Dissertationen zum Thema „Hydrated crystal“

La prise et le durcissement des matériaux de Génie Civil (plâtre, C-S-H) reposent sur des interactions entre cristaux et solutions ioniques. Ces interactions mettent en jeu des équilibres entre phases, leurs frontières (dites périphases) et des phases confinées entre périphases (dites interphases). La partie 1 "Concepts, méthodes et outils" introduit tout d'abord le concept phéno-corpusculaire proposé pour l'étude de ces équilibres, irréductibles à une approche macroscopique via la physique statistique, et d'autre part encore inabordables par la seule voie corpusculaire. Parmi les méthodes originales présentées, la méthode SASP ouvre la voie phéno-corpusculaire en physico-chimie; puis est proposée la méthode OPTASYM pour définir les positions d'atomes H inconnus dans certaines cristaux; enfin est exposée la méthode CAC exploitant simultanément expérience et simulation AFM. Quant aux outils numériques originaux, ils sont essentiellement dévolus au traitement conjoint cristal/solution, encore embryonnaire en modélisation moléculaire. La partie 2 "Equilibre massique de phases, périphases et interphases" s'attache tout d'abord à l'élaboration de structures atomiques complètes de cristaux (gypse, ettringite, thaumasite), de structures de molécules et ions, et de structure de solution grâce à la méthode SASP qui débouche numériquement sur la relation fondamentale concentrations/potentiels chimiques. Ces structures étant définies, leurs interactions sont d'abord traitées par docking entre faces cristallines et molécules ou ions. Puis l'interaction cristal/solution/cristal est présentée via SASP dans le cas d'une solution saturée de gypse. D'où, pour la première fois, l'obtention de la structure d'une interphase d'épaisseur < 1 nm. La partie 3 " Equilibre mécanique de phases, périphases et interphases " présente, tout d'abord, une étude critique de l'estimation par modélisation moléculaire des contraintes totales de cristaux et solutions ioniques. L'introduction du calcul des contraintes partielles, inabordable expérimentalement, est fort prometteuse pour relier résistance à rupture macroscopique et structure atomique. L'équilibre mécanique entre phases, périphases et interphases est tout d'abord examiné en déplacement normal jusqu'à rupture d'adhésion, pour divers couples de faces (120), (010) ou (-101), la solution interphase (CaSO4, CaCl2 ou Na2SO4) étant en situation ionique non équilibrée (pour simuler des états transitoires ou isolés) avec éventuellement de l'acide citrique. Puis cette étude est reprise en situation ionique équilibrée, via la méthode SASP, pour les faces (120) du gypse en solution saturée. Enfin une première illustration de cisaillement est donnée dans le cas d'interphase (120), en solution CaSO4 non équilibrée avec acide citrique. La conclusion souligne les avancées de ce travail en modélisation atomique de solution en présence de cristal, ainsi que ses perspectives placées dans l'optique générale phéno-corpusculaire
The setting and hardening of materials used in civil engineering (plaster, C-S-H) are based on interactions between crystals and ionic solutions. These interactions involve equilibriums between phases, their boundaries (referred to as periphases) and phases confined between periphases (referred to as interphases). Part 1, "Concepts, methods and tools", first introduces the pheno-corpuscular concept proposed for the study of these equilibriums that cannot be addressed in a macroscopic approach via the statistical physics or in a corpuscular approach alone. Among the original methods presented, the SASP method opens up the pheno-corpuscular pathway in physicochemistry; then is presented the OPTASYM method using molecular modelling to propose positions of H atoms unknown in certain crystalline structures; finally is exposed the CAC method based on a simultaneous use of AFM experiment and simulation. The original numerical tools are mainly devoted to joint crystal/solution processing, an area that is still at its beginnings in molecular modelling. Part 2, "Mass equilibrium of phases, periphases and interphases" first addresses the build-up of complete crystal atomic structures (gypsum, ettringite and thaumasite), of molecules and ions structures and of solution structures, the SASP method leading numerically, in this last case, to the fundamental relation between concentrations and chemical potentials. Once these structures have been defined, their interactions are first handled by docking between the crystalline faces and molecules or ions. The crystal/solution/crystal interaction is then presented using SASP, in the case of a saturated solution of gypsum. Whence, for the first time, the structure of an interphase of thickness < 1 nm. Part 3, "Mechanical equilibrium of phases, periphases and interphases", consists, first of all, of a critical study of estimation by molecular modelling of the total stresses of ionic crystals and solutions. The introduction of calculation of partial stresses, which cannot be performed by experiment, is particularly promising for linking macroscopic failure strength and atomic structure. Mechanical equilibrium between phases, periphases and interphases is first examined in normal displacement of various pairs of faces (120), (010) or (-101) until adhesion failure, the solution interphase (CaSO4, CaCl2 or Na2SO4) being in a non-equilibrium ionic situation (to simulate transitory or isolated states), possibly with citric acid. The study is then repeated in an equilibrium ionic situation using the SASP method for the gypsum faces (120) in a saturated solution. Finally, a first illustration of an interphase shearing is given in the case of faces (120), with a non-equilibrated solution of CaSO4 and citric acid. The conclusion underlines the progress made in this work on crystal/solution atomic modelling and its prospects within the overall pheno-corpuscular approach

