Le comportement au feu de matériaux polymères peut changer plus ou moins fortement après vieillissement, mettant en péril les biens et les personnes en cas d’incendie. Ces changements dépendent du système considéré (nature du système retardateur de flamme, de la matrice polymère) et des conditions de vieillissement. Or jusqu’à aujourd’hui, les normes exigent l’évaluation de la réaction au feu d’un matériau juste après fabrication et rarement après un vieillissement représentatif des conditions réelles d’utilisation. L’évolution des caractéristiques des polymères ignifugés au cours du temps est actuellement peu connue, et seules quelques études ont eu lieu à ce sujet. Le travail de cette thèse concerne donc l’impact du vieillissement sur les performances au feu de systèmes complexes de polymères ignifugés. L’étude est basée sur les polymères polyméthacrylate de méthyle (PMMA) et acide polylactique (PLA) ; le système retardateur de flamme est quant à lui constitué de charges phosphorées et de silicates nanométriques. Un protocole de vieillissement et une méthodologie d’étude ont ensuite été mis en place pour déterminer l’influence du vieillissement sur les propriétés de ces matériaux : morphologie, masse molaire des polymères, dégradation des retardateurs de flamme, comportement au feu. Enfin, les caractéristiques des produits émis en phase gaz au cours de la combustion d’échantillons vieillis et non vieillis ont été analysées / The fire behaviour of polymeric materials can be modified after ageing, possibly leading to severe damages. These modifications depend on the chemical nature of the system (polymeric matrix, flame retardant system) and on the ageing conditions. Currently, norms exist, that define fire properties of fresh flame-retarded materials; but only few studies have been performed on aged materials. The aim of this work consists in evaluating the impact of ageing of flame-retarded materials. Firstly, materials have been processed from various formulations. The study focused on poly(methyl methacrylate) (PMMA) and poly(lactic acid) (PLA) polymers; flame-retardant system combining a phosphorus compound and mineral nanoparticles was added. Then an operating procedure has been created to simulate ageing, and a methodology has been developed to assess the characteristics of the composites before and after ageing (viscosity, morphology, fire behaviour). Finally, the combustion aerosols emitted by unaged and aged formulations have been investigated

1994 ändrades den svenska lagstiftningen så att trä blev tillåtet i byggnader över tvåvåningar. Det finns vissa funktionskrav som ska uppfyllas för brandsäkerhet. Dettaarbete innehåller intervjuer med aktörer från byggbranschen som berör deras ochandra aktörers kunskapsnivå i ämnet. Möjligheter att bygga högt med träfasadpresenteras. Studien visar att flera möjligheter för att använda träfasader i höga husges i Boverkets byggregler. Olika aktörerna i byggbranschen uppfattar att de självahar goda kunskaper men att kunskapsbrister i branschen gällande brandskyddskravfinns. / The Swedish legislation of building code was changed in 1994, allowingconstruction of wooden buildings over two floors. To do so there are certainfunctional requirements that must be fulfilled to obtain fire safety. This studydetermines the level of knowledge of different contractors in the constructionindustry in the subject through interviews. The possibilities of using wooden facadesin high-rise building are also presented. The study shows that several possibilities touse wooden facades i high rise buildings are possible according to the legislation.Contractors in the industry consider their knowledge to be sufficient but believesthere is a general lack of knowledge in the industry regarding fire safetyrequirements.

