Dans cette thèse, nous nous sommes intéressés aux systèmes intelligents pour des applicationsmédicales et cosmétiques. Ainsi, nous avons conçu et réalisé trois instruments. Le premier estdédié à la mesure de la mouillabilité de la peau. L’originalité de ce dispositif réside en sa capacité àdonner une image 3D de la goûte de la surface de la peau explorée et de donner le comportementdynamique de la goûte. Cette stratégie nous donnera la possibilité de créer de nouvelles basesde données relatives à la mouillabilité de tout le corps humain. En effet, nous disposons que desdonnées sur la mouillabilité de l’avant-bras. Le deuxième instrument intelligent concerne la mesurede la réflectance d’une surface. Ce dispositif assure une mesure de très haute résolution angulairede la BRDF et une très bonne répétabilité de la mesure. Il a été validé sur la peau pour la mesurede l’ éclat. Et enfin le troisième instrument, basé sur une méthode originale de mesure de vibrationà l’aide d’un système de stéréo-vision associée à un motif périodique. Il a été appliqué pour lamesure du mouvement thoracique et abdominal lors de la respiration. Notre principale motivationpour développer ce système fut la réduction des artefacts, dus aux mouvements d’un patient lorsd’un examen radiologique. / Smart Devices have been widely used by health care and cosmetics professionals. Indeed, they helpin many aspects of clinical practice by providing an efficient way for medical diagnosis, supportingbetter clinical decision-making and improving patient outcomes. In this thesis, we have beeninterested in three applications. The first one is related to the wettability measurement, especially forthe human skin. So we propose, a held-hand device that is based on the contact angle measurementto determine skin wettability. Besides, the device allows the visualization of the liquid dropletspreading in both dynamic and static modes. Moreover, it can measure the top and the left views ofthe droplet and provides the 3D droplet and the skin explored area profiles. The second applicationpermits the skin radiance measurement. For this purpose, we propose a miniaturized device havingan original method for the BRDF measurement associated with 3D profile measurement of the areastudied. As regards the third application, it is a non-invasive method for breath measurement that usesa stereovision system and a pseudo-periodic pattern. This system allows a high-resolution threedimensionaldisplacement measurement for the recording of the thoracoabdominal wall respiratorymovement. The devices developed during this research gives us a high accuracy, a good resolutionand repeatability of measurements.

O objetivo do presente trabalho foi caracterizar as propriedades superficiais de filmes à base de gelatina. Para o qual foram elaborados filmes de: (i) Gelatina plastificado com glicerol (G) (gelatina: 5 g/100 g SFF; glicerol: 30 g/100 g de gelatina), (ii) Gelatina reforçado com montmorilhonita (G/MMT) (gelatina: 5 g/100 g SFF; glicerol: 30 g/100 g de gelatina; MMT: 5 g/100 g de gelatina) e Gelatina plastificado com citrato de acetiltributila (G/ATB) (gelatina: 5 g/100 g SFF; ATB: 50 g/100 de gelatina; lecitina de soja: 60 g/100 g de ATB; etanol: 20 g/100 g SFF). Os filmes foram produzidos mediante o uso de um aplicador automático de filmes \"Spreading\". Logo, os filmes foram submetidos a testes para determinação da espessura, umidade e propriedades óticas (brilho, cor e opacidade). Também foi caracterizada a microestrutura por microscopia eletrônica de varredura (MEV) e microscopia de força atômica (AFM); às imagens obtidas por MEV foi aplicado um analise de imagem mediante o programa Image J, para obter o valor da dimensão fractal (DF). Depois foram caracterizadas as propriedades superficiais de ângulo de contato (AC), molhabilidade ou coeficiente de espalhamento (Se), e energia livre superficial (ELS) mediante a medida do ângulo de contato pelo método da gota séssil (água: 5 µL e 1-Bromonaftaleno: 3 µL). Para o cálculo da ELS também foi aplicado o método de Owens-Wendt. Estas