<p>Wood plastic composite (WPC) materials have seen a continuous market growth worldwide in the last decade. So-called extruded WPC profiles are today mainly used in outdoor applications, e.g. decking, railing and fencing. In outdoor conditions, moisture sorption in the wood component combined with temperature induced movements of the polymer matrix causes deformations of such composites. On the macroscopic scale this may lead to unacceptable warp, cup and bow of the WPC products, but on a microscopic scale, the movements will cause interfacial cracks between the particles and the matrix, resulting in little or no ability to transfer and re-distribute loads throughout the material. Moisture within the composite will also allow fungi and micro organisms to attack the wood particles.</p><p>The conceptual idea of this work is to use a chemically modified wood component in WPCs to enhance their long term performance. These chemically modified wood particles exhibit reduced susceptibility to moisture, resulting in better dimensional stability and a higher resistance to biological degradation as compared to that of unmodified wood. The objective of this thesis is to study the effects of using modified wood in WPCs on their moisture sorption behaviour, micromorphology and microbiological durability. The modification methods used were acetylation, heat treatment and furfurylation.</p><p>Equilibrium moisture content (EMC) and sorption behaviour of WPCs were determined by water vapour sorption experiments. The use of thin sections of the composites enabled EMC to be reached within a comparably short time span. The micromorphology was studied by LV-SEM (low vacuum-scanning electron microscope) using a specially designed sample preparation technique based on UV laser. The biological durability was evaluated by laboratory fungal test methods.</p><p>The moisture sorption experiments showed lower moisture levels for all the composites when modified wood particles were used. This was also reflected in the micromorphological studies where pronounced wood-plastic interfacial cracks were formed due to moisture movement in the composites with unmodified wood particles. The sample preparation technique by UV laser proved to be a powerful tool for preparing surfaces for micromorphological studies without adding mechanical defects caused by the sample preparation technique itself. Results from the durability test showed that WPCs with modified wood particles are highly resistant to decay by fungi.</p>

O desempenho de materiais compósitos plástico-madeira ou ―wood plastic composites‖(WPC) requerem uma avaliação eficiente de sua resistência ao envelhecimento natural ao longo do tempo e contra sua biodeterioração por micro-organismos. Neste sentido, o objetivo deste estudo foi investigar os mecanismos de degradação abiótica e biótica de compósitos termoplásticos com fibras vegetais, a fim de determinar seu comportamento, do ponto de vista da estabilidade, nas condições em que serão usados. A aplicação proposta para estes materiais é sua utilização em ambientes externos, com o propósito de substituir a madeira, em artefatos para construção civil, como portas, janelas, pisos, decks e divisórias. Além disso, a eficácia da utilização do agente de acoplamento (AC) na durabilidade dos compósitos envelhecidos foi investigada. Para a produção dos compósitos foi utilizada a proporção polímero-madeira de 70/30 m/m, sendo que a matriz polimérica foi constituída de uma blenda de polipropileno-copolímero de etileno acetato de vinila (PP-EVA) pós-consumo provenientes de tampas de garrafa, e as madeiras usadas na forma de serragem, utilizando as espécies de eucalipto e pinus. O polipropileno graftizado com anidrido maleico foi usado como AC na proporção de 3 % m/m. As misturas foram processadas por extrusão e os compósitos moldados por compressão térmica e injeção. No teste de degradação por fungos foram utilizados quatro espécies de fungos basidiomicetos, Trametes villosa, Trametes versicolor, Pycnoporus sanguineus e Fuscoporia ferrea, todos de podridão branca. Na degradação abiótica, foram avaliadas as propriedades físicas, mecânicas, térmicas, reológicas, químicas e morfológicas dos compósitos nos diferentes estágios e formas de degradação. Para a degradação biótica, foram realizados ensaios de biodegradação em solo simulado (respirometria) e inoculação com fungos (deterioração fúngica). Os resultados mostraram que as condições climáticas afetaram diretamente as características dos compósitos avaliados, causando mudanças na cor e em sua viscosidade, com o aumento do índice de fluidez dos materiais e também alterações em suas estruturas químicas, com aumento do índice de carbonila, indicando a ocorrência de foto-oxidação das amostras. Em relação aos ensaios de biodegradabilidade, houve uma pequena perda de massa nas amostras avaliadas e formação de biofilmes nas superfícies dos compósitos, verificados por microscopia eletrônica de varredura (MEV). A deterioração fúngica ocorre especialmente na superfície das amostras. O fungo Fuscoporia ferrea foi o mais efetivo na deterioração dos compósitos, com maior perda de massa e até mesmo o surgimento de estruturas de reprodução após o período