Orientadores: Denis José Schiozer, Célio Maschio / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica, Instituto de Geociências / Made available in DSpace on 2018-08-26T04:44:51Z (GMT). No. of bitstreams: 1 Correia_ManuelGomes_D.pdf: 14518557 bytes, checksum: 6bd7fa813367e116cd714b895308f6fb (MD5) Previous issue date: 2014 / Resumo: A construção de modelos robustos que considerem heterogeneidades características de reservatórios carbonáticos, tais como fraturas e vugs, continua sendo um desafio geologia e engenharia de petróleo. O objetivo deste trabalho é desenvolver e aplicar uma metodologia que vise a representação da geologia de reservatórios carbonáticos na simulação de reservatórios, através da integração das etapas de caracterização, transferência de escala e simulação de escoamento. A metodologia segue cinco etapas: (1) divisão do reservatório em unidades características de fluxo (UCF); (2) modelagem geoestatística típica de cada UCF; (3) transferência de escala para cada UCF; (4) modelagem numérica para cada UCF e (5) integração das UCF num modelo único de simulação de reservatórios. A metodologia é aplicada a três UCF considerando fraturas difusas, subsísmicas e vugs isolados. A metodologia apresenta várias vantagens: controle sequencial sobre as propriedades estáticas e pseudo-funções ao longo da transferência de escala; calibração do fluxo realizada sequencialmente de acordo com a escala de heterogeneidades; suporte para a escolha do modelo adequado de simulação numérica; redução do tempo da simulação de escoamento e do tempo relativo ao desenvolvimento de reservatórios carbonáticos dado que a metodologia pode ser aplicada em processos de análise de incerteza; e aperfeiçoamento na integração de heterogeneidades multiescalares na simulação de reservatórios. Para uma representação adequada reservatórios carbonáticos na simulação de fluxo, os seguintes passos são essenciais: os procedimentos de transferência de escala devem ser diferenciados por UCF e respectiva escala das heterogeneidades presentes; a definição de uma solução de referência é importante para a previsão da escolha do modelo de simulação numérica; a aplicação de pseudo-funções é normalmente necessária para efeito de ajuste de escoamento em reservatórios carbonáticos, dada a presença dos efeitos de embebição e forças gravitacionais que não podem ser transferidos pelas técnicas comuns de transferência de escala aplicadas em propriedades estáticas. Este trabalho apresenta uma metodologia e análise que pode ser útil em áreas multidisciplinares de pesquisa dado que integra a modelagem geoestatística de reservatórios carbonáticos com a simulação de reservatórios / Abstract: The construction of robust reservoir models considering geological carbonate heterogeneities, such as fractures and vugs, remains a challenge. The purpose of this work is to perform and apply a methodology aiming a suitable representation of carbonate reservoir geology in reservoir simulation through the integration of characterization, upscaling and flow simulation steps. The methodology follows five elementary steps: (1) division of reservoir into characteristic flow units (UCF); (2) geostatistical modeling for each UCF; (3) upscaling procedure for each UCF; (4) flow simulation modeling for each UCF and (5) integration of all UCF into a single reservoir for flow simulation. The methodology is applied to three UCF considering diffuse fractures, sub-seismic fractures and isolated vugs. The methodology has shown several advantages: sequential control over static properties and pseudo-functions integrated with upscaling procedure; flow match accomplished sequentially by heterogeneity scale, over the upscaling; simplification in definition of the accurate simulation flow model; reduce time consumption in flow simulation and project development as the methodology can be implemented for uncertainty workflows; and improvement of the integration of multiscale heterogeneities in reservoir simulation. For a proper representation of a carbonate reservoir in flow simulation, important steps should be followed: upscaling procedure must be done differently by UCF and consequently by type of heterogeneity scale; flow progress and reservoir pressure drop analysis of a reference solution is helpful to define the flow model selection; pseudo-functions are normally necessary to match procedures in fractured carbonate reservoirs because of dynamic phenomena (imbibition, gravitational forces etc.) that cannot be upscaled by the common averages used for static properties. This work presents a methodology and an analysis that can be useful for multidisciplinary areas of expertise since it integrates geostatistical modeling of carbonate reservoir heterogeneities with reservoir simulation / Doutorado / Reservatórios e Gestão / Doutor em Ciências e Engenharia de Petróleo

