The avoidance of hydrate blockages in deepwater subsea tiebacks presents a major technical challenge with severe implications for production, safety and cost. The successful prediction of when and where hydrate plugs form could lead to substantial reductions in the use of chemical inhibitors, and to corresponding savings in operational expenditure. The diffusivity of the gas hydrate former (methane) or the host molecule (water), through a hydrate film is a key property for such predictions of hydrate plug formation. In this paper, a novel application of Differential Scanning Calorimetry is described in which a hydrate film was allowed to grow at a hydrocarbon-water interface for different hold-times. By determining the change in mass of the hydrate film as a function of hold-time, an effective diffusivity could be inferred. The effect of the subcooling, and of the addition of a liquid hydrocarbon layer were also investigated. Finally, the transferability of these results to hydrate growth from water-in-oil emulsions is discussed.

The flow assurance industry is progressively moving away from avoidance of hydrate formation towards risk management. Risk management allows hydrates to form but prevents hydrates from agglomerating and forming a plug, or delays hydrate formation within the timescale of the residence time of the water in the hydrate-prone section of the flow line. A key factor in risk management for an oil-dominated system is the stability of the emulsified water with gas hydrate formation. It is shown using Differential Scanning Calorimetry (DSC) that gas hydrate formation and dissociation has a destabilizing effect on W/O emulsions, and can even lead to a free water phase through agglomeration and coalescence of dissociated hydrate particles. Gas hydrate formation/dissociation has been shown to cause rapid hydrate agglomeration and emulsion destabilization. High asphaltene content crude oils are shown to resist hydrate destabilization of the emulsion.

A HP micro DSC-VII from SETARAM was used to study the efficiency and mechanism of action of commercial kinetic inhibitors for gas-hydrate formation in drilling fluids (OBM). The main objective was to find a suitable and reliable method of screening for these chemicals. The DSC technique consists in monitoring the heat exchanges, due to phase changes (here hydrate formation or dissociation), either versus time at constant temperature or versus temperature during a heating or cooling program. All products showed a gas hydrate dissociation temperature (at a given pressure) that matched with theoretical and previously published data. Nevertheless, for some additives two thermal signals were observed on the thermograms, one that corresponds to the theoretical value and another at a higher temperature (about +4°C). This second peak is insensitive to the heating rate applied for the dissociation, but the areas ratio (1stpeak/2nd peak) changes with the additive concentration and with the driving force applied during the hydrate formation. Additionally, additive/water and additive/water/THF systems were tested. In each case, two dissociation peaks were also measured. The results allow us to disregard any kinetic effects bonded to this thermal phenomenon, and lead us to infer that some additives may induce non-classical crystalline structures of gas hydrates. To verify these results, crystallographic and spectroscopic experiments must be performed. The stabilities of these new compounds are under study.

Differential scanning calorimetry has been used to study the kinetics of formation of clathrate hydrates in the systems water-CCl3F and water-CH4, in which the water phase was dispersed in an oil phase in the form of an emulsion. CCl3F hydrates were formed at ambient pressure and constant temperatures of -10, -15 and -20 °C. The results showed that the crystallization of both ice and hydrate are in competition at the lowest temperature, whereas only hydrate is formed at -10 or -15 °C. CH4 hydrates were studied using a high-pressure DSC in the range 10 to 40 MPa, at various temperatures. At high driving force, the heat peak related to the formation of hydrates has a regular and symmetric shape, and its height and width depend on the gas pressure and sub cooling degree. At near equilibrium conditions, hydrate formation can be delayed by several hours, but is still clearly observable. A model based on crystal growth theory coupled with a statistical law to take into account the germination in micro sized droplets is proposed.

