Pressure oxidation of refractory gold ores containing carbonate minerals is conducted under neutral/alkaline conditions in order to promote fast kinetics, reduced reagent consumption and suppressing the formation of elemental sulphur and CO2 (which reduces the effectiveness of the process). In this work, both the addition of sodium carbonate and the presence of silica were investigated during the pressure oxidation of pyrite in the presence of calcium carbonate. It was found that the shift to an alkaline leaching environment favours the formation of soluble sulphate products over anhydrite (an industrial scale), but that the increase in kinetics is likely due to an increase in pH and carbonate/bicarbonate concentrations. The presence of silica in the autoclave induces the formation of an in situ iron oxyhydroxide silicate coating and a significant reduction in pyrite oxidation, which was minimized by addition of sodium carbonate.

The purpose of this study was to examine the performance of several generic types of organic protective coatings as a corrosion protection method for the interior of subsea pipelines in sour gas media. The sour gas environment was simulated in the laboratory by the use of an Autoclave and the performance of the organic coatings was studied via the use of Electrochemical Impedance Spectroscopy (EIS) and Linear Polarization Resistance (LPR) tests to determine the coatings resistance, capacitance and corrosion behavior before and after the exposure to sour gas environment. The coating degradation and the corrosion products formed were examined by the use of SEM/EDS. The results indicated that both FBE and Novolac Epoxy coatings had excellent adhesion properties and chemical resistance. The Amine-Cured Novolac Epoxy coating exhibited good adhesion properties and chemical resistance. However, the Phenolic Epoxy coating started to degrade over time and corrosion took place under the coating.

Zeolite membranes have great potential in gas separation applications because of their unique selective properties. The main challenge is in synthesizing defect-free zeolite membranes. In this study, we synthesized silicalite-1 zeolite membranes on ceramic supports composed of Al2O3 and TiO2 using the pore-plugging method. We investigated the effect of the fill-level in the autoclave during the synthesis on the membrane performance. In particular, we were interested in determining the conditions at which the defects' contribution to the total transport is minimized. We adopted and further developed the approach proposed by Carter (2019) to quantify the permeance contribution through defects. Comparing the membrane performance before and after calcination, we proposed several modifications to the original analysis of Carter (2019). Knowing the defect transport contribution, we determined the corrected diffusivity, an intrinsic property of zeolite crystals at a given temperature, of several adsorbed gases on silicalite-1 crystals. The defect's contribution decreased as the autoclave fill-level increased from 94 to 98%. A further increase in the autoclave fill-level introduced more defects and caused the autoclave lid to rupture. Despite the differences in the membranes' performance arising from the autoclave fill-level, the corrected diffusivities of CO2, CH4, and N2 in silicalite-1 showed minimal variation from membrane to membrane. This proves the validity of the proposed characterization method. Moreover, the reported corrected diffusivities are comparable to the literature's values, found using other characterization methods. However, none of the previously used methods is as simple and straightforward as the one we further developed in this study.

Resin infusion of composite parts has continually been reaching to achieve laminate quality equal to, or exceeding, the quality produced with prepreg in an autoclave. In order for this to occur, developers must understand the key process variables that go in to producing a laminate with minimal void content. The purpose of this research is to continue efforts in understanding 1) the effect of process conditions on the resultant void content, with a focus on resin infusion flow rate, 2) applying statistical metrics to the formation, location and size of voids formed, and 3) correlate these metrics with the local mechanical properties of the composite laminate. The variation in dispersion and formation of micro-voids and macro-voids varied greatly between the rates of flow the infusion occurred, especially in the non-crimp carbon fiber samples. Higher flow rates led to lower volumes of micro-voids in the beginning section of the carbon fiber laminates with macro-voids being introduced approximately half-way through infusion. This was determined to have occurred decreasing pressure gradient as the flow front moved away from the inlet. This variation in void content per location on the laminate was more evident in the carbon fiber samples than the fiberglass samples. Micro-voids follow void formation modeling especially when coupled with a pressure threshold model. Macro-void formation was also demonstrated to correlate strongly to void formation models when united with void mobility theories and pressure thresholds. There is a quick decrease in mechanical properties after the first 1-2% of voids signaling strength is mostly sensitive to the first 0-2% void content. A slight decrease in SBS was noticed in fiberglass laminates, A-F as v0 increased but not as drastically as represented in the NCF laminates, G and H. The lower clarity in the exponential trend could be due to the lack of samples with v0 greater than 0% but less than 1%. Strength is not well correlated to void content above 2% and could possibly be related to void morphololgy.

Out-of-autoclave manufacturing processes for composite materials are increasing in importance for aerospace and automotive industries. Vacuum Infusion processes are leading the push to move out of the autoclave. An understanding of the various process parameters associated with resin infusion is necessary to produce quality product. Variance in compaction, resin, and vacuum pressures are studied, concentrating on developing a compaction pressure profile as it relates to fiber volume fraction. The purpose of this research is twofold: (1) to show and quantify the existence of a resin pressure gradient in compression testing using rigid tooling, and (2) to use measured test data to validate and improve resin flow simulation models. One-dimensional compression tests revealed a pressure gradient across the diameter of the compression tool. The pressure gradient follows trends consistent with Darcy's Law. Compression tests revealed fabric hysteresis during compaction as shown in previous studies. Fiber compaction pressure was found to not be directly equal to compressive forces of the Instron when resin is present in the system. The relationship between Instron, resin and compaction pressures is defined. The compression study was used to validate previously developed flow simulation models. Resin pressures are critical to developing an accurate two-dimensional radial flow simulation for low permeability fabrics. It is feasible to determine final fiber volume fraction at a given compaction pressure.