The calcium sulphoaluminate hydrates are important components of Portland cement and constitute the principal matrix formers of some sulphoaluminate cements. Their practical importance lies in the involvement as intermediates and products of the hydration of portland cements under geothermal conditions. Ettringite is a complex mineral (Ca₆[Al(OH)₆]₂(SO₄)₃.26H₂O) formed during the initial stages of Portland cement hydration at ambient temperature, by reaction of sulphate ions released by gypsum (CaSO₄.2H₂O) with tricalcium aluminate (Ca₃Al₂O₆). After exhaustion of gypsum, the remaining tricalcium aluminate in solution reacts with already formed ettringite transforming to monosulphate (Ca₄Al₂(SO₄)(OH)₁₂.xH₂O). At higher temperature (>100°C), ettringite is unstable and transforms to monosulphate. Monosulphates are known to exist is at least four different hydrate forms (x = 8,10,12,14). In this study the stability of calcium sulphoaluminate hydrates were mapped in various environments (variable relative humidity, temperature and alkalinity). The monosulphate hydrates were obtained by hydrothermal synthesis using microwave radiation at 120°C. Their formation is via ettringite thermal decomposition in autoclave conditions under autogenous pressure. It has been shown that a series of calcium sulphoaluminate hydrates can be obtained depending on temperature and water activity. The interconversion of the calcium sulphoaluminate hydrates was found to be an easy and rapid process, whereby metastable phase are readily formed, indicating the lability of Ca-OH-Al-SO₄ system. The kinetics and the mechanism of growth of calcium sulphoaluminate hydrates are known to influence the development of mechanical properties and the characteristics of cements. The ettringite crystal growth process was evaluated from the point of view of its influence on crystal morphology. General crystallisation methods for ettringite synthesis were developed starting from supersaturated solutions of pure phases and its morphology was found to vary with crystallisation factors (temperature for instance); ettringite crystals are generally hexagonal rods with different aspect ratios.

Solubility prediction usually refers to prediction of the intrinsic aqueous solubility, which is the concentration of an unionised molecule in a saturated aqueous solution at thermodynamic equilibrium at a given temperature. Solubility is determined by structural and energetic components emanating from solid-phase structure and packing interactions, solute–solvent interactions, and structural reorganisation in solution. An overview of the most commonly used methods for solubility prediction is given in Chapter 1. In this thesis, we investigate various approaches to solubility prediction and solvation model development, based on informatics and incorporation of empirical and experimental data. These are of a knowledge-based nature, and specifically incorporate information from the Cambridge Structural Database (CSD). A common problem for solubility prediction is the computational cost associated with accurate models. This issue is usually addressed by use of machine learning and regression models, such as the General Solubility Equation (GSE). These types of models are investigated and discussed in Chapter 3, where we evaluate the reliability of the GSE for a set of structures covering a large area of chemical space. We find that molecular descriptors relating to specific atom or functional group counts in the solute molecule almost always appear in improved regression models. In accordance with the findings of Chapter 3, in Chapter 4 we investigate whether radial distribution functions (RDFs) calculated for atoms (defined according to their immediate chemical environment) with water from organic hydrate crystal structures may give a good indication of interactions applicable to the solution phase, and justify this by comparison of our own RDFs to neutron diffraction data for water and ice. We then apply our RDFs to the theory of the Reference Interaction Site Model (RISM) in Chapter 5, and produce novel models for the calculation of Hydration Free Energies (HFEs).