caracterizações foram feitas em ambos os lados do filme, lado ar e lado placa. A natureza do filme de G/ATB influenciou na umidade e as propriedades óticas, enquanto que os filmes de G e G/MMT apresentaram características similares. Em relação à microestrutura e rugosidade, o filme de G apresentou a superfície mais homogênea e lisa, contrario ao observado no filme de G/MMT, que apresentou a maior rugosidade seguida do filme de G/ATB. Foi observado que houve uma relação entre os valores de rugosidade e DF. De acordo com o valor do AC, os filmes apresentaram um caráter hidrofóbico, pois seus valores foram superiores a 65° (em ambos os lados dos filmes), na seguinte ordem: G/MMT > G > G/ATB; sendo que o Se seguiu a mesma tendência. Cabe mencionar também que não foi encontrada uma correlação significativa entre os valores de AC e rugosidade. Em função dos valores de AC, Se e ELS (especificamente a componente polar), o filme de G/ATB apresentou o menor caráter hidrofóbico, pois apresentou menores valores de AC e maiores valores de Se em comparação com os outros dois filmes. Os valores da componente polar da G/ATB foram os maiores, explicando de melhor maneira o caráter menos hidrofóbico deste filme. Pode-se concluir que os filmes à base de gelatina elaborados no presente trabalho têm propriedades hidrofóbicas (AC>65°), sendo a G/MMT o filme com melhores características hidrofóbicas. / The aim of this study was to characterize the surface properties of gelatin-based films. For which, films were produced as following: gelatin plasticized with glycerol (gelatin: 5 g/100 g SFF; glycerol: 30 g/100 g of gelatin), gelatin reinforced with montmorillonite (gelatin: 5 g/100 g SFF; glycerol: 30 g/100 of gelatin; montmorillonite: 5 g/100 g of gelatin), and gelatin plasticized with acetyltributyl citrate (gelatin: 5 g/100 g SFF; acetyltributyl citrate: 50 g/100 of gelatin, soy lecithin: 60 g/100 g acetyltributyl citrate; ethanol: 20 g/100 g SFF). The films were produced by using an automatic film applicator \"Spreading\". Then, the films were tested for determining thickness, humidity and optical property (gloss, color and opacity). Also the microstructure was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM); in the images obtained by SEM it was applied image analysis using Image J program, to get the value of the fractal dimension (FD). After, the surface properties of contact angle (CA), wettability or spreading coefficient (Cs) and surface free energy (SFE) were characterized by measuring the contact angle by the method of the sessile drop (water: 5 µL, 1-Bromonaphthalene: 3 µL). For the calculation of the ELS, it was also applied the method of Owens-Wendt. These characterizations were made on both sides of the film (air side and plate side). The nature of the G/ATB film influenced the moisture and optical properties, while the films of G and G/MMT showed similar values. With regard to microstructure and roughness, the G film presented a more homogeneous and smooth surface, contrary to that was observed in films of G/MMT, who presented the highest roughness followed by G/ATB film. It was observed that there was a relationship between the roughness values and DF. According to the value of the CA, the three films had a hydrophobic character, because their values were above 65° (on both sides of the film), in the following order: G/MMT > G > G/ATB; the Cs followed the same trend. It should be also mentioned that a significant correlation between the values of CA and the roughness was found. According to the values of CA, Cs and SFE (specifically the polar component), the films of G/ATB had the lowest hydrophobicity, because had lower CA values and higher Cs values, as compared to the other two films. The values of the polar component of the film G/ATB were higher, which explains better the less hydrophobic character of this film. It can be concluded that the gelatin-based films produced in this work have hydrophobic properties (CA>65°), being the film G/MMT which showed better hydrophobic characteristics.

