Dans cette étude, nous avons cherché à développer de nouvelles formulations pour améliorer la stabilité thermique et le comportement au feu de trois matrices polymères de grande diffusion: le polyéthylène (PE), le polystyrène (PS) et le polyamide 66 (PA66). Le système intumescent employé consiste à combiner des retardateurs de flammes classiques (polyphosphate d’ammonium (APP) et pentaérythritol (PER)) avec une faible quantité de nanooxydes métalliques dont les propriétés auraient été ajustées sur mesure de façon à améliorer la compatibilité du mélange à l’état fondu, ou encore pour changer le mécanisme de dégradation d’un point de vue chimique (effets catalytiques) ou physiques (effet barrière, viscosité etc…). Une partie importante de cette étude a donc été d’abord consacrée à la synthèse d’oxydes à morphologie, porosité, structure ou fonctionnalités particulières. A cet égard, les silices mésoporeuses possèdent l’avantage de présenter des surfaces spécifiques élevées (700-1400 m²/g) et une taille de pores compatible avec les chaines polymères. En adaptant les conditions de synthèse, nous avons cherché à établir des relations entre certains paramètres relatifs aux silices préparées (tels que la (1) surface spécifique (2) la taille des particules (3) la taille des pores (4) la morphologie et (5) le type de structure (en général SBA-15)) sur la stabilité thermique et le comportement au feu du polyéthylène. Préalablement, les propriétés texturales, structurales et chimiques de ces silices ont été caractérisées par porosimétrie à l’azote à 77K, DRX et FTIR. Globalement, les améliorations apportées par les silices mésostructurées restent modestes par rapport à celles induites par les RF classiques seuls et ceci particulièrement pour les polymères non charbonnants (PE et PS). Ceci est dû probablement à la très grande disparité des teneurs respectives en silice et RF dans les composites testés (1 et 24% en masse, respectivement). L’effet du taux de silice SBA-15 (0,5-10wt%) à taux de charge constant et égal à 25% massique a été également étudié pour les trois matrices polymères. Les valeurs maximales d’IOL (indice limite d’oxygène) sont toujours obtenues pour 1-2% de SBA-15. Les modifications de surface des silices SBA-15 par greffage des différentes fonctions organiques (CTAB, amine, thiol, phénol, phosphonate, acide benzoïque et diphénylphosphate), inorganiques (aluminium, acide phosphorique et acide tungstophosphorique) ou métalliques (cuivre, nickel) ont fait l’objet de caractérisations poussées afin d’évaluer la quantité et la stabilité thermique des espèces greffées ainsi que la nature des liaisons de surface. D’autres types de nanooxydes synthétiques (aluminophosphates, phosphate de zirconium et nanotubes de type titanates) ou commerciaux (CeO2, ZrO2, CeZr et CePr) ont également été étudiés. La plupart de ces échantillons a montré un effet légèrement positif sur la stabilité thermique et le comportement au feu des polymères. De point de vue mécanistique, les analyses réalisées en Py-GC-MS montrent que les oxydes greffés par des acides catalysent la transformation des alcènes et des diènes issus de la décomposition du PE en aromatiques. En présence de SBA-15, l’analyse des résidus carbonés (par DRX, FTIR) montrent la formation de nouvelles phases cristallines phosphosiliciques qui renforcent la couche protectrice. Les phases condensées et gazeuses de quelques formulations performantes en IOL ont été analysée par cône calorimètre et microcalorimètre (PCFC). La substitution d'une fraction d'APP/PER par de la silice SBA-15 a un effet plus marqué sur la stabilité thermique et le comportement au feu de la matrice PA66 (IOL= 48,5 (+10 par rapport au PA66/APP/PER), comparé aux matrices PE (IOL=25 (+0,5 par rapport au PE/APP/PER) et PS (IOL= 24,1 (+0,8 par rapport au PS/APP/PER). De plus, la fonctionnalisation [...] / In this study, we have tried to develop new formulations to improve the thermal stability and fire behavior of three polymer matrices widely used: the polyethylene (PE), the polystyrene (PS) and the polyamide 66 (PA 66). The intumescent system used consists to combine a classical flame retardants (ammonium polyphosphate (APP) and pentaeryhthritol (PER)) with a small amount of nanooxides whose properties can be adjusted in order to improve the compatibility of the melting mixture, or to change the degradation mechanism by a chemical (catalytic effect) or physical (insulating layer, viscosity, etc …) process. The total amount of additives has been set at 25wt%. An important part of this study was consecrated