaging (MAP) of fresh-cut 'Rojo Brillante' persimmons. Overall, the combination of antioxidant dips and a controlled atmosphere composed of 5 kPa O2 (balance N2) was proved to be the most effective combination to control enzymatic browning. This atmosphere maintained the visual quality of persimmon slices within the limit of marketability during 7- 9 days at 5 ºC. On the contrary, high CO2 concentrations (10 or 20 kPa) induced darkening in some tissue areas, associated with a flesh disorder known as 'internal flesh browning'. Later studies confirmed the beneficial effect of an active MAP in 5 kPa O2 compared to passive MAP to improve the visual quality of fresh-cut 'Rojo Brillante' persimmon, showing a synergic effect with the antioxidant dip (10 g L-1 CA + 10 g L-1 CaCl2). Antioxidant edible coatings were prepared from whey protein isolate (WPI), soy protein isolate (SPI), hydroxylpropyl methylcellulose (HPMC) and apple pectin as the polymeric matrix. All edible coatings were amended with the antioxidant combination selected (10 g L-1 CA + 10 g L-1 CaCl2). All the edible coatings tested proved effective to control enzymatic browning of persimmon slices. However, the samples treated with the HPMC- and pectin- based coatings were scored with a better visual quality that the rest of the treatments. In general, free radical scavenging activity and total carotenoid content increased in late-season persimmons; whereas, processing (cutting and storage at 5 ºC), antioxidant dips, controlled atmosphere storage or edible coatings had no clear effect on nutritional quality (vitamin C, free radical scavenging activity, total phenolic content, and carotenoids) of fresh-cut persimmons. / [ES] El caqui persimmon (Diospyros kaki L.) 'Rojo Brillante' es un cultivar astringente que presenta unas propiedades organolépticas y nutricionales excelentes. En la última década, su cultivo en el área mediterránea de España se ha incrementado de manera exponencial con el desarrollo de la tecnología que permite eliminar la astringencia, manteniendo la firmeza del mismo. Esta nueva forma de presentación, aporta numerosas ventajas, entre la que se incluye la posibilidad de ser comercializado como fruta fresca cortada. Sin embargo, el éxito comercial del producto está limitado por el pardeamiento enzimático, la pérdida de firmeza y al crecimiento microbiano. En este contexto, el objetivo de la Tesis ha sido el desarrollo de caqui 'Rojo Brillante' fresco cortado mediante un enfoque que integra el estudio de las características del producto en el momento del procesado y de distintas tecnologías que mantengan la calidad físico-química, sensorial, nutricional y microbiológica del producto durante un periodo que permita su comercialización. En primer lugar, se evaluó el efecto del estado de madurez (MS) en el momento de recolección, el tiempo de almacenamiento a 15 ºC antes del procesado y la aplicación de diferentes antioxidantes en el pardeamiento enzimático y la calidad sensorial y nutricional del caqui 'Rojo Brillante' cortado y almacenado a 5 ºC. La aplicación de 10 g L-1 de ácido ascórbico (AA) ó 10 g L-1 ácido cítrico (CA) controló el pardeamiento enzimático y mantuvo la calidad visual del caqui por encima del límite de comercialización entre 6 y 8 días de almacenamiento a 5 ºC, dependiendo del MS. Sin embrago, la aplicación de estos antioxidantes redujo de manera significativa la firmeza del fruto respecto al control. La combinación de estos antioxidantes con 10 g L-1 de CaCl2 permitió mantener la firmeza en el mismo rango que las muestras control. En un trabajo posterior, la aplicación de 1-metilciclopropeno (1-MCP) permitió procesar caqui almacenado 45 días a 1 ºC con una buena firmeza comercial y el tratamiento antioxidante (10 g L-1 CA + 10 g L-1 CaCl2) consiguió alcanzar un límite de comercialización del producto de 9 días a 5 ºC. La evaluación de distintas atmósferas controladas en combinación con tratamientos antioxidantes (AA o CA), como paso previo al envasado en atmósfera modificada (MAP) del caqui, mostró como más efectiva en el control del pardeamiento enzimático la atmósfera compuesta por 5 kPa O2 (balance N2). Esta atmósfera mantuvo la calidad visual del caqui cortado dentro del límite de comercialización durante 7-9 días a 5 ºC. Por el contrario, la aplicación de altas concentraciones de CO2 (10 ó 20 kPa) dio lugar a un pardeamiento en ciertas zonas de la pulpa que se conoce como 'internal flesh browning'. Estudios posteriores confirmaron el efecto beneficioso del envasado de caqui cortado y tratado con solución antioxidante (CA-CaCl2) en una MAP activa de 5 kPa O2 en la calidad visual del fruto frente a la aplicación de una MAP pasiva. El desarrollo de recubrimientos comestibles con capacidad antioxidante se realizó mediante la incorporación de antioxidantes (10 g L-1 CA + 10 g L-1 CaCl2) a formulaciones