Yes / Thermal degradation of polyamide 6 (PA6)/organoclay nanocomposites is a serious impediment to wider applications of these nanocomposites. In this study, a solution is proposed based on the well‐established use of chain extenders. As in PA6, thermal degradation, in the absence of moisture, produces broken polymer chains with amide end groups, a chain extender with anhydride functionalities, known to be strongly reactive with amide groups, was used to reconnect the chains. Experiments conducted using a laboratory twin‐screw extruder were first checked, through transmission electron microscopy observations, to have produced good organoclay intercalation and exfoliation into PA6. Following from this, samples with the chain extender added were produced and characterized. The data obtained were conclusive in the effectiveness of the chain extender: for the chain extended nanocomposites, there is an enhancement in the value of the complex viscosity by 7 times and in the storage modulus by 88 times, while the tensile modulus increased by 57% compared with the neat PA6. The nonchain extended nanocomposite achieved in comparison an enhancement of 2 times the value of the complex viscosity and 19 times the storage modulus while the tensile modulus increased by 53% compared to the neat PA6. These data provide conclusive proof on the rationale that anhydride functionalities should be sought when developing chain extenders for PA6 nanocomposites. / Government of Turkey

Computational Fluid Dynamics (CFD) codes are being increasingly used in the field of fire safety engineering. They provide, amongst other things, velocity, species and heat flux distributions throughout the computational domain. The various sub-models associated with these have been developed sufficiently to reduce the errors below 10%-15%, and work continues on reducing these errors yet further. However, the uncertainties introduced by using material properties as an input for these models are considerably larger than those from the other sub-models, yet little work is being done to improve these. Most of the data for these material properties comes from traditional (standard) tests. It is known that these properties are not intrinsic, but are test-specific. Thus, it can be expected that the errors incurred when using these in computations can be significant. Research has been held back by a lack of understanding of the basic factors that determine material flammability. The term “flammability” is currently used to encompass a number of definitions and “properties” that are linked to standardised test methodologies. In almost all cases, the quantitative manifestations of “flammability” are a combination of material properties and environmental conditions associated with the particular test method from which they were derived but are not always representative of parameters linked intrinsically with the tested material. The result is that even the best-defined parameters associated with flammability cannot be successfully introduced into fire models to predict ignition or fire growth. The aim of this work is to develop a new approach to the interpretation of standard flammability tests in order to derive the (intrinsic) material properties; specifically, those properties controlling ignition. This approach combines solid phase and gas modelling together with standard tests using computational fluid dynamics (CFD), mass fraction of flammable gases and lean flammability limits (LFL). The back boundary condition is also better defined by introducing a heat sink with a high thermal conductivity and a temperature dependant convective heat transfer coefficient. The intrinsic material properties can then be used to rank materials based on their susceptibility to ignition and, furthermore, can be used as input data for fire models. Experiments in a standard test apparatus (FPA) were performed and the resulting data fitted to a complex pyrolysis model to estimate the (intrinsic) material properties. With these properties, it should be possible to model the heating process, pyrolysis, ignition and related material behaviour for any adequately defined heating scenario. This was achieved, within bounds, during validation of the approach in the Cone Calorimeter and under ramped heating conditions in the Fire Propagation Apparatus (FPA). This work demonstrates that standard flammability and material tests have been proven inadequate for the purpose of obtaining the “intrinsic” material properties required for pyrolysis models. A significant step has been made towards the development of a technique to obtain these material properties using test apparatuses, and to predict ignition of the tested materials under any heating scenario. This work has successfully demonstrated the ability to predict the driving force (in-depth temperature distribution) in the ignition process. The results obtained are very promising and serve to demonstrate the feasibility of the methodology. The essential outcomes are the “lessons learnt”, which themselves are of great importance to the understanding and further development of this technique. One of these lessons is that complex modelling in conjunction with current standard flammability test cannot currently provide all required parameters. The uncertainty of the results is significantly reduced when using independently determined parameters in the model. The intrinsic values of the material properties depend significantly on the accuracy of the model and precision of the data.