to the synthesis of oxides with different morphologies, porosities, structures and functionalities. In this regard, the mesoporous silica has an advantage of having a high surface area (700-1400 m²/g) and a pore size compatible with the polymer chains. By adapting the synthesis conditions, we have aimed to correlate between some parameters related to the prepared silicas (such as (1) the specific surface area (2) particle size (3) pore size (4) morphology and (5) the type of structure (usually SBA-15)) on the thermal stability and fire behavior of different polymer matrices. A comprehensive study has been conducted globally, regardless of the matrix, that the improvements provided by the mesostructured silicas are modest compared to those elicited by classical FR. However, the fire behavior has been improved (particularly LOI) by combining APP/PER system with 1-2wt% of SBA-15. The surface modification of SBA-15 by grafting a different organic functions (CTAB, amine, thiol, phenol, phosphonate, benzoic acid and diphenylphosphate), inorganic species (aluminum, phosphoric acid and tungstophosphoric acid) or metals (copper, nickel) have been the subject of an advanced characterizations in order to assess the amount and the thermal stability of the grafted species, well as the nature of the surface bonds. Other types of synthetic nanooxides (aluminophosphates, zirconium phosphate and titanate nanotubes) or commercial (CeO2, ZrO2, CeZr and CePr) have been also studied. Most of these particles in combination with APP/PER system have shown a slightly positive effect on the thermal stability and fire behavior of polymers. In mechanistic terms, the nanooxides have mainly an effect on enhancing the barrier effect. The analyses carried out by Py/GC/MS showed that the grafted oxides by acidic species catalyze the conversion of alkenes and dienes (resulting from the decomposition of PE) to aromatics. In the presence of SBA-15, the analysis of char (by XRD and FTIR) shows the formation of new crystalline phases which enhance the protective layer.

The presented research report deals with the investigation of magnesium aluminum based layered double hydroxide (LDH) as a potential nanofiller and flame-retardant for polymers with special reference to polyethylene. LDH is a mixed hydroxide of di- and trivalent metal ions that crystallizes in the form of mineral brucite. The basic reason for selecting LDH or more specifically magnesium-aluminum based LDH (Mg-Al LDH) is their typical metal hydroxide-like chemistry and conventional clay-like layered crystalline structure. The former is helpful in the direct participation in flame inhibition through endothermic decomposition and stable char formation. On the other hand, the later makes LDH suitable for polymer nanocomposite preparation, which can address the poor dispersibility problem associated with conventional metal hydroxide type fillers in polyolefin matrix. Besides, unlike layered silicate type clays (often reported for their capability to improve flame retardancy of polymers), LDH being reactive during combustion has higher efficiency to reduce the heat released during combustion of the composites. LDH clay with fixed Al:Mg ratio was synthesized using urea hydrolysis method and characterized. The organic modification of Mg-Al LDH using anionic surfactants has been studied in details. The main purpose of such modification is to enlarge the interlayer distance and to render it more organophilic. The surfactants were selected based on their functionality, chain length, etc and the modification was carried out by regeneration method. In the modified LDHs, the surfactants anions are arranged as a monolayer in the interlayer region and expand the interlayer distance according to their tail size. PE/LDH nanocomposites were prepared by melt-compounding method using a co-rotating tightly intermeshed twin-screw extruder and the morphological, mechanical and flammability properties of the nanocomposites were investigated in details. The X-ray diffraction analysis and electron microscopic analysis show a complex LDH particle morphology with hierarchy of particle size and shape starting from exfoliated particles fragments to particle aggregates over few hundred nm size. The exfoliated LDH platelets are distributed both in the vicinity of large particles and also in the bulk matrix. The melt rheological characterization of the nanocomposites also reflects the similar complex particle morphology. The dynamic oscillatory shear experiments showed that with increasing LDH concentration, the rheological