Global competition is pushing the composites industry to advance and become more cost effective. Liquid Composite Molding or LCM is a family of processes that has shown significant promise in its potential to reduce process times and cost while maintaining high levels of part quality. However, the majority of research and information on composite processes have been related to prepreg-autoclave processing which is significantly different than LCM. In order for LCM processes to gain large scale implementation, significant research is required in order to model and simulate the unique nature of the resin infusion process. The purpose of this research is to aid in the development of in situ void measurement and characterization during LCM processing, particularly for carbon fiber composites. This will allow for the gathering of important empirical data for the validation of models and simulations that aid in the understanding of void formation and movement during LCM. For such data to be useful, it needs to include details on the formation, mobility and evolution of the void over time during infusion. This was accomplished by creating a methodology that allowed for in situ images of voids to be captured during the infusion process. A clear mold was used to visually monitor infusions during RTM with UV dye and lighting to enhance contrast. Consecutive images were acquired through the use of macro lens photography. This method proved capable of yielding high quality images of a variety of in situ voids during infusions with carbon fiber composites. This is believed to be the first instance where this was accomplished. A second methodology was then developed for the analysis of the collected images. This was done by using ImageJ software to analyze and process the acquired images in order to identify and characterize the voids. Success was found in quantifying the size and circularity of a wide range of micro and macrovoids in both a satin weave and double bias NCF woven fabrics. To facilitate the burden of collecting large amounts of data, this process was made to be automated. A user generated macro script could be applied to large sets of images for rapid processing and analysis. This automated method was then evaluated against manually processed images to determine its overall effectiveness and accuracy as tool for validating void theory.

La dynamique des éruptions volcaniques est régie principalement par le processus de dégazage des magmas. Nous avons reproduit expérimentalement les conditions de pression (P) et de température (T) subies par le magma au cours de sa remontée à la surface, afin d'étudier la vésiculation des volatils qui s'exsolvent du silicate liquide. Pour cela nous avons développé, utilisé et validé deux outils expérimentaux permettant l'observation en temps réel du dégazage magmatique. Nous avons utilisé des verres synthétiques hydratés, analogues de magmas rhyolitiques, mis en équilibre en P et T et auxquels nous avons fait subir des décompressions contrôlées provoquant le dégazage de l'eau. Une partie des expériences a été réalisée en cellule à enclume de diamants hydrothermale, permettant l'observation de la vésiculation, pour des conditions P-T de 8-12 kbar, 700-900°C et 7-18 %pds H2O dans le silicate liquide.Dans le cadre des améliorations technologiques associées à ce travail, nous avons participé à la mise au point de capteurs électriques implantés dans les diamants permettant la mesure de la température au plus près de l'échantillon. Les autres expériences ont été réalisées dans un autoclave à chauffage internet transparent permettant une observation de la chambre à échantillons pendant l'expérience, pour des conditions P-T de 1-3 kbar, 700-1000°C, avec 4-7 %pds H2O dans le liquide silicaté. Ces deux outils complémentaires nous ont permis de réaliser des expériences de décompression et d'observer in situ la nucléation, la croissance et la coalescence de bulles d'eau. Les résultats de ces expériences sont présentés et comparés. Leurs implications volcanologiques sont discutées.

The electromagnetic absorption properties of plasmonic nanostructures were utilized to develop mesoscopic sites for highly efficient photothermal generation steam, SERS biosensing, and light-triggered cellular delivery uptake. Plasmonic nanostructures embedded in common thermal solutions produces vapor without the requirement of heating the fluid volume. When particles are dispersed in water at ambient temperature, energy is directed primarily to vaporization of water into steam, with a much smaller fraction resulting in heating of the fluid. Solar illuminated aqueous nanoparticle solution can drive water-ethanol distillation, yielding fractions significantly richer in ethanol content than simple thermal distillation and also produced saturated steam destroying Geobacillus stearothermophilus bacteria in a compact solar powered autoclave. Subwavelength biosensing sites were developed using the plasmonic properties of gold nanoshells to investigate the properties of aptamer (DNA) target complexes. Nanoshells are tunable core-shell nanoparticles whose resonant absorption and scattering properties are dependent on core/shell thickness ratio. Nanoshells were used to develop a label free detection method using SERS to monitor conformational change induced by aptamer target binding. The conformational changes to the aptamers induced by target binding were probed by monitoring the aptamer SERS spectra reproducibility. Furthermore, nanoshells can serve as a nonviral light-controlled delivery vector for the precise temporal and spatial control of molecular delivery in vitro. The drug delivery concept using plasmonic vectors was shown using a monolayer of ds-DNA attached to the nanoshell surface and the small molecular “parcel” intercalated inside ds-DNA loops. DAPI, a fluorescent dye, was used as the molecular parcel to visualize the release process in living cells. Upon laser illumination at the absorption resonance the nanoshell converts photon energy into heat producing a local temperature gradient that induces DNA dehybridization, releasing the intercalated molecules.

