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

Performance of asphalt mixtures depends on the properties of its constituent materials, mixture volumetrics, and external factors such as load and environment. An important material property that influences the performance of an asphalt mixture is the surface free energy of the asphalt binder and the aggregate. Surface free energy, which is a thermodynamic material property, is directly related to the adhesive bond energy between the asphalt binder and the aggregate as well as the cohesive bond energy of the asphalt binder. This thermodynamic material property has been successfully used to select asphalt binders and aggregates that have the necessary compatibility to form strong bonds and resist fracture. Surface free energy, being based on thermodynamics, assumes the asphalt binder is a brittle elastic material. In reality, the asphalt binder is not brittle and dissipates energy during loading and unloading. The total work of fracture is the culmination of all energy inputted into the sample to create two new surfaces of unit area and is dependent on the test geometry and testing conditions (e.g., temperature, loading rate, specimen size, etc.). The magnitude of the bond energy (either adhesive or cohesive) can be much smaller in magnitude when compared to the total work of fracture measured using mechanical tests (i.e., peel test, pull-off test, etc.). Despite the large difference in magnitude, there exists evidence in the literature supporting the use of the bond energy to characterize the resistance of composite systems to cohesive and/or adhesive failures. If the bond energy is to be recognized as a useful screening tool by the paving industry, the relationship between the bond energy and total work of fracture needs to be understood and verified. The effect of different types of modifications (addition of polymers, addition of anti-strip agents, and aging) on the surface free energy components of various asphalt binders was explored in order to understand how changes in the surface free energy components are related to the performance of the asphalt mixtures. After the asphalt binder-aggregate combination was explored, the next step was to study how the surface free energy of water was affected by contact with the asphalt binder-aggregate interface. Aggregates, which have a pH of greater than seven, will cause the pH of water that contacts them to increase. A change in the pH of the contacting water could indicate a change in its overall surface free energy, which might subsequently increase or decrease the water's moisture damage potential. With surface free energy fully explored, the total work of fracture was measured using pull-off tests for asphalt binder-aggregate combinations with known surface free energy components. In order to fully explore the relationship between bond energy and total work of fracture, temperature, loading rate, specimen geometry, and moisture content were varied in the experiments. The results of this work found that modifications made to the asphalt binder can have significant positive or negative effects on its surface free energy components and bond energy. Moreover, the results from the pull-off tests demonstrated that a relationship exists between bond energy (from surface free energy) and total work of fracture (from pull-off tests), and that surface free energy can be used to estimate the performance of asphalt binder-aggregate combinations.

Asphalt binder oxidation in pavements has been proven to be an ongoing process throughout a pavement's service life. Understanding the nature of the oxidation process is a critical step toward better pavement design to achieve greater pavement durability. The main component in asphalt binder oxidation in pavements is binder oxidative hardening. As the aromatic compounds in asphalt binders are oxidized, more polar carbonyl compounds are created, which results in stronger associations between asphalt components and eventually leads to an increase in asphalt elastic modulus and viscosity. Consequently, the performance of pavements is affected directly by asphalt binder hardening. Also, low levels of accessible air voids in pavements potentially relate to binder oxidation according to a recent research study. When the pavements have sufficiently high accessible air voids (4 percent or greater), the oxidation rate is largely determined by the temperature in the pavement. On the other hand, when the percentage of accessible air voids in the pavement is considerably lower (2 percent or less), the hardening rate of binders in pavements is reduced significantly. Field evidence is mounting that asphalt binder oxidization in pavements produces a binder that is more susceptible to thermal and fatigue cracking. While the fundamentals of this oxidation process are fairly well known, predicting quantitatively the rate of oxidation as a function of depth in the pavement, is not straightforward. A thermal and oxygen transport model, coupled with binder reaction kinetics, provides the basis for such calculations. A one-dimensional thermal transport model, coupled with site-specific model parameters and recent improvements in the availability of required input climate data, enables calculation of pavement temperatures throughout the year, which then is used in an asphalt binder oxidation and transport model to calculate binder properties in the pavement over time. Calculated binder property changes with depth and time are compared to measurements of binder oxidation in the field. The work in this study is aimed at understanding the oxidation kinetics of asphalt binders in pavements, determining the impact of accessible air void levels on asphalt hardening, and ultimately developing an improved model of asphalt binder oxidation in pavements.