Considerable research has been done to improve hydrate formation rate. One of the ideas is to introduce mechanical mixing which later tend to complicate the design and operation of the hydrate formation processes. Another approach is to add surfactant (promoter) that will improve the hydrate formation rate and also its storage capacity to be closer to the maximum hydrate storage capacity. Surfactant is widely known as a substance that can lower the surface or interfacial tension of the water when it is dissolved in it. Surfactants are known to increase gas hydrate formation rate, increase storage capacity of hydrates and also decrease induction time. However, the role that surfactant plays in hydrate crystal formation is not well understood. Therefore, understanding of the mechanism through morphology studies is one of the important aspects to be studied so that optimal industrial processes can be designed. In the present study the effect of three commercially available anionic surfactants which differ in its alkyl chain length on the formation/dissociation of hydrate from a gas mixture of 90.5 % methane – 9.5% propane mixture was investigated. The surfactants used were sodium dodecyl sulfate (SDS), sodium tetradecyl sulfate (STS), and sodium hexadecyl sulfate (SHS). Memory water was used and the experiments for SDS were carried out at three different degrees of under-cooling and three different surfactant concentrations. In addition, the effect of the surfactant on storage capacity of gas into hydrate was assessed. The morphology of the growing crystals and the gas consumption were observed during the experiments. The results show that branches of porous fibre-like crystals are formed instead of dendritic crystals in the absence of any additive. In addition, extensive hydrate crystal growth on the crystallizer walls is observed. Also a “mushy” hydrate instead of a thin crystal film appears at the gas/water interface. Finally, the addition of SDS with concentration range between 242ppm – 2200ppm (ΔT =13.10C) was found to increase the mole consumption for hydrate formation by 14.3 – 18.7 times. This increase is related to the change in hydrate morphology whereby a more porous hydrate forms with enhanced water/gas contacts.

There is heightened interest to diversify the range of crystal forms exhibited by active pharmaceutical ingredients (APIs) in the pharmaceutical industry. The crystal form can be regarded as the Achilles' heel in the development of an API as it directly impacts the physicochemical properties, performance and safety of the API. This is of critical importance since the crystal form is the preferred method of oral drug delivery by industry and regulatory bodies. The ability to rationally design materials is a lucrative avenue towards the synthesis of functional molecular solids with customized physicochemical properties such as solubility, bioavailability and stability. Pharmaceutical cocrystals have emerged as a new paradigm in pharmaceutical solid form development because they afford the discovery of novel, diverse crystal forms of APIs, generate new intellectual property and modify physicochemical properties of the API. In addition, pharmaceutical cocrystals are amenable to design from first principles of crystal engineering. This dissertation focuses on the crystal engineering of multi-component crystal forms, in particular pharmaceutical cocrystals and crystalline hydrates. It addresses: (i) the factors involved in the selection of cocrystal formers (ii) design strategies for APIs that exhibit complexity, (iii) the role of water molecules in the design of multi-component crystal forms and (iv) the relationship between the crystal structure and thermal stability of crystalline hydrates. In general, cocrystal former libraries have been limited to pharmaceutically acceptable substances. It was investigated to expand this library to include substances with an acceptable toxicity profile such as nutraceuticals. In other words, can nutraceuticals serve as general purpose cocrystals formers? The model compounds, gallic acid and ferulic acid, were selected since they possess the functional moieties carboxylic acids and phenols, that are known to form persistent supramolecular synthons with complementary functional groups such as basic nitrogen and amides. The result yielded pairs of cocrystals and revealed the hierarchical nature of hydrogen bonding between complementary functional groups. In general, pharmaceutical cocrystals have been designed by determining the empirical guidelines regarding the hierarchy of supramolecular synthons. However, this approach may be inadequate when considering molecules that are complex in nature, such as those having a multiplicity of functional groups and/or numerous degrees of conformational flexibility. A crystal engineering study was done to design multi-component crystal forms of the atypical anti-psychotic drug olanzapine. The approach involved a comprehensive analysis and data mining of existing crystal structures of olanzapine, grouped into categories according to the crystal packing exhibited. The approach yielded isostructural, quaternary multi-component crystal forms of olanzapine. The crystal forms consist of olanzapine, the cocrystal former, a water molecule and a solvate. The role of water molecules in crystal engineering was addressed by investigating the crystal structures of several cocrystals hydrates and their related thermal stability. The cocrystal hydrates were grouped into four categories based upon the thermal stability they exhibit and it was concluded that no structure/stability correlations exist in any of the other categories of hydrate. A Cambridge Structural Database (CSD) analysis was conducted to examine the supramolecular heterosynthons that water molecules exhibit with two of the most relevant functional groups in the context of active pharmaceutical ingredients, carboxylic acids, and alcohols. The analysis suggested that there is a great diversity in the supramolecular heterosynthons exhibited by water molecules when they form hydrogen bonds with carboxylic acids or alcohols. This finding was emphasized by the discovery of two polymorphs of gallic acid monohydrate to it the first tetramorphic hydrate for which fractional coordinates have been determined. Analysis of the crystal structures of gallic acid monohydrate polymorphs revealed that forms I and III exhibit the same supramolecular synthons but different crystal packing and forms II and IV exhibit different supramolecular synthons. Therefore, the promiscuity of water molecules in terms of their supramolecular synthons and their unpredictable thermal stability makes them a special challenge in the context of crystal engineering.

