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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
71

An investigation into some aspects for foamed bitumen technology

Namutebi, May January 2016 (has links)
Despite applications of foamed bitumen technology in pavement construction in various places around the world, there are still several aspects about this technology that are not clear. In addition, knowledge on foamed bitumen technology is mainly empirical and lacks scientific basis. This study addresses some of the aspects for foamed bitumen technology such as: Investigation of any effects in binder composition during the production process for foamed bitumen; assessment of the effect of bitumen source on foamed bitumen characteristics; development of a rational method to optimise foamed bitumen characteristics and conditions; evaluation of aggregate particle coating within foamed bitumen mixes; further improvements in the mix design procedure specifically the method of compaction and optimum bitumen content determination stages are suggested.  Fourier transform infrared spectroscopy techniques were used to investigate any changes in bitumen composition after the production process of foamed bitumen. Fourier transform infrared tests were done on foamed bitumen and neat bitumen specimens for two bitumens with similar penetration grades. Foamed bitumen characteristics of three bitumens were established by producing foamed bitumen at temperatures of 150ºC up to 180ºC and foamant water contents of 1, 2, 3, 4 and 5%. From the analysis of variation of foamed bitumen characteristics (maximum expansion ratio and half-life) at different temperatures a new method based on the equi-viscous bitumen temperature to optimize foamed bitumen conditions and characteristics was proposed. Rice density and surface energy concepts were used to evaluate aggregate particle coating with foamed bitumen. A granite aggregate divided into three different size fractions and three sets of foamed bitumen produced from three bitumen penetration grades were used. A gyratory laboratory compaction procedure for laterite gravels treated with foamed bitumen was established using the modified locking concept. Three laterite gravels with different chemical composition were mixed with foamed bitumen produced from one penetration bitumen grade. The resulting mixes were compacted up to 200 gyrations and the corresponding compaction curve defined in terms of height versus number of gyrations noted. In addition, the optimum moisture content requirements at the modified locking point were determined. 3D packing theory concepts, primary aggregate structure porosity and an indirect tensile strength criteria were employed to determine optimum bitumen content for foamed bitumen mixes.  Fourier infrared techniques revealed that foaming did not cause any changes in the bitumen chemistry, implying that the foamed bitumen production process may possibly be a physical process. Characterisation of foamed bitumen produced from three bitumen penetration grades showed that foamed bitumen characteristics (maximum expansion ratio and half-life) were mainly influenced by binder viscosity rather than the source. The equi-viscous temperature seemed to provide a suitable criterion at which foamed bitumen with optimum characteristics could be produced. Rice density results showed that aggregate size fraction, binder expansion ratio and viscosity influenced aggregate particle coating. For the coarser aggregate fraction, results revealed that binder coating seemed to be mainly influenced by temperature. Whilst for fine aggregate fraction the coating was mainly influenced by surface area. Surface energy results revealed that foamed bitumen exhibited better coating attributes than neat bitumen. A new laboratory compaction procedure for laterite gravels treated with foamed bitumen based on the modified locking point was developed. The modified locking point represents the state at which maximum aggregate particle interlock occurs when mixes are compacted in the field. It is based on the iii analysis of the rate of change for the gyratory compaction curve. The compaction curve in this case is defined in terms of compaction height versus number of gyrations. Gradation analysis beyond the modified locking point showed that aggregate particle breakdown occurred. Analysis of the optimum moisture at the modified locking point revealed that the moisture conditions were less than the aggregate optimum moisture conditions. It is recommended that this point be used to determine the optimal compaction characteristics of foamed bitumen mixes.  Aggregate structure porosity and an indirect tensile strength criteria can be used to determine the bitumen content that could be used in design of foamed bitumen mixes. This would reduce the amount of resources required since the bitumen content could be estimated prior to carrying out the actual laboratory work given that the aggregate grading is known. The aggregate structure can be divided (based on 3D packing theory) into oversize, primary, and secondary structures. The primary structure is mostly responsible for carrying loads whilst the secondary structure fills the voids within the primary structure and provides support to the primary structure. The aggregate size particles constituting the primary structure are deduced as a function of standard sieve sizes using the packing theory concepts. The minimum sieve size for the primary structure is proposed as 1 mm. The oversize structure consists of aggregate particles whose size is greater than the maximum size for the primary structure. The secondary structure consists of aggregate particles whose size is below the minimum size for the primary structure. The primary aggregate structure porosity can be used to establish the starting bitumen content; the bitumen content at which this porosity is 50% is chosen as the initial bitumen content. Indirect tensile strength values corresponding to 50% primary porosity are determined as well as the bitumen contents and compared against the recommended minimum values. / <p>QC 20161012</p>
72

