Thesis (M.S. in chemical engineering)--Washington State University, May 2007. / Includes bibliographical references.

No description available.

Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1994. / Abstract. Includes bibliographical references. Also available via the Internet.

Carbon electrodes have found widespread use in electrochemistry due to its broad versatility and low cost amongst other advantages. Recent innovations in carbon materials have added new dimensions to their utility in electrochemical applications. This thesis aims to investigate aspects of carbon materials, in particular boron-doped diamond (BDD) and nanocarbon composites, mainly for electrochemical analysis and energetics studies. The electrochemical behaviour of estradiol and other endocrine disrupting compounds was examined on the BDD electrode with different surface pretreatments, as well as on a nanocarbon-modified BDD electrode. It was shown that the precise control of surface chemical termination enabled the electrode to be tuned to exhibit diffusional or adsorptive voltammetry at oxidised and hydrogenated BDD interfaces respectively. Adsorption effects were also observed on the modified electrode leading to significant pre-concentration of the analyte onto the nanocarbon and a corresponding lowering of the limit of detection by ca three orders of magnitude to nanomolar levels. Surface modification of the BDD electrodes was then explored using a simple and convenient dropcast technique to deposit microcrystalline copper phthalocyanine onto the electrode. The influence of the surface chemical termination towards the interaction with the modifier compound was demonstrated in relation to the oxygen reduction reaction. Hydrogen terminated BDD modified in such a manner was able to significantly decrease the overpotential for the cathodic reaction by ca 500 mV when compared to the unmodified electrode while modified oxidised BDD showed no such electrocatalysis, signifying greater interaction of the phthalocyanine modifier with the hydrogenated surface. The lack of a further conversion of the peroxide product was attributed to its rapid diffusion away from the triple phase boundary (comprising the phthalocyanine microcrystallite, aqueous solution and BDD electrode) at which the reaction is expected to exclusively occur. Next carbon composites were studied in the form of carbon paste electrodes (CPEs). The practicality of a nanocarbon paste was established by cyclic voltammetry with several well-characterised redox systems commonly used to test electrode activity and was found to exhibit comparable behaviour to the more typical graphitic formulation. Reversible uptake of some analytes was observed at the CPEs, giving rise to complex double peak voltammetry. This uptake phenomenon was then further examined at the nanocarbon paste electrode to monitor the transfer of species between two dissimilar liquid phases. The interfacial behaviour gave rise to voltammetric peaks which were assigned to species originating from the aqueous, binder and carbon phases respectively and this enabled the measurement of Gibbs energies of transfer between oil and aqueous phases. Finally the effect of different ionic liquids as binder for carbon-ionic liquid composite electrodes was studied. Some ionic liquids were demonstrated to offer benefits in comparison to oil in the fabrication of carbon paste type electrode due to an increased adsorption of analytes. The ionic “liquid” (with a melting point above room temperature) <i>n</i>-octyl-pyridinium hexafluorophosphate [C₈py][PF₆] was shown to be useful in combination with carbon nanotubes as a composite electrode or as a modifier to a screen-printed electrode to significantly enhance the sensitivity of electrochemical detection via adsorptive stripping voltammetry. Overall the carbon-based electrodes studied have demonstrated excellent utility as electrode materials in the areas of electrochemical sensing and energetics investigations.

Dans cette thèse, on s’intéresse à quelques aspects spécifiques des matériaux composites aléatoires : la taille minimale du volume élémentaire représentatif et la détermination des propriétés effectives de transport. L’objectif principal est de proposer une méthode numérique efficace permettant une détermination rapide des propriétés effectives. Les propriétés de type transport sont considérées. Il est montré que cette classe de propriétés peuvent être déterminées soit en réalisant des calculs sur un échantillon de grande taille soit en faisant moyenne sur un nombre suffisant de petites réalisations de microstructures. Cependant, pour un type de microstructure donné, la taille des ces petites réalisations ne peut pas être inférieure à une certaine limite minimale. Celle-ci est fortement influencées par plusieurs facteurs tel que type de microstructure, fractions volumiques des constituants, contrastes de propriétés entre phases, nombre de réalisation et précision acquise. Par ailleurs, deux types de représentativités sont étudiées : représentativité géométrique et celle en rapport avec les propriétés de transport. Par conséquent, deux critères distincts de taille minimale sont proposés en se basant sur des propriétés des fonctions de corrélation à deux-points. Comparant à d’autres méthodes proposées dans de large littératures, le critère proposé ici comporte un avantage car il tient compte de la morphologie de microstructure. En conséquence, des calculs numériques comme ceux par les éléments finis ne sont pas nécessaires pour la détermination de la taille minimale de REV. La validation de la méthodologie proposée est effectuée sur plusieurs exemples de microstructures 2D. / The thesis focuses on random composites and some specific features such as: the minimum size of a representative volume element (RVE) and the determination of effective transport properties. The main objective is to formulate a computationally efficient method which would allow for quick determination of effective properties. The effective properties of transport are considered. It is shown that this class of properties can be estimated either by performing calculations over one large sample or by averaging over a sufficient number of smaller microstructure realizations. However, for a given type of microstructure; the size of such smaller realizations can not be smaller than some critical minimum size. It is shown that this critical size of RVE is strongly affected by several parameters. These are: microstructure type, volume fractions of constituents, contrast in mechanical properties of composite phases, number of performed realizations as well as a desired accuracy. Furthermore, two separate types of representativity are introduced: geometrical representativity and representativity with respect to overall transport properties. Therefore, two distinct criteria for the minimum size of RVE are formulated based on the properties of the two-point correlation function. Comparing to other methods proposed in wide literature, the criterion formulated in the thesis gives an advantage: the condition proposed includes microstructure morphology. Therefore, in order to determine the minimum size of RVE none numerical calculations like those of FE are necessary. A validation of proposed methodology is performed on several examples of 2D microstructures.