de incubação, porém não penetrou na parte interna dos materiais. Por respirometria também foi verificado um aumento na geração de CO2 ao longo do período avaliado, indicando que há um início de metabolização das amostras por micro-organismos incubadas no solo, principalmente nas amostras expostas a nove meses de intemperismo natural. A presença das fibras protegeu a matriz de PP-EVA da degradação na face não exposta diretamente ao sol, o que é interessante para aplicações que visam longa vida útil, porém a utilização de aditivos para preservação contra radiação UV, oxigênio e micro-organismos se tornam necessárias para otimização e maior durabilidade destes materiais em estudos futuros. / Performance tests on "wood plastic composites" (WPC) require efficient evaluation of their resistance to natural aging over time and against its biodegradation by microorganisms. In this sense, the objective of this study was to investigate the abiotic and biotic degradation mechanisms of thermoplastic composites with vegetable fibers, in order to determine its behavior from the point of view of stability under conditions that will be used. The proposed application for these materials is their use outdoors, in order to replace the wood, in building construction, such as doors, windows, floors, decks and bulkheads. In addition, the effective use of the coupling agent (CA) in durability of aged composites was investigated. For the production of composite was used wood-polymer ratio of 70/30 w/w, wherein the polymeric matrix is comprised of a blend of polypropylene and ethylene-vinyl acetate copolymer (PP-EVA) from post-consumer caps bottle, and the woods used in the form of sawdust, using the eucalyptus and pine species. The polypropylene grafted with maleic anhydride was used as coupling agent in the proportion of 3% w/w. The mixtures were processed by extrusion and composites molded by injection and thermal compression. In fungal degradation tests were used four species of basidiomycete fungi, Trametes villosa, Trametes versicolor, Pycnoporus sanguineus and Fuscoporia ferrea, all white rot fungi. In abiotic degradation, physical, thermal, mechanical, rheological, chemical and morphological properties of composites at different stages of degradation and shapes were evaluated. For biotic degradation, biodegradation tests were performed on soil (respirometry) and inoculated with fungi (fungal deterioration). The results showed that the climatic conditions directly affect the characteristics of the evaluated composites, causing changes in color and its viscosity with increasing melt flow index of the materials and also changes in their chemical structures with increased carbonyl index of samples exposed to natural weathering, thus indicating a photo-oxidation of the samples. Regarding the degradation tests, there was a small weight loss in the evaluated samples, and growth of microorganisms on the surface of composites, evidenced by scanning electron microscopy (SEM). The fungal deterioration occurs especially on the surface. The fungus Fuscoporia ferrea was the most effective in composites deterioration, with greater weight loss and even the emergence of reproductive structures after the incubation period, but did not penetrate inside the material. By respirometry also can be seen an increase in the generation of CO2 over the months, indicating a beginning of metabolism of the samples incubated by microorganisms in the soil, especially in samples exposed to 9 months of natural weathering. The presence of fibers protected the PP-EVA matrix of degradation in the face not exposed to direct sunlight, which is interesting for applications that aim to long life, but the use of additives for preservation against UV radiation, oxygen and microorganisms become necessary for optimization and durability of these materials in future studies.

O desempenho de materiais compósitos plástico-madeira ou ―wood plastic composites‖(WPC) requerem uma avaliação eficiente de sua resistência ao envelhecimento natural ao longo do tempo e contra sua biodeterioração por micro-organismos. Neste sentido, o objetivo deste estudo foi investigar os mecanismos de degradação abiótica e biótica de compósitos termoplásticos com fibras vegetais, a fim de determinar seu comportamento, do ponto de vista da estabilidade, nas condições em que serão usados. A aplicação proposta para estes materiais é sua utilização em ambientes externos, com o propósito de substituir a madeira, em artefatos para construção civil, como portas, janelas, pisos, decks e divisórias. Além disso, a eficácia da utilização do agente de acoplamento (AC) na durabilidade dos compósitos envelhecidos foi investigada. Para a produção dos compósitos foi utilizada a proporção polímero-madeira de 70/30 m/m, sendo que a matriz polimérica foi constituída de uma blenda de polipropileno-copolímero de etileno acetato de vinila (PP-EVA) pós-consumo provenientes de tampas de garrafa, e as madeiras usadas na forma de serragem, utilizando as espécies de eucalipto e pinus. O polipropileno graftizado com anidrido maleico foi usado como AC na proporção de 3 % m/m. As misturas foram processadas por extrusão e os compósitos moldados por compressão térmica