Many of Brazil\'s pre-salt basins are located in ultra-deep waters, and the high heterogeneities of its offshore carbonate reservoirs make the extraction of representative rock samples difficult, risky and expensive. Synthetic plugs are required to understand oilfield properties and the behavior of oil in reservoirs where natural plugs cannot be extracted. Specifically, in cases where it is necessary to reproduce representative mineralogical and petrophysical characteristics from carbonates reservoir, it is evident that there are a lack of publications focusing on synthetic plug construction. In this work, the construction of synthetic plugs is studied, using a combination of published methodologies to achieve an alternative construction of synthetic carbonate plugs for laboratory scale studies. The obtained plugs used a procedure based on disintegrated rock matrices with known particle sizes and particle size ratio, uniaxial compaction with controlled load force and velocity, CaCO3 solubility control by changing temperature and pH and bonding material. Consolidation, wettability and petrophysical properties of the synthetic plugs were evaluated to characterize them. Generally, it was observed that the porosity and permeability features of the synthetic plugs were within the range of carbonate reservoirs. However, without reproducing a heterogeneous pore structure normally present in natural samples. On the other hand, wettability properties of the resulted synthetic plugs were similar to the natural carbonate plugs. Further studies are necessary to obtain more similar chemical and petrophysical properties to the natural samples. / A localização em águas ultra profundas das reservas petrolíferas do pré-sal brasileiro e a alta heterogeneidade dos seus reservatórios carbonáticos dificultam a aquisição de uma amostra de rocha representativa, além de ser uma operação de risco e de alto dispêndio. Plugues sintéticos são utilizados para compreensão das propriedades dos campos petrolíferos e para avaliação do comportamento dos hidrocarbonetos em reservatórios onde plugues reais não podem ser adquiridos. Especificamente, nos casos onde são necessários reproduzir características representativas mineralógicas e petrofísicas dos reservatórios carbonáticos, sendo notório a falta de publicações voltada para construção de plugues sintéticos. No presente trabalho, estudou-se a construção de plugues sintéticos empregando metodologias já difundidas, visando a construção de plugues carbonáticos sintéticos para utilização em escala laboratorial. Os plugues obtidos foram construídos utilizando matrizes de rochas desintegradas com tamanhos e proporções de partículas conhecidos, compactação uniaxial com força e velocidades controladas e controle de solubilidade de CaCO3, variando apenas temperatura, pH e proporções de material cimentante. Foram avaliadas as propriedades petrofísicas, a molhabilidade e a consolidação dos plugues sintéticos para posterior caracterização dos mesmos. Comumente, observou-se que os valores de porosidade e permeabilidade dos plugues sintéticos se encontravam dentro do intervalo de valores obtidos em reservatórios carbonáticos reais. No entanto, não reproduziram a estrutura heterogênea dos poros, normalmente presente em amostras de rochas naturais. Em contrapartida, as propriedades de molhabilidade dos plugues sintéticos se apresentaram análogas aos plugues de rochas carbonáticas naturais. Estudos complementares são necessários para obtenção de propriedades químicas e petrofísicas mais próximas das amostras reais.