behavior of the nanocomposite melts deviates strongly from that of the unfilled polyethylene. Thermogravimetric analysis (TGA) shows that LDH significantly improves the thermal stability of the polymer matrix in comparison to the unfilled polymer. The flammability studies of the PE/LDH nanocomposites have been reported in terms of various standard methods, like limited oxygen index (LOI), cone-calorimetry and UL-94 vertical and horizontal burn tests. The cone-calorimetric investigation shows that the nanocomposites have significantly lower burning rate and heat released during combustion. With increasing concentration of LDH though the LOI value of the nanocomposite increases marginally, the burning behavior, like dripping, rate of burning, etc are significantly improved. The flammability performance of LDH in combination with other commonly used flame-retardant (magnesium hydroxide) was also investigated. It has been observed that in polyethylene, a 50 wt% combination filler (4:1 weight ratio of magnesium hydroxide and LDH) can provide similar flammability ratings (like V0 rating in UL94 test, no dripping, etc) as that observed with 60 wt% magnesium hydroxide alone.

Problemställning och syfte: Bromerade flamskyddsmedel (BFR) används i många varor och produkter. Polybromerade difenyletrar (PBDEs) är en av dessa och deras kemiska struktur liknar den i miljögiftet PCB och kan på samma sätt lagras upp i miljön samt skada människor och djur. På arbetsplatser där BFR förekommer riskerar medarbetarna att exponeras. I den här studien har olika BFR undersökts i samband med servicearbete på flygplan. Målet har varit att jämföra förekomsten i damm och luft, samt blod (serum) med resultat från tidi­gare studier. Metod: Damm- och luftprovtagning har genomförts vid olika faser av service­arbetet. Proverna har analyserats med avseende på olika typer av BRF. Dess­utom har medarbetarnas upptag av BRF via blodprov (serum) undersökts. Resultat: Undersökningen har visat att samtliga former av PBDE samt övriga BFR förekommer i höga koncentrationer i damm och luft i flygplanen, men med ojämn fördelning. Analyserna av serum visade att flygmekanikerna har förhöjda nivåer jämfört med svensk allmänhet och jämförbar nivå med högexponerade yrkesgrupper. Medarbetarnas ålder, år i yrke och arbetad tid i flygplan den senaste månaden uppvisade inget samband i förhållande till PBDE i serum. Slutsats: Koncentrationerna av BFR i damm och luft är högre än i de flesta andra miljöer och koncentrationerna i serum är högre än de flesta referens­gruppers. För att minska risken för exponering behöver insatserna för att mini­mera dammet via städning förbättras. Dessutom bör informationen gällande hygien och användning av personlig skyddsutrustning repeteras för medarbe­tarna. Samtliga yrkeshygieniska åtgärder bör fastställas och hanteras i det systematiska arbetsmiljöarbetet via rutiner och handlingsplaner. / Presentation and aim: Brominated flame retardants (BFRs) are used in many materials and products. Polybrominated diphenyl ethers (PBDEs) are the most well known and because of their structures, similar to that of PCB, they have been proposed to possibly affect health and environment. Occupational exposure has been an issue for years and this study investigated BRF in aircraft mainte­nance. The aim of this study was to assess the presence and levels of BRFs in dust, air and blood (serum) and compare the results with different references. Method: Dust and air were sampled in different phases of the work with the air­craft and analysis of a spectrum of BFR was performed. In addition, serum from employees was sampled and analyzed for the presence of PBDEs. Result: PBDEs and other BFRs were found in dust and air samples at high con­centrations. Serum concentrations in the technicians were slightly higher to those observed in the general Swedish population and in the same magnitude as some highly exposed occupational references. Years of work, age or time spent in the aircraft before giving blood seems not to have an impact on the level of BFRs in serum. Conclusion: This study shows high concentrations of BFR in dust and air in the aircraft and the concentrations of PBDEs in serum were high compared to most reference groups. To minimize the risk for exposure, it is important to focus on industrial hygiene improvements to minimize the amount of dust in working areas. The personal hygiene and use of personal safety equipment can also be improved and the routines should be described and included in the appropriate documentation regarding work environment.