Contribuição ao entendimento do efeito de agente coloidisante no processo de pelotização de concentrado de minério de ferro. / Contribution to the understanding of the effect of colloidal agent in the process of pelletizing iron ore concentrate.

Moraes, Sandra Lucia de 07 November 2014 (has links)
O uso de aglomerantes na pelotização a quente de minério de ferro visa cumprir duas funções: (1) aumentar a resistência da pelota antes do aquecimento (resistência a verde) e (2) evitar o colapso das pelotas durante a queima, quando a expulsão dos gases gerados pela vaporização de água e de voláteis tende a destruir a pelota. A bentonita é o aglomerante mais empregado industrialmente, e seu mecanismo de ligação no processo de ganho de resistência da pelota já foi amplamente estudado e compreendido. Várias tentativas de substituição da bentonita na pelotização de minério de ferro recorrem ao uso de aglomerantes orgânicos cuja composição apresente propriedades aglomerantes em conjunto com dispersantes. O presente trabalho visou contribuir para o melhor entendimento do mecanismo inerente ao uso de agente coloidisante na aglomeração do material particulado no processo de pelotização, por meio da avaliação da influência dos agentes coloidisantes em comparação aos aglomerantes Peridur® e bentonita no processo de pelotização de concentrado de minério de ferro. Para este fim, foram realizados ensaios de bancada visando a identificação de possíveis ações dos aglomerantes/dispersantes na viscosidade, potencial zeta e grau de dispersão das misturas, bem como a sua influência na liberação/aglomeração dos finos. Os resultados destes parâmetros foram confrontados com os resultados de caracterização das pelotas confeccionadas com os diferentes aglomerantes/ dispersantes pelos quais foi possível identificar que os dispersantes tem forte atuação sobre o conteúdo de finos do concentrado de minério de ferro. A ação principal se dá pela remoção das partículas ultrafinas que recobrem os grãos mais grosseiros presentes na amostra e as dispersam, no caso dos dispersantes, aumentando a disponibilidade do conteúdo de finos <4 µm, principalmente os finos menores que 1 µm (coloides). No caso do aglomerante orgânico, observa-se também essa ação, no entanto, os finos presentes são aglomerados na faixa entre 26 e 4 µm. / The use of binders for iron ore pelletizing is required to: (1) increase the pellet strength before heating (green strength); (2) prevent the collapse of the pellets during firing, when the gases generated by water vaporization could create cracks. Bentonite is the main binder used in industry, and its binding mechanism in iron ore pellets has been widely studied and understood. Efforts to solve the problems of using bentonite in iron ore pelletizing have focused on the use of organic binders whose composition presents dispersant properties. The objective of this study is to evaluate the influence of colloidal agents compared to binders, Peridur® and bentonite, in the pelletizing process of iron ore concentrate aiming to contribute with the understanding the action of these agents in the mechanisms of agglomeration of the pellets. With this goal, bench tests were carried out to identify possible actions of binders/dispersant in the viscosity, zeta potential and degree of dispersion of the mixtures, as well as its influence on the liberation/agglomeration of the fine particles. The results of these parameters were compared with the results of the characterization of the pellets prepared with different binders/dispersants. By this study, it was identified that the dispersant has a strong influence on the fine particle content on the iron ore concentrate. The main action takes place by the removal of ultrafine particles overlying coarser grains in the sample and the scatter, in the case of dispersants, increasing the availability of fine content <4 micrometers. In the case of the organic binder, this action is also observed; however, the fines are agglomerated in the range between 4 and 26 micrometers.
73