Ce travail de thèse porte sur l’analyse de l'impact de la corrosion sur la durabilité des structures renforcées par ancrage. L'étude est basée sur des analyses théoriques ainsi que la modélisation expérimentale et numérique.Le travail débouche sur le développement d'une nouvelle méthode pour évaluer la durabilité des structures renforcées par ancrage. L'originalité de ce travail réside dans l'utilisation d’un modèle visco-plastique, ainsi que la méthode de l'élément composite pour l'analyse des contraintes et des déformations induites par la corrosion dans le béton renforcé par ancrage.Les principaux résultats de ce travail sont:• Le mécanisme de corrosion du béton renforcé par ancrage est revisité et discuté.• Des formules théoriques sont établies pour les contraintes induites par la corrosion, elles sont ensuite appliquées à l'analyse des expériences réalisées en laboratoire.• Un modèle 3D est développé pour étudier le champ de contraintes induites par les actions conjointes de la force d'arrachement et la force d'expansion par la rouille.L'analyse de la répartition des contraintes dues à l’expansion montre que la contrainte axiale du boulon décroit selon une fonction exponentielle. Dans le plan perpendiculaire au boulon, la contrainte radiale au sein de la couche de mortier passe de la traction à la compression ; la contrainte de cisaillement entre le boulon et le mortier suit une variation linéaire. / The thesis includes analysis of the impact of corrosion on the durability of blot-reinforced structures. The study is based on theoretical analyses as well as experimental and numerical modeling. The work results in establishing a new method to evaluate the durability of corroded anchorage system. The originality of this work lies on the use of the visco-plastic theory as well as the composite element method for the analysis of stresses and strains induced in the blot-reinforced concrete by the corrosion.The principle achievements of this work are:• The corrosion mechanism of blot-reinforced concrete is revisited and discussed.• Theoretical formulas of corroded expansion force are established and applied to the analysis of laboratory experiments.• A spatially analytical model of bolt rust is established to study the 3D stress field of the bolt under the joint action of pullout force and rust expansion force.Analysis of the stress distribution due to expansion shows that the axial stress of the bolt is distributed in the form of exponential decay function; in the plane perpendicular to the bolt, radial stress within the mortar protective layer is in transition from tensile stress to compressive stress, shear stress between the bolt and mortar follows linear variation.