The heat capacity and the enthalpy of crystallization of the crystalline phases at the end of cooling must be known in order to determine the excess energy of mixing two pure triglycerides, trilaurin and trimyristin, cooled at different cooling rates. The present investigation was carried out using Differential Scanning Calorimetry, DSC, Modulated Differential Scanning Calorimetry, MDSC®, and Thermal Relaxation (in a Physical Properties Measurement System, PPMS). It was found that enthalpy of crystallization values can be measured to within ? 2% (SE) with DSC Q100 TA Instruments. To achieve this, an experimental procedure and a data analysis method are proposed. It was not possible in this study to obtain accurate and reproducible heat capacity values using a DSC Q100 instrument. The values were shown to be significantly by the position of the sample pan in the measuring sensor. PPMS Cp values were within the literature values.

Aluminum (Al) powder metallurgy (PM) provides a cost effective and environmentally friendly means of creating lightweight, high performance, near net shape components, relative to conventional casting/die casting technology. Unfortunately, the current lack of commercially available Al alloy powder blends has hindered development in this field as a result of the limited scope of mechanical properties available; especially under elevated temperature conditions common to many automotive applications. As such, the objective of this research was to attempt to improve the versatility of current Al PM technology through the incorporation of Fe and Ni transition metal additions into an emerging Al- 4.4Cu-1.5Mg-0.2Sn alloy, as this technique is known to enhance the elevated temperature stability of wrought/cast Al alloys through the formation of stable, Fe/Ni aluminide dispersoids. Initial experimentation consisted of evaluating the feasibility of incorporating Fe and Ni both elementally and pre-alloyed, through a series of tests related to their PM processing behaviour (compressibility, sintering response) and sintered product performance (ambient tensile properties). Results confirmed that pre-alloying of the base Al powder was the most effective means of incorporating Fe and Ni as all such specimens achieved properties similar or slightly superior to the unmodified alloy. Of the pre-alloyed systems considered, that containing 1%Fe+1%Ni displayed the most desirable results in terms of mechanical performance and microstructural homogeneity of the Fe/Ni dispersoid phases present in the sintered product. Bars of the baseline system and that modified with pre-alloyed additions of 1Fe/1Ni were then sintered industrially to gain a preliminary sense of commercial viability and obtain additional specimens for elevated temperature exposure tests. Results confirmed that the sintering response, tensile properties and microstructures were essentially identical in both alloys whether they were sintered in a controlled laboratory setting or an industrial production environment. Furthermore, DSC data indicated that S (Al2CuMg)-type phases were the dominant precipitates formed during heat treatment. The effects of elevated temperature exposure were assessed in the final stage of research. Both alloys were found to exhibit comparable behaviour when exposed to the lowest (120°C) and highest (280°C) temperatures considered. Here, the alloys showed no obvious degradation at 120°C. Conversely, exposure at 280°C prompted a steady decline in yield strength for both alloys with significant precipitate coarsening noted as well. Despite these similarities, differences emerged during isochronal tests at intermediate temperatures. Here, DSC data indicated that the precipitates present in the pre-alloyed material were stable at temperatures up to 160°C while those in the unmodified alloy had begun to overage under the same exposure conditions. These differences were accompanied by increased stability in tensile yield strength for the pre-alloyed material. In all, this study has indicated that the use of Al powder pre-alloyed with Fe/Ni additions is feasible for press-and-sinter PM technology and that the sintered product exhibits improved elevated temperature stability under certain conditions.