No description available.

Pesquisas e publicações sobre polímeros luminescentes vêm sendo desenvolvidas nos últimos anos devido à inovação acadêmica, porém ainda no âmbito nacional possuem aplicação industrial limitada. Marcadores ópticos processados são pouco explorados devido à dificuldade de processamento dos materiais poliméricos luminescentes com estabilidade de luminescência. Os materiais utilizados para o processamento de polipropileno luminescente foram Poliamida 6 (PA6) dopada com complexo sintetizado de [Eu(tta)3(H2O)2] obtida através do processo de diluição do polímero e técnica de derramamento. As poliolefinas, por serem inertes, não se adequam ao procedimento comum de dopagem, assim no presente trabalho, o polipropileno luminescente foi preparado indiretamente por dopagem com poliamida dopada com complexo de európio em processamento por extrusão. As técnicas de caracterização utilizadas foram a Análise Térmica (TG), Calorimetria Exploratória Diferencial (DSC), Difração de Raios-X (XRD), Espectroscopia de infravermelho (FT-IR) e estudo das propriedades fotoluminescentes. A blenda PP/PA6:Eu(tta)3 processada apresentou propriedades luminescentes observadas nas transições intraconfiguracionais de bandas finas 4f6 - 4f6 relativas aos níveis de excitação de energia 7F0 → 5L6 (394nm), 7F0 → 5D3 (415nm), 7F0 → 5D2 (464nm), 7F0 → 5D1 (525nm) e 7F0 → 5D0 (578nm). Tanto a blenda de PP/PA6:Eu(tta)3 e os filmes de PA6:Eu(tta)3 quando expostos a luz UV (365nm) apresentaram luminescência vermelha. Os resultados de TG mostraram que sob atmosfera de O2 o PP dopado PA6:Eu(tta)3 apresentou maior estabilidade do que o PP puro. Neste trabalho foi possível processar PP/PA6:Eu(tta)3 com propriedades térmicas e fotoestabilidade, que permitem sua utilização com marcador óptico em processamentos. / Research and publications about luminescent polymers have been developed in the last years for the academic innovation; however the industrial application has been very limited in this area. Processed Optical markers are few explored due to the difficult to process luminescent polymeric materials with stable luminescence. The materials used of processing luminescent polypropylene (PP) were polyamide 6 (PA6) doped with europium complex [Eu(tta)3(H2O)2] obtained through the dilution and casting process. Due to their inercy, polyolefins do not fit into the common procedure of doping, in consequence, in this work luminescent polypropylene was indirectly prepared by polyamide 6 doped with europium complex through extrusion process. Product characterization was done using Thermalgravimetry analysis (TG), Differential Scanning Calorimetric (DSC), X-Ray Diffraction (XRD), Infrared spectroscopy (FTIR) and fotoluminescence of emission and excitation. The blend PP/PA6:Eu(tta)3 presented luminescent properties, after semi-industrial process, as observed in the narrow bands of intraconfiguration transitions - 4f6 relatives to energy levels 7F0 → 5L6 (394nm), 7F0 → 5D3 (415nm), 7F0 → 5D2 (464nm), 7F0 → 5D1 (525nm) e 7F0 → 5D0 (578nm) of emission spectrum. Red light of the pellets or film is emitted when excited in UV lamp (365nm). TG results showed under O2 atmosphere that PP doped with PA6:Eu(tta)3 was more stable than pure PP. In this work luminescent PP/PA6:Eu(tta)3 was processed with properties of thermal and photo stability which can be used as optical marker in polymer processing.