Orientador: José Vicente Hallak d'Angelo / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-21T11:05:01Z (GMT). No. of bitstreams: 1 Marins_Gabrielde_M.pdf: 4193921 bytes, checksum: e80672b42613eddad46d14b2c94e31c8 (MD5) Previous issue date: 2012 / Resumo: No processo Kraft para produção de papel e celulose, os cavacos de madeira são cozidos em um digestor com uma solução aquosa denominada licor branco, constituída de hidróxido de sódio (NaOH) e sulfeto de sódio (Na2S). Durante o cozimento uma pasta fibrosa é produzida. Esta pasta é filtrada e segue para o branqueamento. O produto filtrado chama-se licor negro, devido à mudança da sua cor nesta etapa. O licor negro possui aproximadamente 15 % de sólidos em massa. Ele é bombeado para a unidade de recuperação, na qual ele será concentrado em evaporadores de múltiplosefeitos até 75 % de sólidos em massa. Em seguida, ele é bombeado para uma caldeira onde é queimado, para recuperar os sais inorgânicos e, principalmente, fornecer calor para geração de calor. Durante a evaporação do licor negro, quando a porcentagem em sólidos ultrapassa 50 %, ocorre a precipitação de sais inorgânicos. Estes sais se depositam nas superfícies de troca térmica dos evaporadores diminuindo sua eficiência e causando prejuízos à indústria. Os principais sais que causam este problema são o carbonato de sódio (Na2CO3) e o sulfato de sódio (Na2SO4). O objetivo do presente trabalho foi testar e validar um método experimental para a determinação da quantidade de Na2CO3 presente em amostras industriais de licor negro. Além disso, também foram analisadas algumas propriedades físico-químicas do licor negro, como massa específica, teor de sólidos e viscosidade. Com os resultados obtidos, tentou-se obter uma correlação entre o teor de carbonato de sódio e as demais propriedades do licor que foram determinadas. Os resultados das análises das características físico-químicas demonstraram coerência e boa reprodutibilidade, porém, os resultados das análises de teor de carbonato de sódio não foram satisfatórios e mostraram que a técnica deve ser aperfeiçoada / Abstract: In the Kraft process for pulp and paper production, wood chips are cooked in a digester with an aqueous solution named white liquor, consisted by sodium hydroxide (NaOH) and sodium sulfide (Na2S). During this cooking process, wood chips are transformed generating a fibrous paste and a liquid solution. This paste is filtered and separated from the liquid solution, named black liquor due to its color. The paste goes to the bleaching stage to produce cellulose. Black liquor contains inorganic and organic (mainly lignin) compounds from wood. Initially this black liquor contains approximately 15 mass/% of solids and is sent to the recovery unit to have this concentration raised to approximately 75 mass/% to be burned in a recovery boiler in order to generate power and recover inorganic reactants, recycling them to the process. The concentration process of black liquor occurs in a multiple effect evaporators unit. During this process, when the concentration of solids exceeds 50%, the precipitation of inorganic salts (mainly Na2CO3 and Na2SO4) begins. These salts are deposited in the heat transfer surfaces of the evaporator tubes, reducing their efficiency, leading to a reduction in the production capacity. The scope of this work was testing and validate an experimental method to estimate the content of Na2CO3 present in industrial black liquor samples. Moreover, some black liquor's physical-chemical properties as density, solids content and viscosity were also analyzed. An attempt to develop a predictive model to evaluate sodium carbonate content from the other properties was made. The results obtained for physical-chemical properties have shown a good consistency. However, the results of sodium carbonate analyses were not satisfactory, showing that the technique must be improved / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química

A new design of closely intermeshing co-rotating twin-screw compounding extruder, developed at Brunel University, has been utilized in the development of quantitative techniques for characterization of dispersive and distributive mixing in thermoplastics materials prepared by extrusion compounding. Image analysis procedures were used to quantify mixing of polypropylene composites containing calcium carbonate filler using reflected light microscopy on polished surfaces, and transmitted light microscopy of microtomed pigmented sections. Stereological statistics have been applied to raw sample data; results are discussed in relation to mechanistic phenomena influencing particle agglomeration, dispersion and distribution of fillers in thermoplastics. Dispersive or intensive mixing determined from calcium carbonate filled polypropylene specimens showed that processing parameters had no significant influence except when filler was added midway along the machine although the melting zone was highlighted as having a marked effect on the rate of filler dispersion. Premixing of filler and polymer introduced additional agglomeration into the filler. A series of model experiments were undertaken to assess the influence of specific parameters. In this context moisture content emerged as having the single most important effect on filler compaction. Distributive or extensive mixing of carbon black pigmented specimens was very significantly affected by the presence of segmented disc elements at the end of the screws. These elements produced more than a six-fold increase in distributive mixing in the extrudate.