Polymers are added to asphalt binders primarily to stiffen the binder at higher temperatures and thus to protect the pavement against rutting at summertime temperatures early in the pavement's life. Also, it has been noted that polymers typically increase the ductility of a binder and that some polymer-asphalt combinations are especially effective. Furthermore, it is hypothesized that enhancing a binder's ductility, and maintaining this enhancement with binder oxidative aging, contributes to enhanced binder durability in pavements. However, polymer-asphalt interactions and how they might contribute to improved binder performance is not well understood. The goal of this work was to probe the relationship of polymer morphology on asphalt binder rheology and mixture durability. Experiments were conducted on asphalt mixtures and binders, and as a function of oxidative aging. PFC mixtures, which are an open mixture designed to allow enhanced water drainage, were of specific interest. These mixtures were tested for Cantabro Loss, an indicator of a mixture's likelihood of failure by raveling. Asphalt binders were tested using dynamic shear rheometry (DSR), which provided the DSR function, (G' /η'/G'), a measure of binder stiffness that includes both the elastic modulus and the flow viscosity), ductility (used to measure the elongation a binder could withstand before failure), gel permeation chromatography (GPC), used to estimate the relative amount of polymer) and fluorescence microscopy (used to image the polymer morphology in the asphalt binder). From these data, relationships were assessed between binder morphology and binder rheology and between binder rheology and mixture durability, all as a function of binder oxidative aging. Polymer morphology related to ductility enhancement. Polymer morphology related to a change in the DSR function, relative to the amount of polymer, as measured by the polymer GPC peak height. Cantabro loss correlated to the DSR function (R2=0.963). The overall conclusion is that polymer morphology, as indicated by fluorescence microscopy, relates to both the rheological properties of the binder and the Cantabro loss of the mixture. These relationships should yield a better understanding of polymer modification, increased mixture durability (decreased raveling) and improved rheological properties (DSR function and ductility).

Applications involving high electrical conduction require complex components that are difficult to be manufactured by conventional processes. Laser sintering (LS) is an additive manufacturing technique that overcomes these drawbacks by offering design flexibility. This study focuses upon optimizing the process of laser sintering to manufacture functional prototypes of components used in high electrical conduction applications. Specifically, components for two systems – high current sliding electrical contacts and fuel cells – were designed, manufactured and tested. C-asperity rails were made by LS and tested in a high current sliding electrical setup. Corrugated flow field plates were created by LS and their performance in a direct methanol fuel cell (DMFC) was tested. This is the first experimental attempt at using laser sintering for manufacturing such complex components for use in high electrical conduction applications. The second part of this study involves optimization the laser sintering process. Towards this, efforts were made to improve the green strength of parts made by LS. Particle size of graphite/ phenolic resin and addition of nylon/11 and wax were tested for their effect upon green strength. Of these, significant improvement of green strength was observed by altering the particle size of the graphite/ phenolic resin system. New methods of improving green strength by employing fast cure phenolic resins with carbon fiber additions were successfully demonstrated. This study also identified a binder system and process parameters for indirect LS of stainless steel –for bipolar plate compression/ injection mold tooling. All the experimental results of this study lead us to believe that laser sintering can be developed as a robust and efficient process for the manufacture of specialized components used in advanced electrical conduction systems. / text

Asphalt mixtures or asphalt concrete are used to pave about 93% of about 2.6 million miles paved roads and highways in the US. Asphalt concrete is a composite of aggregates and asphalt binder; asphalt binder works as a glue to bind the aggregate particles. The mechanical response of the asphalt binder is dependent on the time/rate of loading, temperature and age. An asphalt concrete mixture inherits most of these characteristics from the asphalt binder. Also the asphalt binder plays a critical role in providing the asphalt concrete the ability to resist tensile stresses and relaxing thermally induced stresses that can lead to fatigue and low temperature cracking, respectively. Hence, it is very important (but not sufficient) to ensure that asphalt binders used in the production of asphalt concrete are inherently resistant to cracking, rutting and other distresses that a pavement may undergo. Current binder specification (AASHTO M-320) to evaluate its fatigue cracking is based on the stiffness of the binder and not on its tensile strength. Also, measurements following current specifications are made on test specimens subjected to a uniaxial mode of loading that does not produce the same stress state in the binder as in the case of asphalt concrete. Another challenge in being able to produce binders with inherently superior performing characteristics is the fact that the asphalt binders produced in a refinery do not have a consistent chemical composition. The chemical composition of asphalt binder depends on the source and refining process of crude oil. There is a need to better quantify the tensile strength of asphalt binder and understand the relationship between the chemical composition of asphalt binders and its mechanical properties. The knowledge from this study can be used to engineer asphalt binders that have superior performance characteristics. The objective of this research was to quantify the tensile strength of asphalt binder, develop a metric for the tensile strength and identify the relationship between chemical composition and mechanical properties of asphalt binder. Laboratory tests were performed on binders of different grades using a poker chip geometry to simulate confined state by varying the film thickness, rate of loading and modes of loading. The chemical properties of asphalt binder were studied based on SARA fractionation. The findings from this research showed that the modified correspondence principles can unify and explain the rate and mode dependency of asphalt binder. This study also quantified the relationship between chemical composition, and rheological and mechanical properties of asphalt binder. Finally, a composite model was developed based on the individual properties of chemical fractions which could predict the dynamic modulus of the asphaltenes doped and resins doped binder. / text