El nostre país ha estat devastat seriosament pels incendis forestals durant els darrers anys, causant greus conseqüències sobre les persones i el medi ambient i destruint una de les fonts de riquesa i equilibri més preuades del territori. A més, les repercussions econòmiques i socials han estat de gran importància.Aquesta tesi doctoral pretén trobar solucions als greus problemes que els incendis forestals representen al nostre país. Se centra en el camp de l'extinció, i més concretament, en l'aplicació de productes retardants a llarg terminiactuant com a tallafocs químics del front d'incendi. Aquesta és una tècnica d'extinció que ofereix enormes possibilitats d'èxit; amb tot, presenta grans incògnites pel que fa a la seva eficàcia i operativitat, a causa de les importants llacunes existents en el seu coneixement sobretot a mitjana i gran escala.Aquesta tesi té dos objectius específics; d'una banda, el de dissenyar una nova metodologia experimental per a l'estudi de l'efecte dels retardants a llarg termini, que permeti extreure la màxima informació sobre les principals variables que determinen el comportament d'un incendi, i de l'altra, el d'obtenir un model matemàtic que predigui l'efecte d'un tractament retardant sobre un front d'incendi, donats els paràmetres d'aplicació.Per a la consecució d'aquests objectius, ha estat dut a terme un extens programa experimental de laboratori a la Universitat de Coimbra (Portugal) i a la Universitat Politècnica de Catalunya (on ha estat dissenyada i posada en funcionament una instal·lació a tal efecte) i també han estat realitzades dues campanyes experimentals a camp, amb vegetació típicament mediterrània. En aquests experiments han estat implementats diferents sistemes d'adquisició de dades de la velocitat de propagació, la velocitat de combustió, la temperatura i la potència calorífica radiant del front d'incendi.Amb el tractament i anàlisi de les dades experimentals han estat detallats els principals fenòmens físics que ocorren quan un front d'incendi transcorre sota l'efecte duna formulació retardant. Finalment, a partir d'aquesta anàlisi, ha estat validat un model teòric de propagació d'incendis forestals basat en el mecanisme de transferència de calor per radiació. Aquest model ha estat adaptat per tal que pugui contemplar l'efecte del tractament retardant i esdevingui una eina predictiva en aquest sentit. / Forest fires have seriously devastated our region during the last years, causing human and environmental damage and destroying one of the most valuable source of wealth and balance of our country. Their economic and social consequences have been very important.This thesis tries to find solutions to the serious problems originated by wildland fires represent in our country. It is focused on the field of extinction and more specifically on the application of long-term fire retardants, which acts as firebreaks of the fire front. This is an extinction technique that offers great possibilities of success; however, it presents many uncertainties related to its efficacy and operational capacity, due to the lack of knowledge at medium and large scale.This PhD thesis has two main objectives; the first one involves designing a new experimental methodology for the study of the effect of long-term fire retardants, which allows extracting the maximum information on the main fire behaviour variables. The later aims at the achievement of a mathematical model to predict the effect of a certain retardant treatment, applied to a fire front, given its application parameters.Wide laboratory experimental programs have been carried out in the University of Coimbra (Portugal) and in the Politechnic University of Catalunya (where an experimental installation had to be designed and started) and two field experimental campaigns with typical Mediterranean vegetation have been realised as well, in order to achieve these objectives. Different data acquisition systems have been implemented so that rate of spread, combustion velocity, temperatures and heat flux by radiation of the fire front could have been recorded.The main physical phenomena that take place in a fire front treated with a retardant formulation have been detailed by means of data analysis.Finally, a theoretical mathematical model based on the radiative heat transfer mechanism has been validated through this analysis. This model has been adapted aiming at the consideration of retardant treatment effects and the achievement of a predictive tool to evaluate them.