Reports an investigation of the effects of chemical and physical weathering on submerged karst surfaces that pairs laboratory studies with computer modeling studies. The first study attempts to quantify the production of carbonate fines; soluble sediments produced by the incomplete dissolution of karst minerals during chemical weathering. Results show carbonate fine production in relation to dissolutional action; Chalk: 42.8%; Coquina: 2.6%; Dolomite: 3.1%; Gray Limestone: 4.8%; Ocala Limestone: 3.1%; Shell Limestone: 6.1%; Travertine: 8.6%. Due to the use of hydrochloric acid as opposed to carbonic acid these results may not be fully valid for application to natural speleogenic processes. The Limestone Weathering Model, a numerical-computer model, was developed using these experimental findings as minimal values compared with published rates. Reported as the actual volume of rock mass lost to both dissolution and to carbonate fine production, the rates for carbonate fine production ranged from 5.8% to 10.9% (year 1- 5.8%, year 2- 8.5%, year 3- 9.7%, year 4-10.3%, year 5- 10.9%), with a mean value for carbonate fine production of 9%, but a continuing rate after five years approaching 11%. The second study uses metrological laser scanning to measure the erosive loss due hydraulic shearing force and corrasion on submerged limestone surfaces. The rates for material removed using increasing velocity values (0.3m/s, 0.5m/s, 1.0m/s, 1.5m/s, 2.0 m/s, 2.5m/s) during flow durations of less than 6 minutes duration were : 1) Hydraulic shearing force- 0.3µm/s, 0.5µm/s, 0.4-1.7µm/s, 2.5 µm/s, 5.5 µm/s, 2) Corrasion- 0.3 µm/s, 0.7 µm/s, 1.5 µm/s, 1.5-1.8 µm/s, 8.9 µm/s, 8.1 µm/s. The study model was modified to return these rates for hydraulic shearing force limited by the depth of the chemical corrosion of the surface. The model returns % rock volume lost to hydraulic shearing force compared to dissolutional rate (1mm/y) for 3 flow velocities (0.03m/s<, 1.0m/s<, 2.5m/s<) on 4 timing schedules: Annual 7.8,14.3,19.6, Semiannual 21.1,21.1,69.7, Quarterly- 32.8,43.6, 70.9, Monthly- 80.0, 109.3, 200.3. Model demonstrates significant effect (7.8% to 200% over dissolutional rate) on speleogenic rates from even infrequent, moderate changes in flow velocities due to storm events. Study’s results support the significance of chemical weathering by disaggregation and physical weathering by hydraulic shearing force as major factors in the processes of karst speleogenesis.

