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>

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. 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. 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 in vivo using mouse embryos as the pattern seen in vitro 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 in vitro. 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. 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.

The environmental occurrence and behaviour of the brominated flame retardant (BFR) decabromodiphenyl ethane (dbdpe) has only been studied to a limited extent. It is structurally similar to decabromodiphenyl ether (decaBDE), which makes it conceivable that dbdpe may also become an environmental contaminant of concern. A method for environmental analysis and comparative assessments of dbdpe and decaBDE was developed. Both BFRs were studied in: a mass balance of the Henriksdal WWTP in Stockholm (Paper I); an international survey of sewage sludge (Paper II); sediment along a transect from Henriksdal WWTP to the outer archipelago of Stockholm and from isolated Swedish lakes (Paper III); and a benthic food web from the Scheldt estuary (Paper IV). Dbdpe was found in sludge from every country surveyed, indicating that it may be a worldwide concern. The WWTP mass balance showed that virtually all of the BFRs were transferred from wastewater to sludge. A small fraction was emitted via the effluent, confirming emissions to the aquatic environment. In the marine sediment, the BFR levels close to the WWTP outfall were high. They decreased along the transect to low levels in the outer archipelago. The study of lake sediment showed a widespread presence of dbdpe in the Swedish environment and provided evidence that it originates from long range atmospheric transport. In the food web, dbdpe did bioaccumulate to a small extent which was similar to decaBDE. The transfer of the BFRs from sediment to benthic invertebrates was low, while transfer from prey to predator was higher. Biodilution was observed rather than biomagnification. This work suggests that the persistence, the susceptibility to long range atmospheric transport, and the potential for bioaccumulation are similar for dbdpe and the regulated decaBDE that it is replacing. Thus, there is a risk that a problematic environmental pollutant is being replaced with a chemical that is equally problematic. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.

This thesis aims at developing a method of chemical aftertreatment for reduction of free formaldehyde release of a tetrakis (hydroxymethyl) phosphonium chloride (THPC) urea precondensate, ammonia cured durable flame retardant finished cotton fabric, by preventing the formation of free formaldehyde. Formaldehyde is toxic and carcinogenic. According to the worldwide standards, acceptable limit of free formaldehyde release, for the fabrics that have skin contact, is only 75 ppm (measured by water extraction method). In this research, a cotton fabric flame retardant finished in an industrial plant in Pakistan is used. Fabric is finished by the application of THPC urea precondensate and ammonia cured, oxidized and washed. After finishing, it is not aftertreated with sodium metabisulfite that is a commonly used aftertreatment method for the reduction of free formaldehyde release. Aftertreatment with sodium metabisulfite has various problems that include large number of hot washings and there is an increase in the formaldehyde release during fabric storage. If the fabric has 75 ppm of free formaldehyde, there is often an increase in free formaldehyde release during fabric storage. There is a very limited research on the aftertreatment methods and few reports of application of these aftertreatments on flame retardant fabrics have been published. In this research, two methods of aftertreatments are developed to reduce the free formaldehyde contents to 75 ppm or less. One is the aftertreatment with a combination of resorcinol 1% and diethylene glycol 4%. The other is the combination of resorcinol 1% and boric acid 6%. For both these aftertreatments, ammonium acetate 0.5% is used as a catalyst. Fabric is padded with the solution and then dried at 130̊ C for 8 minutes. After drying, fabric is rinsed with water at 40̊ C. The aftertreatment methods developed in this research have shown a long term effect in keeping the formaldehyde release below 75 ppm during fabric storage that is not available with other conventional aftertreatment methods. These aftertreatment methods have no adverse effect on the flame retardancy of the THPC ammonia cured finished fabric and the fabric is soft as compared to the original flame retardant finished fabric and to the fabric after treated with existing methods. These new developed methods have industrial application because there is no use of any solvent and there is no use of any special equipment for the aftertreatment.