Vacuum bags in conjunction with autoclaves are currently employed to generate the consolidation pressures and temperatures required to manufacture aerospace level composites. As the scale of continuous fiber composite structures increases autoclaving becomes prohibitively expensive or impossible. The objective of this work is to develop flexible magnetic clamping structures to increase the consolidation pressure in conventional vacuum bagging of composite laminates, thereby obviating the need for an autoclave. A ferromagnetic rubber, which consists of rubber filled with iron, is being developed as a conformable and reusable vacuum bag that provides increased consolidation through attractive forces produced by electromagnets. Experiments and finite element modeling indicate that consolidation pressure in the range of 100 kPa can be generated by such a device with realistic power requirements. The effects of the magnetic clamping device process parameters on the consolidation pressure magnitude are modeled and characterized. In addition, a method for the efficient design of the magnetic clamping device is developed.

La corrosion des gaines de crayons combustible, en alliage de zirconium, limite la durée de vie des crayons dans les réacteurs à eau légère. Les industriels ont pour objectif à moyen terme d'augmenter la durée des cycles en réacteur, le nombre de cycles et de soumettre ces gaines à des conditions plus sollicitantes. Dans ce cadre, de nouveaux alliages, notamment le Zr-1%Nb, destinés à remplacer le Zircaloy-4 ont été récemment développés et présentent une résistance accrue à la corrosion en réacteur. Améliorer la compréhension des mécanismes de corrosion de ces alliages est donc un enjeu industriel majeur, pour prédire le comportement à long terme de ces matériaux.<br />L'oxydation de deux familles d'alliages a été étudiée sous vapeur d'eau (pression comprise entre 100 millibars et 100 bars) : les alliages de type Zircaloy, dont la composition est basée sur celle du Zircaloy-4 et ceux de type Zr-x%Nb à différentes teneurs en niobium (0,2 ; 0,4 et 1%). Nos objectifs pour ces deux familles d'alliage étaient de comprendre les différences de réactivité de ces matériaux entre la basse et la haute pression de vapeur d'eau, en estimant les variations de la vitesse avec cette variable et l'influence de chaque élément d'addition sur la vitesse. Pour les alliages au niobium, une analyse approfondie de la ségrégation du niobium en surface a également été menée.<br />Au cours de ce travail, une thermobalance à suspension magnétique a été développée et mise en œuvre pour suivre in-situ l'oxydation à haute pression (jusqu'à 50 bars). Cette expérimentation est, à notre connaissance, unique en son genre. Au cours de cette étude, un large domaine de pression a ainsi été balayé en associant expérimentations en thermobalance (0,1-10 bars) et en autoclave (10-100 bars).<br />Les couches d'oxyde formées ont ensuite été caractérisées par différentes techniques telles que le MEB, le MET-HR, la DRX, l'ESCA, la marco- et microphotoélectrochimie (MPEC et mPEC), le SIMS après échange isotopique en H₂¹⁸O.<br />Pour les alliages de la famille du Zircaloy, nous avons confirmé le rôle prépondérant des précipités Zr(Fe,Cr)₂ sur la résistance à la corrosion des gaines, et validé la croissance de la vitesse d'oxydation du zirconium quasi-pur avec la pression partielle de vapeur d'eau. A l'opposé de la très grande stabilité cinétique du Zircaloy-4, dont la vitesse est indépendante de la pression de vapeur d'eau et donc contrôlée par la diffusion de l'oxygène dans la couche, nos résultats nous ont conduits à proposer une étape limitante de réaction d'interface dans le cas du zirconium pur, associée à une forte dégradation de la couche liée à une croissance des grains catalysée par la vapeur d'eau, à l'origine des décohésions entre des amas de cristallites. Les précipités Zr(Fe,Cr)₂ , au travers de la dissolution du fer dans la matrice de zircone environnante, pourraient, en stabilisant la zircone quadratique, assurer l'intégrité de la couche.<br />Pour les alliages Zr-x%Nb et plus particulièrement pour l'alliage Zr-1%Nb, la vitesse d'oxydation est dépendante de la pression partielle de vapeur d'eau. A cela s'ajoute un accroissement sensible de la ségrégation en niobium à la surface, mise en évidence par ESCA, sous la forme Nb₂O₅, mise en évidence par MPEC. La vitesse d'oxydation et la ségrégation en niobium montrent toutes deux une dépendance homographique en fonction de la pression. L'originalité de l'exploitation de ces résultats réside essentiellement dans la proposition d'un mécanisme simple prenant à la fois en compte la ségrégation et l'oxydation. Une étape limitante de diffusion des ions hydroxydes adsorbés dans la couche externe de l'oxyde permet de décrire la majorité des résultats expérimentaux obtenus sur les alliages Zr-x%Nb.