In this thesis H-bonded systems (natural gas hydrates, water clusters, and crystal ice) are studied by density functional theory (DFT) computations. Natural gas hydrates (NGHs) play an important role in energy and environmental fields: NGHs are considered as a promising backup energy resource in the near-future due to their tremendous carbon content; improper exploration of NGHs could induce geological disasters and aggravate the greenhouse effect. In addition, many technologies based on gas hydrates are being applied and developed. The thermodynamic stabilities of various water cavities in different clathrate crystalline phases occupied by hydrocarbon gas molecules are studied by dispersion-corrected hybrid functionals. The Raman spectra of C-C and C-H stretching vibrations of hydrocarbon molecules in various water cavities in the solid state are derived. The trends of C-H stretching vibrational frequencies are found to follow the prediction by the “loose cage ─| tight cage” model. In addition, the trends and origins of 13C NMR chemical shifts of hydrocarbon molecules in various NGHs are presented. These theoretical results will enlarge the database of C-C and C-H stretching vibrational frequencies and 13C NMR parameters of hydrocarbon molecules in NGHs, and provide valuable information to help identify the types of clathrate phases and varieties of guest molecules included in NGHs samples taken from natural sites. The behavior of water clusters may help to understand the properties of its liquid and solid states. The thermodynamic stabilities and IR spectra of a small-, medium-, and large-sized water cluster are studied in this work. After full optimization of (H2O)20,54,100 using the hybrid functional B3LYP, the electronic energies, zero-point energies, internal energies, enthalpies, entropies, and Gibbs free energies of the water clusters are computed. The OH stretching vibrational IR spectra of (H2O)20,54,100 are also presented and split into sub-spectra for different H-bond types based on the specific contributions from each group. It is found that the OH stretching vibrational frequencies of water are sensitive to the conformations of the H-bonds and the vibrations of the H-bonds belonging to different types are located in separated regions in the IR spectra. Thus, the spectroscopic fingerprints will reflect the H-bond topology of the water molecules in a water cluster. Ice XI has been suggested to be involved in the process of planetary formation as a considerable electric field might be formed from the ferroelectric ice XI in space. IR and Raman spectroscopic technology can be directly used to identify the occurrence of ferroelectric ice XI in laboratory or extraterrestrial settings. Due to the difficulty for DFT to describe non-covalent systems, the performance of 16 different DFT methods applied on the ice Ih, VIII, IX, and XI crystal phases are assessed. Based on the computational accuracy and cost, the IR and Raman spectra of ice Ih and XI are derived and compared. The librational vibrations are found to be the identifier which can be used to distinguish ice Ih and ice XI in the universe. In addition, the existence only one kind of H-bond in ice Ih is demonstrated from the overlapping sub-spectra for different types of H-bonded pair configurations in 16 isomers of ice Ih. The region of water under negative pressure is an exotic land in lack of exploitation. Guest free clathrate hydrate (clathrate ice) of sII type has been recently confirmed experimentally at negative pressure. Does any other clathrate ice phase exist at negative pressure region? Since clathrate hydrate are isostructural with silica clathrate minerals and semiconductor clathrates, and crystal structure prediction by analogy with known structures and first-principles computations is an effective way to find new crystalline phases of solid materials, we are motived to look for new clathrate ice phases from silica or semiconductor clathrate materials based on first-principles computations. Borrowing the idea new clathrate frameworks of ZnO and SiC can be constructed by connecting their bubble clusters in different ways, new clathrate ice phases (sL, sL_I, sL_II, and sL_III) are generated by connecting the water bubble clusters according to different rules. Using the non-local dispersion-corrected vdW-DF2 functional, clathrate ice sL with ultralow density (0.6 g/cm3) is predicted by first-principles phase diagram computations to be stable under larger negative pressures than the sII phase. The phase diagram of water is thus extended into the lower negative pressure region.

