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Materials and Device Engineering for Efficient and Stable Polymer Solar CellsHansson, Rickard January 2017 (has links)
Polymer solar cells form a promising technology for converting sunlight into electricity, and have reached record efficiencies over 10% and lifetimes of several years. The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor materials in the active layer. To achieve longer lifetimes, degradation processes in the materials have to be understood. In this thesis, a set of complementary spectroscopy and microscopy techniques, among which soft X-ray techniques have been used to determine the morphology of polymer:fullerene based active layers. We have found that the morphology of TQ1:PC70BM films is strongly influenced by the processing solvent and the use of solvent additives. We have also found, by using soft X-ray techniques, that not only the light-absorbing polymer TQ1, but also the fullerene is susceptible to photo-degradation in air. Moreover, the fullerene degradation is accelerated in the presence of the polymer. Additionally, this thesis addresses the role of the interfacial layers for device performance and stability. The commonly used hole transport material PEDOT:PSS has the advantage of being solution processable at room temperature, but this layer is also known to contribute to the device degradation. We have found that low-temperature processed NiOx is a promising alternative to PEDOT:PSS, leading to improved device performance. Even for encapsulated polymer solar cells, some photo-induced degradation of the electrical performance is observed and is found to depend on the nature of the hole transport material. We found a better initial stability for solar cells with MoO3 hole transport layers than with PEDOT:PSS. In the pursuit of understanding the initial decrease in electrical performance of PEDOT:PSS-based devices, simulations were performed, from which a number of degradation sources could be excluded. / With the increasing global demand for energy, solar cells provide a clean method for converting the abundant sunlight to electricity. Polymer solar cells can be made from a large variety of light-harvesting and electrically conducting molecules and are inexpensive to produce. They have additional advantages, like their mechanical flexibility and low weight, which opens opportunities for novel applications. In order for polymer solar cells to be more competitive, however, both the power conversion efficiencies and lifetimes need to further improve. One way to achieve this is to optimize the morphology of the active layer. The active layer of a polymer solar cell consists of electron donating and electron accepting molecules whose distribution in the bulk of the film is a major factor that determines the solar cell performance. This thesis presents the use of complementary spectroscopy and microscopy methods to probe the local composition in the active layer of polymer solar cells. The stability of the active layer is studied and the interplay between the photo-degradation of the donor and acceptor molecules is investigated. Additionally, this thesis addresses how the interfacial layers between the active layer and the electrodes can influence device performance and stability. / <p>I publikationen felaktigt ISBN 978-91-7063-739-1</p>
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Materials aspects in spin-coated films for polymer photovoltaicsAnselmo, Ana Sofia January 2013 (has links)
Polymer-based photovoltaics have the potential to contribute to boosting photovoltaic energy conversion overall. Besides allowing large-area inexpensive processing, polymeric materials have the added benefit of opening new market applications for photovoltaics due to their low-weight and interesting mechanical properties. The energy conversion efficiency values of polymer photovoltaics have reached new record values over the past years. It is however crucial that stability issues are addressed together with efficiency optimization. Understanding fundamental materials aspects is key in both areas. In the work presented in this thesis, the morphology of polymer:fullerene films and its influence on device performance was studied, as well as the effect of light exposure on the surface of fullerene films. Several polyfluorene copolymers were used for the morphology studies, where the effects of changing spin-coating solvent and of side chain engineering were investigated with dynamic secondary ion mass spectrometry (dSIMS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Polymer-enriched surfaces were found in all blend films, even in the cases with homogeneous distributions in the bulk. Side chain engineering of the polymer led to gradual changes in the compositional variations perpendicular to the surface, and to slight variations in the photocurrent. The electronic structure of the fullerene derivative PCBM was studied in detail and the spectroscopic fingerprint of the materials was analysed by comparison with theoretically simulated spectra. Photo-stability studies done in air showed that the surface of fullerene films underwent severe damages at the molecular level, which is evident from changes in the valence band and X-ray absorption spectra. These changes were explained by transitions from sp2-type to sp3 hybridization of the carbon atoms in the cage that resulted in the destruction of the fullerene cage.
