Antimony trioxide (Sb203) and halogenated additives are used together in flameretarded formulations due to their synergistic retardant properties. A study has been made to determine the effects of adding different grades of Sb203 (dSD particle sizes 0.11 um, 0.52um and 1.31 um) into ABS polymer either alone or with commercial brominated materials (BTBPE, TBBA, DBDPO) and an experimental bromine grade (sDBDPO). The Sb20 3 was added at 4wt% loadings and the bromines at 20wt% loadings. The results consider the influence of the additives on processing, mechanical, morphological and flame retardant properties. All compounds were produced using a twin-screw co-rotating extruder and then an injection moulder was used to mould notched impact (falling weight testing), flexural, LOI and UL-94 flame test bars. Samples of all the compounded formulations were titrated to determine Sb20 3 and Br contents. Fracture surface, morphology, size and dispersion analysis was carried out using both SEM and TEM equipment. Osmium tetroxide (OS04) staining was used to determine relative locations of filler particles and polybutadiene phase. Additions of the different antimony trioxide grades showed that the 0.52um and 1.31 um grades lowered impact energy absorption (-25 to -30%) when added at 4wt% loading. The use of a sub-micron size grade (0.1 um) did not significantly lower impact properties (-3%) and had similarly small effects on the flexural modulus and flexural strength. Additions of the brominated materials had much greater effects causing large reductions in impact properties (-20 to :70%). The presence of the bromines generally increased flexural modulus and lowered flexural strength with the exception of TB BA, which increased both modulus and strength. Compounds containing both 1.31 um Sb203 and bromines suffered a further reduction in impact energies, with the bromine properties dominating. Using the 0.1 um Sb20 3 grade again improved impact and flexural properties compared to the 1.31 um grade. The 0.1 um grade resulted in improvements in fire resistance as measured by the UL-94 properties when used with all bromine grades.

De nouvelles matrices thermoplastiques à base de poly(méthacrylate de méthyle) (PMMA) pouvant entrer dans la composition de matériaux composites ont été synthétisées et caractérisées du point de vue de leur température de transition vitreuse (par calorimétrie différentielle à balayage) et de leur dégradation thermique (par analyse thermogravimétrique et par microcalorimétrie). La stratégie suivie était d’incorporer dans les chaînes de PMMA des unités de répétition comportant un groupement latéral phosphoré retardateur de flamme via une copolymérisation radicalaire du MMA avec un monomère phosphoré. Un ensemble de monomères phosphorés retardateurs de flamme ont été synthétisés à partir de l’oxyde de 9,10-dihydro-9-oxa-10-phosphaphenanthrène-10 (DOPO) en faisant varier la nature de la fonction polymérisable (styrénique, acrylique, méthacrylique), la nature de l’atome lié au phosphore (oxygène, carbone, azote) et la longueur du bras espaceur. Nous avons montré qu’en adaptant la structure et la quantité des unités de répétition phosphorées, la température de transition vitreuse du matériau était maintenue proche de celle du PMMA alors que la dégradation thermique des matériaux était déplacée vers de plus hautes températures. Comparativement les mélanges physiques de PMMA et de DOPO avec une même teneur en élément phosphore présentent une température de transition vitreuse significativement plus basse / Novel poly(methyl methacrylate) (PMMA) thermoplastic matrices which can be used in the elaboration of composite materials have been synthesized and characterized from the point of view of their glass transition temperature (by differential scanning calorimetry) and their thermal degradation (by thermogravimetric analysis and by pyrolysis combustion flow calorimetry). The strategy followed was to incorporate in the PMMA chains repeat units comprising a flame retardant phosphorous side group via a radical copolymerization of MMA with a phosphorus-containing monomer. A set of phosphorus-containing flame retardant monomers has been synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide (DOPO) by varying the nature of the polymerizable function (styrenic, acrylic, methacrylic), the nature of the atom bound to the phophore (oxygen, carbon, nitrogen) and the length of the spacer arm. We have shown that by adapting the structure and the quantity of the phosphorus repeating units, the glass transition temperature of the material was kept close to that of the PMMA while the thermal degradation of the materials was shifted to higher temperatures. Comparatively, physical blends of PMMA and DOPO with equivalent phosphorus contents exhibited significantly lower glass transition temperatures