La durabilité des matériaux employés en génie civil est remise en question par le vieillissement physico-chimique de ces matériaux pouvant engendrer des dégradations significatives qui peuvent mettre en péril la stabilité des structures du génie civil. Pour pallier à certains inconvénients des bétons hydrauliques, l'utilisation des matériaux composites à l'instar des bétons de résine, qui possèdent des qualités remarquables par rapport aux matériaux de construction conventionnels, s'avère très intéressant.À l'heure actuelle, les freins majeurs quant aux développements des bétons résines sont d'une part le coût de la résine dont le taux varie, selon l'application industrielle, de 5% à 25% et d'autre part leurs comportements aux températures élevées et au feu puisque les liants dans ces bétons sont des substances organiques qui résistent beaucoup moins à la chaleur que les matières inorganiques. L'objectif de l'étude est de favoriser le développement des bétons résines par la diminution du taux de la résine en optimisant les constituants du béton et l'amélioration de leurs ténues aux températures élevées par l'ajout des additions tout en assurant des performances mécaniques raisonnables. L'optimisation de la formulation du béton est menée sur deux étapes ; la première vise à optimiser le squelette granulaire (sable 0/4 et Gravier 4/10, silico-calcaires) expérimentalement en confrontant les résultats à ceux issus du modèle d'empilement compressible. La deuxième étape vise à optimiser la fraction massique du liant époxydique (6%, 9%, 13% et 16%) sur la base des essais de caractérisation mécaniques et physiques. Le deuxième objectif de l'étude a était menée par l'ajout des ignifugeants appartenant à deux familles différentes c'est-à-dire les hydroxydes de métal et les produits phosphorés inorganiques. Les propriétés physiques, thermiques et mécaniques des bétons additionnées et témoins, avant et après exposition à un cycle de chauffage-refroidissement de la température ambiante à une température de consigne de 100°C, 150°C, 200°C, 225°C et 250 °C avec une vitesse de montée fixée à 0.5°C/min, ont été évaluées par les techniques de caractérisation usuelles en plus des essais d'analyses chimiques et thermiques.Cette étude aboutit à la formulation d'un béton optimal en terme de composition et à évaluer l'effet de l'addition des ignifugeants surtout sur les propriétés thermiques et mécaniques.Mots clés : béton de résine, optimisation, température élevée, ignifugeants, propriétés mécaniques, propriétés physiques, propriétés thermiques. / The material used in civil engineering applications must be re-evaluated because of their physicochemical ageing which can generate significant damages and hence put the stability of civil engineering structures in danger.The replacement of the hydraulic concrete by composite materials as the polymer concrete which offer higher properties compared to conventional construction materials seems to be very interesting. At the present time, the major restrain for the development of polymer concrete are on one hand the cost of the polymer whose ratio varies according to the industrial applications between 5% and 25%, and on the other hand their behaviour when exposed to high temperatures or fire since the resin acting as binder in these polymer concretes are organic substances which are more sensitive to heat than the inorganic matters as cement.The aim of this study was to help the development of polymer concrete by optimizing the formulation and improving their behaviour when exposed the high temperatures by incorporating additions while keeping acceptable mechanical performances.The optimisation of the formulation is done in two steps; the first step consists of optimising the aggregates content (Natural River sands 0/4 mm and crushed gravels 4/10 mm). Experimental results are compared to those given by means Compressible Packing Model. The second step consists of optimizing the amount of polymer (6%, 9%, 13% et 16%) based on mechanical and physical tests.The second aim of this work was fulfilled by the incorporation of two flame retardants belonging to metal hydroxide and phosphorous components types. Physical, thermal and mechanical properties of concretes with or without flame retardant, before and after heating-cooling cycle from ambient temperature to exposure temperature of 100°C, 150°C, 200°C, 225°C et 250 °C with a rate of 0.5°C/min, are evaluated by common characterisation tests besides chemical and thermal ones. This study has leading to obtaining an optimum polymer concrete and evaluates the effect of flame retardant particularly on the thermal and mechanical properties.Keywords: polymer concrete, optimization, high temperatures, flame retardant, mechanical properties, physical properties, thermal properties.