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Sondando o acoplamento magnetoelástico e magnetoelétrico em novos materiais magnetoresistentes e multiferróicos através de interações dos raios-x com a matéria / Investigating the magnetoelastic and magnetoeletric coupling in magnetoresistent and multiferroic materials through X-ray interaction with matterAzimonte Bottan, Carla 05 August 2009 (has links)
Orientador: Eduardo Granado Monteiro da Silva / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-13T21:32:58Z (GMT). No. of bitstreams: 1
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Previous issue date: 2009 / Resumo: Nesta tese de doutorado empregamos a união de diferentes técnicas com intuito de estudar as correlações entre as propriedades magnéticas, elétricas e cristalinas em alguns óxidos de metais de transição de interesse atual. Dentre eles se encontram os compostos da família das perovskitas duplas A2FeReO6 (A = Ba, Ca) e o multiferróico DyMn2O5. Esses materiais apresentam extraordinário potencial para aplicações e otimizações de novos dispositivos baseados nos materiais parentes ferroelétricos e ferromagnéticos. Realizamos medidas de dicroísmo circular magnético de raios-x, difração de raios-x e magnetização-dc. Esses dados, conjuntamente com resultados prévios de difração de nêutrons e cálculos de teoria de banda, mostraram um incipiente ordenamento orbital no sistema meiometal Ba2FeReO6, onde os elétrons de condução se encontram na fronteira da transição metalisolante. Para o composto Ca2FeReO6, a união dessas técnicas nos proporcionou um maior entendimento sobre a transição metal-isolante (TMI ~ 150 K), levando à proposta de um mecanismo até então nunca descrito para uma transição deste tipo, onde há competição entre um estado colinear otimizando a interação de Dupla Troca e um estado não colinear e localizado estabilizado pela energia magnetocristalina do Re. No multiferróico DyMn2O5, as medidas de difração anômala de raios-x com aplicação de campo elétrico, fundamentadas na teoria dos pares de Friedel, possibilitaram pela primeira vez a verificação experimental do deslocamento atômico médio dos íons de Mn nessa estrutura que leva à ferroeletricidade, até então não identificado por medidas convencionais de difração de raios-x ou nêutrons. De maneira geral, o trabalho descrito nesta tese esteve focado no estudo dos acoplamentos magnetocristalino e magnetoelétrico em materiais meio-metálicos que apresentam magnetoresistência de tunelamento e em multiferróicos. O desenvolvimento desta área é condição básica e necessária para viabilizar uma nova geração de dispositivos relacionados à spintrônica / Abstract: In this doctoral thesis, different techniques were employed to study the correlations between electrical, magnetic and crystalline properties in some transition metal oxides of current interest, such as the double perovskite family A2FeReO6 (A = Ba, Ca) and the multiferroic DyMn2O5. These materials offer extraordinary potential for the application and optimization of new devices based on ferroelectric and ferromagnetic related materials. X-ray magnetic circular dichroism (XMCD), x-ray diffraction and dc-magnetization measurements were performed. These data, associated with previous neutron results and band structure calculations, show an incipient orbital order in half-metallic Ba2FeReO6 where the conduction electrons are in the proximity of a metal-insulator transition. For the Ca2FeReO6 compound, the combination of these techniques provided insight into the metal-insulator transition (TMI ~ 150K), leading to the proposal of a new mechanism for this type of transition, according to which a competition between a double-exchange-like collinear state and a localized non-collinear state stabilized by the Re magnetocrystaline energy takes place. In the multiferroic DyMn2O5, anomalous x-ray diffraction experiments with the application of electric fields, and an interpretation based on Friedel pairs theory, allowed us to see, for the first time, the experimental confirmation of Mn ferroelectric atomic displacements in this structure leading to the ferroelectricity, so far unidentified by conventional x-ray diffraction and neutron diffraction experiments. In summary, the research described in this thesis was focused in the study of the magnetocrystalline and magnetoelectric coupling in half-metallic materials with tunneling magnetoresistance, as well as in multiferroics. Further development of this area is a basic and necessary condition to bring life to a new generation of devices related to spintronics / Doutorado / Física da Matéria Condensada / Doutor em Ciências
