La stabilité optique nonlinéaire du colorant (Disperse red 1) dopé dans différent polymères amorphes préparés par spin-coating ou incorporé dans un polymère préparé par le processus auto-assemblé Layer-by-Layer (LBL) a été étudiée. La relaxation de rotation du colorant est analysée en mesurant la variation de susceptibilité de second ordre induite par le poling tout-optique. Nous montrons que la température de transition vitreuse du polymère n'est pas le seul facteur qui influe sur la stabilité de rotation libre du colorant. Par contre, l'architecture de polymère (la polarité de la chaîne polymère) joue un rôle sur la stabilité de rotation. Nous discutons du ralentissement de la relaxation de rotation moléculaire sur le poling tout-optique. Un modèle ‘restoring torque' est introduit pour étudier la stabilité d'orientation intrinsèque du colorant dans polymère préparé par le processus auto-assemblé Layer-by-Layer.<br /><br />La propriété optique nonlinéaire de second ordre d'oxyde de zinc est étudiée a l'échelle de millimètre jusqu'à nano-mètre. L'effet de surface sur l'augmentation de réponse de la génération de second harmonique est montré. Nous suggérons que la génération de second harmonique induite par le champ électrique crée par la séparation des charges est l'origine de l'augmentation proéminent des susceptibilités à second ordre. <br /><br />Nous discutons la réponse significative d'optique nonlinéaire de second ordre de fullerène (C60) et phthalocyanine de cuivre (CuPc) qui sont de nature centro-symétrique. L'influence d'épaisseur de couche et le substrat nous montre l'origine de la génération de second harmonique : la génération de second harmonique induite par le champ électrique de la séparation de charge à l'interface du substrat et de la couche. Elle n'est pas causée par des mécanismes d'optique nonlinéaire aux ordres plus élevés. En plus, la technique ‘Kelvin Probe' est introduite pour analyser quantitativement le transfert de charge à l'interface.

An aqueous nanoparticle dispersion is a complex fluid whose mobility in porous media is controlled by four key factors: the conditions necessary for the stability of nanoparticle dispersions, the kinetics of nanoparticle aggregation in an unstable suspension, the rheology of stable or unstable suspensions, and the interactions between the nanoparticles and oil/water interface and mineral surfaces. The challenges in controlling nanoparticle transport come from the variations of pH and ionic strength of brine, the presence of stationary and mobile phases (minerals, oil, water and gas), the geochemical complexity of reservoir rocks, and pore-network. The overall objective of this work is to achieve a better understanding of nanoparticle transport in porous media based on a systematic experimental and theoretical study of above factors. For this purpose, the critical conditions for the aqueous stability of nanoparticles are identified and fit by a theoretical model, which describes the interaction energy between silica nanoparticles. Above critical conditions nanoparticle aggregation becomes significant. A model for the aggregation kinetics is developed and validated by experiments. A mechanistic model for predicting the viscosity of stable and unstable silica nanoparticle dispersions over a wide range of solid volume fraction is developed. This model is based on the concept of effective maximum packing fraction. Adsorption experiments with silica nanoparticles onto quartz, calcite and clay surfaces and interfacial tension measurements provide insightful information on the interaction of the nanoparticles with minerals and decane/water interface. The extent of nanoparticle adsorption on mineral/water and decane/water interfaces is evaluated based on DLVO theory and Gibbs’ equation. Visual observations and analytical methods are used to understand the interaction of nanoparticles with clay. The characterization of nanoparticle behavior in bulk phases is built into an understanding of nanoparticle transport in porous media. In particular, the rheology of nanoparticle dispersions flowing through permeable media is compared with those determined using a rheometer. In the presence of residual oil, the retention of silica nanoparticles at water/oil interface during steady flow is investigated. The results from batch experiments of nanoparticle adsorption are used to explain the flow behavior of these nanoparticles in a glass bead pack at residual oil saturation. / text