Les hydrates de gaz sont des composés cristallins stables à haute pression et à basse température, très répandus sur terre, notamment dans les fonds marins au niveau des marges continentales, où ils contribuent à la stabilité des sédiments par leur cohésion et leur adhésion aux surfaces minérales. Cependant, le comportement mécanique des hydrates en soi a été peu ou pas étudié à l’échelle du pore. L’objectif de cette thèse est d’étudier les conditions de stabilité et les propriétés mécaniques en traction de l’hydrate de méthane à l’échelle du pore, dans une configuration comparable à celle qu’on peut trouver dans les milieux poreux sédimentaires.Ici, nous étudions d’abord par microscopie optique les conditions de formation, de croissance et de dissociation de l’hydrate de méthane à l’interface eau/CH4 dans un micro-capillaire en verre utilisé à la fois comme un pore modèle et comme une cellule optique résistante à haute pression et à basse température. Ensuite, en développant une méthode originale in situ et sans contact : "dépression thermo-induite" on détermine les propriétés mécaniques en traction d’une coquille polycristalline d’hydrate de méthane. L’hydrate est nucléé à basse température sur l’interface eau/CH4, qui est rapidement recouverte d’une "croûte" polycristalline d’hydrate. À partir de cette croûte, l’hydrate pousse de part et d’autre de l’interface : dans l’eau sous forme "d’aiguilles" cristallines, dans le gaz, sous forme de "filaments" cristallins, et enfin entre le substrat et le gaz sous forme d’un "halo". Le halo qui est un film polycristallin avançant sur le substrat, en chevauchant un film d’eau, ralentit et finit par s’immobiliser et s’accrocher au substrat. À partir de ce moment, "la coquille" polycristalline, constituée de la croûte et du halo, forme une barrière entre l’eau et le gaz. Les tests de traction sont effectués par génération d’une dépression dans le compartiment eau en augmentant la température à pression de méthane constante.Les propriétés élastiques en traction de la coquille (module élastique et contrainte de rupture) sont déterminées en fonction de la taille des grains, contrôlée ici par les deux paramètres : le sous-refroidissement par rapport à la température d’équilibre, et le temps de mûrissement. On trouve un comportement élastoplastique à caractères ductile et fragile mélangés. Nos données de contrainte de rupture s’insèrent dans un écart de cinq ordres de grandeurs de taille de grain, et de trois ordres de grandeurs de la contrainte de rupture (entre des données de simulation à l’échelle nanomètrique et des données expérimentales à l’échelle millimétrique). L’effet de taille de grain sur la contrainte de rupture de l’hydrate de méthane peut être un facteur contribuant à la déstabilisation des pentes continentales
Gas hydrates are ice-like crystals stable at high pressure and low temperature. They are ubiquitous on earth, notably at the edges of continental shelves, where they contribute to the mechanical stability of marine sediments, by hydrate cohesion and hydrate adhesion to mineral particles. However, the mechanical behavior of gas hydrates at pore scale has been hardly or not at all studied. The purpose of this thesis is to study the stability conditions and the tensile mechanical properties of methane hydrate at pore scale in a representative pore habit of gas hydrate in a sedimentary medium.Here, using optical microscopy, first the formation, growth and dissociation conditions of methane hydrate are investigated across a water/CH4 interface in glass micro-capillaries used both as a pore model and as an optical cell resisting high pressure and low temperature. Then by developing a contactless and an in situ method, "thermally induced depressing", tensile mechanical properties of polycrystalline methane hydrate shell are determined. At low enough temperature, the hydrate nucleates as a polycrystalline "crust" over the water/CH4 interface. From this crust, the hydrate continues growing on both sides of the interface: in the water as "needle like crystals", in the gas as "hair like crystals", and finally between the gas and the substrate as a polycrystalline film, the "halo". The halo advances slowly on the substrate, riding over a water film, and comes to rest and adheres to the substrate. From then on, the "shell" (crust and halo) isolates the water from the gas. Tensile tests are carried out by generating a depression in the water compartment by increasing temperature at constant methane pressure.Tensile elastic properties of the shell (elastic modulus and the tensile strength) are determined as a function of the grain size, controlled here by two parameters, supercooling compared to the equilibrium temperature and the annealing time. We find elastoplastic behavior, with mixed ductile and brittle characteristics. Our data on tensile strength contribute to fit the gap of five orders of magnitude of grain size, and three orders of magnitude of tensile strength (between molecular simulations at nanometre scale and current experiment at millimetre to centimetre scale). The effect of grain size on the tensile strength of methane hydrate could be a factor contributing to the destabilization of continental slopes