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Quantificação de metais em aguas e sedimentos do reservatorio Billings por fluorescencia de raios X com reflexão total e radiação Sincrotron (SR-TXRF) / Quantification of metals in water and sediments of the Billlings dam by Synchronton radiation total reflection X-Ray fluorescence (SR-TXRF)Sampaio, Sergio Arnaud 26 February 2007 (has links)
Orientador: Silvana Moreira / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Civil, Arquitetura e Urbanismo / Made available in DSpace on 2018-08-10T23:35:00Z (GMT). No. of bitstreams: 1
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Previous issue date: 2007 / Resumo: A Represa Billings é o maior reservatório de água da região metropolitana de São Paulo, com aproximadamente 100 km² em espelho de água. Sua bacia hidrográfica ocupa mais de 500km² em seis municípios da região. Ao seu redor concentra-se o maior parque industrial da América do Sul e somente suas margens são ocupadas por quase um milhão de habitantes. A qualidade de suas águas é, portanto, motivo constante de preocupação de toda a sociedade. Neste trabalho aplica-se a Espectrometria de Fluorescência de Raios X, com Reflexão Total e excitação por Radiação Síncrotron (SR-TXRF), para a identificação e quantificação de metais em águas e sedimentos da Represa Billings. Foram quantificados os metais Cr, Ni, Cu, Zn e Pb, freqüentemente investigados em trabalhos na área ambiental, já que são largamente usados em processos industriais e estão presentes em vários produtos de consumo doméstico. Para o trabalho de campo, foram coletadas amostras em dezoito pontos, incluídas as margens e a porção central da represa, localizados em regiões com ocupação residencial e industrial, como também em regiões preservadas, próximos de pontos de monitoramento adotados pela Companhia de Tecnologia de Saneamento Ambiental do Estado de São Paulo (CETESB). As amostras de água e de sedimentos, bem como as amostras certificadas e padrões, foram analisadas no Laboratório Nacional de Luz Síncrotron ¿ LNLS situado no pólo de alta tecnologia, em Campinas-SP. Foi estabelecida uma comparação entre as concentrações de metais obtidas e os valores de referência para águas e para sedimentos, recomendados pela legislação em vigor. Os resultados obtidos indicam concentrações acima dos valores permitidos para o cobre, generalizada para todos os locais de amostragem, como também para o chumbo na grande maioria desses locais. Os demais metais estudados também apresentaram concentrações acima do permitido para alguns dos pontos de amostragem. O trabalho destaca as vantagens e os aspectos relevantes da técnica de análise (SR-TXRF), considerada como não destrutiva e com baixos limites de detecção (partes por bilhão). Outras vantagens são: a sensibilidade analítica para uma ampla faixa de elementos, com um preparo simples e rápido de amostras e facilidade de operação, e que por isso tem apresentado grande desenvolvimento nos últimos anos, com crescente aceitação da comunidade científica. A finalidade de contexto social é contribuir para a preservação dos mananciais locais e o aproveitamento racional de suas águas / Abstract: The Billings dam is the largest water reservatory in the metropolitan region of Sao Paulo, with approximately 100 km2 of area. Its watershed takes up more than 500 km2 in 6 counties of the region. Around the dam is located the largest industrial region of South America and only its borders have about 1 million inhabitants. The water quality is a constant concern to society. On this study, it is applied the synchrotron radiation total reflection X-ray fluorescence (SRTXRF) analysis for identification and quantification of metals in water and sediments of the Billings dam. Metals such as Cr, Ni, Cu, Zn and Pb were analyzed and investigated by environmental work tasks, as they are largely used in industrial processes and are present in various domestic consumers¿ products. As far as experimental work, samples were collected in 18 locations, including the