e injeção. No teste de degradação por fungos foram utilizados quatro espécies de fungos basidiomicetos, Trametes villosa, Trametes versicolor, Pycnoporus sanguineus e Fuscoporia ferrea, todos de podridão branca. Na degradação abiótica, foram avaliadas as propriedades físicas, mecânicas, térmicas, reológicas, químicas e morfológicas dos compósitos nos diferentes estágios e formas de degradação. Para a degradação biótica, foram realizados ensaios de biodegradação em solo simulado (respirometria) e inoculação com fungos (deterioração fúngica). Os resultados mostraram que as condições climáticas afetaram diretamente as características dos compósitos avaliados, causando mudanças na cor e em sua viscosidade, com o aumento do índice de fluidez dos materiais e também alterações em suas estruturas químicas, com aumento do índice de carbonila, indicando a ocorrência de foto-oxidação das amostras. Em relação aos ensaios de biodegradabilidade, houve uma pequena perda de massa nas amostras avaliadas e formação de biofilmes nas superfícies dos compósitos, verificados por microscopia eletrônica de varredura (MEV). A deterioração fúngica ocorre especialmente na superfície das amostras. O fungo Fuscoporia ferrea foi o mais efetivo na deterioração dos compósitos, com maior perda de massa e até mesmo o surgimento de estruturas de reprodução após o período de incubação, porém não penetrou na parte interna dos materiais. Por respirometria também foi verificado um aumento na geração de CO2 ao longo do período avaliado, indicando que há um início de metabolização das amostras por micro-organismos incubadas no solo, principalmente nas amostras expostas a nove meses de intemperismo natural. A presença das fibras protegeu a matriz de PP-EVA da degradação na face não exposta diretamente ao sol, o que é interessante para aplicações que visam longa vida útil, porém a utilização de aditivos para preservação contra radiação UV, oxigênio e micro-organismos se tornam necessárias para otimização e maior durabilidade destes materiais em estudos futuros. / Performance tests on "wood plastic composites" (WPC) require efficient evaluation of their resistance to natural aging over time and against its biodegradation by microorganisms. In this sense, the objective of this study was to investigate the abiotic and biotic degradation mechanisms of thermoplastic composites with vegetable fibers, in order to determine its behavior from the point of view of stability under conditions that will be used. The proposed application for these materials is their use outdoors, in order to replace the wood, in building construction, such as doors, windows, floors, decks and bulkheads. In addition, the effective use of the coupling agent (CA) in durability of aged composites was investigated. For the production of composite was used wood-polymer ratio of 70/30 w/w, wherein the polymeric matrix is comprised of a blend of polypropylene and ethylene-vinyl acetate copolymer (PP-EVA) from post-consumer caps bottle, and the woods used in the form of sawdust, using the eucalyptus and pine species. The polypropylene grafted with maleic anhydride was used as coupling agent in the proportion of 3% w/w. The mixtures were processed by extrusion and composites molded by injection and thermal compression. In fungal degradation tests were used four species of basidiomycete fungi, Trametes villosa, Trametes versicolor, Pycnoporus sanguineus and Fuscoporia ferrea, all white rot fungi. In abiotic degradation, physical, thermal, mechanical, rheological, chemical and morphological properties of composites at different stages of degradation and shapes were evaluated. For biotic degradation, biodegradation tests were performed on soil (respirometry) and inoculated with fungi (fungal deterioration). The results showed that the climatic conditions directly affect the characteristics of the evaluated composites, causing changes in color and its viscosity with increasing melt flow index of the materials and also changes in their chemical structures with increased carbonyl index of samples exposed to natural weathering, thus indicating a photo-oxidation of the samples. Regarding the degradation tests, there was a small weight loss in the evaluated samples, and growth of microorganisms on the surface of composites, evidenced by scanning electron microscopy (SEM). The fungal deterioration occurs especially on the surface. The fungus Fuscoporia ferrea was the most effective in composites deterioration, with greater weight loss and even the emergence of reproductive structures after the incubation period, but did not penetrate inside the material. By respirometry also can be seen an increase in the generation of CO2 over the months, indicating a beginning of metabolism of the samples incubated by microorganisms in the soil, especially in samples exposed to 9 months of natural weathering. The presence of fibers protected the PP-EVA matrix of degradation in the face not exposed to direct sunlight, which is interesting for applications that aim to long life, but the use of additives for preservation against UV radiation, oxygen and microorganisms become necessary for optimization and durability of these materials in future studies.