Surfactants both change the wettability and lower the interfacial tension by various degrees depending on the type of surfactant and how it interacts with the specific oil. Ultra low IFT means almost zero capillary pressure, which in turn indicates little oil should be produced from capillary imbibition when the surfactant reduces the IFT in naturally fractured oil reservoirs that are mixed-wet or oil-wet. What is the transport mechanism for the surfactant to get far into the matrix and how does it scale? Molecular diffusion and capillary pressure are much too slow to explain the experimental data. Recent dynamic laboratory data suggest that the process is faster when a pressure gradient is applied compared to static tests. A mechanistic chemical compositional simulator was used to study the effect of pressure gradient on chemical oil recovery from naturally fractured oil reservoirs for several different chemical processes (polymer, surfactant, surfactant-polymer, alkali-surfactant-polymer flooding). The fractures were simulated explicitly by using small gridblocks with fracture properties. Both homogeneous and heterogeneous matrix blocks were simulated. Microemulsion phase behavior and related chemistry and physics were modeled in a manner similar to single porosity reservoirs. The simulations indicate that even very small pressure gradients (transverse to the flow in the fractures) are highly significant in terms of the chemical transport into the matrix and that increasing the injected fluid viscosity greatly improves the oil recovery. Field scale simulations show that the transverse pressure gradients promote transport of the surfactant into the matrix at a feasible rate even when there is a high contrast between the permeability of the fractures and the matrix. These simulations indicate that injecting a chemical solution that is viscous (because of polymer or foam or microemulsion) and lowers the IFT as well as alters the wettability from mixed-wet to water-wet, produces more oil and produces it faster than static chemical processes. These findings have significant implications for enhanced oil recovery from naturally fractured oil reservoirs and how these processes should be optimized and scaled up from the laboratory to the field. / text