borders and in the central part of the dam, which were located in both residential and industrial regions, as well as in preserved regions, near the places where monitoring was adopted by the Technology and Environmental Company of São Paulo State (CETESB). The water and sediment samples, as well as the certified ones were analyzed in the Brazilian Synchrotron Light Laboratory (LNLS) located in the high technology pole in Campinas, SP. A comparison was established between the metal concentration obtained and the reference values for water and sediments, recommended by Brazilian laws. The results registered a concentration higher than permissive values for Cu, generalized to all sample locations, as well as to Pb in the majority of these places. Other metals studied also showed a concentration higher than permissive values in some points. The job features the advantages and relevant aspects of the SR-TXRF technique. Advantages as not destructive, with low detection limits, high sensitivity for several elements, simple and quick sample preparation, ease operation among others) that shows great development in the past years, with a growing acceptance in the scientific community. The purpose within the social context is to contribute to the local water sources preservation and the rational usage of its waters / Mestrado / Recursos Hidricos / Mestre em Engenharia Civil
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Transformações de fase associadas ao processamento termomecânico do aço inoxidável supermartensítico 12Cr/6Ni/2Mo/0,1Ti / Phase transformations related to the thermomechanical processing of a 12Cr/6Ni/2Mo/0,1Ti supermartensitic stainless steelEscobar Atehortua, Julian David, 1988- 23 August 2018 (has links)
Orientadores: Paulo Roberto Mei, Antonio Jose Ramirez / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-23T10:44:00Z (GMT). No. of bitstreams: 1
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Previous issue date: 2013 / Resumo: Neste trabalho foram estudadas as modificações metalúrgicas provocadas por tratamentos térmicos e soldagem por atrito com pino não consumível SAPNC do aço inoxidável supermartensítico AISM 12Cr/6Ni/2Mo/0,1Ti. As chapas de AISM foram fornecidas após laminação a quente e recozimento, com propriedades mecânicas e microestrutura fora do estabelecido pelos requisitos técnicos de controle de qualidade de materiais usados na indústria de transporte de petróleo e gás. Foi utilizada uma metodologia experimental que se consistiu em duas frentes de estudo: 1) Uso de tratamentos térmicos para reproduzir as condições microestruturais empregadas industrialmente; 2) Desenvolvimento de parâmetros de processamento superficial e soldagem de juntas por atrito. Para reproduzir as condições microestruturais das chapas usadas em campo foram realizados diferentes revenimentos intercríticos, em patamares de 610, 625, 650, 670, 700 e 720 °C durante 2,5 horas. Para estudar a cinética de transformação de fases foi usado um simulador termomecânico Gleeble 3S50¿ acoplado a uma fonte de radiação síncrotron, na instalação XTMS pertencente ao Laboratório Nacional de Luz Síncrotron (LNLS). Para o desenvolvimento de parâmetros de processamento e soldagem por atrito foi utilizado um equipamento dedicado para SAPNC no Laboratório Nacional de Nanotecnologia. Os estudos foram feitos empregando uma ferramenta de compósito de nitreto de boro cúbico policristalino com matriz metálica da liga de tungstênio-rênio (25% Re) na forma de pino cônico com rosca, medindo entre 9,2 e 9,5 mm de comprimento e ombro convexo de 25 mm de diâmetro. Foram avaliadas velocidades de rotação na faixa entre 200 e 400 RPM, e velocidades de avanço entre 75 e 100 mm.min-1. Foram reproduzidas as condições de dureza e fração de fases de uma tubulação comercial de AISM, mediante revenimentos intercríticos. A melhor temperatura de revenimento intercrítico foi 610°C, pois conseguiu gerar uma matriz de martensita revenida, com presença de 15% de Foi possível obter um processamento com bom acabamento e livre de defeitos internos, usando 250 RPM e 100 mm.min-1. Para a soldagem de dois passes de juntas de chapas de 17,9 mm de espessura, a melhor combinação de parâmetros foi 300 RPM e 100 mm.min-1. Para os dois estados de fornecimento (recozido; temperado e revenido), a zona misturada consistiu de blocos martensita