O desempenho de materiais compósitos plástico-madeira ou ―wood plastic composites‖(WPC) requerem uma avaliação eficiente de sua resistência ao envelhecimento natural ao longo do tempo e contra sua biodeterioração por micro-organismos. Neste sentido, o objetivo deste estudo foi investigar os mecanismos de degradação abiótica e biótica de compósitos termoplásticos com fibras vegetais, a fim de determinar seu comportamento, do ponto de vista da estabilidade, nas condições em que serão usados. A aplicação proposta para estes materiais é sua utilização em ambientes externos, com o propósito de substituir a madeira, em artefatos para construção civil, como portas, janelas, pisos, decks e divisórias. Além disso, a eficácia da utilização do agente de acoplamento (AC) na durabilidade dos compósitos envelhecidos foi investigada. Para a produção dos compósitos foi utilizada a proporção polímero-madeira de 70/30 m/m, sendo que a matriz polimérica foi constituída de uma blenda de polipropileno-copolímero de etileno acetato de vinila (PP-EVA) pós-consumo provenientes de tampas de garrafa, e as madeiras usadas na forma de serragem, utilizando as espécies de eucalipto e pinus. O polipropileno graftizado com anidrido maleico foi usado como AC na proporção de 3 % m/m. As misturas foram processadas por extrusão e os compósitos moldados por compressão térmica e injeção. No teste de degradação por fungos foram utilizados quatro espécies de fungos basidiomicetos, Trametes villosa, Trametes versicolor, Pycnoporus sanguineus e Fuscoporia ferrea, todos de podridão branca. Na degradação abiótica, foram avaliadas as propriedades físicas, mecânicas, térmicas, reológicas, químicas e morfológicas dos compósitos nos diferentes estágios e formas de degradação. Para a degradação biótica, foram realizados ensaios de biodegradação em solo simulado (respirometria) e inoculação com fungos (deterioração fúngica). Os resultados mostraram que as condições climáticas afetaram diretamente as características dos compósitos avaliados, causando mudanças na cor e em sua viscosidade, com o aumento do índice de fluidez dos materiais e também alterações em suas estruturas químicas, com aumento do índice de carbonila, indicando a ocorrência de foto-oxidação das amostras. Em relação aos ensaios de biodegradabilidade, houve uma pequena perda de massa nas amostras avaliadas e formação de biofilmes nas superfícies dos compósitos, verificados por microscopia eletrônica de varredura (MEV). A deterioração fúngica ocorre especialmente na superfície das amostras. O fungo Fuscoporia ferrea foi o mais efetivo na deterioração dos compósitos, com maior perda de massa e até mesmo o surgimento de estruturas de reprodução após o período de incubação, porém não penetrou na parte interna dos materiais. Por respirometria também foi verificado um aumento na geração de CO2 ao longo do período avaliado, indicando que há um início de metabolização das amostras por micro-organismos incubadas no solo, principalmente nas amostras expostas a nove meses de intemperismo natural. A presença das fibras protegeu a matriz de PP-EVA da degradação na face não exposta diretamente ao sol, o que é interessante para aplicações que visam longa vida útil, porém a utilização de aditivos para preservação contra radiação UV, oxigênio e micro-organismos se tornam necessárias para otimização e maior durabilidade destes materiais em estudos futuros. / Performance tests on "wood plastic composites" (WPC) require efficient evaluation of their resistance to natural aging over time and against its biodegradation by microorganisms. In this sense, the objective of this study was to investigate the abiotic and biotic degradation mechanisms of thermoplastic composites with vegetable fibers, in order to determine its behavior from the point of view of stability under conditions that will be used. The proposed application for these materials is their use outdoors, in order to replace the wood, in building construction, such as doors, windows, floors, decks and bulkheads. In addition, the effective use of the coupling agent (CA) in durability of aged composites was investigated. For the production of composite was used wood-polymer ratio of 70/30 w/w, wherein the polymeric matrix is comprised of a blend of polypropylene and ethylene-vinyl acetate copolymer (PP-EVA) from post-consumer caps bottle, and the woods used in the form of sawdust, using the eucalyptus and pine species. The polypropylene grafted with maleic anhydride was used as coupling agent in the proportion of 3% w/w. The mixtures were processed by extrusion and composites molded by injection and thermal compression. In fungal degradation tests were used four species of basidiomycete fungi, Trametes villosa, Trametes versicolor, Pycnoporus sanguineus and Fuscoporia ferrea, all white rot fungi. In abiotic degradation, physical, thermal, mechanical, rheological, chemical and morphological properties of composites at different stages of degradation and shapes were evaluated. For biotic degradation, biodegradation tests were performed on soil (respirometry) and inoculated with fungi (fungal deterioration). The results showed that the climatic conditions directly affect the characteristics of the evaluated composites, causing changes in color and its viscosity with increasing melt flow index of the materials and also changes in their chemical structures with increased carbonyl index of samples exposed to natural weathering, thus indicating a photo-oxidation of the samples. Regarding the degradation tests, there was a small weight loss in the evaluated samples, and growth of microorganisms on the surface of composites, evidenced by scanning electron microscopy (SEM). The fungal deterioration occurs especially on the surface. The fungus Fuscoporia ferrea was the most effective in composites deterioration, with greater weight loss and even the emergence of reproductive structures after the incubation period, but did not penetrate inside the material. By respirometry also can be seen an increase in the generation of CO2 over the months, indicating a beginning of metabolism of the samples incubated by microorganisms in the soil, especially in samples exposed to 9 months of natural weathering. The presence of fibers protected the PP-EVA matrix of degradation in the face not exposed to direct sunlight, which is interesting for applications that aim to long life, but the use of additives for preservation against UV radiation, oxygen and microorganisms become necessary for optimization and durability of these materials in future studies.