Gas hydrates can cause serious economic/safety concerns in oil and gas production operations. Recently, low dosage polymeric Kinetic Hydrate Inhibitors (KHIs) have seen increasing industry use as alternatives to traditional thermodynamic inhibitors (e.g. methanol, glycol). To date, KHIs have been primarily understood to work by delaying/interfering with the hydrate nucleation process, inhibiting the onset of hydrate growth for a significant ‘induction time’ (ti) period. If the induction time exceeds fluid residence time in the hydrate region, then hydrate formation/plugging is avoided. However, due to nucleation being probabilistic, induction time data measured in standard laboratory KHI evaluation studies are often highly stochastic, making KHI assessment problematic and time-consuming To address this problem, the primary aim of this project was to develop a crystal growth inhibition (CGI) based approach to KHI evaluation. In this technique gas hydrate growth and dissociation patterns in the presence of KHI polymers were carefully inspected to evaluate repeatability of features and the existence of any consistency between runs and transferability between set ups within KHI systems. Extensive studies using this method show that KHIs - rather than being solely ‘nucleation delayers’ - induce a number of highly repeatable, well-defined hydrate crystal growth inhibition regions as a function of subcooling, ranging from complete inhibition, through reduced growth rates to ultimate failure with increasing subcooling. These crystal growth inhibition properties, in addition to offering further protection against hydrate formation/plugging (e.g. if hydrate nucleation does occur), provide a means to evaluate formulations much more rapidly and reliably. These measured CGI regions have shown good correlation with traditional induction time data, meaning CGI methods can be used to both rapidly approximate ti patterns and support/confirm ti test results, speeding up the KHI evaluation process while giving greatly increased operator confidence in inhibitor performance. Furthermore in this project, the new approach has been applied for evaluating the performance of different types of kinetic hydrate inhibitors as well as assessing the influence of various other components (e.g. liquid hydrocarbons, salts and thermodynamic inhibitors) on KHI performance. Moreover, studies have been conducted on KHI evaluation in different hydrate structure systems (i.e., Structure I, structure II and structure H) systems in the presence of several different single, binary and multi-component gases. For this purpose in all experiments undertaken throughout this thesis, with the application of the newly developed CGI technique, crystal growth inhibition regions have been measured for different systems and from the extent of these regions, hydrate inhibition properties of each KHI system has been evaluated and analysed. Results of these studies proved that the pendant group of a polymer plays a major role on the KHI inhibition properties. Also investigations of different guest gas/hydrate structure systems using the new CGI technique indicated that guest/cage occupancy plays an important role in hydrate inhibition and different hydrate structure systems (e.g. s-I, s-II and s-H) are inhibited differently by the same KHI. For instance, PVCap performance was considerably superior in s-II and s-H forming systems compared to s-I forming systems (e.g. methane), supporting stronger polymer adsorption on s-II or s-H hydrate crystal surfaces. Also through the newly developed CGI studies, it was found that while the presence of NaCl enhances PVCap methane hydrate inhibition, a carbonate salt like K2CO3 can have a generally negative effect on PVCap performance. In addition to that, test on liquid hydrocarbons proved that the presence of these compounds can slightly deteriorate PVCap performance. Moreover, results indicated that the combination of thermodynamic inhibitors and PVCap show better performance than thermodynamic inhibitors alone although glycols generally acted as ‘top-up’ thermodynamic inhibitor with PVCap which was a much better compared to the performance of alcohols with PVCap.

Determination par diffraction rx des arrangements atomiques de neuf phases cristallines hydratees. Les polyedres de coordination des cations s'organisent en trois types structuraux : chaines simples (cd); empilement en couches (cd); chaines mixtes (cd,ca). Quatre phases possedent des structures caracterisees par une pseudo-symetrie marquee. Les macles et les transformations orientees, observees sur certains cristaux, sont interpretees par l'existence de pseudo-symetrie locale et de parentes structurales entre blocs atomiques des hydrates concernes