Le bassin paléoprotérozoïque (2,1 à 2,0 Ga) de Franceville, situé au Sud-est du Gabon, est étudié depuis des décennies pour son fort potentiel métallifère (uranium et manganèse), depuis 2010, pour avoir livré les plus anciens macro-organismes multicellulaires connus à ce jour, repoussant la limite de l'apparition de la vie multicellulaire complexe à 2,1 Ga. Cette période, est synchrone de grands bouleversements ayant affectés à l'échelle du Globe la chimie de l'atmosphère et des océans et correspond à la mise en place de la formation FB de la série sédimentaire du Francevillien. C'est dans la région de Mvengué, au centre du bassin, que le stratotype de la formation FB a été initialement défini. L'objectif de cette étude est de pouvoir apporter de nouvelles informations sur les conditions de sédimentation et de diagenèse précoce de ces sédiments, et de mieux comprendre la mise en place de la sédimentation carbonatée essentiellement au sein de niveaux de black shales et d'intercalations silto-gréseuses.<br/>Dans la zone de Mvengué, les dépôts de la formation FB sont composés d'unités déposées dans un environnement marin avec des profondeurs variables en dessous de la limite d'action des vagues de tempête. On distingue les unités (1) FB1b comprenant des pélites noires, des grès intercalaires et des pélites rubanées ou dolomites litées, (2) FB1c formée par l'alternance de black shales et de grès noirs et enfin (3) FB2a caractérisée par les grès massifs ou grès de Poubara. La variabilité verticale est identique dans les différents sondages. Les analyses pétrographiques, minéralogiques et chimiques montrent que ces sédiments ont subi une diagenèse modérée. Toutefois, les effets de cette diagenèse est variable selon les faciès.<br/>Les carbonates sont associés aux black shales, de manière souvent diffuse, ils peuvent s'exprimer en lits et bancs individualisés à Mvengué, mais également en concrétions sur le site de Moanda, où elles apparaissent sur une épaisseur de 12 m intercalées dans les niveaux de black shale de l'unité FB1c. Ces concrétions, ovoïdes à lenticulaires, de taille centimétrique à décamétrique, forment des alignements au sein de 8 niveaux successifs. Quelle que soit leurs formes, leurs relations géométriques avec les lamines de l'encaissant black shale argue en faveur d'une mise en place dans un sédiment encore meuble, bien avant le début de la compaction. En se développant les concrétions ont incorporé une fraction argileuse semblable à celle de l'encaissant et dont la composition est relativement homogène depuis leur bordure externe jusqu'à leur centre. Les analyses isotopiques du carbone et de l'oxygène de la phase carbonatée et du carbone de la phase organique ainsi que les relations morphologiques et texturales indiquent que la dolomitisation ayant générée ces concrétions s'est effectuée durant les premiers stades de la diagenèse et a été favorisée par l'oxydation bactérienne de la matière organique conduisant à l'augmentation de l'alcalinité des eaux interstitielles des sédiments. / The Paleoproterozoic (2.1 to 2.0 Ga) Franceville Basin, South-east of Gabon, has been studied for decades for its high metalliferous (primarily uranium and manganese) potential. The discovery of the oldest known macro-multicellular organisms in the FB Formation in the basin in 2010 caused a repositioning of the appearance of complex multicellular life to 2.1 Ga in Earth history. This period is synchronous with great upheavals that affected the global chemistry of the atmosphere and oceans, and corresponds to the deposition of the FB Formation in the Franceville Basin. Core samples from the FB Formation were sampled from the centre of the basin (MVengué syncline) and the western flank of the basin (Moanda) for comparative analyses. The objective of this study is to provide new information on precipitation conditions of the early diagenetic carbonate cements and concretions associated with the organic-rich black shales and siltstones in the FB Formation using facies analyses, petrographic, and geochemical techniques.<br/>At the basin centre, the FB Formation is composed of sedimentary units that reflect deposition in a deep marine environment with variable depths below the limit of storm wave actions. Three units can be distinguished: (1) FB1b consisting of black shales, fine grained sandstones, and laminated mudstones or layered dolomites; (2) FB1c consisting of alternating black shales and sandstones; and (3) FB2a that is characterized by massive sandstone (namely the Poubara sandstone). Detailed analytical studies showed that these sediments have undergone moderate diagenetic modifications. However, the degree of diagenesis varies between different lithofacies.<br/>The carbonates are commonly diffused within the associated black shales throughout the FB Formation. In addition, at the Mvengué, the carbonates are present as individual beds, and as ovoid to lenticular centimeters to tens of centimeters thick concretions at Moanda, where they occur interlayering the FB1c black shales at eight levels. Irrespective of their form of occurrence, their relationships with the laminated black shale argues in favour of their formation before significant compaction. As a result, the incorporated clay minerals in the concretions are similar to the host rocks (black shales) and their composition is relatively homogenous from the edge to the centre. Isotope analyses of carbon and oxygen in the carbonates and of carbon in the organic matter, as well as the morphological and textural relationships suggest that the dolomitiation processes at the origin of the concretions, occurred during the early diagenetic stage, were favoured by bacterial oxidation of organic matter resulting in increasing pore water alkalinity in the sediments.