a base de proteína de suero lácteo (WPI), proteína de soja (SPI), hidroxipropilmetilcelulosa (HPMC) y pectina. Todos los recubrimientos fueron efectivos controlando el pardeamiento enzimático del caqui cortado, siendo las muestras recubiertas con HPMC y pectina las mejor evaluadas visualmente. En general, el procesado, la aplicación de antioxidantes, el envasado en atmósferas controladas y los distintos recubrimientos comestibles estudiados, si bien no mostraron un efecto claro en los parámetros de calidad nutricional evaluados, no tuvieron un efecto negativo en los mismos. Por otra parte, los frutos cosechados a final de campaña tuvieron mayor actividad antioxidante y contenido en carotenoides. / [CAT] El caqui persimmon (Diospyros kaki L.) 'Rojo Brillante' és un cultiu astringent que presenta unes propietats organolèptiques i nutricionals excel¿lents. En la última dècada, el seu cultiu en l'àrea mediterrània d'Espanya s'ha incrementat de manera exponencial amb el desenvolupament de la tecnologia que permet eliminar l'astringència, mantenint la fermesa del mateix. Esta nova forma de presentació, aporta un gran nombre d'avantatges, entre els quals s'inclou la possibilitat de comercialitzar-lo com fruita fresca processada. No obstant, l'èxit comercial del producte està limitat per pardetjament enzimàtic, la pèrdua de fermesa i el creixement microbià. L'objectiu de la Tesis ha estat en el desenvolupament de caqui 'Rojo Brillante' tallat en fresc mitjançant un enfocament que integra l'estudi de les característiques del producte en el moment del processat i de diferents tecnologies en el manteniment de la qualitat físico-química, sensorial, nutricional i microbiològica del producte durant un període que permeta la seua comercialització. En primer lloc, es va avaluar l'efecte de l'estat de maduresa (MS) en el moment de recol¿lecció, el temps d'emmagatzemament a 15ºC abans del processat i l'aplicació de diferents tractaments antioxidants en el pardetjament enzimàtic i la qualitat sensorial i nutricional del caqui 'Rojo Brillante' tallat i emmagatzemat a 5 ºC. L'aplicació de 10 g L-1 d'àcid ascòrbic (AA) o 10 g L-1 d'àcid cítric (CA) va controlar el pardetjament enzimàtic i va mantenir la qualitat visual del caqui per damunt del límit de comercialització entre 6-8 dies d'emmagatzemament a 5 ºC, depenent del MS. No obstant, l'aplicació d'antioxidants va reduir de manera significativa la fermesa del fruit comparat amb el control. La combinació d'aquestos antioxidants amb 10 g L-1 de CaCl2 va permetre mantenir la fermesa en el mateix rang que les mostres control. En un treball posterior, l'aplicació de 1-metilciclopropeno (1-MCP) va permetre processar caqui emmagatzemat 45 dies a 1 ºC amb una bona fermesa comercial i a més, el tractament antioxidant (10 g L-1 CA + 10 g L-1 CaCl2) va aconseguir un límit de comercialització del producte tallat de 9 dies a 5 ºC. L'avaluació de diferents atmosferes controlades en combinació amb tractaments antioxidants (AA o CA), com a pas previ a l'envasament en atmosfera modificada (MAP) del caqui 'Rojo Brillante, va mostrar com a més efectiva en el control del pardetjament enzimàtic l'atmosfera composta per 5 kPa O2 (balanç N2). Aquesta atmosfera va mantenir la qualitat visual del caqui tallat dins del límit de comercialització durant 7-9 dies a 5 ºC. Per contra, l'aplicació d'altes concentracions de CO2 (10 ó 20 kPa) va donar lloc a un pardetjament en certes zones de la polpa, el qual és conegut com 'internal flesh browning'. Estudis posteriors van confirmar l'efecte beneficiós de l'envasament de caqui tallat i tractat amb solució antioxidant (CA-CaCl2) en una MAP activa de 5 kPa O2 millorant la qualitat visual de la fruita front a l'aplicació de una MAP passiva. El desenvolupament de recobriments comestibles amb capacitat antioxidant es va realitzar mitjançant la incorporació d'antioxidants (CA-CaCl2) en formulacions a base de proteïna de sèrum làctic (WPI), proteïna de soia (SPI), hidroxipropilmetilcel-lulosa (HPMC) i pectina. Tots els recobriments van ser efectius controlant el pardetjament enzimàtic del caqui tallat. No obstant, les mostres recobertes amb HPMC i pectina van ser millor avaluades visualment que la resta de tractaments. En general, el processat, l'aplicació d'antioxidants, l'envasament en atmosferes controlades i els distints recobriments comestibles estudiats, si bé no van mostrar un efecte clar en els paràmetres de la qualitat nutricional avaluats, no van tindre un efecte negatiu en els mateixos. Per altra banda, els fruits recol¿lectats a final de temporada van tenir major activitat antioxidant i contingut en / Sanchís Soler, E. (2016). Effect of processing on the physicochemical, sensory, nutritional and microbiological quality of fresh-cut 'Rojo Brillante' persimmon [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/62588 / TESIS