Ces travaux de thèse portent sur la photodégradation de retardateurs de flamme bromés  (RFB) : décabromodiphényléther (BDE -209), tétrabromobisphénol A (TBBPA), TBBPA bis (allyl) éther (TBBPA-BAE) et TBBPA bis (2,3-dibromopropyl) éther (TBBPA- DBPE) en milieu solide et dans des échantillons réels. Nous avons d’abord caractérisé par chromatographie en phase liquide-haute résolution couplée à la spectrométrie de masse (LC-HR-MS) le BDE-209 et ses produits de dégradation dans des échantillons de textiles issus de sièges auto des véhicules hors usage (VHUs) des années 90. Puis, nous avons mené des expériences prouvant que ces produits de dégradation étaient d’origine photochimique. Dans un deuxième temps, nous avons étudié l’effet du polystyrène sur la photodégradation du BDE-209, TBBPA et ses dérivés et l’effet de ces RFBs sur la photodégradation du polystyrène. Des analyses par différentes techniques spectroscopiques et chromatographiques (IR, ATR-FTIR, GC-MS, SEC) ont mis en évidence un net effet d’accélération réciproque. La SEC (chromatographie d’exclusion stérique) a révélé une augmentation drastique des coupures de chaîne du PS avec fragmentation. En outre, des photoproduits résultant de l'oxydation du PS et de sa bromation par Br· ont été observés pour la première fois. L’existence de ces sous-produits suggère un nouveau mécanisme de transformation de PS en présence de RFB. Certains de ces photoproduits migrent dans l’eau et l’air, pouvant causer une pollution environnementale. / The main objective of this PhD thesis was to evaluate the photodegradation of brominated flame retardants (BFRs): decabromodiphenyl ether (BDE-209), tetrabromobisphenol A (TBBPA), TBBPA bis (allyl) ether (TBBPA-BAE) and TBBPA bis(2,3-dibromopropyl) ether (TBBPA-DBPE) in solid medium and real samples. As a first step, we characterized by liquid chromatography high-resolution-mass spectrometry (LC-HR-MS) the BDE-209 and its degradation products in textile samples from car seats of end-of-life vehicles (ELVs) of the 1990s. Then we demonstrated that these products were formed by photodegradation. In a second step, we investigated the effect of polystyrene on the photodegradation of BDE-209, TBBPA and its derivatives and the effect of these RFBs on the photodegradation of polystyrene. Analyses carried out by chromatography and spectroscopy techniques (IR, ATR-FTIR, GC-MS, SEC) revealed significant and mutual acceleration effects. SEC (exclusion size chromatography) showed a drastic increase in chain breaks of PS. Morover, additional photoproducts that may result from PS oxidation and Br • bromination has been observed for the first time. The formation of these byproducts suggests a new PS transformation mechanism in the presence of BFR. Some of these photoproducts can migrate into water and air causing environmental pollution.

The Chrysanthemum (Dendranthema grandiflora Tzvelev) and Lisianthus (Eustoma grandiflorum Raf.) are species of ornamental plants of great prominence in the Brazilian and international floriculture. In the cultivation of ornamental plants in pots, is usually performed chemical control of plant growth seeking its standardization. This research aimed to evaluate the responses of these two species to plant growth retardant, sprayed on cutting cultivars conducted in pots in order to obtain a differentiated product, and also define the optimal dose for producing quality plant pots suited to commercial standards. The survey consists of tests in a randomized design. Lisianthus in the model is 3 x 5 factorial, with three cultivars ('Echo Pure White', 'Mariachi Misty Pink' and 'Echo Yellow') and five doses of Paclobutrazol (0, 16, 32, 48 and 64 mg.L-1) applied in spraying. The Chrysanthemum uses 2 x 4 factorial design, frequency of application being tested weekly and biweekly and plant growth retardant Daminozide (0, 2.000, 4.000 and 6.000 mg.L-1) on the cultivar 'Yellow Spithoven'. The results show that the cultivar of Lisianthus 'Echo Yellow' is the most suitable for growing in pots and the best fit is achieved with these commercial spraying of 64 mg.L-1 of Paclobutrazol. The cultivar of Chrysanthemum 'Yellow Spithoven' has driven its growth Daminozide and can be grown in pots, and 2.000 mg L-1 produces the weekly sprayed potted plants of better quality. / O Crisântemo (Dendranthema grandiflora Tzvelev) e o Lisianthus (Eustoma grandiflorum Raf.) são espécies de plantas ornamentais de grande destaque na floricultura brasileira e internacional. Nos cultivos de plantas ornamentais em vaso, normalmente é realizado o controle químico do crescimento da planta buscando a sua padronização. Esta pesquisa teve como objetivos avaliar as respostas dessas duas espécies a retardantes de crescimento de plantas, pulverizados sobre cultivares de corte conduzidas em vaso, visando obter-se um produto diferenciado, e ainda, definir a melhor dose para produção de vasos com plantas de qualidade adequados aos padrões de comercialização. A pesquisa foi constituída de ensaios, no delineamento inteiramente casualizado. No Lisianthus, o modelo foi bifatorial 3 x 5, com três cultivares ( Echo Pure White‟, Mariachi Misty Pink‟ e Echo Yellow‟) e cinco doses de Paclobutrazol (0, 16, 32, 48 e 64 mg.L-1) aplicadas em pulverização. Com o Crisântemo utilizou-se o modelo bifatorial 2 x 4, sendo testada a freqüência de aplicação semanal e bissemanal e o retardante de crescimento vegetal Daminozide (0, 2.000, 4.000 e 6.000 mg.L-1) sobre a cultivar Yellow Spithoven‟. Os resultados evidenciaram que, das cultivares de Lisianthus, a Echo Yellow‟ é a mais apropriada para o cultivo em vaso e a melhor adequação comercial destes é conseguida com a pulverização de 64 mg.L-1 de Paclobutrazol. A cultivar de Crisântemo Yellow Spithoven‟ tem seu crescimento controlado por Daminozide, podendo ser cultivada em vaso, e 2.000 mg.L-1 pulverizados semanalmente produziram os vasos com plantas de melhor qualidade.