Pesquisas e publicações sobre polímeros luminescentes vêm sendo desenvolvidas nos últimos anos devido à inovação acadêmica, porém ainda no âmbito nacional possuem aplicação industrial limitada. Marcadores ópticos processados são pouco explorados devido à dificuldade de processamento dos materiais poliméricos luminescentes com estabilidade de luminescência. Os materiais utilizados para o processamento de polipropileno luminescente foram Poliamida 6 (PA6) dopada com complexo sintetizado de [Eu(tta)3(H2O)2] obtida através do processo de diluição do polímero e técnica de derramamento. As poliolefinas, por serem inertes, não se adequam ao procedimento comum de dopagem, assim no presente trabalho, o polipropileno luminescente foi preparado indiretamente por dopagem com poliamida dopada com complexo de európio em processamento por extrusão. As técnicas de caracterização utilizadas foram a Análise Térmica (TG), Calorimetria Exploratória Diferencial (DSC), Difração de Raios-X (XRD), Espectroscopia de infravermelho (FT-IR) e estudo das propriedades fotoluminescentes. A blenda PP/PA6:Eu(tta)3 processada apresentou propriedades luminescentes observadas nas transições intraconfiguracionais de bandas finas 4f6 - 4f6 relativas aos níveis de excitação de energia 7F0 → 5L6 (394nm), 7F0 → 5D3 (415nm), 7F0 → 5D2 (464nm), 7F0 → 5D1 (525nm) e 7F0 → 5D0 (578nm). Tanto a blenda de PP/PA6:Eu(tta)3 e os filmes de PA6:Eu(tta)3 quando expostos a luz UV (365nm) apresentaram luminescência vermelha. Os resultados de TG mostraram que sob atmosfera de O2 o PP dopado PA6:Eu(tta)3 apresentou maior estabilidade do que o PP puro. Neste trabalho foi possível processar PP/PA6:Eu(tta)3 com propriedades térmicas e fotoestabilidade, que permitem sua utilização com marcador óptico em processamentos. / Research and publications about luminescent polymers have been developed in the last years for the academic innovation; however the industrial application has been very limited in this area. Processed Optical markers are few explored due to the difficult to process luminescent polymeric materials with stable luminescence. The materials used of processing luminescent polypropylene (PP) were polyamide 6 (PA6) doped with europium complex [Eu(tta)3(H2O)2] obtained through the dilution and casting process. Due to their inercy, polyolefins do not fit into the common procedure of doping, in consequence, in this work luminescent polypropylene was indirectly prepared by polyamide 6 doped with europium complex through extrusion process. Product characterization was done using Thermalgravimetry analysis (TG), Differential Scanning Calorimetric (DSC), X-Ray Diffraction (XRD), Infrared spectroscopy (FTIR) and fotoluminescence of emission and excitation. The blend PP/PA6:Eu(tta)3 presented luminescent properties, after semi-industrial process, as observed in the narrow bands of intraconfiguration transitions - 4f6 relatives to energy levels 7F0 → 5L6 (394nm), 7F0 → 5D3 (415nm), 7F0 → 5D2 (464nm), 7F0 → 5D1 (525nm) e 7F0 → 5D0 (578nm) of emission spectrum. Red light of the pellets or film is emitted when excited in UV lamp (365nm). TG results showed under O2 atmosphere that PP doped with PA6:Eu(tta)3 was more stable than pure PP. In this work luminescent PP/PA6:Eu(tta)3 was processed with properties of thermal and photo stability which can be used as optical marker in polymer processing.