Cerâmicas porosas moldáveis e autoligadas no sistema \'AL IND.2\'\'O IND.3\'-\'MG\'\'AL IND.2\'\'O IND.4\' / Self-binding castables porous ceramics in the \'AL IND.2\'\'O IND.3\'-\'MG\'\'AL IND.2\'\'O IND.4\' system

Arruda, Cezar Carvalho de 09 November 2018 (has links)
A formação de espinélio de aluminato de magnésio (\'MG\'\'AL IND.2\'\'O IND.4\'; espinélio), através da combinação de óxido de alumínio (\'AL IND.2\'\'O IND.3\'; alumina) com geradores de poros à base de óxido de Magnésio (\'MG\'\'O\'; magnésia) ou hidróxido de magnésio (\'MG\'(\'OH)IND.2\'; HM), resulta em estruturas de elevada porosidade (acima de 50%) e com baixa tendência a densificar mesmo em temperaturas elevadas (1500-1650°C). Devido a isso, esse sistema tem grande potencial de aplicação tecnológica para isolamento térmico e filtração em altas temperaturas. Considerando sua utilização em larga escala como isolante térmico verifica-se a necessidade de desenvolvimento de novas rotas de síntese mais eficazes. A reação de hidroxilação do \'MG\'\'O\' pode ser controlada, utilizando como matéria-prima tanto a magnésia sínter como com a magnésia caustica, desta forma, a expansão de peças de cerâmicas porosas feitas a base de \'MG\'\'O\' também podem ser controladas. Deste modo, neste trabalho pretende-se investigar uma nova rota para a obtenção de espinélio utilizando o \'MG\'\'O\' como ligante hidráulico e incorporar poros, in situ, utilizando-se da decomposição do HM em uma matriz de alumina. Os resultados mostraram que a área superficial específica (ASE) da magnésia influencia fortemente nas propriedades mecânicas do material moldado, comprovando que para as ASEs maiores a magnésia é viável como ligante hidráulico, sendo 0,6 MPa para o modulo de ruptura por compressão diametral, o melhor resultado deste trabalho, enquanto o sistema à base de cimento de aluminato de cálcio (CAC) teve 0,5 MPa de módulo de ruptura, e o sistema à base de \'alfa\'-Bond teve 0,3 MPa de módulo, ambos sistemas de ligantes hidráulicos conhecidos na literatura. A grande diferença no módulo de ruptura por compressão diametral mostrou que o tempo de cura e a ASE da magnésia influenciaram-no fortemente.Enquanto, as amostras com alta ASE de magnésia, em torno de ~60 \'M POT.2\'/g, tiveram 0,6 MPa de módulo de ruptura, as amostras com baixa ASE, ~1 \'M POT.2\'/g, não tiveram alteração no módulo de ruptura. Verificou-se também um aumento gradual no módulo de ruptura segundo a ASE, para um valor intermediário de ASE, ~30 \'M POT.2\'/g, o módulo foi de 0,4 MPa, valor ainda comparável a outros sistemas que se utilizam ligantes hidráulicos. Observou-se que a expansão das amostras durante a cura foi influenciada pela sua ASE, quanto maior a ASE, maior a expansão. Os resultados de PTG e do módulo de ruptura combinados com as imagens de MEV e os difratogramas, das amostras calcinadas, mostraram a influência da temperatura e da ASE na formação da cerâmica porosa por essa rota, sendo a temperatura uma variável de controle já conhecida, observada no diagrama de equilíbrio de fases. Entretanto, a influência da ASE do \'MG\'\'O\' para o controle da formação do espinélio é desconhecido da literatura / Magnesium aluminate spinel (\'MG\'\'AL IND.2\'\'O IND.4\'; spinel) formation by the combination of aluminum oxide (\'AL IND.2\'\'O IND.3\'; alumina) with magnesium oxide (\'MG\'\'O\', magnesium) or magnesium hydroxide (\'MG\'(\'OH) IND.2\'; HM), results in structures of high porosity (above 50%) and with low tendency to densify even at elevated temperatures (1500-1650°C). Due to this, this system has great potential of technological application for thermal insulation and filtration in high temperatures. Considering its large scale use as thermal insulation, it is necessary to develop new and more efficient routes of synthesis. The hydroxylation reaction of \'MG\'\'O\' can be controlled using both sinter magnesia and caustic magnesia as a feedstock, so the expansion of porous ceramic pieces made with \'MG\'\'O\'can also be controlled. Thus, in this work we intend to investigate a new route to obtain spinel using \'MG\'\'O\' as a hydraulic binder and to incorporate pores, in situ, using the decomposition of HM in an alumina matrix. The results showed that the specific surface area (ASE) of the magnesia strongly influences the mechanical properties of the molded material, proving that for the larger ASEs the magnesia is viable as a hydraulic binder, being 0.6 MPa for the diametral compression rupture modulus, the best result of this work, while the calcium aluminate cement (CAC) system had 0.5 MPa of modulus of rupture, and the \'alfa\'-Bond based system had 0.3 MPa of modulus, both systems of hydraulic binders known in the literature. The large difference in the diametral compression rupture modulus showed that the curing time and the ASE of the magnesia strongly influenced it. While high ASE magnesia samples, around ~60 \'M POT.2\'/g, had 0.6 MPa of modulus of rupture, samples with low ASE, ~1 \'M POT.2\'/g, had no change in modulus of rupture. There was also a gradual increase in the ASE burst modulus, for an ASE intermediate value ~30 \'M POT.2\'/g, the modulus was 0.4 MPa,a value still comparable to other systems using hydraulic binders. It was observed that the expansion of the samples during curing was influenced by their ASE, the higher the ASE, the greater the expansion. The results of PTG and the rupture modulus combined with SEM images and the diffractograms of the calcined samples showed the influence of temperature and ASE on the formation of the porous ceramic by this route, the temperature being a known control variable, observed in the phase equilibrium diagram. However, the influence of \'Mg\'\'O\' ASE on the control of spinel formation is unknown in the literature
74