No description available.

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]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/2186

Dans le cadre de la protection de l’environnement et du consommateur, CTC effectue des tests enchimie analytique sur de nombreux paramètres en matrices aqueuses, cuir et textile. Les nouvelles substancesmises sur le marché ainsi que les réglementations évoluant sans cesse, le développement de nouvellesméthodes d’analyses est donc nécessaire.Plusieurs méthodes analytiques ont ainsi été développées. Pour l’analyse des rejets d’effluents industriels desinstallations classées et pour l’analyse d’innocuité de produits utilisant le cuir ou le textile (chaussures,maroquinerie, prêt-à-porter…).Les chloroalcanes ont été dosés en chromatographie gazeuse (GC) associée à la spectrométrie de masse (MS)utilisant l’ionisation chimique, à la fois en matrices aqueuses (limite de quantification, LQ, à 0,6 μg/l) et sur lescuirs (LQ à 2 mg/kg).Une analyse des alkylphénols et alkylphénols ethoxylates a été développée pour les matrices aqueuses parGC/MS (LQ à 0,05 μg/l).Plusieurs familles de retardateurs de flammes ont ensuite été étudiées. Les polybromodiphénylethers peuventêtre dosés dans les eaux (LQ<0,05 µl) et le cuir (LQ <= µg/kg), par GC/MS en ionisationchimique.L’hexabromocyclododécane et des organophosphates, par chromatographie liquide et spectrométrie de masseen tandem pour des matrices textiles (LQ à 6 mg/kg). Des hydrocarbures aromatiques polycycliques dans le cuir ont ensuite été analysés par GC/MS-MS (LQ à 250 μg/kg).Enfin, une méthode multirésidus portant sur plusieurs familles de micropolluants organiques a été mise aupoint en GC/MS pour les rejets d’effluents (LQ <0,1 µg/l) / Taking in account the increasing needs and demands in environmental and consumer protection, CTCis always seeking improvement in analytical methods and development of new ones dealing with leather,fabrics and aqueous samples. In this thesis, several new methods were developed to be able to handleanalytical requests dealing with leather and textile materials being parts of shoes, clothes and other leathergoods.A GC/MS method using chemical ionization was developed to detect short polychlorinated alkanes down to aconcentration of 0.6 μg/L in aqueous sample and 2 mg/kg in leather samples. Alkylphenols and theirethoxylates were similarly determined by GC/MS down to 0.05 μg/L.Flame retardants are another large class of chemicals becoming suspicious. Polybromodiphenylethers weredetermined in aqueous samples and leathers. The respective GC/MS highest limits of quantification (LOQ)were0.05 µg/l and 80 μg/kg. Other members of this class are hexabromocyclododecane andorganophosphates. Both were determined by LC/MS-MS with LOQ of about 6 mg/kg.Carcinogenic polyaromatic hydrocarbons were also determined in leather samples using GC/MS-MS down to250 μg/kg.The last improved GC/MS analytical method was handling sewage sludge seeking multi residues of organicpolluants down to the 0.1 µg/l level or below. The analytical performances developed or improved allowedfor an efficient and useful control of the various sample received from the CTC customers and followinginternational quality rules

Les retardateurs de flamme (RF) sont des substances utilisées dans de nombreux produits synthétiques pour limiter la propagation du feu et ainsi améliorer la sécurité des habitations et des lieux publics. En raison de leur stabilité, de leur bioaccumulation et de leur toxicité, l’utilisation massive de certains RF, en particulier halogénés parmi lesquels la famille de Dechloranes, génère cependant un problème de contamination de l’environnement qui pose aujourd’hui la question d’éventuelles répercussions sur la santé humaine. Les Dechloranes ont été détectés pour la première fois dans l’environnement en 2006 et préoccupent, depuis, la communauté scientifique et les autorités sanitaires. Le présent travail avait pour objectif de contribuer à combler le manque manifeste de données sur les niveaux de prévalence en Dechloranes.Pour ce faire, une stratégie analytique ciblée, dédiée à l’identification et à la quantification des Dechloranes à l’état de traces (pg/g) dans des denrées alimentaires d’origine animale (DAOA) et des huiles végétales et basée sur un couplage GC-HRMS a été développé. Une attention