nova com refinamento progressivo de grão em direção à raiz dos cordões. Foram identificadas 3 zonas termicamente afetadas (ZTA) em relação às 5 que ocorrem na soldagem a arco. Não foram encontradas as ZTAs i e ii (de alta temperatura), suprimindo completamente a precipitação de ferrita delta. A ZTA iii (de austenitização completa) era totalmente constituída de martensita nova. A ZTA iv (de austenitização intercrítica) de chapas recozidas era formada por uma mistura de martensita nova e martensita revenida. A ZTA iv de chapas temperadas e revenidas apresentou uma mistura de martensita nova, martensita revenida e austenita revertida / Abstract: In this research, metallurgical changes due to heat treatments and friction stir welding of a high alloyed supermartensitic stainless steel SMSS 12Cr/6Ni/2Mo/0, 1Ti were studied. SMSS plates were received after hot rolling and annealing. Mechanical properties and microstructure were out of the technical requirements established for materials quality control used in the oil and gas transportation. An experimental methodology was used to evaluate two different areas: 1) The use of heat treatments to replicate the microstructural conditions used in field applications. 2) Development of friction stir processing and welding parameters. The microstructural conditioning was conducted by using different intercritical tempering temperatures: 610, 625, 650, 670, 700 and 720 °C during 9000 seconds. To study the kinetics of phase transformation during heating, soaking and cooling, it was used a thermomechanical simulator Gleeble3S50¿, coupled to a source of synchrotron radiation, at XTMS facility belonging to the Brazilian Synchrotron Light Laboratory. The development of friction stir processing and welding parameters was conducted in dedicated equipment for FSW at the National Laboratory for Nanotechnology. A composite W-Re (matrix)/PCBN reinforced tool with 9.2 to 9.5 mm long threaded conical pin and convex threaded shoulder was used. Spindle speeds between 400 RPM and 200 RPM, and welding speeds between 100 and 75 mm.min-1, were evaluated. It was possible to replicate the hardness and phase fractions of a commercial SMSS pipe by using an intercritical tempering. The best temperature was 610 °C, since it can generate a tempered martensite matrix with 15% of reverted austenite and 2% of fresh martensite after cooling at room temperature. It was also possible to obtain a sound defect-free processing using 250 rpm and 100 mm.min-1. To perform a two passes welding joint of 17.9 mm thickness, the best combination of parameters to obtain good surface quality and minimal amount of internal defects was 300 RPM and 100 mm.min-1. For the two microstructural conditions evaluated (hot rolled and annealed; and quenched and tempered), the nugget zone consisted of blocks of fresh martensite with progressive grain refinement toward the root of the welded passes. Three heat affected zones HAZ, were identified, regarding the five reported by arc welding. The HAZ i and ii (high temperature) were not found, completely suppressing the delta ferrite precipitation. The HAZ iii (fully austenitized) consisted of fresh martensite. The HAZ iv (partially austenitized) of hot-rolled and annealed plates consisted of a mixture of fresh martensite and tempered martensite. The HAZ iv of quenched and tempered plates consisted of a mixture of fresh martensite, tempered martensite and reverted austenite / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica
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Contribution des nanostructures dans les agrégats protéiques et d’émulsions stabilisées par des protéines en vue de la protection de vitamine / Contribution of nanostructures in protein aggregates and protein-stabilized lipid nanoparticles for vitamin protectionShukat, Rizwan 24 May 2012 (has links)