O trabalho visou realizar um estudo sobre o comportamento mecânico e de inflamabilidade de estruturas aeronáuticas de interior fabricadas a partir de compósitos reforçados por fibras naturais, especificamente compósitos de resina fenólica com fibras de algodão e de sisal, verificando assim, a possibilidade de substituir compósitos sintéticos. Num primeiro momento, análises experimentais foram executadas para determinar as propriedades mecânicas dos materiais. Em seguida, análises computacionais foram realizadas, empregando as propriedades referentes aos compósitos sintéticos e reforçados por fibras naturais, utilizando critérios de falha e tendo como referência o desempenho do compósito sintético para uma dada estrutura aeronáutica de interior. Além disso, foram efetuadas análises do seu comportamento quanto à inflamabilidade. A incorporação de retardantes de chama foi necessária para que os compósitos reforçados por fibras naturais atendessem aos requisitos de certificação aeronáutica. Após o processo de aditivação, observou-se um aumento do módulo de elasticidade à flexão (55% para o compósito de algodão, 16% para o compósito de sisal) e a diminuição da tensão de ruptura à flexão dos compósitos reforçados por fibras naturais analisados (45% para o compósito de algodão, 55% para o compósito de sisal). No entanto, com o aumento da espessura da estrutura aeronáutica adotada (5,2% para o compósito de algodão, 10,7% para o compósito de sisal), conclui-se que a substituição do compósito sintético pelo natural seria viável. Isto acarretaria em um aumento de massa em 6,2%, caso a estrutura fosse fabricada em compósito reforçado por fibra de sisal. Finalmente, constatou-se que a fração mássica de aditivo utilizada tem grande potencial de otimização e, que a eficiência dos compósitos reforçados por fibras naturais ainda pode ser melhorada. / This dissertation has aimed to study the mechanical behavior and the flammability of aeronautical interior structures manufactured from composites reinforced by natural fibers, specifically phenolic resin and cotton and sisal fibers composites, verifying the possibility of synthetic composites replacement. Firstly, experimental analyses were performed to determine the mechanical properties of the materials. Then, computational analyses were carried out, using properties of synthetic composites and composites reinforced by natural fibers. Also, failure criteria were applied, considering the synthetic composite performance of an interior aeronautical structure as reference. Furthermore, the behavior regarding flammability was analyzed. The addition of flame retardants was necessary for the composites reinforced by natural fibers in order to attend the aeronautical certification requirements. After the addition of flame retardants, an increase in the flexural modulus of elasticity (55% for the cotton composite, 16% for the sisal composite) and a decrease in the flexural stress at break (45% for the cotton composite, 55% for the sisal composite) were observed. However, with an increase of the thickness of the aeronautical structure (5.2% for the cotton composite, 10.7% for the sisal composite), it was concluded that the replacement would be feasible, which would lead to a increase of the mass equal 6.2% for the sisal fiber composite. Finally, it was evidenced that the used flame retardant mass fraction has a great potential for optimization and that the natural composites efficiency can be improved.