Wood Plastic Composites (WPC) bilden eine inzwischen beträchtlich wachsende Produktgruppe der Naturfaserverbundwerkstoffe. Diese kombinieren vorteilhafte anwendungstechnische Eigenschaften mit vergleichsweise kostengünstiger Verfügbarkeit. Derzeit sucht die europäische WPC-Industrie intensiv nach neuen Anwendungsbereichen, die für diese Werkstoffgruppe geeignet sind. Anwendungen von Spritzgießteilen aus WPC, z.B. in der Automobil- oder Möbelindustrie, könnten die jährliche Produktion enorm erhöhen. Hierfür müssten jedoch auch die Eigenschaften die hohen Erwartungskriterien erfüllen.Eine Vielzahl vorgängiger Arbeiten zeigt starke Abhängigkeit der Eigenschaften der WPC von der Art und der Morphologie der Holzfaser, der Kunststoffmatrix, dem Zuschlag von Additiven und der Folge daraus von den Verarbeitungsparameter. Das Ziel der vorliegenden Arbeit liegt in der Suche nach Zusammenhängen zwischen der systematischen Rezepturvariation, den Eigenschaften des Verbundes und der Verarbeitungsgüte beim Compoundieren und Spritzgießen von WPC. Die Fließeigenschaften werden in Abhängigkeit definierter Rezepturparameter quantitativ erfasst. Systematische Rezepturvariationen zur Wasseraufnahme und zum Einfluss von Additiv-Wachsen werden ebenfalls im Rahmen dieser Arbeit analysiert. Nicht zuletzt werde untersucht, wie verschiedene Verarbeitungstechnologien (Direktextrusion, Extrusion aus fertigen Compounds und Spritzgießen) die Eigenschaften von WPC mit vergleichbarer Zusammensetzung beeinflussen.

Wood plastic composite (WPC) materials have seen a continuous market growth worldwide in the last decade. So-called extruded WPC profiles are today mainly used in outdoor applications, e.g. decking, railing and fencing. In outdoor conditions, moisture sorption in the wood component combined with temperature induced movements of the polymer matrix causes deformations of such composites. On the macroscopic scale this may lead to unacceptable warp, cup and bow of the WPC products, but on a microscopic scale, the movements will cause interfacial cracks between the particles and the matrix, resulting in little or no ability to transfer and re-distribute loads throughout the material. Moisture within the composite will also allow fungi and micro organisms to attack the wood particles. The conceptual idea of this work is to use a chemically modified wood component in WPCs to enhance their long term performance. These chemically modified wood particles exhibit reduced susceptibility to moisture, resulting in better dimensional stability and a higher resistance to biological degradation as compared to that of unmodified wood. The objective of this thesis is to study the effects of using modified wood in WPCs on their moisture sorption behaviour, micromorphology and microbiological durability. The modification methods used were acetylation, heat treatment and furfurylation. Equilibrium moisture content (EMC) and sorption behaviour of WPCs were determined by water vapour sorption experiments. The use of thin sections of the composites enabled EMC to be reached within a comparably short time span. The micromorphology was studied by LV-SEM (low vacuum-scanning electron microscope) using a specially designed sample preparation technique based on UV laser. The biological durability was evaluated by laboratory fungal test methods. The moisture sorption experiments showed lower moisture levels for all the composites when modified wood particles were used. This was also reflected in the micromorphological studies where pronounced wood-plastic interfacial cracks were formed due to moisture movement in the composites with unmodified wood particles. The sample preparation technique by UV laser proved to be a powerful tool for preparing surfaces for micromorphological studies without adding mechanical defects caused by the sample preparation technique itself. Results from the durability test showed that WPCs with modified wood particles are highly resistant to decay by fungi. / QC 20101116

No description available.

Polymeric composites reinforced with bio-materials have advantages over composites with synthetic reinforcements. Bio-based composites use low-cost and renewable reinforcements, have nonabrasive properties for machining, have improved damping characteristics, and have potential for energy recycling. However, the limited use of bio-based composites is because their mechanical properties are typically much lower than those of synthetic composites. The objective of this study was to combine state-of-the-art imaging tools with emerging numerical modeling methods for an integrated, multi-level characterization of bio-based reinforcements and their composites. Digital photography (2D) will allow collection of full-field digital images of the surface of sample composites, which will be used for characterization of the morphological structure of fillers (copper wire or wood particle) and of model composites. Mechanical experiments (tension load) on isolated fillers and on model composites will allow imaging of the deformed material. By correlating relative positions of thousands of surface features between consecutive images, digital image correlation (DIC) algorithms can be used to map surface deformation fields and calculate surface strain fields. Digital imaging methods can only record deformations and strains. The interpretation of those strains in terms of material properties, such as position-dependent modulus of a heterogeneous composite material, requires simultaneous modeling. The modeling must use morphology-based methods that can handle anisotropy, heterogeneity, and the complex structure of bio-based composites such as wood plastic composites. This research used the material point method (MPM) as a modeling tool. MPM is a particle-based, meshless method for solving problems in computational mechanics. The crucial advantage of MPM over other methods is the