Les polyesters insaturés sont des résines thermodurcissables particulièrement appréciées pour leur facilité de mise en œuvre et leur coût modéré. Cependant, comme tous les polymères organiques ils ont une réaction au feu médiocre, ce qui est critique dans un certains nombres de d'applications. L'objectif de cette thèse était d'élaborer de nouvelles formulations de résines ayant un comportement au feu amélioré. La première stratégie développée a été le greffage de monomères phosponés dans la matrice polyester. Des monomères méthacryliques et styrénique ont été synthétisés et utilisés pour remplacer une partie du styrène dans la résine. La stabilité thermique des résines modifiées est diminuée, mais leur comportement au feu est globalement meilleur. Des effets du phosphore en phase gazeuse et en phase condensée ont pu être mis en évidence.Dans une seconde partie, une sélection de particules se distinguant par leur nature, leur taille et leur facteur de forme a été testée. Si l'impact des ces charges est assez limité lorsqu'elles sont utilisées individuellement, des tests calorimétriques ont révélé que certaines combinaisons de particules pouvaient améliorer significativement la réaction au feu des résines. Enfin, des associations d'additifs phosphorés et de particules submicroniques ont été investiguées. Le polyphosphate d'ammonium se distingue des autres additifs par un impact très important sur le comportement au feu et particulièrement par le charbonnement important qu'il engendre, cependant sa combinaison avec des charges inorganiques ne s'est pas révélée probante. / Unsaturated polyesters are thermoset resins particularly appreciated for their low cost and easy processing. Nevertheless one of their main drawbacks is their poor fire resistance. The aim of this PhD thesis was to prepare new resin formulations with an improved fire behaviour. The first part of this work was dedicated to the grafting of phosphorous monomers in the polyester matrix. Methacrylic and styrenic monomers were synthesized and used to replace of part of the styrene in the resin. Resin thermal stability was decreased, but on the whole their fire behaviour was improved. Condensed phase and gas phase effects of phosphorus were highlighted.In a second part, a screening of various kinds of particles with different sizes was performed. Calorimetric tests revealed that, while the effect of these particles used alone is limited, a decrease of resin flammability could be achieved with specific combinations. Finally, commercial phosphorous additives were associated with submicronic fillers. From all the additives tested, ammonium polyphosphate stands out, with a powerful impact on the resin fire reaction and especially a much increased charring. However, its combination with inorganic particles was not conclusive.