Polypropylene (PP) has excellent mechanical and chemical properties. Thus, it is used in a wide range of applications. However, like for most polymers, the high flammability of PP limits its application in various fields requiring specific flame-retardant standards. Some of halogenated flame retardants are restricted by European Community directives ROHs, WEEE and REACH. Now metallic hydroxides flame retardants are widely used in industry, but the high loading (about 60 wt %) seriously destroys the mechanical properties of polymeric materials. To improve the performance of flame retardant polymers, an environment-friendly electron beam (EB) technology has been successfully used in modifying flame retardant and polymer matrix. In this work, high efficient functional intumescent flame retardants and functional surfactant are designed and prepared for EB technology. In-depth studies the thermal stability, fire behavior and mechanical properties of these flame retardant PP composites have been studied. The possible graft-linking and cross-linking mechanisms of such EB modified composites can be well established. Specially, it is shown that the novel surfactant has better thermal stability in comparison to traditionally used modifiers. Another part of this work deals with the exploration of novel allylamine polyphosphate (AAPP) as flame retardant crosslinker for PP by electron beam (EB) treatment. Multifunctional AAPP showed unique efficient intumescent flame retardant properties. The limiting oxygen index (LOI) value and the effective melt drop resistance in UL-94 test of multifunctional flame retardant PP composites is greatly enhanced. In the cone calorimeter test, a reduction of peak heat release rate, total heat release and smoke production is achieved. Moreover, EB treatment increased the thermal stability of these designed flame retardant PP composites. Furthermore, AAPP provided an excellent quality of char residue in the combustion stage due to P−N−C and P−O−C structure. In addition, synergistic mechanism of AAPP with montmorillonite (MMT) was explored. Finally, different EB parameters have been used to modify fire retardant polymer nanocomposites. The effects of EB treatment on thermal stability, fire behavior and mechanical properties of fire retardant PP nanocomposites have been discussed. The heat release, the production of toxic gases and the mass loss of EB modified fire retardant PP nanocomposites are delayed in accordance to the result of cone calorimeter test. Based on these results high performance fire retardant polymer nanocomposites can be developed for industrial applications such as insulated material of wire, cable, etc.

Novel uses of wheat gluten (WG) proteins, obtained e.g. as a coproduct from bio-ethanol production, are presented in this thesis. A flame-retardant foam was prepared via in-situ polymerization of hydrolyzed tetraethyl orthosilicate (TEOS) in a denatured WG matrix (Paper I). The TEOS formed a well-dispersed silica phase in the walls of the foam. With silica contents ≥ 6.7 wt%, the foams showed excellent fire resistance. An aspect of the bio-based foams was their high sensitivity to fungi and bacterial growth. This was addressed in Paper II using a natural antimicrobial agent Lanasol. In the same paper, a swelling of 32 times its initial weight in water was observed for the pristine WG foam and both capillary effects and cell wall absorption contributed to the high uptake. In Paper III, conductive and flexible foams were obtained using carbon-based nanofillers and plasticizer. It was found that the electrical resistance of the carbon nanotubes and carbon black filled foams were strain-independent, which makes them suitable for applications in electromagnetic shielding (EMI) and electrostatic discharge protection (ESD). Paper IV describes a ‘water-welding’ method where larger pieces of WG foams were made by wetting the sides of the smaller cubes before being assembled together. The flexural strength of welded foams was ca. 7 times higher than that of the same size WG foam prepared in one piece. The technique provides a strategy for using freeze-dried WG foams in applications where larger foams are required. Despite the versatile functionalities of the WG-based materials, the mechanical properties are often limited due to the brittleness of the dry solid WG. WG/flax composites were developed for improved mechanical properties of WG (Paper V). The results revealed that WG, reinforced with 19 wt% flax fibres, had a strength that was ca. 8 times higher than that of the pure WG matrix. Furthermore, the crack-resistance was also significantly improved in the presence of the flax. / <p>QC 20170524</p>

No description available.