Οι υψηλές θερμοκρασίες λειτουργίας των κελιών καυσίμου στερεού ηλεκτρολύτη (Solid Oxide Fuel Cells - SOFCs), οδηγούν σε σημαντική επιβάρυνση των σημείων συνένωσης και στεγανότητας των στοιχείων των επί μέρους εξαρτημάτων των κελιών, που διατάσσονται σε στοιβάδες. Στα σημεία συνένωσης και εναλλακτικά στα μέχρι σήμερα χρησιμοποιούμενα συγκολλητικά, με βάση ενώσεις υαλοκεραμικών, εξετάζεται η χρήση ενός συνδυασμού υλικών αποτελούμενων από κεραμικό οξείδιο ως μονωτικό (isolation layer), καθώς κι ένα μεταλλικής βάσης υλικό ως συγκολλητικό. Κατά τη συγκόλληση στον αέρα, χωρίς χρήση κενού ή προστατευτικού αερίου, το μεταλλικής βάσης συγκολλητικό έρχεται σε επαφή με την επίστρωση μονωτικού (MgO, MgAl2O4 ή ένα μίγμα MgO + MgAl2O4) και με τα μεταλλικά στοιχεία των κελιών (φερριτικοί χάλυβες, Cr ≈ 22%, Mn ≈ 0.6%). Οι κύριες απαιτήσεις που πρέπει να ικανοποιεί το συγκολλητικό είναι η καλή προσαρμογή των διαφορετικών συντελεστών θερμικής διαστολής, μακροχρόνια αντοχή στις οξειδωτικές συνθήκες λειτουργίας των κελιών, ισχυρό δεσμό και απουσία χημικής φύσης αλληλεπιδράσεων στη σχηματιζόμενη διεπιφάνεια, για τη διατήρηση της μηχανικής ευστάθειας και της χαμηλής αεριοδιαπερατότητας της συγκόλλησης. Οι φυσικοχημικές και μηχανικές ιδιότητες του καθαρού αργύρου (Ag) ως συγκολλητικό, ικανοποιούν εν γένει τις παραπάνω απαιτήσεις, μειονεκτώντας όμως, ως προς τη δημιουργία ισχυρού δεσμού στις σχηματιζόμενες διεπιφάνειες. Προσθέτοντας στον Ag το διεπιφανειακά ενεργό οξείδιο του χαλκού (CuO), βελτιώνεται σημαντικά η διαβρεξιμότητα του κεραμικού (μονωτικό) και του μετάλλου (φερριτικός χάλυβας), από το τήγμα του κράματος Ag+CuO (γωνία επαφής θ < 90ο) και συνεπώς η ισχύς του δεσμού στις διεπιφάνειες.. Στόχος της παρούσας εργασίας είναι η επιλογή του κατάλληλου τρόπου προσθήκης του CuO στον Ag, ώστε να επιτευχθεί ένας ισχυρός δεσμός μεταξύ του συγκολλητικού και των υλικών προς συγκόλληση, αποφεύγοντας τον εκτεταμένο σχηματισμό προϊόντων αντίδρασης στις διεπιφάνειες. Πραγματοποιήθηκαν δύο τρόποι προσδιορισμού της γωνίας επαφής, της κεραμικής και μεταλλικής φάσης, με πειράματα διαβροχής. Στη συνέχεια, για τον έλεγχο της μακροχρόνιας ευστάθειας των συγκολλήσεων, μέρος των δοκιμίων υποβλήθηκαν σε θερμική ανόπτηση στους Τ=1073 Κ για χρονικό διάστημα t=1000 h, στον αέρα. Μετά το πέρας των πειραμάτων πραγματοποιήθηκε έλεγχος της διεπιφάνειας με μεθόδους ηλεκτρονικής μικροσκοπίας και μικροανάλυσης. / For mobile applications, the rapid heating rates and the high operating temperatures of solid oxide fuel cells (SOFCs) lead to increased stress on the joining and sealing points of the material components used for the development of planar SOFC stacks. At the junctions of the metallic components and alternatively to the currently used glass-ceramic solders the possible use of oxide ceramic as an insulation layer in combination with air braze filler metal was examined. The joining of the components in air, without the use of vacuum or inert gases, requires that the filler metal forms strong interfacial bonds with both the ceramic (insulating layer) and the additional sheet (ferritic steel). In addition, it should be resistant to oxidation at the high operating temperatures and its thermal expansion coefficient should match those of the materials to be joined. When ceramic and metal are joined, the presence of a ductile interfacial phase compensates the differences in the thermal expansion coefficients of the phases involved. Also, it is necessary for the mechanical stability of the bond, that the binding partners are well wetted by the interfacial phase. Both Ag and Cu provide high mechanical strength, ductility, and thermal, as well as electrical conductivity. Although Ag is more expensive than Cu, it is preferred as a basis metal due to the lower process temperature and the lower oxygen affinity. A problem in using pure Ag is the poor wetting properties, at the liquid state, when in contact with oxide ceramic and steel. The high values of the contact angle (θ>120o) measured in oxide ceramic/Ag systems at oxygen concentrations of 0-3 ppm is reduced in air, but overall, the systems remain non-wetting (θ>90°). Good wetting (θ<<90o) is crucial for a strong interfacial bond between the phases in contact and simultaneously ensures the mechanical stability and gas tightness of the joints. Wetting can be improved by adding an interfacial active compound that is soluble in the noble metal solvent. A suitable material is CuO, which forms a pseudo-binary alloy with Ag in the solid state, as they present mutual solubility in the liquid state [11]. Depending on the percentage of CuO in the mixture, small contact angles (θ<20o) can be achieved in oxide ceramics/Ag + CuO systems. Requirements on the ceramic insulation layer include a high electrical and thermal resistance, a high thermal expansion coefficient, stability under mechanical pressure, structural stability and oxidation resistance at high operating temperatures. The most suitable ceramics for these requirements are MgO, MgAl2O4 or a mixture of MgO and MgAl2O4. The proposed Ag + CuO brazes come in contact with the ferritic steel of the interconnect part and with the additional sheet, as well as with the SOFC's electrolyte, 8 mol% Yttria-stabilized Zirconia (8YSZ), in the cell periphery. Ferritic steels, which have a Cr content above 20 wt% and a Mn content below 1 wt%, form a double outer layer in air that consists of Cr2O3 on the inside, towards the steel side, and a MnCr2O4 spinel phase on the outside. During the wetting experiment, the active CuO contained in the liquid Ag migrates towards the interface and a mixed oxide interface layer can be formed by reaction with the diffused cations Fe, Cr and Mn from the steel. The formation of the reaction zone improves the wetting behaviour (θ<90ο), but due to its higher brittleness, the mechanical interface stability of the composite can be reduced. In the present work, the amount of CuO additive in Ag filler metal and the way in which this additive is applied, varied to achieve good wetting properties, and stable braze’s joints. The aim was to achieve a strong interfacial bond between the contacting phases and to prevent extensive interface reactions. Reaction products that form during the early stages of the brazing process must remain constant at the operating conditions. For this reason, the long-term stability after heat treatment in air, of the material combination oxide / brazes/ steel was examined after wetting experiments.

No description available.