A project studied wetting of iron, nickel and platinum by molten MnO-SiO2 (MS) and CaO-Al2O3-SiO2 (CAS) slags of eutectic composition to contribute to understanding of wetting behaviour of solid metal-molten oxide systems relevant to steelmaking. Novel results of dynamic wetting behaviour by the sessile drop method were obtained under strongly reducing atmosphere (oxygen partial pressure 10-20 -- 10-18 atm). Terminal contact angles (after 240 min) for MS slag were: for iron substrates -5??2??(1350??C), 9+-2?? (1390??C), 6+-2 (1450??C); nickel -- 3+-2??(1350 and 1390??C); and platinum --15+-2??(1350 and 1390??C), 12+-2??(1450??C). Contact angles with CAS slag were: iron -- 55+-2??(1350??C), 60+-2?? (1390??C), 44+-2?? (1450??C); nickel -- 59+-2??(1350??C), 60+-2?? (1390??C); and platinum -- 15+-2?? (1350, 1390 and 1450??C). Values for interfacial tension, work of adhesion, spreading parameter (S) and interaction coefficient (Ф) were also determined. Work of adhesion for all three substrates with MS slag changed in a very narrow range 910 - 930 mJ/m2. Interfacial tension with this slag was 1,480 mN/m for Ni at 1350-1390??C, and 1,880-1,890 mN/m for Pt in the temperature range 1,350-1,450??C. For iron, interfacial tension was 1,720 mN/m at 1350??C (γ-Fe); it decreased to 1590-1580 mN/m with increasing temperature to 1390 and 1450??C (-Fe). Lower work of adhesion and higher interfacial tension was found for metals with CAS slag. Wetting properties of Pt substrate with MS slag were close to that with CAS slag, while Fe and Ni substrates showed better wetting by MS slag in comparison with CAS slag. This was attributed to higher reactivity of Fe and Ni with MS slag, particularly reduction of MnO. Although MnO was also reduced in reaction with Pt, oxygen adsorption in contact with both slags was a major factor governing wettability of Pt. Dissolution of manganese in nickel and platinum substrates at elevated temperatures modified the interface chemistry, causing formation of a liquid alloy phase. Degree of silica reduction from MS slag was much smaller in comparison with MnO reduction (negligible for Pt); it was very minor from CAS slag. Concentration profiles of Mn and Si across the interface and along the metal surface were used to estimate diffusion coefficients. Diffusion along metal surfaces was generally higher by 1 to 2 orders of magnitude than across the interface. Reduction of oxides and adsorption of oxygen modify the metal-oxide interface, making wetting dynamic. They have a profound on interfacial properties.

The interaction at the surfaces of load bearing implant biomaterials with tissues and physiological fluids is an area of crucial importance to all kinds of medical technologies. To achieve the best clinical outcome and restore the function of the diseased tissue, several surface engineering strategies have been discussed by scientific community throughout the world. In the current work, we are focusing on one such technique based on laser surface engineering to achieve the appropriate surface morphology and surface chemistry. Here by using a pulsed and continuous wave laser direct melting techniques we synthesize three dimensional textured surfaces of calcium phosphate (Ca-P) based surface chemistry on Ti-6Al-4V. The influence of each processing type on the micro texture and phase evolution and thereby its associated effect on wettability, in vitro bioactivity, and in vitro biocompatibility are systematically discussed. For samples processed using the pulsed laser, it was realized that with increasing laser scan speed and laser pulse frequency there was a transition from surface textures with sharp circular grooves to surface textures with radial grooves and thereby improved hydrophilicity. For CW laser processing the results demonstrated improved hydrophilicity for the samples processed at 100 μm line spacing as compared to the samples processed at 200 μm line spacing. Owing to the importance of Si for cartilage and hard tissue repair, a preliminary effort for synthesizing Ca-P-SiO2 composite coating on Ti-6Al-4V surface were also conducted. As a future potential technique we also explored the Laser Interference Patterning (LIP) technique to achieve the textured surfaces and developed understanding on their wetting behavior. In the current work, by adjusting the laser processing parameters we were able to synthesize textured coatings with biocompatible phases. The in vitro bioactivity and in vitro vi biocompatibility of the coatings were proved by the precipitation of an apatite like phase following immersion in simulated body fluid (SBF), and increased proliferation and spreading of the MC3T3-E1 like cells. The results and understanding of the current research is encouraging in terms of looking at other bio-ceramic precursor compositions and laser process parameter window for synthesizing better textured biocompatible coatings.