Study of Rheological Behaviour of Coating Paste containing conductive polymer complex

IQBAL, KASHIF January 2010 (has links)
Conducting polymer coating is the new developing area in the field of advanced textiles. In this project the rheological behaviour of paste containing conducting polymer was studied during formulation to coating application. The literature study is done by keeping all the contents of project in mind and a wide area of conductive polymer, coating methods, binder system and rheology modifier is covered. The rheological behaviour of different fluid containing newtanion and non-newtanion behaviour is discussed for better understanding of the project working. Polyester fabric was coated by knife coating method. In paste formulation, the chemicals used were polyurethane binder with two HEUR based rheology modifiers. A lot of experiments were performed to determine the right amount of rheology modifier alone or in combination for paste formulation and coating application and interesting findings were observed during the experimental work which had been justified in results and analysis. After application, the coated fabric was checked for resistivity. / Program: Magisterutbildning i textilteknologi
75

Optimering av pigmenttryck / Optimization of pigment print

CENTRÉN, REBECCA, PERSSON, JESSICA January 2010 (has links)
En pigmentpasta består av ett antal olika kemikalier som alla bidrar med en specifik egenskap. Färgpigment, bindemedel och förtjockare är de tre komponenter som måste finnas i tryckpastan. Nackdelar med pigmenttryck är att trycket kan få dålig färg- och gnidhärdighet eftersom pigmentet inte tas upp av fibern utan binder till substratet genom ett bindemedel. Gnid- och tvätthärdighet bestäms nästan helt av vilket bindemedel som används. Vid pigmentryckning är bindemedlen som används oftast vattenbaserade syntetiska emulsionspolymerer.Syftet med detta examensarbete var att undersöka hur man kan optimera pigmenttryck och dess färg- och gnidhärdighet. En del av arbetet bestod av en laborationsdel där målet var att utvärdera hur olika fixeringsparametrar och olika bindemedel i en pigmentpasta kan påverka slutresultatet.I experimentet användes fyra olika bindemedel; Jaypol B2, Jaypol B3, Tubifast AS 40 och Tubifast ABN 10. För varje bindemedel gjordes två olika pastor. En pasta med 200 g/kg bindemedel och en pasta med 300 g/kg bindemedel. På proverna utfördes tester för gnidhärdighet och färghärdighet mot tvätt för att kunna utvärdera de olika bindemedlen. Testerna visade ett klart samband mellan en ökad koncentration av bindemedel i tryckpastan och en bättre färg- och gnidhärdighet. För att få bra egenskaper på ett pigmenttryck är det viktigt att det fixeras ordentligt. Om trycket inte fixeras tillräckligt kan inte bindemedlet binda fast pigmentet till textilen vilket ger dåliga härdigheter. Testerna visade att det inte finns någon optimal fixeringstid eller temperatur som gäller för alla tryck. Varje enskilt tryck kräver speciella förhållanden för att få så optimala egenskaper som möjligt. / <p>A pigment paste consists of a number of different chemicals that all contribute with a specific property. Color pigment, binder and thickener are the three components that must exist in the printing paste. The disadvantage of pigment printing is that the print may have poor color and crock fastness because the pigment is binding to the substrate by a binder and is not being absorbed by the fiber. Wash and crock fastness are determined almost entirely by which binder that are used. The binders that are used in pigment printing are usually