Through a discipline termed “comparative sedimentology”, modern carbonate depositional environments have been used extensively as analogs to aid in the interpretation of equivalent fossil systems. Using field samples, GIS and remote sensing data for three isolated carbonate platforms in the Pacific, this thesis seeks to examine relationships between grain texture and grain type and their environment of deposition. The motivation is to highlight relationships that have the potential to better understand facies relations on carbonate platforms, and thereby reduce uncertainty and increase accuracy of subsurface exploration. The results of this study show that on Raivavae, Tubuai, and Bora Bora: French Polynesia grain texture and type of collected sediment samples could be used to predict water depth and relative distance lagoonward from the reef rim with ≥ 73% and ≥ 67% accuracy, respectively. The predictive relationships; however, were largely site specific. The exception being that the same relationship between water depth and the abundance of mud and coral could be used on both Raivavae (accuracy = 81%) and Tubuai (accuracy = 78%). Additionally, the abundance of coral and Halimeda in sediment samples were able to classify samples as belonging to either the platform margin or platform interior environments on Raivavae, Tubuai, and Bora Bora with 75%, 65%, and 65% accuracy, respectively. Overall, the results of this study suggest that the abundance of coral holds potential to be utilized as a proxy for distance from the reef rim on modern and ancient isolated carbonate platforms dating back to the Miocene geological epoch.

Abstract Heat exchangers are used in industrial processes to transfer energy from one source to another. Heat exchangers improve the energy efficiency of processes and therefore increase the profitability and decrease the environmental impact of production. Effectiveness of heat exchangers may be diminished by fouling, in which unwanted material deposits on the heat transfer surface reducing the heat transfer and increasing the pressure drop of the system. Due to fouling, the energy demand, and the operation and maintenance costs of industrial processes increase significantly. In addition, fouling causes considerable environmental effects due to the increased energy demand and the use of additives and cleaning chemicals. In this thesis, the crystallization fouling of calcium carbonate on heat transfer surfaces was studied using experimental and modeling methods with the aim to reduce fouling by increasing the understanding of the crystallization fouling phenomenon and providing a validated model for studying crystallization fouling on heat transfer surfaces. The fouling experiments were conducted in a laboratory scale set-up to study the crystallization fouling mechanism under controlled conditions. Based on the knowledge and data gained from the experiments, a crystallization fouling model was developed, and validated in various conditions. As a result, the most important parameters affecting crystallization fouling were identified, and the governing sub-processes were determined. The developed model was used to optimize the surface temperature of a heat exchanger to provide the maximum heat transfer rate when the heat exchanger is subject to fouling at various cleaning intervals. In addition, the used methods were applied in the study of the abatement of fouling by surface modifications. Based on the results, the studied crystallization process is governed by the surface integration sub-process. In addition, the residence time of the fluid at the wall affects the mass deposition. The results showed that the surface temperature and the shear stress are the most important parameters affecting fouling in the studied