This thesis examines the formation of Polyelectrolyte Multilayers (PEM) on cellulose fibres as a new way of influencing the fibre surface and the adhesion between wood fibres. The aim of the study was to enhance the fundamental understanding of the adsorption mechanisms behind the formation of Polyelectrolyte Multilayers on cellulose fibres; to study how the properties of the layers can be influenced and to show how the properties of the layers influence the adhesion between the fibres and the strength of paper sheets made from the PEM treated fibres. Different polyelectrolyte systems are known to form PEMs with different properties, and in this work two different polymer systems were extensively studied: poly(dimethyldiallylammonium chloride) (PDADMAC) / poly(styrene sulphonate) (PSS), which are both strong polylectrolytes (i.e. are highly charged over a wide range of pH) and poly allylaminehydrochloride (PAH) /poly acrylic acid (PAA), which are both weak polyelectorlytes (i.e. sensitive to pH changes). PEMs were also formed from PAH/ poly(3,4-ethylenedioxythiophene):PSS (PEDOT:PSS), in order to form electrically conducting PEMs on fibres and PEM-like structures were formed from polyethylene oxide (PEO) and polyacrylic acid (PAA). In order to study the influence of the PEM on adhesion and paper strength, fibres were treated and used to form sheets which were physically tested according to determine the tensile index and strain at break. Both these systems were studied using different molecular mass fractions. High molecular mass PDADMAC/PSS (>500k/1000k) had a significantly greater influence as a function of the number of layers than low molecular mass PDADMAC/PSS (30k/80k). In contrast, sheets made from high molecular mass PAH/PAA (70k/240k) showed a significantly lower increase in strength than sheets made from low molecular PAH/PAA investigated earlier. Both these systems had a greater influence on paper strength when the cationic polyelectrolyte was adsorbed in the outermost layer. The amount of polyelectrolytes adsorbed on the fibres was determined using polylectrolyte titration (PET) and destructive analytical methods. Adsorption to model surfaces of silicon oxide was studied before the adsorption on fibres, in order to understand the influence on PEM properties of parameters such as salt concentration and adsorption time. Adhesion studies of surfaces coated with PAH/PAA using AFM, showed an increase in adhesion as a function of the number of adsorbed layers. The adhesion was higher when PAH was adsorbed in the outermost layers. Individual fibres were also partly treated using a Dynamic Contact Angle analyser (DCA) and were studied with regard to their wettability. In general, the wettability was lower when the cationic polymer was outermost. The level of adhesion and paper strength are discussed in terms of rigidity and wettability and the PEMs demonstrating a large number of free chain ends, a large chain mobility and a low wettability was found to have the greatest influence to adhesion and paper strength. / QC 20100823

The transport of components and phases plays a fundamental role in the success of an EOR process. Because many reservoirs have harsh conditions of salinity, temperature and rock heterogeneity, which limit process options, a robust system with flexibility is required. Systematic experimental study of formulations capable to transport surfactant as foam at 94°C, formulated in sea water, is presented. It includes methodology to conduct core floods in sand packs using foaming surfactants and to develop “surfactant blend ratio- salinity ratio maps” using equilibrium phase behavior to determine favorable conditions for oil recovery in such floods. Mathematical model able to reproduce the foam strength behavior observed in sand packs with the formulations studied is presented. Visualization of oil recovery mechanism from matrix is realized using a model system of micro-channels surrounded by glass beads to mimic matrix and fractures respectively. The observations illustrate how components may distribute within the matrix, thereby releasing oil into the fractures. The use of chemicals to minimize adsorption is required when surfactant adsorption is important. The presence of anhydrite may limit the use of sodium carbonate to reduce adsorption of carbonates. A methodology is presented to estimate the amount, if any, of anhydrite present in the reservoir. The method is based on brine software analysis of produced water compositions and inductively coupled plasma (ICP) analysis of core samples. X-ray powder diffraction (XRD) was used to verify the mineralogy of the rock. X-ray photoelectron spectroscopy (XPS) was used to obtain surface composition for comparison with bulk composition of the rock. Adsorption of surfactants was measured using dynamic and static adsorption experiments. Determining the flow properties of the rock samples via tracer analysis permitted the simulation of the dynamic adsorption process using a mathematical model that considers the distribution of adsorbed materials in the three different regions of pore space. Using this method allows one to predict adsorption in a reservoir via simulation.