water-based synthetic emulsion polymers. The purpose of this study was to examine how to optimize a pigment print and its color and crock fastness. The work included a laboratory test where the focus was to evaluate how different fixation parameters and different binders in a pigment paste can affect the final result. In the experiment four different binders were used; Jaypol B2, Jaypol B3, Tubifast AS 40, Tubifast ABN 10. For each binder two different pastes were made. One paste with 200 g/kg binder and one paste with 300 g/kg binder. Tests were made on the samples for crock fastness and color fastness to washing with the purpose to evaluate the various binders. The tests showed a clear correlation between an increased concentration of binder in the printing paste and a better color and crock fastness. In order to obtain good properties of a pigment print it is vital that the fixation is done properly. If the print is not adequately fixated the binder cannot attach the pigment to the fabric, resulting in poor fastness. The tests showed that there is no optimal fixation time or temperature for all prints. Each individual print requires special settings to obtain as optimal properties as possible</p><p>Program: Textilingenjörsutbildningen</p>
76

Efeito do teor e granulometria de borracha, do tempo e da temperatura de mistura e do tempo de armazenamento sobre propriedades do ligante asfalto-borracha / Effect of particle size and content of rubber, the mixing time and temperature and the storage time on the rubber asphalt binder properties

Ferro, Claudia Cristina 23 January 2004 (has links)
A produção de um ligante modificado com a borracha de pneus usados tem-se tornado viável em virtude do aumento da rigidez a temperaturas elevadas e da flexibilidade a baixas temperaturas que ele proporciona no revestimento dos pavimentos flexíveis, contribuindo para amenizar dois dos principais defeitos que afetam este tipo de pavimento, a saber, a deformação permanente nas trilhas de roda e as trincas por fadiga. Em acréscimo, consegue-se diminuir a quantidade de pneus dispostos em aterros sanitários, disponibilizando espaço e evitando problemas ambientais e de saúde pública, pois o acúmulo de pneus facilita a procriação de insetos e de outros vetores de doenças. Utilizando-se ensaios tradicionais e ensaios do método Superpave, neste trabalho são analisados os efeitos dos principais fatores que condicionam o comportamento do ligante asfalto-borracha (teor granulometria das partículas de borracha, tempo e temperatura de mistura, mantida constante em 155ºC) e as alterações nas propriedades físicas do ligante asfalto-borracha durante o tempo de armazenamento. / The production of a modified binder with used tire has become possible because of the increase in the stiffness at high temperature and the flexibility at low temperature that it brings to the surface layers of flexible pavements. The asphalt-rubber binders help to prevent two of the most important problems that affect flexible pavements, that is, the permanent deformation in the wheel tracks and fatigue cracking. In addition, it is possible to reduce the amount of tires disposed in sanitary landfills, increasing the service-life and avoiding environmental and health problems. Using traditional tests and tests of the Superpave method, this study analyses the effects of the main factors that affects the behavior of the asphalt-rubber binder (content and gradation of rubber particles, reaction temperature fixed in 155ºC and time) and the changes in the physical properties of asphalt-rubber binder during the storage time.
77