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

The cost of manufacturing high quality composite components can be significantly reduced by using Out of Autoclave (OOA) processes if they can achieve final parts with a finish quality as high as that obtained using an autoclave process. Much research has been carried out recognising that regardless of the reinforcement fibre orientation, manufacturing of preimpregnated (prepregs) carbon components is much affected during its forming stage by fibre deformation and failure modes. This work sought to reduce wrinkling in the moulding of prepregs by introducing slip layers within the lay-up. Three types of slip layers were used: a dry fabric, a resin rich layer and a resin film. In order for the slip layers to be fully incorporated into the final laminate the resin content within the slip layer must be adjusted prior to crosslinking. In the case of dry fabric layer, additional resin must be introduced and in the case of a resin rich layer and resin film layer, excess resin has to be removed. The laminates used in the project were based on 2/2 twill and unidirectional carbon prepregs. These were manufactured by either Resin Infusion (RI) or Vacuum Bagging (VB). Resin adjustments were made at the same time. The 2/2 twill and unidirectional carbon prepregs were first characterised by Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Thermal Analysis (DMTA) before RI and VB. Dry 2/2 twill and unidirectional carbon fabrics and/or Resin Film (for VB) or fabrics and Epoxy Resin (for RI) were introduced in several plybooks and then cured. Final parts were either made of 2/2 twill carbon or unidirectional carbon. The parts were used to investigate the relationship between individual plies during the consolidation of a plybook. The first characterisations were done on flat laminates. Also two moulds were manufactured and used to produce new parts for further characterisations. The first, an aluminium mould was machined using a Computer Numerical Control (CNC). The second mould was a fan blade, made using chopped strand mats. The final parts had 3, 4 or 6 plies. These parts were characterised using Optical Microscopy (OM), Scanning Electron Microscopy (SEM), and Torsion testing. The results provide a first step towards understanding how the friction at a ply/ply level can be influenced by the "starving" or the "enriching" of resin in a plybook during its consolidation. The work showed that in OOA manufacturing, the friction at a ply/ply level can be controlled by introducing Resin Film, Dry or Resin Rich Fabrics in a prepreg plybook. It was demonstrated that introducing lubrication to control ply friction during forming can result in quality part as high as that obtained from a traditional composite forming process. As the final parts were made using a fixed die mould and a vacuum bag, most of the plies in the layups could deform individually and accommodate interply shear. Torsion testing on a number of a random selection of samples showed negligible effects on shear stresses, strengths and modulus within the parts were negligible. It is argued that the flexibility of the vacuum bag could have had an impact on the layups during forming. The plies could conform to the mould easier. This work has potential for other applications. For example in match die moulding, introducing wet lubrication could improve interply shear during forming and help in improving accuracy and geometrical conformity of final parts. Furthermore, developing techniques to control friction during forming in OOA can be attractive to industries which could not afford to invest in this OOA prepreg technology. OOA processing times have become very attractive to industries such as the sporting good, automotive, wind energy and transportation. These industries could explore the opportunity presented by the work in this EngD thesis.