In present study, high energy electrons were used to modify blends based on RP and PP under two conditions: stationary and in-stationary conditions. Modification of blend under stationary condition is a process which is established in industrial application and where required absorbed dose is applied to form parts (after molding) at room temperature and in solid state. On the contrary, the modification of blend with high energy electrons under in-stationary condition is a new process (electron induced reactive processing) where required absorbed dose is applied to a molten state during melt mixing process. The modification of blend based on RP and PP under stationary condition resulted in slightly enhancement of tensile properties while the modification of this blend under in-stationary condition resulted in deterioration of tensile properties due to degradation of the PP matrix. Thus, special grafting agent (GA) is required for improving the tensile properties. The effect of different GAs on tensile, thermal, dynamic mechanical as well as morphological properties and melt flow properties of blends based on RP and PP were determined. The optimum absorbed dose for modification of blend based on RP and PP under both conditions was evaluated. In addition, the effect of treatment parameters of electron induced reactive processing was investigated.

In this thesis different mechanical properties for shotcrete (sprayed concrete) such as compression strength, bond strength, bending tensile strength, elastic modulus, free and restrained shrinkage as a function of its age was investigated. One of the main issues was to investigate the difference between ordinary cast concrete and shotcrete. Reliable material data for young and hardening shotcrete is scarce which in the past have made such comparisons difficult. Also, less accurate data representative for cast concrete has often been used in numerical modelling and design analyses. The focus of the project has particularly been on the properties bond strength and restrained shrinkage for which two new testing methods has been developed and evaluated. Microstructural studies have also been performed as a complement to the bond strength testing. The bond to rock is one of the most important properties for shotcrete used as rock reinforcement. During the very first time after spraying the physical properties and the bond to the rock depend on the set accelerator and the micro structure that is formed. The investigation of early age bond strength of shotcrete is of great importance both from a production perspective and a safety perspective. The newly developed method was tested and evaluated and proved that it can be used for bond strength testing already from a couple of hours after shotcreting. The bond, or adhesion, depends on several factors such as texture of the rock, the type of accelerator, application technique, etc. In this work the development of the microstructure in the interfacial transition zone (ITZ) and strength of the bond was investigated. The results show that the bond strength is related to the hydration process, i.e. the strength gain of the shotcrete. The early development of the ITZ was here studied using a scanning electron microscope (SEM) making it possible to observe changes over time, before and after proper cement hydration. Restrained shrinkage cracking of shotcrete, especially in the case of shotcrete sprayed on soft drains that are parts of a tunnel lining not continuously bonded to the rock, can be detrimental for the sustainability of an infrastructure tunnel system. Maintenance and repair costs can be high over time. It is shown that the developed test method realistically captures the behaviour of shotcrete drains on hard rock in situ. The method can be used in the evaluation of different technical solutions for avoiding or minimizing shrinkage cracks in shotcreted soft drains. It can also be used to assess the performance of shotcrete fully bonded to a rock surface, with respect to the ability to prevent cracking or to distribute possible shrinkage damage into several fine cracks instead of one wide. / <p>QC 20140526</p>

Surface-assisted directed assembly allows ultrasoft and replusive functional polymeric “colloids” to assemble into the organized supramolecular ultrathin films on a monomolecular level. This study aims at achieving a fundamental understanding of molecular morphology and responsive behavior of major classes of branched star-shaped polymers (star amphiphilic block copolymers and star polyelectrolytes) and their aggregation into precisely engineered functional ultrathin nanofilms. Thus, we focus on elucidating the role of molecular architecture, chemical composition, and intra/intermolecular interactions on the assembly behavior of highly-branched entities under variable environmental and confined interfacial conditions. The inherent molecular complexity of branched architectures facilitates rich molecular conformations and phase states from the combination of responsive dynamics of flexible polymer chains (amphiphilic, ionizable arms, multiple segments, and free chain ends) and extened molecular design parameters (number of arms, arm length, and segment composition/sequence). These marcromolecular building components can be affected by external conditions (pH, salinity, solvent polarity, concentration, surface pressure, and substrate nature) and transformed into a variety of complex nanostructures, such as two-dimensional circular micelles, core/shell unimicelles, nanogel particles, pancake & brush micelles, Janus-like nanoparticles, and highly nanoporous fractal networks. The fine balance between repulsive mulitarm interactions and surface energetic effects in the various confined surfaces and interfaces enables the ability to fabricate and tailor well-organized ultrathin nanofilms. The most critical findings in this study include: (1) densely packed circular unimicelle monolayers from amphiphilic and amphoteric multiblock stars controlled by arm number, end blocks, and pH/pressure induced aggregation, (2) monolayer polymer-metal nanocomposites by in-situ nanoparticle growth at confined interfaces, (3) on-demand control of exponentially or linearly grown heterogeneous stratified multilayers from self-diffusive pH-sensitive star polyelectrolyte nanogels, (4) core/shell umimicelle based microcapsules with a fractal nanoporous multidomain shell morphology, and (5) preferential binding and ordering of Janus-like unimicelles on chemically heterogeneous graphene oxide surfaces for biphasic hybrid assembly. The advanced branched molecular design coupled with stimuli responsive conformational and compositional behavior presents an opportunity to control the lateral diffusion and phase segregation of branched compact supermolecules on the surface resulting in the generation of well-controllable monolayers with tunable ordering and complex morphology, as well as to tailor their stratified layered nanostructures with switchable morphological heterogeneity and multicompartmental architectures. These surface-driven star polymer supramolecular assemblies and interfaces will enable the design of multifunctional nanofilms as hierarchical responsive polymer materials.