A reciclagem de resíduos sólidos tem se tornado cada vez mais relevante devido a alguns fatores como os impactos ambientais ocasionados com o seu descarte inadequado, ao rigor crescente de legislação específica e ao custo elevado para o gerenciamento apropriado destes resíduos. Na área de materiais poliméricos, os resíduos poliméricos podem ser de origem pósconsumo ou pós-industrial. Alguns rejeitos industriais poliméricos possuem características estruturais ou químicas que impossibilitam o seu reaproveitamento direto no processo que o gerou, como é o caso filmes multicamadas de polietileno de baixa densidade (PEBD) com poliamida 6 (PA6), usados para a produção de embalagens. O presente trabalho teve como objetivo central o reaproveitamento de rejeitos de filmes multicamadas de PEBD com PA6 na forma de blendas recicladas destes polímeros, fazendo uso de agente compatibilizante e variação na composição das blendas com a incorporação de PA6 virgem, a fim de produzir materiais com propriedades adequadas e custo compatível para a aplicação comercial. O desenvolvimento experimental foi dividido em três etapas que consistiram na avaliação do teor mais adequado de agente compatibilizante de fases da blenda (etapa 1), na determinação do comportamento das propriedades das blendas não compatibilizadas em diferentes composições de rejeito do filme multicamada e PA6 virgem (etapa 2) e na associação do uso de compatibilizante com variação das composições das blendas (etapa 3). A partir da execução experimental das atividades das etapas 1 e 2 do trabalho foi possível determinar que o teor de 2,5% do agente compatibilizante polietileno grafitizado com anidrido maleico (PEg- AM) é o mais adequado para compatibilizar as blendas poliméricas e que a maioria das suas propriedades das blendas apresentam um comportamento próximo ao aditivo linear, que leva em consideração somente as propriedades iniciais dos componentes poliméricos PEBD e PA6 isolados. Os diversos materiais gerados no desenvolvimento desta pesquisa apresentam desempenho de propriedades e custo de produção variáveis em função do teor de PA6 nas blendas, que podem viabilizar o uso deste material reciclado em aplicações comerciais específicas. / Recycling of solid waste has been an important issue due to some factors such as environmental damage caused by inappropriate discards, increasing rigor of specific legislation and high cost to the appropriate management of these waste. Polymeric waste can be originated from post-consume or post-industrial sources. Some polymeric waste have chemical or structural characteristics that difficult their direct reuse in the same productive process such as multilayer film of low density polyethylene (LDPE) and polyamide 6 (PA6), which are used for packing. The aim of this work has been the study the mechanical recycling of multilayer films of PEBD and PA6 as PEBD/PA6 blends with adequate properties and compatible cost for commercial applications. The experimental development has been performed in 3 steps, which correspond to evaluation of more adequate content of compatibilizer agent for interface of blends (step 1), determination of behavior of the properties of blends without compatibilizer agent on different compositions of waste form multilayer films (step 2) and production of blends with compatibilizer agent graphitized polyethylene with maleic anhydride (PE-g-MA) (step 3). Has been verified that the content of 2.5% of PE-g-MA is more adequate to be used in the compatibilization of recycled PEBD/PA blends and that the performance of the blends dependents of the content of PA6 in the material. The recycled materials have potential for commercial applications.