Engineering applications of the recently developed zinc-aluminium casting alloys have been restricted due to certain inherent disadvantages such as segregation. However, segregation can be overcome by thorough mh:!ng of the melt and close temperature control or by rapid solidification of the melt, which can be achieved by squeeze casting. A more serious problem exists in service if components are subjected to a modest temperature increase to about 80°C, when there is a drastic loss of strength. It was therefore thought that the incorporation of ceramic fibres in the matrix could improve the properties of the material at modestly elevated temperatures. In the majority of engineering applications, stresses exist in more than one direction, so castings with isotropic properties are preferred and consequently reinforcement of composite in three dimensions would be necessary to maintain isotropic properties. An investigation was conducted to establish the influence of squeeze casting on the mechanical properties and structure of ZA-8, ZA-12 and ZA-27 alloys. The relationship between these factors and controlled process variables such as die temperature and applied squeeze pressure was established. The mechanical properties of the castings at room temperature and the effect of ageing at 95°C on tensile strength and dimensional changes were established. The results showed a substantial improvement in the tensile strength of the 'as-cast' squeeze cast alloys when compared with the 'as-cast' gravity die cast alloys. In the case of ZA-27 alloy, squeeze casting significantly improved ductility, which is a feature of benefit for all composite systems. The results also showed that pressure and die temperature substantially affect dimensional changes of the alloys when aged at 95°C. A major aspect of the research was the evaluation of the mechanical properties of the fibre reinforced ZA-27 alloy at elevated temperatures. Short silicon carbide fibres were randomly oriented in the matrix to obtain isotropic properties by a technique involving squeeze infiltration, followed by remelting and dispersal in the melt using specially designed equipments. Squeeze casting was used in the final stage of the composite fabrication. Castings of squeeze cast composite (with up to 10% volume fibre) and squeeze infiltrated composite (with up to 18-20% volume fibre) were produced with a sound structure and with fibres that were uniformly distributed and randomly oriented in three dimensions. It was found that the reaction between the fibres and molten alloy must be closely controlled for optimum properties of the composite. In this respect, the optimum time of contact between the fibre and the molten alloy was experimentally determined. It was found that the fibre supplied was of inferior tensile strength, which resulted in poor tensile strength of the tested composite up to a temperature of 100°C. However, the fibre brought substantial Improvement ln the tensile strength of the composite when tested at temperatures of 150 to 250°C. The modulus of elasticity of the composite was substantially improved at room temperature as well as at elevated temperature. The fatigue life of the squeeze cast composite was improved compared with squeeze cast matrix alloy (fibre-free). Squeeze cast composites with 3% volume fibre showed an Improvement in tribological properties compared with squeeze cast matrix alloy and squeeze cast and squeeze infiltrated composites with higher volume percentage of fibre. Wear of cutting tools was adversely affected by the presence of fibre.

La porosité d'une plaque composite carbone / époxy de type RTM est connue par tomographie X. Une méthode de détermination de cette porosité par mesure de l'atténuation des ondes longitudinales à travers l'épaisseur de cette plaque est proposée. Ces mesures sont effectuées sur des surfaces de dimensions variables (quelques cm2 à quelques mm2) et permettent l’obtention de cartographies. Une correspondance porosité (tomo X) – atténuation (onde US) est déduite et analysée en fonction de la structure du matériau composite. Dans chaque cas, on estime la qualité des relations obtenues et on en déduit les limites de validité de la correspondance porosité-atténuation. Des premiers résultats de tomographie acoustiques sont obtenus. / The porosity of a composite plate in carbon / epoxy of type RTM is known by used of tomography X. A method of determination of this porosity by measure of the mitigation of the longitudinal waves through the thickness of this kind of plate is proposed. These measures are made on surfaces of different sizes (from some cm2 to some mm2) and allow the obtaining of cartographies. A correspondence porosity (tomo X) - Mitigation (US wave) is deducted and analyzed according to the structure of the composite material. In every case, we estimate the quality of the obtained relations and we deduct the limits of validity of the correspondence between porosity and mitigation. First results of acoustic tomography are obtained.

The study deals with the chemical and flame retardant (FR) treatment of woven flax fabric and preparation and characterization of flax reinforced phenolic composites. Sheets of flax fabric were subjected to chemical treatments using NaOH and silane coupling agents. A phosphate-based flame retardant (DAP) was applied to decrease the flammability of the flax fabric. The effect of the chemical treatments and FR treatments on the thermal and flammability properties of the fabric and composites was investigated using thermogravimetric analysis (TGA), vertical flame resistance test and cone calorimeter. The mechanical properties of the flax fabric and composites, before and after environmental ageing, were investigated. Ageing studies were carried out by exposing the samples in an environmental chamber at specified conditions for two weeks. TGA results showed that the treatment of the fabric with FR shifts the decomposition temperature to lower level and increases the char residue. Vertical flame resistance testing showed that FR treatment of the flax fabric improved the flammability properties. There was no after flame and afterglow observed for FR treated flax fabric due to self-extinguishment after removal of the flame. Flax Fabric without FR burned completely and there was no result for the char length due to the complete destruction of the fabric. The FR treatment, however, seemed to have had a negative effect on the tensile strength of the flax fabric. This was further intensified upon exposure of FR treated flax fabric to high temperatures during ageing studies which drastically reduced the tensile strength by more than 90%, and the flax fabric were found to be brittle and darker in visual appearance. TGA results of flax/phenolic composites showed that for composites containing chemically treated and FR treated flax fabric the decomposition temperatures shifted to lower temperatures; however there was no significant difference in the amount of char residue. Untreated flax/phenolic composites exhibited the lowest char residue. Cone calorimeter results showed that the peak heat release rate (PHRR), smoke production rate (SPR) and carbon dioxide (CO2) emission rate was reduced for the flax/phenolic composite produced using FR treated flax fabric. The tensile strength of these composites was reduced while there was an increase in modulus value. Exposure of the FR treated composites to high temperatures further reduced the tensile strength and increased the E-modulus. Both FR treated and untreated composites changed in colour and the FR treated composites were found to be brittle after exposure to high temperatures.

No description available.