relative ease of translating pixels from digital images into material points in the analysis. Thus digital images (2D) used in our experiments were used as direct input to the MPM software, so that the actual morphologies, rather than idealized geometries, were modeled. This procedure removes typical uncertainties connected with idealization of the internal features of modeled materials. It also removes variability of specimen to specimen due to morphology variations. Full-field imaging techniques and computer modeling methods for analysis of complex materials have developed independently. This research Coupled imaging and modeling and used inverse problem methodology for studying bio-particulate composites. The potential of coupling experiments with morphology-based modeling is a relatively new area. This work studied the morphology and mechanical properties of copper wire (for validation experiments) and wood particles used for reinforcement in polymer composites. The goal was to determine the in situ mechanical and interfacial properties of copper wire and then wood particles. By comparison of DIC results to MPM, the conclusion is MPM simulation works well by simulating 3D composite structure and using Matlab software to do qualitative and quantitative comparisons. Copper validation tests showed that copper wire is too stiff compared to polymer such that the inclusion modulus had low effect on the surface strains (DIC experimental results). Wood particle worked better because modulus of wood is much lower than copper. By qualitative comparison of the wood particle specimens, we could deduce that the in situ properties of wood particles are lower than bulk wood. Quantitative analysis concentrated on small area and got more exact results. In a 90 degree particle quantitative study, MPM simulations were shown to be capable of tracking the structure of wood particle plastic, which involved failure. The entire approach, however, is not very robust. We can get some results for mechanical properties, but it does not seem possible to extract all anisotropic properties from a few DIC tests, as some researcher have suggested. / Graduation date: 2012

The current sensitiveness about environment, sustainable development and petroleum depletion restrictions, are promoting new research in the field of high environmental efficiency materials and technologies. In the last decades, important advances in the field of renewable and/or biodegradable polymers have been reached; nevertheless, these polymers still find some restrictions at industrial scale. On the other hand, with the aim of protecting forests areas, legislation is promoting the development of polymer materials and composites that could potentially substitute wood. These materials, called Wood Plastic Composites (WPC), combine a polymeric matrix, mainly from petroleum-based polymers, with a reinforcement that comes from the wastes generated by the wood industry. Currently, the concept of WPCs has been widened including any polymer (independently from its origin and/or biodegradability) and any lignocellulosic component coming from industry. The present work has been focused on the development, formulation, analysis and optimization of WPCs from a renewable polymer matrix, polylactic acid (PLA) and lignocellulosic reinforcements from hazelnut shell flour wastes (HSF). Due to the intrinsic fragility of PLA and its low impact resistance, new formulations containing epoxidized linseed oil (ELO) have been developed. The obtained results show that the hazelnut shell flour allows obtaining stiffer materials, as much as stiffer as the hazelnut shell flour content increases. On the other hand, the impact strength decreases with increasing hazelnut shell flour with regard to neat PLA. The results also suggest that epoxidized linseed oil (ELO) provides a dual effect: on one hand its plasticization effect is evident as the glass transition temperature (Tg) is reduced due to increased polymer chain mobility. On the other hand, the obtained results also suggest a compatibilizing effect, due to the interactions between the oxirane groups in ELO and the hydroxil groups in both lignocellulosic filler and terminal groups in PLA chains. Addition of ELO improves in a remarkable way the overall properties of these biocomposites. This research also assesses the effect of the water uptake and the biodegradation or disintegration in compost conditions, to offer a range of formulations with high potential technology transfer to industry. / La actual sensibilidad por el medio ambiente, el desarrollo sostenible y las limitaciones de los recursos fósiles, están propiciando que la tecnología de materiales dirija sus investigaciones al desarrollo de materiales de alto rendimiento ambiental. En las últimas décadas se han conseguido grandes avances en polímeros de origen renovable y/o biodegradables, aunque todavía encuentran ciertas limitaciones a nivel industrial. Por otro lado, la protección de las áreas forestales, desde el plano legislativo, está impulsando el desarrollo de materiales plásticos y compuestos que imitan el acabado de la madera. Estos materiales, conocidos como Wood Plastic Composites (WPC), combinan una matriz polimérica, fundamentalmente de origen petroquímico, con un refuerzo procedente de residuos de la industria maderera. Actualmente, el concepto de WPCs se ha ampliado y contempla cualquier tipo de matriz polimérica (independientemente de su origen y/o biodegradabilidad) y cualquier componente de tipo lignocelulósico procedente de diversas industrias. El presente trabajo se ha centrado en el desarrollo, formulación, análisis y optimización de WPCs basados en matrices poliméricas de origen renovable, ácido poliláctico (PLA) y refuerzos lignocelulósicos procedentes de la cáscara de avellana en forma de harina. Dada la fragilidad intrínseca del PLA y su baja resistencia al impacto se han desarrollado