particulière a été portée à la maîtrise des contaminations procédurales, eu égard au caractère ubiquitaire de certains composés. L’application de la méthode développée à 378 échantillons de poissons d’eaux douces de surface en France et de DAOA et huiles végétale collectées en France, au Liban et dans quatre pays d’Afrique subsaharienne a permis de brosser le premier état des lieux des niveaux de contamination environnementale et alimentaire dans ces pays, jusqu’à estimer l'exposition alimentaire de leurs populations à ces composés persistants et émergents. / Flame retardants (FR) are substances used in many synthetic products to limit the spread of fire and thus improve the safety of homes and public places. Due to their stability, bioaccumulation and toxicity, certain FRs, in particular halogenated ones among which the family of Dechloranes, are widely used, generating an issue of environmental contamination with potential repercussions on human health. Dechloranes were detected for the first time in the environment in 2006 and have since raised concerns to the scientific community and health authorities. The purpose of this paper is to help fill the obvious gap in data on prevalence levels of Dechloranes. To this end, a targeted analytical strategy dedicated to the identification and quantification of trace amounts of Dechloranes (pg/g) in animal foods (DAOA)and vegetable oils based on a GC-HRMS method has been developed. Particular attention has been paid to the control of procedural contaminations, given the ubiquitous nature of certain compounds. This method was applied to 378 samples of surface freshwater fish in France and DAOA and vegetable oils collected in France, Lebanon and four sub-Saharan African countries, and draw for the first time an inventory of levels of environmental and food contamination in these countries to estimate the dietary exposure of their populations to these persistent and emerging compounds

Large and ever-increasing numbers of chemicals, including large quantities of a broad spectrum of organic compounds are used in modern society. More than 30 000 of the more than 100 000 chemical substances registered in the EU are estimated to be daily used, of which many will be discharged into the waste-streams handled by municipal sewage treatment plants (STPs). The main objective of the work underlying this thesis was to improve understanding of the relationships between the characteristics of sewage contaminants and their sewage treatment efficiency. Further objectives were to examine the relationships between socio-economic uses of chemicals and sludge quality, and the effects of regulatory actions on sludge quality. The quality of the sewage sludge and the levels and distribution patterns of the sludge contaminants, both within and between the STPs, seem to remain quite constant over time. The overall findings indicate that the levels of contaminants in sewage sludge seem to be largely independent of the location, size and treatment techniques applied at the STPs, and generally, of the types of human activity connected to them. The total and relative concentrations of the sludge contaminants were found to be fairly constant on a dry weight basis, with some exceptions, indicating that the pollutants originate from broad usage and diffuse dispersion rather than (industrial) point sources. The proportion of cyclic methylsiloxanes recovered in sludge seems to strongly depend on their vapour pressure, which decreases with the number of siloxane units. The higher water solubility and biodegradability of organophosphorus flame retardants and plasticizers than polybrominated diphenyl ethers (PBDEs) were also reflected in lower percentages (relative to their national use) found in sludge. Significant time-trends in levels of a-third of the sludge contaminants included in the annual national measurement program were detected over a period of seven years. The levels of compounds displaying significant time-trends generally decreased following declines in the quantities used nationally. However, a quarter of these compounds showed increasing trends, of which the linear methylsiloxanes followed the same trend as used quantities. The decaBDE was also found to be increasing in sludge, probably as a result of the phase-out of pentaBDE and octaBDE. The results indicate