Water-flooding in water-wet fractured reservoirs can recover significant amounts of oil through capillary driven imbibition. Unfortunately, many of the fractured reservoirs are mixed-wet/oil-wet and water-flooding leads to poor recovery as the capillary forces hinder imbibition. Surfactant injection and immiscible gas injection are two possible processes to improve recovery from fractured oil-wet reservoirs. In both these EOR methods, the gravity is the main driving force for oil recovery. Surfactant has been recommended and shown a great potential to improve oil recovery from oil-wet cores in the laboratory. To scale the results to field applications, the physics controlling the imbibition of surfactant solution and the scaling rules needs to be understood. The standard experiments for testing imbibition of surfactant solution involves an imbibition cell, where the core is placed in the surfactant solution and the recovery is measured versus time. Although these experiments prove the effectiveness of surfactants, little insight into the physics of the problem is achieved. This dissertation provides new core scale and pore scale information on imbibition of anionic surfactant solution into oil-wet porous media. In core scale, surfactant flooding into oil-wet fractured cores is performed and the imbibition of the surfactant solution into the core is monitored using X-ray computerized tomography(CT). The surfactant solution used is a mixture of several different surfactants and a co-solvent tailored to produce ultra-low interfacial tension (IFT) for the specific oil used in the study. From the CT images during surfactant flooding, the average penetration depth and the water saturation versus height and time is calculated. Cores of various sizes are used to better understand the effect of block dimension on imbibition behavior. The experimental results show that the brine injection into fractured oil-wet core only recovers oil present in the fracture; When the surfactant solution is injected, the CT images show the imbibition of surfactant solution into the matrix and increase in oil recovery. The surfactant solution imbibes as a front. The imbibition takes place both from the bottom and the sides of the core. The highest imbibition is observed close to the bottom of the core. The imbibition from the side decreases with height and lowest imbibition is observed close to the top of the core. Experiments with cores of different sizes show that increase in either the length or the diameter of the core causes decrease in the fractional recovery rate (%OOIP). Numerical simulation is also used to determine the physics that controls the imbibition profiles. %The numerical simulations show that the relative permeability curves strongly affect the imbibition profiles and should be well understood to accurately model the process. Both experimental and numerical simulation results imply that the gravity is the main driving force for the imbibition process. The traditional scaling group for gravity dominated imbibition only includes the length of the core to upscale the recovery for cores of different sizes. However based on the measurements and simulation results from this study, a new scaling group is proposed that includes both the diameter and the length of the core. It is shown that the new scaling group scales the recovery curves from this study better than the traditional scaling group. In field scale, the new scaling group predicts that the recovery from fractured oil-wet reservoirs by surfactant injection scales by both the vertical and horizontal fracture spacing. In addition to core scale experiments, capillary tube experiments are also performed. In these experiments, the displacement of oil by anionic surfactant solutions in oil-wet horizontal capillary tubes is studied. The position of the oil-aqueous phase interface is recorded with time. Several experimental parameters including the capillary tube radius and surfactant solution viscosity are varied to study their effect on the interface speed. Two different models are used to predict the oil-aqueous phase interface position with time. In the first model, it is assumed that the IFT is constant and ultra-low throughout the experiments. The second model involves change of wettability and IFT by adsorption of surfactant molecules to the oil-water interface and the solid surface. Comparing the predictions to the experimental results, it is observed that the second model provides a better match, especially for smaller capillary tubes. The model is then used to predict the imbibition rate for very small capillary tubes, which have equivalent permeability close to oil reservoirs. The results show that the oil displacement rate is limited by the rate of diffusion of surfactant molecules to the interface. In addition to surfactant flooding, immiscible gas injection can also improve recovery from fractured oil-wet reservoirs. In this process, the injected gas drains the oil in the matrix by gravity forces. Gravity drainage of oil with gas is an efficient recovery method in strongly water-wet reservoirs and yields very low residual oil saturations. However, many of the oil-producing fractured reservoirs are not strongly water-wet. Thus, predicting the profiles and ultimate recovery for mixed and oil-wet media is essential to design and optimization of improved recovery methods based on three-phase gravity drainage. In this dissertation, we provide the results from two- and three-phase gravity drainage experiments in sand-packed columns with varying wettability. The results show that the residual oil saturation from three-phase gravity drainage increases with increase in the fraction of oil-wet sand. A simple method is proposed for predicting the three-phase equilibrium saturation profiles as a function of wettability. In each case, the three-phase results were compared to the predictions from two-phase results of the same wettability. It is found that the gas/oil and oil/water transition levels can be predicted from pressure continuity arguments and the two-phase data. The predictions of three-phase saturations work well for the water-wet media, but become progressively worse with increasing oil-wet fraction. / text