The productivity of most gas condensate wells is reduced significantly due to condensate banking when the bottom hole pressure falls below the dew point. The liquid drop-out in these very high rate gas wells may lead to low recovery problems. The most important parameter for determining condensate well productivity is the effective gas permeability in the near wellbore region, where very high velocities can occur. An understanding of the characteristics of the high-velocity gas-condensate flow and relative permeability data is necessary for accurate forecast of well productivity. In order to tackle this goal, a series of two-phase drainage relative permeability measurements on a moderate permeability North Marmara &ndash / 1 gas well carbonate core plug sample, using a simple synthetic binary retrograde condensate fluid sample were conducted under reservoir conditions which corresponded to near miscible conditions. As a fluid system, the model of methanol/n-hexane system was used as a binary model that exhibits a critical point at ambient conditions. The interfacial tension by means of temperature and the flow rate were varied in the laboratory measurements. The laboratory experiments were repeated for the same conditions of interfacial tension and flow rate at immobile water saturation to observe the influence of brine saturation in gas condensate systems. The laboratory experiment results show a clear trend from the immiscible relative permeability to miscible relative permeability lines with decreasing interfacial tension and increasing velocity. So that, if the interfacial tension is high and the flow velocity is low, the relative permeability functions clearly curved, whereas the relative permeability curves straighten as a linear at lower values of the interfacial tension and higher values of the flow velocity. The presence of the immobile brine saturation in the porous medium shows the same shape of behavior for relative permeability curves with a small difference that is the initial wetting phase saturations in the relative permeability curve shifts to the left in the presence of immobile water saturation. A simple new mathematical model is developed to compute the gas and condensate relative permeabilities as a function of the three-parameter. It is called as condensate number / NK so that the new model is more sensitivity to temperature that represents implicitly the effect of interfacial tension. The new model generated the results were in good agreement with the literature data and the laboratory test results. Additionally, the end point relative permeability data and residual saturations satisfactorily correlate with literature data. The proposed model has fairly good fitness results for the condensate relative permeability curves compared to that of gas case. This model, with typical parameters for gas condensates, can be used to describe the relative permeability behavior and to run a compositional simulation study of a single well to better understand the productivity of the field.

A functional nanometer-scale hybrid coating layer with multi-walled carbon nanotubes (MWCNTs) and/or nanoclays, as mechanical enhancement to ‘heal’ surface microcracks and environmental barrier layer is applied to alkaliresistant glass (ARG) fibres. The nanostructured and functionalised traditional glass fibres show both significantly improved mechanical properties and environmental corrosion resistance. Early warning material damage can be achieved by carbon nanotubes concentrated interphases in the composites. / Eine funktionale nanometerskalige Hybridbeschichtung mit multi-walled carbon nanotubes (MWCNTs) und/oder Nanoclay wurde als mechanische Verbesserung des „Ausheilens“ von Oberflächen-Mikrorissen und Barriereschicht gegenüber Umwelteinflüssen auf alkaliresistente Glasfasern (ARG) appliziert. Die nanostrukturierten und funktionalisierten traditionellen Glasfasern zeigen signifikant verbesserte mechanische Eigenschaften und Korrosionsbeständigkeit. Die Frühwarnung des Materialversagens kann durch Carbon Nanotubes, konzentriert in der Grenzschicht der Composites, erreicht werden.