The quality of asphalt depends on quality and type of components. The e main characteristic of asphalt is the composition – binder content and aggregate graduation. There are developed many methods for the evaluation of asphalt content. This work analyzes the methods of asphalt content determination. Also there are compared to methods: solvent extraction and ignition method. For the evaluation of these methods the researches of 50 samples have been made. The samples were taken from the asphalt pavement and others were made in laboratory. When results of research were analyzed by principles of statistics. The conclusions and recommendations are presented at the end of the research paper.

Baigiamajame darbe analizuojamas sapropelio kaip rišiklio panaudojimas termoizoliacinių sapropelio-šiaudų plokščių gamyboje. Šiems tyrimams buvo pasirinktas užpelkėjusio Dobilios ežero, esančio Kauno rajone, organinis sapropelis. Bandiniai buvo gaminami su skirtingu sapropelio-šiaudų kiekiu juose ir formuojami specialioje tyrimams pagamintoje formoje. Suformuotų bandinių masė buvo apie 130g. Suformuotų bandinių sapropelio kiekis kito nuo 15% iki 35%. Presavimo slėgis buvo 0,25; 0,5; 0,75; 1,0 MPa. Buvo nustatomas tiriamų bandinių, tankis atsparumas lenkimui ir gniuždymui, taip pat apskaičiuojamas šiluminis laidumas. Raktiniai žodžiai: sapropelis, šiaudai, plokštelės, lenkimas, gniuždymas, stipris. / This Master Thesis analyses the appliance of sapropel as a binder in a heat insulation plate production. For the research was chosen a silt of a waterlogged lake Dobilė, located in Kaunas region. All samples were formed with specially made form for research. Every sample had different quantity of sapropel and strawdust. Forming weight of samples were approx 130g. A chosen quantity of sapropel variated from 15 to 35 percents in a sample. The mix of sapropel and strawdust in a form was pressed by 0,25; 0,5; 0,75; 1,0 MPa pressure. During the research samples were analysed their resistance to compression and flexure, estimated sample density and thermal conductivity. Keywords: binder, sapropel, plate, compression, flexure, straw.

The KENTRACK program is a finite element based railway trackbed structural design program that can be utilized to analyze trackbeds having various combinations of all-granular and asphalt-bound layered support. It is applicable for calculating compressive stresses at the top of subgrade, indicative of potential long-term trackbed settlement failure. Furthermore, for trackbeds containing asphalt layer, it is applicable for calculating tensile strains at the bottom of the asphalt layer, indicative of potential fatigue cracking. The program was recently expanded to include both English and international units. A procedure has been incorporated to provide a path to save results in a text formation in post-Windows XP operating systems. More importantly, properties of performance graded (PG) asphalt binders and the Witczak E* predictive model have been incorporated in the 4.0 Version of the program. Component layers of typical trackbed support systems are analyzed while predicting the significance of layer thicknesses and material properties on design and performance. The effect of various material parameters and loading magnitudes on trackbed design and evaluation, as determined and predicted by the computer program, are presented. Variances in subgrade modulus and axle loads and the incorporation of a layer of asphalt within the track structure have significant effects on subgrade vertical compressive stresses and predicted trackbed service lives. The parameter assessments are presented and evaluated using sensitivity analysis. Recommendations for future research are suggested.

In this study, the possibilities to produce metallic glass as binder phase in hard metal by means of powder metallurgical methods have been investigated. The aim of the study was to do an initial investigation about metallic glass as alternative binder phase to cobalt in hard metal. Production of samples with metallic glass forming alloys and an amorphous powder as binder phase in hard metal by means of quenching and hot pressing have been performed. Moreover, mechanical alloying of metallic glass forming powder to achieve amorphicity has been performed. The samples and powders were analyzed by means of XRD, LOM, STA, SEM and EDS. The results showed that no glass formation of the binder phase was achieved by quenching, hot pressing or mechanical alloying. However, interesting information about glass formation by means of metallurgical methods was obtained. The main conclusion was that production of metallic glass by means of metallurgical methods is complicated due to changes in the binder phase composition throughout the production process as well as requirements of high cooling rates when quenching and high pressures when hot pressing.