This thesis describes the development and uses of equipment and methods based upon the use of quartz crystal microbalance (QCM) technology for measurements involving major Flow Assurance issues, namely wax, asphaltene and hydrate in addition to ice formation in processing facilities, deposition of diesel performance additives in injectors and evaluation of anti-depositional paint coatings. For wax, the use of QCM for accurate measurements of the solubility of wax in synthetic binary and quaternary mixtures of n-alkanes is demonstrated and validated against literature data and model predictions. The use of the QCM for measurements of wax appearance temperature (WAT) and wax disappearance temperature (WDT) for stabilised and live reservoir fluids is presented. The development of QCM based equipment for investigating the effect of temperature gradient on wax deposition tendency at ambient and high pressure is described. The development and validation of the application of QCM technology for comparing and optimising dose rates for wax inhibitors at atmospheric and high pressure is presented. Wax case studies employing the developed equipment and methods are included. In the case of asphaltenes the potential use of QCM based equipment for measuring asphaltene onset in standard solvent titration measurements is shown. In addition by comparing step-wise and continuous injection results, potential errors in asphaltene stability measurements are highlighted. QCM tests with live fluids show that asphaltene onset can be readily detected in reservoir fluids at high pressure/high temperature conditions. In addition reversibility of asphaltene deposition can be demonstrated. Measurement of the effectiveness of asphaltene inhibitor treatments in terms of reducing solids deposition is demonstrated at operating conditions. Asphaltene case studies using the developed equipment and methods are presented. With hydrates, the development of QCM based equipment for measurement of hydrate dissociation points is presented. The use of QCM to identify solids forming in a dew pointing and mercaptan removal unit is described. The development of high pressure/high temperature equipment to detect deposition of diesel performance additives in injectors is presented. Finally the evaluation of anti-deposition coatings for scale and wax is described.

Compose etudiees : axmnoy, zh::(2)o a = na, k, rb, cs, mn (phyllomanganates) et mno::(1,93-1,98), zh::(2)o (type mno::(2) nongamma epsilon ). Pour les phyllomanganates, l'etude des variations des parametres cristallins et de la teneur en eau z en fonction de la temperature t et de l'hygrometrie rh confirme la structure lamellaire. Mesures de conductivite en fonction de t et rh. La structure des composes de type mno::(2) nongamma epsilon est basee sur une intercroissance de reseaux de type rutile et ramsdellite

Carbonate minerals play a very important role in nature, they represent some of the most diverse and common mineral species on the Planet. They are directly involved in the carbon dioxide (CO2) cycle acting as relatively stable long term chemical storage reservoirs, moderating both global warming trends and oceanaquatic chemistry through carbonate buffering systems. A range of synthetic metal carbonates have been synthesised for analysis under multiple experimental conditions, in order to study the variation in physical and chemical properties such as phase specificity, metal substitution, hydration/hydroxy carbonate formation under varying partial pressures of CO2 and thermal stability. Synthetic samples were characterised by a variety of instrumental analysis techniques in order to investigate chemical purity and phase specificity. Some of the techniques included, vibrational spectroscopy (IR/Raman), thermal analysis (TGA-MS) (thermal Raman), X-Ray diffraction (XRD) and electron microscopy (SEM-EDX). From the instrumental characterisation techniques, it was found that single phase smithsonite, hydrozincite, calcite and nesquehonite could successfully be synthesised under the conditions used. Minor impurities of other minerals and / or phases were found to form under specific chemical or physical conditions such as in the case of hydrozincite / simonkolleite if zinc chloride was used during hydrothermal synthesis.

Hydrated sodium-magnesium sulfate minerals are common in many continental evaporite settings around the world. The crystallization sequence of these minerals depends on such parameters as the composition of the parent brine, the temperature, the evaporation rate of the brine, and the differences in the atomic structure and water content of the minerals. The atomic structures of konyaite [Na2Mg(SO4)2·5H2O] and sodium-magnesium decahydrate [Na2Mg(SO4)2·10H2O], a newly described sulfate salt, have been determined from single-crystal X-ray diffraction experiments. The refined structures are discussed and compared to that of blödite [Na2Mg(SO4)2·4H2O]. The arrangement and importance of hydrogen bonds within all three structures are also discussed, and have been further investigated by infrared spectroscopy. Löweite [Na12Mg7(SO4)13·15H2O] was included in this experiment to provide a low-hydration end-member. Differences in water content and the importance of hydrogen bonds in the respective structures were clearly reflected in the generated infrared spectra. The growth conditions of the decahydrate, konyaite, blödite, löweite, and other phases of the Na2O-MgO-H2O system, as well as their stability relationships, were studied in a temperature-controlled crystal-growth experiment. Konyaite and the decahydrate phase were found as first precipitates over a range of temperatures and brine compositions where they are not considered to be the thermodynamically stable phase. The importance of evaporation rate in the formation of these, and other metastable phases, is discussed in relation to inland saline systems. Possible localities where the decahydrate could exist in nature are discussed, and challenges for future research are presented.
Thesis (Master, Geological Sciences & Geological Engineering) -- Queen's University, 2010-09-16 09:02:33.843