that the STP removal efficiency of anthropogenic substances, in Sweden, is generally good and that STPs, at least those in cold climates, do not efficiently remove certain polar contaminants. A non-targeted screening (by use of environmetrics and GCxGC-TOFMS) was performed and found to fulfil the objective to assess the STP removal efficiency, with emphasis to systematically analyse which compound classes that are not efficiently removed using the current STP technology. Many polar aromatic compounds were identified to be poorly removed. The acquired data on levels, profiles and variations in sludge contaminants (sludge quality) extend both the available information and understanding of the degree and nature of sludge contamination, which should help attempts to track changes in its contaminants and revisions, if necessary, of guideline values. This thesis also contributes to improve the knowledge base for the development of future STP technologies, and that archived sewage sludge can be used in retrospective analysis of new and emerging pollutants.

The first of a series of mass mortalities of Nile crocodiles in the Olifants and Letaba rivers in the Kruger National Park (KNP) was reported in the winter of 2008. The present study investigated the levels and possible effects on eggshell thickness of inorganic elements and organic pollutants in Nile crocodile eggs from these rivers, and comparing them with eggs from a reference crocodile farm and a reference dam inside the KNP. The egg contents were analyzed for chlorinated organic compounds and brominated flame retardants. Eggshells and egg contents were analyzed for inorganic elements. The elemental concentrations in the eggshells and contents were low when compared with previous studies. The highest concentrations were found in the eggs from the reference crocodile farm. The eggs from the reference dam and the crocodile farm had thicker shells, and the eggs from the Olifants and Letaba rivers had thinner shells. Not all eggs in a female develop at the same rate, while eggshell formation presumably occurs at the same time for all eggs. As a result, the elemental profile of egg contents may differ between eggs of the same clutch, but less so for the shells. Weak or no associations were found between the elemental concentrations of the content and eggshells and eggshell thinning. A possible organic pollutant–induced eggshell thinning effect was found. The compounds found were not at levels that could have caused the mortalities, but may affect the sex ratios through endocrine disruption. Further studies are therefore required. / Thesis (M.Sc (Environmental Science))--North-West University, Potchefstroom Campus, 2011.

The first of a series of mass mortalities of Nile crocodiles in the Olifants and Letaba rivers in the Kruger National Park (KNP) was reported in the winter of 2008. The present study investigated the levels and possible effects on eggshell thickness of inorganic elements and organic pollutants in Nile crocodile eggs from these rivers, and comparing them with eggs from a reference crocodile farm and a reference dam inside the KNP. The egg contents were analyzed for chlorinated organic compounds and brominated flame retardants. Eggshells and egg contents were analyzed for inorganic elements. The elemental concentrations in the eggshells and contents were low when compared with previous studies. The highest concentrations were found in the eggs from the reference crocodile farm. The eggs from the reference dam and the crocodile farm had thicker shells, and the eggs from the Olifants and Letaba rivers had thinner shells. Not all eggs in a female develop at the same rate, while eggshell formation presumably occurs at the same time for all eggs. As a result, the elemental profile of egg contents may differ between eggs of the same clutch, but less so for the shells. Weak or no associations were found between the elemental concentrations of the content and eggshells and eggshell thinning. A possible organic pollutant–induced eggshell thinning effect was found. The compounds found were not at levels that could have caused the mortalities, but may affect the sex ratios through endocrine disruption. Further studies are therefore required. / Thesis (M.Sc (Environmental Science))--North-West University, Potchefstroom Campus, 2011.