Submitted by Izabel Franco (izabel-franco@ufscar.br) on 2016-09-14T11:47:49Z No. of bitstreams: 1 DissLDCC.pdf: 4367646 bytes, checksum: 6ea0bbaf8821a92bf7348237ecee172b (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-15T13:42:07Z (GMT) No. of bitstreams: 1 DissLDCC.pdf: 4367646 bytes, checksum: 6ea0bbaf8821a92bf7348237ecee172b (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-15T13:42:14Z (GMT) No. of bitstreams: 1 DissLDCC.pdf: 4367646 bytes, checksum: 6ea0bbaf8821a92bf7348237ecee172b (MD5) / Made available in DSpace on 2016-09-15T13:42:20Z (GMT). No. of bitstreams: 1 DissLDCC.pdf: 4367646 bytes, checksum: 6ea0bbaf8821a92bf7348237ecee172b (MD5) Previous issue date: 2014-09-22 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Nanocomposites based on polyamide 6 (PA6) and acrylonitrile-butadienestyrene (ABS) blends compatibilized with styrene-maleic anhydride-acrylonitrile (SANMA) and methyl methacrylate-maleic anhydride (MA-MMA) were prepared by melt blending in a twin screw extruder through different mixing protocols. The nanoclay incorporation effect, different compatibilizing systems and components mixing sequence were evaluated in morphological, mechanical, thermal, thermomechanical and rheological properties. Evidences of chemical interactions between PA6 and reactive copolymers were observed by torque rheometry. XRD analysis indicates an exfoliated structure for all the nanocomposites due to the good interaction between PA6/OMMT. The significant increase in nanocomposites viscosity when compared with their respective ternary blends corroborates the results obtained by XRD. TEM micrographs show a strong influence of both reactive copolymers on polymer blends morphology, where the presence of SANMA and MMA-MA is responsible for reducing the dispersed phase particle size when compared to the uncompatibilized blend. TEM images confirm the existence of an exfoliation structure in all nanocomposites. The addition of both reactive copolymers significantly increased the ternary blends toughness when compared with PA6/ABS. Furthermore, the nanoclay incorporation enhanced the elasticity modulus and HDT of the nanocomposites but also reduced the toughness and the elongation at break when compared with their respective compatibilized blends. / Nanocompósitos baseados em blendas de poliamida 6 (PA6) e acrilonitrila-butadieno-estireno (ABS) compatibilizadas com os estirenoacrilonitrila- anidrido maleico (SANMA) e metacrilato de metila-anidrido maleico (MMA-MA), foram preparadas por mistura no estado fundido em uma extrusora de rosca dupla corotacional através de diferentes sequências de mistura. Foram analisadas a influência da incorporação das nanopartículas lamelares de argila, dos diferentes agentes de compatibilização e da sequência de mistura dos componentes na morfologia, propriedades mecânicas, térmicas, termomecânicas e reológicas dos materiais. Evidencias de reações químicas entre a PA6 e os copolímeros reativos foram observadas por reometria de torque. Ensaios de DRX fornecem indícios da formação de estrutura esfoliada para todos os nanocompósitos decorrente da boa interação entre PA6/OMMT. O significativo aumento da viscosidade dos nancompósitos quando comparados com suas respectivas blendas ternárias corroboram os resultados obtidos por DRX. As micrografias de MET evidenciam a forte influencia da incorporação de ambos os copolímeros reativos na morfologia das blendas poliméricas onde a presença, tanto do SANMA quanto do MMA-MA, é responsável pela redução do tamanho de partícula da fase dispersa quando comparadas com a blenda não compatibilizada. Adicionalmente as imagens obtidas por MET reafirmam o alto grau de esfoliação da argila em todos os nanocompósitos estudados. Além de refinar a morfologia, a adição de ambos os copolímeros reativos aumentou significativamente a tenacidade das blendas ternárias em relação à blenda PA6/ABS. Por fim, a incorporação de nanoargila foi responsável pelo incremento no módulo de elasticidade e HDT dos nanocompósitos, resultado esse acompanhado pela redução da tenacidade e da deformação na ruptura quando comparados com suas respectivas blendas compatibilizadas.