Nous avons cherché à évaluer l'impact de conditions opératoires pour la préparation d'agrégats protéiques et d'émulsions stabilisées par des protéines en vue de la protection de l'α-tocopherol, servant de modèle de molécules d'intérêt, hydrophobes et sensibles. Les matrices protéiques ont été formées à partir d'un concentrat de protéines de lactosérum (6 wt% de WPC, pH 6.5 et 65 à 75°C), en présence ou absence de 4% α-tocopherol. Le mélange (65°C -15 min) des protéines en solution sans ou avec α-tocopherol a donné lieu à la formation de particules avec modification de charge (de -42 à -51 mV) et de taille (de 183 à 397 nm). Ces paramètres ont diminué davantage sous l'effet d'homogénéisation sous haute pression à 1200 bar que à 300 bar, alors qu'une meilleure protection de l'α-tocopherol a été observée après 8 semaines conservation. Les mécanismes impliqués dans la formation des matrices protéiques correspondantes ont été décrits sur la base de procédés de dénaturation-agrégation de protéines sériques, à partir de résultats obtenus par calorimétrie différentielle à balayage (DSC), spectrofluorescence, diffusion multiple de la lumière et électrophorèse SDS-PAGE. Les matrices lipidiques ont été préparées à partir de phases aqueuses contenant (6 wt% or 3 wt% de WPC) et lipidiques (20 %) en présence ou absence de lécithines (1.5%) avec ou sans α-tocopherol (4%), et par application d'une première étape de dispersion (65°C - 15 min) suivie d'une homogénéisation sous pression à 300 ou 1200 bar. Les nanoparticles lipidiques formées à plus haute pression étaient de taille et concentration protéique de surface plus faibles et de degré d'encapsulation de l'α-tocopherol plus faible (près de 15 %). L'analyse par DSC en modes balayage et isothermes des particules lipidiques a montré que plus leur taille est faible, plus le sur-refroidissement est important, l'apparition des cristaux de matière grasse plus retardée, et leur développement à 4°C moins important. Ces effets sont accentués dans les gouttelettes contenant l'α-tocopherol. La diffraction aux grands et petits angles de rayons X (synchrotron Soleil), couplée à la DSC, a montré la co-existence des polymorphes 2Lα, 2Lβ' et 2Lβ dans toutes les émulsions, mais à des proportions différentes. Les cristaux 2Lβ étaient plus développés dans les gouttelettes de plus petite taille et contenant du tocopherol en présence de lécithins, celles qui présentaient la plus forte dégradation chimique d'α-tocopherol pendant une conservation à long-terme. / We investigated effects of processing conditions for the preparation of protein aggregates and protein-stabilized lipid droplets, as matrix carriers of sensitive lipophilic bioactive compounds, with α-tocopherol as a model. Protein-based matrices were formed from whey protein concentrate (6 wt% WPC, pH 6.5 and 65 to 75°C), in presence or absence of 4% α-tocopherol. Mixing the protein solutions without or with α-tocopherol (65°C for 15 min) led to changes in particle surface charges (from -42 to -51 mV) and sizes (from 183 to 397 nm). These parameters decreased more under further high pressure homogenisation at 1200 bar than 300 bar, in parallel with increased vitamin protection over 8 week's storage. Molecular mechanisms involved in formation of corresponding α-tocopherol-loaded protein matrix were described on the basis of heat- and high-pressure-induced whey protein denaturation and aggregation, as evidenced by differential scanning calorimetry (DSC), spectrofluorescence, multi-light scattering and SDS-PAGE electrophoretic patterns. Lipid-based matrices were developed from aqueous phases (80 wt%) containing WPC (6 wt% or 3 wt%) and lipid phases (20 wt%) in presence or absence of lecithins and/or 4% α-tocopherol, and by using a first dispersion step (65°C for 15 min) followed with HPH at 300 or 1200 bar. Our results showed that increasing HPH was accompanied by formation of lipid nanoparticles with decreasing size and protein surface concentration with an increase in α-tocopherol degradation (up to 15 wt% for 1200 bar). DSC in scanning and isothermal modes showed that reduction in lipid droplet size was accompanied by retardation in crystalline fat development under storage at 4°C, with further reduction in crystalline fat development along with further increase in supercooling for lipid droplets containing α-tocopherol. Fat polymorphism observed using time-resolved synchrotron X-ray scattering at wide and small angles (WAXS and SAXS) coupled with DSC, showed co-existence of 2Lα, 2Lβ' and 2Lβ polymorphs in all the emulsions, but at different proportions. It was observed that 2Lβ polymorphs were more prominent in lipid droplets with lower size and containing α-tocopherol in presence of lecithins that were shown to present the lowest long-term stability of α-tocopherol against chemical degradation.