Efeito do teor e granulometria de borracha, do tempo e da temperatura de mistura e do tempo de armazenamento sobre propriedades do ligante asfalto-borracha / Effect of particle size and content of rubber, the mixing time and temperature and the storage time on the rubber asphalt binder properties

Claudia Cristina Ferro 23 January 2004 (has links)
A produção de um ligante modificado com a borracha de pneus usados tem-se tornado viável em virtude do aumento da rigidez a temperaturas elevadas e da flexibilidade a baixas temperaturas que ele proporciona no revestimento dos pavimentos flexíveis, contribuindo para amenizar dois dos principais defeitos que afetam este tipo de pavimento, a saber, a deformação permanente nas trilhas de roda e as trincas por fadiga. Em acréscimo, consegue-se diminuir a quantidade de pneus dispostos em aterros sanitários, disponibilizando espaço e evitando problemas ambientais e de saúde pública, pois o acúmulo de pneus facilita a procriação de insetos e de outros vetores de doenças. Utilizando-se ensaios tradicionais e ensaios do método Superpave, neste trabalho são analisados os efeitos dos principais fatores que condicionam o comportamento do ligante asfalto-borracha (teor granulometria das partículas de borracha, tempo e temperatura de mistura, mantida constante em 155ºC) e as alterações nas propriedades físicas do ligante asfalto-borracha durante o tempo de armazenamento. / The production of a modified binder with used tire has become possible because of the increase in the stiffness at high temperature and the flexibility at low temperature that it brings to the surface layers of flexible pavements. The asphalt-rubber binders help to prevent two of the most important problems that affect flexible pavements, that is, the permanent deformation in the wheel tracks and fatigue cracking. In addition, it is possible to reduce the amount of tires disposed in sanitary landfills, increasing the service-life and avoiding environmental and health problems. Using traditional tests and tests of the Superpave method, this study analyses the effects of the main factors that affects the behavior of the asphalt-rubber binder (content and gradation of rubber particles, reaction temperature fixed in 155ºC and time) and the changes in the physical properties of asphalt-rubber binder during the storage time.
78

Measurement of gas evolution from PUNB bonded sand as a function of temperature

Samuels, Gregory James 01 July 2011 (has links)
The chemical binders used to make sand molds and cores thermally decompose and release gas when subjected to the high temperature conditions in sand casting processes. Computational models that predict the evolution of the binder gas are being introduced into casting simulations in order to better predict and eliminate gas defects in metal castings. These models require knowledge of the evolved binder gas mass and molecular weight as a function of temperature, but available gas evolution data are limited. In the present study, the mass and molecular weight of gas evolved from PUNB bonded sand are measured as a function of temperature for use with binder gas models. Thermogravimetric analysis of bonded sand is employed to measure the binder gas mass evolution as a function of temperature for heating rates experienced in molds and cores during casting. The volume and pressure of gas evolved from bonded sand are measured as a function of temperature in a specially designed quartz manometer during heating and cooling in a furnace. The results from these experiments are combined with the ideal gas law to determine the binder gas molecular weight as a function of temperature. Thermogravimetric analysis reveals that the PUNB binder significantly decomposes when heated to elevated temperatures, and the PUNB binder gas mass evolution is not strongly influenced by heating rate. During heating of PUNB bonded sand at a rate of 2°C/min, the binder gas molecular weight rapidly decreases from 375 g/mol at 115°C to 99.8 g/mol at 200°C. The molecular weight is relatively constant until 270°C, after which it decreases to 47.7 g/mol at 550°C. The molecular weight then steeply decreases to 30.3 g/mol at 585°C and then steeply increases to 47.2 g/mol at 630°C, where it remains constant until 750°C. Above 750°C, the binder gas molecular weight gradually decreases to 33.3 g/mol at 898°C. The present measurements are consistent with the molecular weights calculated using the binder gas composition data from previous studies. The binder gas is composed of incondensable gases above 709°C, and the binder gas partially condenses during cooling at 165°C if the bonded sand is previously heated below 507°C.
79