conditions, and therefore, they should be defined accurately. For this purpose, CFD was found to provide a useful tool. The developed models were found to predict reliably the experimental conditions. Therefore, the thesis shows that the developed model facilitates the design of heat exchangers, but also assists in minimizing the fouling of heat exchangers. / Tiivistelmä Lämmönvaihtimia käytetään teollisissa prosesseissa siirtämään energiaa kohteesta toiseen. Lämmönvaihtimet parantavat prosessien energiatehokuutta ja siten lisäävät tuotannon kannattavuutta ja vähentävät ympäristövaikutuksia. Lämmönvaihdinten energiatehokkuutta heikentää kuitenkin likaantuminen, jossa lämmönsiirtopinnalle muodostuu kerrostuma, joka heikentää lämmönsiirtoa ja aiheuttaa virtausvastusta. Likaantuminen lisää lämmönvaihdinten energiankulutusta ja käyttökustannuksia sekä aiheuttaa merkittäviä ympäristöpäästöjä kasvaneen energiantarpeen sekä lisä- ja puhdistusaineiden käytön vuoksi. Tässä työssä tutkittiin kalsium karbonaatin aiheuttamaa lämmönsiirtopintojen kiteytyvää likaantumista käyttäen sekä kokeellisia että mallinnusmenetelmiä. Työn tavoitteena oli lisätä tietoa kiteytyvästä likaantumisesta sekä kehittää validoitu laskentamalli, jolla voidaan tutkia lämmönsiirtopintojen kiteytyvää likaantumista. Likaantumiskokeet tehtiin laboratoriomittakaavan koelaitteessa, jolla voidaan tutkia likaantumismekanismia hallituissa olosuhteissa. Kokeista saadun tiedon ja aineiston perusteella kehitettiin kiteytyvää likaantumista kuvaava malli, joka validoitiin eri olosuhteissa. Tulosten perusteella identifioitiin tärkeimmät kiteytyvään likaantumiseen vaikuttavat parametrit sekä määritettiin rajoittavat osa-prosessit. Kehitettyä mallia käytettiin lämmönsiirtoprosessin optimoinnissa. Lisäksi käytettyjä metodeja sovellettiin tutkimukseen, jossa likaantumista pyrittiin vähentämään pintamodifikaatioiden avulla. Tulosten perusteella tutkittu kiteytymisprosessi on pinta-integraation rajoittama. Lisäksi havaittiin, että fluidin viipymäaika lämmönsiirtopinnalla vaikuttaa likaantumisnopeuteen. Tulokset osoittivat, että pintalämpötila ja leikkausjännitys ovat tärkeimmät kiteytyvään likaantumiseen vaikuttavat tekijät tutkituissa olosuhteissa. Näin ollen niiden tarkka määrittely on erittäin tärkeää likaantumisnopeuden mallintamiseksi luotettavasti. Virtauslaskenta (CFD) osoittautui hyödylliseksi työkaluksi näiden parametrien määrittämisessä. Tulosten perusteella kehitetty malli ennustaa luotettavasti kokeellisia olosuhteita. Näin ollen tämä työ osoittaa, että kehitettyä mallia voidaan käyttää apuna paitsi lämmönvaihtimien suunnittelussa myös lämmönsiirtopintojen kiteytyvän likaantumisen vähentämisessä.

Vor dem Hintergrund des steigenden Lithiumbedarfs und der Ungleichverteilung der weltweiten Lithiumvorkommen gilt es auch, kleinere, heimische Vorkommen, wie die Zinnwalditlagerstätte bei Zinnwald/Cínovec, für eine mögliche Lithiumgewinnung zu untersuchen. Hierfür wurden zur Darstellung von Lithiumcarbonat zwei Verfahren entwickelt, optimiert und ökonomisch bewertet. Dabei konnte gezeigt werden, dass insbesondere das Direktcarbonatisierungsverfahren mit überkritischem CO2 aufgrund des geringen Chemikalienverbrauchs, der hohen Selektivität für Lithium, als auch dem breiten Anwendungsspektrum für weitere primäre und sekundäre Lithiumressourcen ein vielversprechender Ansatz für eine technische Umsetzung darstellt. Des Weiteren wurde die elektrodialytische Darstellung von Lithiumhydroxid untersucht und optimiert. Mittels einer erstellten Simulation wurden hierfür nicht nur Anforderungen an prozessierbare Ausgangslösungen definiert, sondern auch ein Aufbau zur Erhöhung der Prozessstabilität entwickelt, der eine kontinuierliche Filtration eines oder mehrerer Kreisläufe der Elektrodialyse erlaubt.