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β-nucleated isotactic polypropylene with different thermomechanical histories investigated by synchrotron X-rayChen, Jianhong 16 April 2015 (has links) (PDF)
Isotactic polypropylene (iPP), as one of the most versatile commodity thermoplastic polymers, is a polymorphic material having several crystal modifications, among which the β-form exhibits higher performance including excellent impact strength and improved elongation at break.Up to now, the effective and convenient way to prepare the iPP with high content of β-phase has been successfully achieved by addition of certain β-nucleating agent. Since the coexistence of β-nucleating agent and flow (shear flow, extensional flow or mixed), which usually exists in common industrial processing, makes the crystallization process more complex, their combined effect on the structure evolution of polymers, especially in the early stage of crystallization is still not well understood. The mechanical properties of iPP depend strongly on its crystallinity, crystal orientation and morphology determined by the conditions during preparation.
On the other hand, the mechanical properties of polymers can also be modulated by deformation processing, which is directly related to the deformation-induced structure transition. However, the transition mechanism of different crystal forms and structure-property correlation still remain unclear. In this thesis, time-resolved synchrotron X-ray scattering was firstly used for the in-situ study of the structural and morphological developments of β-nucleated iPP during shear-induced crystallization. It was found that the crystallization process was strongly influenced by the concentration of β-nucleating agent, shear rate and shear temperature. Then extension-induced crystallization was investigated by a novel melt draw experiment, where a different crystallization mechanism compared to the shear-induced crystallization was found.
Subsequently, β-nucleated iPP samples with different thermomechanical histories were scanned by synchrotron X-ray microbeam to construct their overall morphological distributions, including distributions of crystallinity, lamellar thickness, orientation, etc. Finally, these morphology-identified samples were investigated by in-situ synchrotron X-ray measurements coupled with mechanical testing to follow the structure evolution during deformation at elevated temperature. It was found that the deformation behaviour of β-nucleated iPP was closely associated with its initial morphology, its subsequent variation during stretching as well as the stretching conditions including the stretching rate and stretching temperature. The current study would not only contribute to the development of crystallization and deformation theory but also be beneficial for the material design.
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β-nucleated isotactic polypropylene with different thermomechanical histories investigated by synchrotron X-rayChen, Jianhong 10 March 2015 (has links)
Isotactic polypropylene (iPP), as one of the most versatile commodity thermoplastic polymers, is a polymorphic material having several crystal modifications, among which the β-form exhibits higher performance including excellent impact strength and improved elongation at break.Up to now, the effective and convenient way to prepare the iPP with high content of β-phase has been successfully achieved by addition of certain β-nucleating agent. Since the coexistence of β-nucleating agent and flow (shear flow, extensional flow or mixed), which usually exists in common industrial processing, makes the crystallization process more complex, their combined effect on the structure evolution of polymers, especially in the early stage of crystallization is still not well understood. The mechanical properties of iPP depend strongly on its crystallinity, crystal orientation and morphology determined by the conditions during preparation.
On the other hand, the mechanical properties of polymers can also be modulated by deformation processing, which is directly related to the deformation-induced structure transition. However, the transition mechanism of different crystal forms and structure-property correlation still remain unclear. In this thesis, time-resolved synchrotron X-ray scattering was firstly used for the in-situ study of the structural and morphological developments of β-nucleated iPP during shear-induced crystallization. It was found that the crystallization process was strongly influenced by the concentration of β-nucleating agent, shear rate and shear temperature. Then extension-induced crystallization was investigated by a novel melt draw experiment, where a different crystallization mechanism compared to the shear-induced crystallization was found.
Subsequently, β-nucleated iPP samples with different thermomechanical histories were scanned by synchrotron X-ray microbeam to construct their overall morphological distributions, including distributions of crystallinity, lamellar thickness, orientation, etc. Finally, these morphology-identified samples were investigated by in-situ synchrotron X-ray measurements coupled with mechanical testing to follow the structure evolution during deformation at elevated temperature. It was found that the deformation behaviour of β-nucleated iPP was closely associated with its initial morphology, its subsequent variation during stretching as well as the stretching conditions including the stretching rate and stretching temperature. The current study would not only contribute to the development of crystallization and deformation theory but also be beneficial for the material design.
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