o comportamento, frente ao envelhecimento físico, do sistema diglicidil éter do bisfenol-A (DGEBA) curado com diaminodifenilmetano (DOM) foi estudado em função da estrutura química, induzida pela cura, e do tempo de envelhecimento. Sistemas estequiométricos foram submetidos a Calorimetria Diferencial de Varredura (DSC) e Análise Térmica Dinâmico-Mecânica (DMTA). A cura isotérmica da resina epóxi foi realizada em uma etapa a 115°C e 135°C, por 20, 30, 45, 60 e 90 mino As amostras foram envelhecidas a 100°C por períodos de 4 até 72h. A extensão do envelhecimento físico foi associado com a área do pico endotérmico que aparece na região da transição vítrea, de acordo com os termogramas de DSC. Foi observado que a entalpia de relaxação aumenta gradualmente com o tempo de envelhecimento. Por DMT A, observou-se variações na magnitude do fator de perda (tan õ), no pico máximo, em função do grau de cura e do tempo de envelhecimento. O módulo dinâmico de armazenamento a 100°C (E'1CX)) deslocou-se para valores maiores assim como a Tg, medida através do pico a da curva log E", com o aumento do tempo de envelhecimento. A velocidade de envelhecimento e as energias de ativação da transição α foram obtidas a partir de parâmetros dinâmico-mecânicos e após associados com as diferentes histórias de cura e envelhecimento do material. De modo geral, a velocidade de envelhecimento (Ra) decresce com o aumento do grau de reticulação para sistemas curados a 115°C e passa por um mínimo para as amostras curadas a 135°C. As energias de ativação mostram uma tendência crescente com o tempo de envelhecimento. Concluiu-se que a técnica de DMTA é muito sensível às mudanças estruturais devido à cura e ao envelhecimento físico realizados nos sistemas investigados. Os resultados dinâmico-mecânicos obtidos para as misturas curadas segundo diferentes histórias térmicas salientam a importância da seleção adequada das condições de cura para que se possam obter as melhores propriedades destes materiais. / Physical aging behavior of diglycidyl ether of bisphenol-A (DGEBA) cured with diaminodiphenylmethane (DDM) have been investigated as a function of chemical structure, induced by cure, and aging time. Stoichiometric systems have been submitted to Differencial Scanning Calorimetry (DSC) and Dynamic Mechanical Thermal Analysis (DMTA) measurements. The isothermal curing of the epoxy resin was carried out in one step at 115°C and at 135°C for 20, 30, 45, 60 and 90 mino Samples were aged at 100°C for periods of time from 4 to a maximum of 72 h. The extent of physical aging has been measured by the area of the endothermic peak which appears within the glass transition region according to DSC thermograms. The enthalpy relaxation was found to increase gradually with aging time. Variations on magnitude of the loss factor (tan õ), on the maximum peak, have been observed as a function of degree of cure and aging time. The dynamic storage modulus at 100°C ( E' 100) changed with increasing physical aging to higher values as well as the glass transition temperature (Tg) as measured by the a peak on log E" curves. Aging rates and α transition activation energies were obtained through DMT A parameters analysis and then associated with different curing and aging histories of the material. Generally, the aging rate (Ra) decreases with increasing crosslinking degree for the systems cured at 115°C and passes through a minimum for those cured at 135°C. The activation energies demonstrate a tendecy to increase with aging time. It was concluded that the DMTA technique is very sensitive to structural changes in the investigated epoxy systems due to curing and physical aging . The DMTA results obtained from mixtures cured with different thermal histories underline the importance of adequate selection of curing conditions in order to obtain the optimum properties for these materiais.

A conformação de dispositivos médicos implantáveis a partir de uma blenda exige o desenvolvimento de um produto com propriedades próximas do comportamento ideal, combinando propriedades térmicas e mecânicas e boa resposta tecidual. O Poli (ácido láctico-co-glicólico) (PLGA) e o Poli (isopreno) (IR) foram escolhidos como componentes da blenda com finalidade de promover boa biocompatibilidade e características mecânicas especificas. As blendas foram obtidas por dissolução dos polímeros em solvente orgânico, seguida de secagem. Para determinar a influência do teor de IR sobre as propriedades da blenda, foram realizados ensaios de espectroscopia na região de infravermelho por transformada de Fourier (FTIR), calorimetria diferencial de varredura (DSC), análise dinâmico-mecânica (DMA), microscopia óptica por luz polarizada (POM), análise de dureza, ensaio de tração e análise de viabilidade celular. A presença de IR na blenda provocou alteração na estrutura molecular semi-cristalina do PLGA, bem como influenciou o comportamento mecânico analisado a partir da curva tensão-deformação do material. A blenda se mostrou biocompativel em ambiente celular e em ensaios preliminares em animais, apresentando potencial para aplicação como biomaterial. / The conformation of an implantable medical device from a polymeric blend requires the development of a product with properties as close as possible of ideal behavior with the combination between thermal and mechanical properties and good tissue response. The poly (lactic-co-glycolic acid) (PLGA) and the poly (isoprene) (IR) were chosen as the blend components to promote good biocompatibility and specific mechanical characteristics. The blends were obtained by dissolution of polymers in organic solvent, followed by drying. In order to determine the IR content influence over the blend properties, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), polarized light optical microscopy (POM), hardness analysis, tensile test and cell viability test were carried out. The IR presence caused changes in semi-crystalline molecular structure of PLGA, as well as actuated over the mechanical response analyzed on material’s stress-strain curve. The blend showed itself biocompatible at cellular environment and at preliminary animal tests, presenting potential for application as biomaterial.