Avec l’augmentation de la pression de confinement, le comportement mécanique des calcairespasse d’un comportement fragile à un comportement ductile. Le régime fragile estcaractérisé par une compaction élastique suivie d’une dilatance macroscopique due à despropagations de fissures. Lorsque les fissures coalescent, la rupturemacroscopique est reliéeà une chute de contrainte. Le régime ductile est caractérisé par une compaction élastiquesuivie d’une déformation macroscopique diffuse. La déformation est accommodée par uneplasticité intracristalline (dislocations, macles) et/ou une fracturation des grains. L’objectif decette thèse est d’examiner expérimentalement les paramètres influant sur le comportementmécanique des calcaires de porosité intermédiaire et de modéliser ce comportement. Lesexpériences ont été réalisées sur le calcaire de Tavel (porosité de 14.7%). / The mechanical behaviour of limestones is brittle at low confining pressure and becomesductile with the increase of the confining pressure. The brittle behaviour is characterisedby a macroscopic dilatancy due to crack propagation, leading to a stress drop when crackscoalesce at failure. The ductile behaviour is characterised by a a diffuse deformation due tointra-crystalline plasticity (dislocation movements and twinning) and microcracking. The aimof this work is to examine the influence of temperature, pore fluid, strain rate, and time onthe mechanical behaviour. Triaxial deformation experiments were performed on white Tavellimestone (porosity 14.7%). The macroscopic behaviour is then modelled.Constant strain rate triaxial deformation experiments and stress-stepping creep experimentswere performed. Elastic wave velocities were inverted in term of axial crack densities. Themechanical behaviour is brittle for constant strain rate deformation experiments performed atPc · 55 MPa. In this case, inelastic deformation is due to cracks propagation. For Pc ¸ 70 MPa,elastic compaction is followed by an inelastic compaction. Porosity collapse is due to intracrystallineplasticity and micro-cracking. After some inelastic compaction, volumetric strainturns to dilatancy because crack nucleate at dislocation pile-ups and their contribution to thestrain becomes predominant compared to plastic pore collapse. In the brittle regime, watersaturationdecreases the differential stress at the onset of crack propagation and enhancesmacroscopic dilatancy. Temperature decreases the confining pressure at the brittle-semibrittle(ductile) transition. A model describing the macroscopic behaviour is derived from (1) a crackpropagation law, (2) a plasticity law for a porous medium, and (3) a law for nucleation of newscracks due to local dislocation pile-ups. The model predicts the volumetric strain, the stresstensor, and the evolution of damage, as a function of applied deformation. Theoretical resultsare in good agreement with experimental observations.

M.Sc. / Certain carbonate bearing formations in the Paleoproterozoic Pretoria Group and its Griqualand West equivalent exhibit remarkable geochemical and stable isotopic signatures. The 8'3Ccarb isotopic signatures from the Duitschland and Silverton Formations exhibit large positive excursions, which seemingly coincide with a significant increase in atmospheric oxygen between 2.4 and 2.0 Ga. The Duitschland Formation with its distinctive basal unconformity is composed primarily of limestone and dolomite units, interbedded with two compositionally different shale units and quartzite. Toward the base of the formation there is a distinct conglomeratic quartzite which forms a sequence boundary above which isotopic and geochemical signatures change dramatically. Normal marine isotopic signatures characterize the lower portion of the succession while above the sequence boundari, the carbonates are enriched in "C. This enrichment, however, appears to be the result of local processes occurring within a closed basin. Furthermore it is apparent that the Duitschland Formation (with its three distinct marker beds) is the equivalent of the Rooihoogte Formation and therefore constitutes the base of the Pretoria Group. The Mooidraai Dolomite Formation which outcrops only locally in the Northern Cape Province, is characterized by fenestral and microbially laminated dolomite. The geochemical properties are relatively homogeneous with increases in the FeO and MnO concentrations, resulting from post depositional diagenesis. The stable isotope signatures of these dolomites represent normal marine signatures. There is, however, a depletion in the 813C and 8180 signatures in the ankeritic and sideritic lithofacies, which suggests that this succession was deposited from a stratified water column with respect to the total dissolved CO2. The positive 6 13C excursion present in the carbonates of the Lucknow Formation in Griqualand West, traditionally grouped with the Olifantshoek Group can be correlated with carbonates near the top of the Silverton Formation in the Transvaal area. The latter also displays distinctly positive 6 43C values. One possibility is that if these successions were deposited in closed anoxic basins and that the isotopic anomalies are the result of local processes such as fermentive diagenesis and methanogenesis. However, the close association of the carbonates with shallow marine orthoquartzites suggests that these were deposited in an open marine system and that the positive 8 !3C values reflect a shift in the composition of the ocean water at the time of deposition of the carbonates at 2.2 Ga. Other carbonates present in the Pretoria Group, namely from the Vermont and Houtenbek Formations, display normal open marine 8' 3C values of close to zero. A systematic stratigraphic compilation of all 6 43C values available from the Transvaal Supergroup indicates that two clear-cut positive 5' 3C excursions are present. These excursions were apparently short-lived and well defined and did not occur over an extended period of time as suggested by earlier studies based on global compilations with large uncertainties in radiometric ages of deposits.