A reciclagem de resíduos sólidos tem se tornado cada vez mais relevante devido a alguns fatores como os impactos ambientais ocasionados com o seu descarte inadequado, ao rigor crescente de legislação específica e ao custo elevado para o gerenciamento apropriado destes resíduos. Na área de materiais poliméricos, os resíduos poliméricos podem ser de origem pósconsumo ou pós-industrial. Alguns rejeitos industriais poliméricos possuem características estruturais ou químicas que impossibilitam o seu reaproveitamento direto no processo que o gerou, como é o caso filmes multicamadas de polietileno de baixa densidade (PEBD) com poliamida 6 (PA6), usados para a produção de embalagens. O presente trabalho teve como objetivo central o reaproveitamento de rejeitos de filmes multicamadas de PEBD com PA6 na forma de blendas recicladas destes polímeros, fazendo uso de agente compatibilizante e variação na composição das blendas com a incorporação de PA6 virgem, a fim de produzir materiais com propriedades adequadas e custo compatível para a aplicação comercial. O desenvolvimento experimental foi dividido em três etapas que consistiram na avaliação do teor mais adequado de agente compatibilizante de fases da blenda (etapa 1), na determinação do comportamento das propriedades das blendas não compatibilizadas em diferentes composições de rejeito do filme multicamada e PA6 virgem (etapa 2) e na associação do uso de compatibilizante com variação das composições das blendas (etapa 3). A partir da execução experimental das atividades das etapas 1 e 2 do trabalho foi possível determinar que o teor de 2,5% do agente compatibilizante polietileno grafitizado com anidrido maleico (PEg- AM) é o mais adequado para compatibilizar as blendas poliméricas e que a maioria das suas propriedades das blendas apresentam um comportamento próximo ao aditivo linear, que leva em consideração somente as propriedades iniciais dos componentes poliméricos PEBD e PA6 isolados. Os diversos materiais gerados no desenvolvimento desta pesquisa apresentam desempenho de propriedades e custo de produção variáveis em função do teor de PA6 nas blendas, que podem viabilizar o uso deste material reciclado em aplicações comerciais específicas. / Recycling of solid waste has been an important issue due to some factors such as environmental damage caused by inappropriate discards, increasing rigor of specific legislation and high cost to the appropriate management of these waste. Polymeric waste can be originated from post-consume or post-industrial sources. Some polymeric waste have chemical or structural characteristics that difficult their direct reuse in the same productive process such as multilayer film of low density polyethylene (LDPE) and polyamide 6 (PA6), which are used for packing. The aim of this work has been the study the mechanical recycling of multilayer films of PEBD and PA6 as PEBD/PA6 blends with adequate properties and compatible cost for commercial applications. The experimental development has been performed in 3 steps, which correspond to evaluation of more adequate content of compatibilizer agent for interface of blends (step 1), determination of behavior of the properties of blends without compatibilizer agent on different compositions of waste form multilayer films (step 2) and production of blends with compatibilizer agent graphitized polyethylene with maleic anhydride (PE-g-MA) (step 3). Has been verified that the content of 2.5% of PE-g-MA is more adequate to be used in the compatibilization of recycled PEBD/PA blends and that the performance of the blends dependents of the content of PA6 in the material. The recycled materials have potential for commercial applications.

In this study, commercially available isotactic polypropylene (PP) and nylon-6 (PA6) blends and laminates were prepared, to develop a material with optimal water vapour and oxygen barrier properties. The effect of compatibilizers on phase dispersion has been investigated using three commercial Polybond's, PB3002, PB1001, and PB3009. Three compatibilizers prepared in-house were also used as, maleic anhydride(MA) grafted on PP, MA and butyl methacrylate(BMA) co-polymer grafted on PP, and BMA grafted on low density polyethylene. The effect of two silanes( methacrylate functional and vinyl functional) on PP were also investigated and also the plasticization of PA6 with formic acid. The results were compared with a commercial blend of PP and PA6, Orgalloy R-6000. Light microscopy with phase and fluorescence contrast has been used for morphological evaluation. Chemical changes were studied by Fourier Transform Infrared Spectroscopy and rheology by dynamic and steady state measurements. Barrier properties were determined gravimetrically for water vapour and organic solvents, and for oxygen by an Oxtran apparatus. The results have shown that phase dispersion can be more easily explained by molecular interactions than by the rheological parameters. The blend slip factor has been improved however by compatibilizers and consequently the phase dispersion, which had little effect on the barrier properties of the blends and indeed the laminates were more effective water vapour barriers. The availability of particular functional groups, which can interact with the permeant is the most important parameter, which can be affected by processing and blending conditions. The addition of hydrophobic functional groups into polypropylene was therefore the most effective method for enhancing the barrier properties of polypropylene. Cross-linking of the matrix polymer has improved the barrier properties to a lesser extent. It has also been shown, that PP solvent permeability (particularly di-chloromethane) can be improved, by silane addition.

No description available.