Successful field waterflood is a crucial prerequisite for improving the performance before EOR methods, such as ASP, SP, and P flooding, are applied in the field. Excess water production is a major problem in mature waterflooded oil fields that leads to early well abandonment and unrecoverable hydrocarbon. Gel treatments at the injection and production wells to preferentially plug the thief zones are cost-effective methods to improve sweep efficiency in reservoirs and reduce excess water production during hydrocarbon recovery. There are extensive experimental studies performed by some researchers in the past to investigate the performance of gels in conformance control and decreasing water production in mature waterflooded reservoirs, but no substantial modeling work has been done to simulate these experiments and predict the results for large field cases. We developed a novel, 3-dimensional chemical compositional and robust general reservoir simulator (UTGEL) to model gel treatment processes. The simulator has the capability to model different types of microgels, such as preformed particle gels (PPG), thermally active polymers (TAP), pH-sensitive microgels, and colloidal dispersion gels (CDG). The simulator has been validated for gel flooding using laboratory and field scale data. The simulator helps to design and optimize the flowing gel injection for conformance control processes in larger field cases. The gel rheology, adsorption, resistance factor and residual resistance factor with salinity effect, gel viscosity, gel kinetics, and swelling ratio were implemented in UTGEL. Several simulation case studies in fractured and heterogeneous reservoirs were performed to illustrate the effect of gel on production behavior and water control. Laboratory results of homogeneous and heterogeneous sandpacks, and Berea sandstone corefloods were used to validate the PPG transport models. Simulations of different heterogeneous field cases were performed and the results showed that PPG can improve the oil recovery by 5-10% OOIP compared to waterflood. For recovery from fractured reservoirs by waterflooding, injected water will flow easily through fractures and most part of reservoir oil will remain in matrix blocks unrecovered. Recovery from these reservoirs depends on matrix permeability, wettability, fracture intensity, temperature, pressure, and fluid properties. Chemical processes such as polymer flooding (P), surfactant/polymer (SP) flooding and alkali/surfactant/polymer (ASP) flooding are being used to enhance reservoir energy and increase the recovery. Chemical flooding has much broader range of applicability than in the past. These include high temperature reservoirs, formations with extreme salinity and hardness, naturally fractured carbonates, and sandstone reservoirs with heavy and viscous crude oils. The recovery from fractured carbonate reservoirs is frequently considered to be dominated by spontaneous imbibition. Therefore, any chemical process which can enhance the rate of imbibition has to be studied carefully. Wettability alteration using chemicals such as surfactant and alkali has been studied by many researchers in the past years and is recognized as one of the most effective recovery methods in fractured carbonate reservoirs. Injected surfactant will alter the wettability of matrix blocks from oil-wet to water-wet and also reduce the interfacial tension to ultra-low values and consequently more oil will be recovered by spontaneous co-current or counter-current imbibition depending on the dominant recovery mechanism. Accurate and reliable up-scaling of chemical enhanced oil recovery processes (CEOR) are among the most important issues in reservoir simulation. The important challenges in up-scaling CEOR processes are predictability of developed dimensionless numbers and also considering all the required mechanisms including wettability alteration and interfacial tension reduction. Thus, developing new dimensionless numbers with improved predictability at larger scales is of utmost importance in CEOR processes. There are some scaling groups developed in the past for either imbibition or coreflood experiments but none of them were predictive because all the physics related to chemical EOR processes (interfacial tension reduction and wettability alteration) were not included. Furthermore, most of commercial reservoir simulators do not have the capability to model imbibition tests due to lack of some physics, such as surfactant molecular diffusion. The modeling of imbibition cell tests can aid to understand the mechanisms behind wettability alteration and consequently aid in up-scaling the process. Also, modeling coreflood experiments for fractured vuggy carbonates is challenging. Different approaches of random permeability distribution and explicit fractures were used to model the experiments which demonstrate the validity and ranges of applicability of upscaled procedures, and also indicate the importance of viscous and capillary forces in larger scales. The simulation models were then used to predict the recovery response times for larger cores.