[pt] O Acrilonitrila-Butadieno-Estireno (ABS) é um polímero de grande uso industrial, sendo empregado em inúmeros produtos. Muitas de suas aplicações necessitam de uma elevada resistência a combustão seja pela presença de cargas elétricas (Efeito Joule) ou a exposição a ambientes de altas temperaturas. No entanto, o ABS, de modo semelhante a maioria dos polímeros, não é tão resistente a combustão, sendo necessário o emprego de aditivos Retardantes de Chamas (RC). A introdução desses aditivos pode, entretanto, acarretar alteração nas propriedades mecânicas, de forma que é necessário se comparar o comportamento do material com e sem aditivos. Particularmente importante é o comportamento a longo prazo, como a fluência. Assim, nesse trabalho foi avaliado o comportamento a fluência do ABS sem aditivo e de três sistemas ABS/RC. Foi usado um sistema empregando um aditivo comercial à base de bromo (ABS − Br), que serviu como base de comparação e dois sistemas recentemente desenvolvidos, empregando bio-retardantes, a saber: ácido tânico (TA) e polifosfato de amônio (APP). Os resultados dos ensaios mostraram que o aditivo comercial não acarretou variação da vida em fluência em relação ao ABS sem aditivo. Por outro lado, os resultados indicaram que a vida em fluência foi reduzida quando o aditivo APP foi incorporado e que aumentou quando o TA foi adicionado. Os dados experimentais dos ensaios de fluência foram usados para avaliar o comportamento viscoelástico dos quatro grupos de materiais. O ABS teve seu comportamento adequadamente representado pelo modelo de Burgers, assim como a ABS com aditivo à base de bromo. O modelo que melhor descreveu o comportamento do ABS com APP foi o modelo modificado de Burgers (Streched Burgers). Nem todas as amostras do ABS com TA apresentaram fluência no intervalo de tempo usado e o modelo que melhor descreveu o comportamento foi o do sólido linear padrão. / [en] Acrylonitrile-Butadiene-Styrene (ABS) is a polymer of great industrial use, being used in numerous products. Many of its applications require a high resistance to combustion, either due to the presence of electrical charges (Joule Effect) or exposure to high temperature environments. However, ABS, like most polymers, is not as resistant to combustion, requiring the use of Flame Retardant (RC) additives. The introduction of these additives can, however, lead to changes in the mechanical properties, so it is necessary to compare the behavior of the material with and without additives. Particularly important is long-term behavior such as fluency. Thus, in this work, the creep behavior of ABS without additive and of three ABS/RC systems was evaluated. A system employing a commercial bromine-based additive (ABS − Br) was used, which served as a basis for comparison and two recently developed systems employing bio-retardants, namely: tannic acid (TA) and ammonium polyphosphate (APP) . The test results showed that the commercial additive did not cause a change in creep life compared to ABS without additive. On the other hand, the results indicated that the creep life was reduced when the APP additive was incorporated and that it increased when the TA was added. Experimental data from creep tests were used to evaluate the viscoelastic behavior of the four groups of materials. ABS had its behavior adequately represented by the Burgers model, as well as ABS with bromine-based additive. The model that best described the behavior of ABS with APP was the modified Burgers model (Streched Burgers). Not all ABS samples with TA showed fluence in the time interval used and the model that best described the behavior was the standard linear solid.

No description available.