Nouveaux monomères biosourcés à haute rigidité à destination des revêtements polyesters / Development and exploitation of new high rigidity biobased monomers

Gouteyron, Antoine 19 November 2015 (has links)
Les résines polyesters sont des composants présents dans une majorité des revêtements et matériaux utilisés aujourd'hui. Ils sont obtenus par polycondensation de polyols, polyacides et monoacides. Les réglementations évoluant (REACH) et le public étant de plus en plus sensible à l'origine et l'impact des produits qu'il consomme, la substitution des produits pétrosourcés vers des matières premières renouvelables semble évidente. De nouveaux polyesters, composés majoritairement de monomères biosourcés, ont donc été synthétisés. L'acide L-(+)-tartrique a été principalement étudié, ce monomère quadri-fonctionnel étant peu utilisé dans la chimie des matériaux bien que disponible en grandes quantités et peu coûteux. Afin de caractériser les polyesters, différents tests utilisés dans l'industrie ont été mis en place, les caractéristiques physico-chimiques pouvant varier d'une application à l'autre. Différents mécanismes de réticulation ont également été explorés afin d'adapter les polyesters aux contraintes de résistance et de séchage requises. Ces mécanismes incluent la réaction entre les hydrazides et les méthyles cétones ainsi que celle des dérivés du Bore et des hydroxyles à température ambiante. La solubilité des polyesters synthétisés a également été étudiée afin d'obtenir un produit soluble en phase aqueuse capable de devenir insoluble après réticulation et séchage / Polyester binders are the main components of the coatings and materials used nowadays. They are obtained by the condensation of polyols, polyacids and monoacids. Evolving regulations (REACH) and the public being increasingly sensitive to the origin and impact of the products it consumes, petro based compounds substitution to renewable raw materials seems obvious. New polyesters, mainly composed of biobased monomers were therefore synthesized. The L-(+)-tartaric acid was mainly studied, this quad-functional monomer being barely used in materials chemistry, although available in large quantities and inexpensive. To characterize polyesters, various tests used in the industry have been established, the physicochemical characteristics may vary from one application to another. Different crosslinking mechanisms have also been explored to adapt polyesters constraints of resistance and drying. These mechanisms include the reaction between the hydrazide and methyl ketones, as well as the derivatives of Boron and hydroxyl at room temperature. The solubility of the synthesized polyesters was also studied in order to obtain a water soluble material capable of becoming insoluble after crosslinking and drying
80

Mise en forme de zéolithes : contrôle des propriétés acides des zéolithes et description de l’interface zéolithe / liant / Zeolite shaping : control of the zeolite acid properties and description of the zeolite - binder interface