Despite many excellent properties of wood which make it suitable for many applications, it suffers from a number of disadvantages limiting its use. For instance, modification is needed to reduce water sorption and to improve decay resistance, dimensional stability and weathering performance. In addition, wood/liquid interaction such as water wettability on wood plays an important role in design and characteristics of many processes and phenomena such as adhesion, coating, waterproofing, wood chemical modification, and weathering. This thesis focuses on enhancing the understanding of wetting of wood, with emphasis on modified wood. The influence of surface chemical composition of wood and its microstructural characteristics on wetting and swelling properties has also been studied. A multicycle Wilhelmy plate technique has been developed to evaluate wetting properties of porous materials, such as wood, in which the samples were subjected to repeated immersions and withdrawals in a swelling liquid (water) and in a non-swelling liquid (octane). This method was utilized to dynamically investigate contact angle, sorption and swelling properties, as well as dimensional stability of unmodified, chemically and surface modified wood samples. Scots pine sapwood and heartwood samples were utilized to establish the principles of the technique. Acetylated and furfurylated wood samples with different level of modification were thereafter examined utilizing the developed technique for wetting measurements. A perimeter model based on a linear combination of the measured force and final change in sample perimeter was suggested to evaluate the dynamic dimensional stability of wood veneers. The feasibility of this method for studying dynamic wettability was investigated by measuring the changes of advancing and receding contact angles over repeated cycles on surface modified wood samples, created by combining liquid flame spray and plasma polymerisation methods. X-ray photoelectron spectroscopy (XPS) and X-ray computed tomography (XCT) were employed to study the surface chemical composition and microstructural properties of the samples, respectively. Three different kinetic regimes were observed in the wetting measurements: i) fast wetting and spreading of the liquid on the wood surface, ii) void filling and wicking and iii) swelling, which was the slowest of the three. The multicycle Wilhelmy plate method was found to be suitable for studying liquid penetration, sorption, and dimensional stability of swelling materials. The results demonstrate that the wetting properties of wood are highly affected by surface chemistry and microstructure. It was shown that using both swelling and non-swelling liquids in wetting measurements allow to distinguish between capillary liquid uptake and swelling. Based on this, for chemically modified samples, it was demonstrated that acetylation mostly reduces swelling, while furfurylation reduces both swelling and capillary uptake. This is in line with the microstructural study with X-ray computed tomography where a significant change in the porosity was found as a result of furfurylation, conversely acetylation left the total porosity values unchanged. Wetting results for hydrophobised wood samples demonstrate that the multi-scale roughness obtained by combination of nanoparticle coating and plasma polymerization increased both the hydrophobicity and the forced wetting durability compared to the micro-scale roughness found on wood modified with plasma polymerisation alone. / <p>QC 20151029</p> / Sustainable wood modification