Les travaux proposés portent sur la caractérisation par rayons X des matériaux, en vue du tri de certains d'entre eux dans un flux de déchets. L'objectif final du tri est la valorisation de certains matériaux par le biais des circuits de recyclage. Deux méthodes d'analyse utilisant les rayons X sont décrites : la méthode par transmission bi-énergie et la fluorescence X. Ces deux méthodes sont abordées sous un angle théorique et expérimental. Le mémoire se compose de trois parties. La première partie présente le contexte général de l'étude, les différents scénarios de tri envisagés, les différentes méthodes existantes ainsi que les machines de tri industrielles déjà commercialisées. La seconde partie est consacrée à l'analyse par transmission X bi-énergie. Dans cette partie nous présentons tout d'abord le principe de la décomposition d'un matériau dans une base de deux autres matériaux. Ensuite nous utilisons un code de simulation analytique développé au laboratoire afin d'une part d'optimiser la géométrie du détecteur mais également de prévoir les performances de cette méthode en fonction des scénarios et des matériaux recherchés. Nous avons introduit un critère permettant de quantifier la performance d'un scénario donné. Cette méthode a permis de montrer que plusieurs scénarios de tri et en particulier celui du tri des retardateurs de flamme dans un flux de plastiques sont envisageables par cette méthode. Un prototype de machine industrielle a été construit par la société Bertin Technologies et installé dans les locaux de la société Pellenc ST pour réaliser des tests en conditions réelles de tri. Les résultats de simulation ont été comparés aux essais en conditions réelles. Cette partie se conclue avec une introduction aux méthodes multi-énergie. La troisième et dernière partie s'intéresse à la fluorescence X. L'objectif est de mettre au point une méthode permettant d'identifier la nature du matériau en tenant compte des contraintes industrielles (temps d'acquisition faible), c'est-à-dire lorsque le niveau de signal contenu dans le spectre de fluorescence est faible et bruité. Un banc expérimental a été mis au point au laboratoire et a permis de définir la limite de détection qui dépend du matériau analysé et du temps d'acquisition pour réaliser la mesure. Le second point développé dans cette partie est la mise au point d'une technique de simulation de fluorescence combinant le calcul analytique et le calcul par méthode Monte Carlo. L'avantage de cette technique est d'avoir une méthode de simulation plus rapide par rapport à un calcul qui serait réalisé entièrement par Monte Carlo. En conclusion, nous discutons de la complémentarité des informations issues de ces différentes techniques ainsi que leurs avantages et inconvénients. / The proposed work focuses on the characterization of materials by X-ray to sort some of them in a waste stream. The main aim is the valorization of certain of these materials through recycling loops. Two methods of analysis using X-rays are described : dual energy X-ray transmission and X-ray fluorescence. These two methods are discussed from a theoretical and experimental point of view. The memory consists of four parts. The first part presents the general context of the study, the different sorting scenarios considered, the existing methods and industrial sorting systems already in application. The second part is devoted to analysis by dual energy X-ray transmission. In this section we first present the principle of decomposition of a material in a basis of two other materials. Then we use the VXI simulation tool to optimize the geometry of the detector and to predict the performances of the method according to the scenarios and refined materials. This method showed that several sorting scenarios and particularly sorting of flame retardants in plastic flow are possible by this method. An industrial prototype was built by Bertin Technologies and installed in the premises of Pellenc ST to realize sorting tests under actual conditions. Then the results of simulation have been compared to these tests. This section concludes with an introduction of multi-energy methods. The third part deals with X-ray fluorescence. The aim is to develop a method to identify the nature of the material even if the signal contained in its fluorescence spectrum is low and noisy. A experimental bench was developed in the laboratory to define the limit of detection wich depends on the material analyzed and the acquisition time of the measurement. The second point developed in this part is the development of a simulation technique that combines fluorescence analytical calculation and Monte Carlo calculation. The advantage of this technique is to have a faster simulation method compared to a calculation that would be fully realized by Monte Carlo. In conclusion, we discuss the complementarity of information extracted from these different techniques and their respective advantages and drawbacks.

<p>Developmental toxicology is an important part of preclinical drug toxicology as well as environmental toxicology. Assessing reproductive and developmental toxicity is especially expensive and time demanding, since at least two generations of animals are needed in the tests. In light of this there is a great need for alternative test methods in many areas of developmental toxicity testing.</p><p>The complete set of RNA transcripts in any given organism is called the transcriptome. Proteomics refers to the study of the proteins in a given organism or cell population. The work of this thesis has focused on the use of high throughput screening methods in transcriptomics and proteomics to search for molecular markers of developmental toxicity.</p><p>We have studied the global gene expression effects of the developmentally toxic substance valproic acid (VPA) using microarray technology. Several genes were found that display the same gene expression pattern <i>in vivo</i> using mouse embryos as the pattern seen <i>in vitro</i> using the embryocarcinoma cell line P19. Based on these observations, the gene Gja1 was suggested as one potential molecular marker of VPA induced developmental toxicity and potential marker of histone deacetylase (HDAC) inhibition <i>in vitro</i>. </p><p>Using 2D-DIGE technology, which measures relative protein abundances, the effect of neonatal exposure to the flame retardant PBDE-99 was studied in mouse brain (cortex, hippocampus and striatum) 24 hr after exposure. Differentially expressed proteins in the cortex and the striatum indicate that PBDE-99 may alter neurite outgrowth.</p><p>Finally, we have suggested several improvements in the use of the 2D-DIGE technology. Novel methods for normalizing data were presented, with several advantages compared to existing methods. We have presented a method named DEPPS that makes use of all identified proteins in a dataset to make comprehensive remarks about biological processes affected.</p>