formulaciones con plastificantes de alto rendimiento medioambiental derivados de aceite de linaza epoxidado (ELO). Los resultados obtenidos indican que la harina de cáscara de avellana permite obtener materiales más rígidos cuanto mayor es su contenido. A medida que se incrementa el contenido de harina de cáscara de avellana, la energía de impacto del compuesto disminuye con respecto a la del PLA virgen. Los resultados demuestran que el plastificante de aceite de linaza epoxidado (ELO) ofrece un efecto dual: por un lado, actúa como plastificante, con la consiguiente reducción de la temperatura de transición vítrea (Tg) e incremento de movilidad de cadenas poliméricas. Por otro lado, los resultados sugieren un efecto compatibilizante, resultado de la interacción de los grupos oxirano del ELO con los grupos hidroxilo del refuerzo lignocelulósico y con grupos terminales de la cadena de PLA. La incorporación de aceite de linaza epoxidado mejora sustancialmente las propiedades globales de los biocompuestos. Esta investigación también revisa el efecto de la humedad en los procesos de absorción de agua, así como la biodegradación o desintegración en condiciones de compostaje, ofreciendo un grupo de formulaciones con alto potencial de transferencia a escala industrial. / L'actual sensibilitat pel medi ambient, el desenvolupament sostenible i les restriccions lligades als recursos fòssils, estan propiciant que la tecnologia de materials dirigisca les seues recerques cap al desenvolupament de materials d'alt rendiment ambiental. En les últimes dècades s'han aconseguit importants avanços en polímers d'origen renovable i/o biodegradables, malgrat que encara troben certes limitacions a nivell industrial. D'altra banda, amb l'objectiu de protegir les àrees forestals, la legislació està, també, propiciant el desenvolupament de materials plàstics i compòsits que imiten l'aparença de la fusta. Aquests materials, coneguts com Wood Plastic Composites (WPC), combinen una matriu polimèrica, fonamentalment d'origen petroquímic, amb un reforç procedent de residus de la indústria de la fusta. Actualment, el concepte de WPCs s'ha ampliat i contempla qualsevol tipus de matriu polimèrica (independentment del seu origen i/o biodegradabilidad) i qualsevol component de tipus lignocel·lulòsic procedent de diverses indústries. El present treball s'ha centrat en el desenvolupament, formulació, anàlisi i optimització de WPCs basats en matrius polimèriques d'origen renovable, àcid polilàctic (PLA) i reforços lignocel·lulòsics procedents de la corfa d'avellana en forma de farina. Donada la fragilitat intrínseca del PLA i la seua baixa resistència a l'impacte, s'han desenvolupat formulacions amb plastificants d'alt rendiment mediambiental derivats de l'oli llinós epoxidat (ELO). Els resultats obtinguts indiquen que la corfa d'avellana, en forma de farina, permet obtindré materials més rígids, tant més quan major és la quantitat de farina de corfa d'avellana. A mesura que s'incrementa el contingut en farina de corfa d'avellana, l'energia d'impacte disminueix en comparació amb el PLA verge. Els resultats obtinguts demostren que el plastificant d'oli llinós epoxidat (ELO) ofereix un efecte dual: per una banda, actua com a plastificant, amb la associada disminució de la temperatura de transició vítria (Tg) i l'increment de la mobilitat de les cadenes. Per altra banda, els resultats suggereixen un efecte compatibilitzant, resultat de les interaccions entre els grups oxirà de l'ELO amb els grups hidroxil del reforç lignocel·lulòsic i els grups terminals en les cadenes polimèriques de PLA. La incorporació d'oli llinós epoxidat millora substancialment les propietats globals dels biocompòsits. Aquest recerca també revisa l'efecte de la humitat en els processos d'absorció d'aigua així com la biodegradació o desintegració en condicions de compostatge, oferint un grup de formulacions amb alt potencial de transferència a escala industrial. / Balart Gimeno, JF. (2017). Desarrollo y caracterización de WPCs basados en ácido poliláctico (PLA) y refuerzos derivados de la cáscara de avellana [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/85982 / TESIS

<p>  </p> <p>Globally, communities are embracing the cured-in-place-pipe (CIPP) process due to the need to address damaged buried water and sewer pipes. CIPP involves the chemical manufacture of a new plastic pipe inside an existing buried water and sewer pipe, without the need for excavation. The process is popular because it can be 80% less costly than alternative methods and construction workers can be present for hours to not days to weeks. However, as CIPP use has grown, so have the number of hazardous material (HAZMAT) incidents caused by using this practice. Evacuations of daycare centers, schools, homes, healthcare, institutional, and other buildings have been caused. In some cases, chemical exposure victims have required medical assistance and hospital admission. For decades, organizations within the CIPP industry and municipalities have encouraged chemical waste discharge into ambient air, resulting in preventable exposures. Recent work has indicated tons of volatile organic compounds (VOC) may be released during a single CIPP project into the air. Chemicals released include hazardous air pollutants (HAP), carcinogens (CAR), endocrine disrupting chemicals (EDR), and other compounds with little toxicological information. While polymer composites have been manufactured for other applications for more than 50 years, little information exists about what chemicals and materials are used to manufacture CIPPs. As CIPP use has grown along with the number of bystander chemical exposures, concerns about the type, magnitude, and toxicity of chemical emissions from CIPP projects have markedly increased. To reduce the potential for human harm and environmental degradation, a better understanding of CIPP composite chemistry and manufacturing