La demande actuelle du marché du transport en matériaux composites à matrice polymère est en augmentation importante afin de remplacer les pièces aujourd’hui fabriquées en alliages métalliques par des matériaux plus légers et performants. Actuellement couramment utilisés, les composites thermodurcissables présentent l’inconvénient de ne pas être recyclables. Aussi, un des objectifs du projet « Résines idéales » durant lequel cette thèse a été réalisée est de mettre au point de nouveaux composites à matrice thermoplastique, doués de propriétés équivalentes. Parmi celles-ci, le comportement au feu est un enjeu essentiel pour leur développement et l’objectif de cette thèse est de développer de nouveaux systèmes retardateurs de flamme pour des matériaux composites thermoplastiques à fibres continues. Dans un premier temps, un screening des retardateurs de flamme phosphorés potentiellement efficaces a été effectué. L’étude de l’influence du renfort taffetas sur la stabilité thermique et le comportement au feu a également été réalisée (cône calorimètre, IOL, UL94). Ensuite, afin d’améliorer le comportement au feu, et en particulier, de satisfaire aux normes feu aéronautiques (les plus exigeantes), nous avons étudié des mélanges binaires et ternaires de retardateurs de flamme constitués du RF phosphoré sélectionné et d’autres charges : alumine, hydroxyde d’aluminium (ATH), graphite expansé, et 9,10-dihydro-9-oxy-10-phosphaphenanthrene-10-oxide (DOPO). Dans chaque cas, la stabilité thermique et le comportement au feu ont été caractérisés et discutés / The present demand of polymer-matrix composite materials in the transport market is significantly increasing, to replace the work-pieces actually manufactured in metal alloys, the polymer-matrix composite being lighter and more performant. Thermoset composites are currently and widely used however this kind of composites presents a severe drawback due to their non- recyclable character. One of the objectives of the “Résines idéales” project and of this thesis is to develop new composites made from thermoplastic matrix, endowed with similar properties. Among them, the fire behavior is a major challenge and the aim of this work is to develop new flame retardant systems for thermoplastics composites reinforced with continuous fibers. Firstly, we have performed a screening of potentially effective phosphorus flame retardants. Also, we have studied the influence of the reinforcement taffetas on the thermal stability and fire behavior. For that, various tests have been performed such as cone calorimeter, LOI and UL-94. Then, to improve the fire behavior and particularly to satisfy the aeronautical fire standards (the most challenging), we have studied binary and ternary mixtures of flame retardants constituted by the selected phosphorus flame retardant and other additives: alumina, aluminum hydroxide (ATH), expanded graphite and 9,10-dihydro-9-oxy-10-phosphaphenanthrene-10-oxide (DOPO). In each case, the thermal stability and fire behavior have been characterized and discussed

Polymers are subjected to physical and chemical changes during their processing, service life, and further recovery, and they may also interact with impurities that can alter their composition. These changes substantially modify the stabilisation mechanisms and mechanical properties of recycled polymers. The assessment of the quality properties of recycled polymers is therefore crucial to guarantee the performance of recyclates in further applications. Three key quality properties have been defined for this quality analysis: degree of mixing (composition), degree of degradation, and presence of low molecular weight compounds (degradation products, contaminants, additives). Furthermore, detailed knowledge about how the different stages of their life cycle affect the degree of degradation of polymeric materials is important when discussing their further waste recovery possibilities and the performance of recycled plastics. A dual-pronged experimental approach employing multiple processing and thermo-oxidation has been proposed to model the life cycle of recycled high-impact polystyrene (HIPS used in packaging applications, and electrical and electronic equipment (E&E). Both reprocessing and thermo-oxidative degradation are responsible for coexistent physical and chemical effects (chain scission, crosslinking, apparition of oxidative moieties, polymeric chain rearrangements, and physical ageing) on the microstructure and morphology of polybutadiene (PB) and polystyrene (PS) phases; these effects ultimately influence the long-term stability, and the rheological and mechanical behaviour of HIPS. The PB phase has proved to be the initiation point of HIPS degradation throughout the life cycle. Thermo-oxidation seems to have more severe effects on HIPS properties; therefore, it can be concluded that previous service life may be the part of the life cycle with the greatest influence on the recycling possibilities and performance of HIPS recyclates in second-market applicat / Vilaplana Domingo, FJ. (2008). Analytical strategies for the quality assessment of recycled high-impact polystyrene (HIPS) [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/2186 / Palancia

This graduate work deals with the study and preparation of gel polymer electrolytes with flame retardants for lithium-ion batteries. The theoretical part describes the types of electrolytes, their features, benefits, how they differ and where they are used in detail. The basis of this section is gel electrolytes with flame retardants, to measure their electrical and electrochemical properties. The experimental part deals with the preparation of samples of gel electrolytes with different percentages of flame retardant, where varied species of flame retardants and measuring their electrical conductivity and potential windows. Impedance spectroscopy, cyclic voltammetry and dynamic-analytical thermal analysis were selected as measuring methods.

The thesis deals with the influence of low-flammable electrolytes on negative electrodes. The thesis describes materials used in lithium-ion batteries and functions of individual components. There is also a description of conductometry and electron microscopy, which is used in the practical part, ie during measurement. All findings are summarized at the end of the thesis.