Demaret, Coralie 28 March 2019 (has links)
Les zéolithes sont des aluminosilicates cristallins possédant une microporosité organisée et régulière de taille moléculaire. Les zéolithes ZSM-5 sont largement employées dans l’industrie comme catalyseurs acides mais leur application commerciale requiert des objets de taille millimétrique pour leur résistance mécanique, pour diminuer la perte de charge dans les réacteurs et pour diluer l’acidité de la zéolithe, principalement par ajout de liant, peptisant... La mise en forme est l’étape clé dans le processus d’industrialisation d’un catalyseur car les additifs peuvent modifier les propriétés intrinsèques de la zéolithe après mise en forme. Les objectifs de la thèse sont donc d’identifier et de rationaliser les conséquences physico-chimiques de la mise en forme sur les propriétés des zéolithes en étudiant l’accessibilité, la concentration et la force de leurs sites acides, ainsi que de décrire la nature de l’interface zéolithe/liant. Pour cela, une approche multi-techniques a été mise en œuvre. Elle combine des mises en forme modèles, tout en faisant varier la nature du liant et de la zéolithe ZSM-5, des caractérisations texturales, spectroscopiques (infra-rouge, RMN) et de microscopies, de l’acidité (adsorption-désorption de molécules sondes suivies par analyses thermiques et spectroscopiques), et tests catalytiques modèles. La caractérisation des propriétés des zéolithes utilisées dans cette étude (de différentes tailles de cristaux et de différents rapports Si/Al) a été menée préalablement à celles des matériaux mis en forme. Les grands cristaux de zéolithes se sont révélés plus acides mais moins actifs en catalyse. Une partie des Al des petits cristaux forment des aluminols dont l’acidité est plus faible que celle des sites pontés. De plus, l’ensemble des sites pontés ne contribue pas à la réaction catalytique, seule une partie du cristal est efficace. Durant ce travail, deux types de liants ont été utilisés : l’alumine et la silice qui sont largement employées dans l’industrie. Le but a été de mettre en évidence, dans un premier temps, les effets de la mise en forme sur une zéolithe et un liant donné puis d’estimer l’impact de la nature de la zéolithe (taille de cristal et rapport Si/Al). Pour le liant de type alumine, un bouchage partiel de la microporosité est suspecté indépendamment de la taille des cristaux et du rapport Si/Al de la zéolithe. Un phénomène d’alumination de la structure de la zéolithe par création de sites pontés a été mis en évidence. Pour le liant de type silice, le paramètre critique à prendre en considération lors de la mise en forme est sa teneur en cations sodium. Le phénomène d’échange ionique a été mis en évidence, les propriétés acides et catalytiques des catalyseurs s’effondrent mais de manière réversible. Cet effet augmente quand la taille des cristaux de zéolithes diminue et quand le rapport Si/Al augmente / Zeolites are crystalline and microporous aluminosilicates with an ordered and regular structure of molecular dimension. ZSM-5 zeolites are widely used in the industry as acid catalysts but their commercial application requires millimeter-sized bodies for mechanical strength and dilution of the zeolite acidity mainly, by addition of binder, peptizer... Shaping of zeolite is the key step of the process for the industrialization of a catalyst because the additives may modify the intrinsic properties of zeolites after shaping. The aims of this PhD thesis are to identify and rationalize the physico-chemical impacts of shaping on the zeolite properties by studying the accessibility, the concentration and the strength of acid sites, as well as to describe the zeolite/binder interface. To do this, a multi-technical approach was set up. It combines model shaped materials, by varying the type of binder and ZSM-5 zeolite, textural, spectroscopic (IR, NMR) and acid characterizations, microscopy and catalytic testing. The characterization of zeolites used in this study (various crystal sizes and Si/Al ratios) was carried out prior of those of shaped materials. Large crystals have been shown more acid but less active in catalysis. Some of Al of the small crystals form aluminols whose acidity is weaker than that of bridging sites. Moreover, all the bridging sites do not contribute to the catalytic reaction, only a part of the crystal is efficient. During this work, two types of binders were used: alumina and silica which are widely used in the industry. The strategy was to highlight, in a first step, the shaping impacts on a ZSM-5 and a given binder and then, to estimate the impact of the zeolite nature (crystal size and Si/Al ratio). For the alumina-type binder, a partial pore blocking is suspected, independently of the crystal size and the Si/Al ratios. A phenomenon of alumination of the zeolite structure was found. For the silica-type binder, the critical parameter is the content of sodium cations inside the binder before the shaping. An ion exchange phenomenon was highlighted and the acid and catalytic properties of the materials collapse but in a reversible way. This impact increases when the crystal size decreases and when the Si/Al ratio increases

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