is needed. This dissertation aimed to elucidate the processes that control the composition of waste generated during plastic CIPP manufacture and ascertain how to modify the manufacturing practice to minimize impacts on composite integrity and emission toxicity. </p> <p>Chapter 1 focused on indoor VOC exposure simulation and styrene contamination/ decontamination to evaluate the risk of occupant exposure during CIPP installation. Styrene is a common monomer used in many CIPP resins and can be discharged into the air at CIPP worksites. A review of prior incidents revealed that CIPP waste (liquid, organic chemicals, etc.) could enter nearby buildings through multiple routes including windows, doors, or heating, ventilation, and air conditioning outdoor air intakes. When CIPP is manufactured inside a sanitary sewer pipe, waste can enter buildings through sewer laterals of nearby buildings and through foundation cracks. Study results showed that plumbing seal backflows in bathrooms caused by sewer repair work are hydraulically possible: the minimum pressure required to displace water in the plumbing trap was estimated to be 0.995 kPa and 8.85 kPa for a sink and toilet, separately. These pressures are much lower than those applied by the contractor during the sewer lining (up to 193.05 kPa). Based on the indoor exposure events, the dissipation potential of vapors, as well as the hydraulic calculations, indoor air chemical contamination and decontamination profiles were also examined. A mass balance model of chemical vapor dispersion was developed. Modeling results revealed that bathroom exhaust fan operation during a CIPP project can increase the indoor styrene concentration by enhancing the inflow of styrene-containing air from the sink and toilet. However, the styrene concentration decreased as air leaked across the bathroom door due to reduced suction in the plumbing. Based on incident reviews, chemical magnitudes, and modeling results it was concluded that CIPP waste discharge should be treated as hazardous material discharge, because of its threat to human health. Actions are needed to reduce waste generation and contain the waste, so it does not leave the worksite. Chapter 2 aimed to determine the manufacturing conditions that most influence chemical residual left in the thermally manufactured CIPP. Bench-scale testing of multiple styrene- and non-styrene composites revealed the manufacturing conditions (curing time, temperature, initiator loading) necessary to produce a high integrity composite while minimizing chemical residual and air emissions. Even though the VOC loading of the non-styrene resin (4 wt.%) was much less than that of styrene resin (39 wt.%), the non-styrene resin did contain HAP, EDR, CAR compounds including ethylbenzene, 2-ethylhexanoic acid, methacrylic acid, styrene, toluene, and <em>m</em>-xylene. Study results also revealed that by changing initiator loading a drastic reduction in the amount of styrene (-42 wt.%) and styrene oxide (-33 wt.%) residual left in the newly manufactured composite was achieved. Discoveries prompted a new hypothesis that this decreased residual also prompted a decreased amount of VOCs emitted into the air. The explanation is that this occurs because that a greater amount of the monomer styrene was incorporated into the resin during polymerization and not permitted to enter the air. Despite decades of polymer composite use, this study provides a new fundamental understanding of composite chemicals and techniques for reducing air pollutant emissions during plastic composite manufacture. In Chapter 3, the complexity of organic vapor chemicals found in the air during thermal heating of CIPP composites was explored and quantified. The emission rate of a popular monomer, styrene, was quantified from the materials before, during, and after composite manufacture. Scaling up bench-scale results, 1.9 to 14 US tons and 0.18 to 1.35 US tons of VOCs (0.05 to 0.36 US tons and 0.001 to 0.007 US tons of styrene) were estimated to be emitted during curing of styrene- and non-styrene CIPPs (i.e., typically 1-3 m of diameter pipes). By modifying standard air sampling methods, previously undetectable chemicals associated with CIPP manufacture were found in the styrene-laden air. These include acetophenone, benzaldehyde, phenol, and 1,3,5-trimethylbenzene. Results have immediate relevance to improved air monitoring for public and worker safety. Further, results can be used to examine the cumulative health and environmental risks of the CIPP pollutant mixtures. Chapter 4 focused on identifying CIPP technology/knowledge gaps and feedback from health officials from multiple state and federal agencies. Through this study, a public health workgroup was assembled to include disciplinary experts and 13 federal, state, and city health agencies and public health associations. Building on dialogue with U.S. health officials, the state of knowledge pertaining to CIPP chemical exposures, mitigation, and response actions was reviewed. Topics included 1) CIPP manufacturing process and waste; 2) sewers and buildings; 3) chemical exposure and health; 4) chemical risk assessment; 5) risk communication. This study helped establish relationships among federal, state, and city officials to improve public health response. Additionally, a primer for CIPP chemical fate and transport, as well as assisting in identifying and prioritizing public health information needs was developed. Identification and prioritization of current public health knowledge gaps and proposed practices for reducing exposures to the public and workers were reported. CIPP-related bench and research results throughout the dissertation can serve as an important basis for environmental policy and public health guidelines on the prevention and mitigation aspects of environmental and human health impacts resulting from CIPP manufacturing practices.</p>