In this paper we will discuss the first successful molecular simulation studies exploring the statesteady crystal growth of sI and sII methane hydrates. Since the molecular modeling of the crystal growth of gas hydrates has proven in the past to be very challenging, we will provide a brief overview of the simulation framework we have utilized to achieve heterogeneous growth within timescales accessible to simulation. We will probe key issues concerning the nature of the solid/liquid interface for a variety of methane hydrate systems and will make important comparisons between various properties. For example, the interface demonstrates a strong affinity for methane molecules and we find a strong tendency for water molecules to organize into cages around methane at the growing interface. The dynamical nature of the interface and its microfaceted features will be shown to be crucial in the characterization of the interface. In addition to the small and large cages characteristic of sI and sII hydrates, water cages with a 51263 arrangement were identified during the heterogeneous growth of both sI and sII methane hydrate and their potential role in cross-nucleation of methane hydrate structures will be discussed. We will describe a previously unidentified structure of methane hydrates, designate structure sK, consisting of only 51263 and 512 cages, and will also show that a polycrystalline hydrate structure consisting of sequences of sI, sII and sK elements can be obtained. In this paper we will also detail a variety of host defects observed within the grown crystals. These defects include vacant cages, multiple methane molecules trapped in large cages, as well as one or more water molecules trapped in small and large cages. Finally, preliminary results obtains for THF and CO2 hydrates will be presented and their behaviour contrasted to that of methane hydrate.

Structure I and II gas hydrates were observed in the same sediment cores of a mud volcano in the Kukuy Canyon, Lake Baikal. The sII gas hydrate contained about 13-15% of ethane, whereas the sI gas hydrate contained about 1-5% of ethane and placed beneath the sII gas hydrate. We measured isotopic composition of dissociation gas from both type gas hydrates and dissolved gas in pore water. We found that ethane δD of sI gas hydrate (from -196 to -211 ‰) was larger than that of sII (from -215 to -220 ‰), whereas methane δ13C, methane δD and ethane δD in both hydrate structures were almost the same. δ13C of methane and ethane in gas hydrate seemed several permil smaller than those in pore water. These results support the following idea that the current gas in pore water is not the source of these gas hydrates of both structures. Isotopic data also provide useful information how the “double structure” gas hydrates formed.

Ice-associating proteins (IAPs) are proteins that interact directly with ice crystals, either by offering a site for nucleation, i.e. ice nucleating proteins (INPs), or by binding to nascent crystals to prevent addition of more water molecules, i.e. antifreeze proteins (AFPs). AFPs have been found to inhibit the formation of clathrate-hydrates, ice-like crystalline solids composed of water-encaged guest molecules. Study of AFP-hydrate interaction is leading to a greater understanding of AFP adsorption and of the mechanism behind the “memory effect” in hydrates, wherein previously frozen crystals reform more quickly after a brief melt. AFP is currently the only known memory inhibitor. Such a low-dosage hydrate inhibitor (LDHI) is of great interest to the oil and gas industry, as hydrate formation and reformation in the field is a huge problem. Bacterial AFPs, though largely uncharacterized, may be the best candidates for large-scale production of hydrate inhibitors, given the difficulties in obtaining AFP from other sources. The popular kinetic inhibitors (KIs) polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap) were used for points of comparison in experiments exploring the hydrate-inhibition activity of several ice-associating bacteria and proteins. The addition of the soil microbe, Chryseobacterium, increased the average lag-time to tetrahydrofuran (THF) hydrate formation by 14-fold, comparable to PVP or PVCap. Samples containing Pseudomonas putida, a bacterium having both ice-nucleation protein (INP) and AFP activity, had lag-times double that of the control. Solutions with P. putida and Chryseobacterium sometimes formed hydrate slurries of stunted crystal nuclei instead of solid crystals. No inhibition of memory or nucleation was noted in bacterial assays, however bacteria with INP activity was linked to unusually rapid memory reformation. Quartz crystal microbalance experiments with dissipation (QCM-D) showed that a tight adsorption to SiO2 and resistance to rinsing are correlated with a molecule’s inhibition of hydrate formation and reformation. These results support a heterogeneous nucleation model of the memory effect, and point to the affinity of AFP for heterogeneous nucleating particles as an important component of memory inhibition.
Thesis (Master, Biology) -- Queen's University, 2008-05-30 15:20:38.749

In the present study the effect of one commercially available anionic surfactant on the formation/dissociation of hydrate from a gas mixture of 90.5 % methane – 9.5% propane mixture was investigated. Surfactants are known to increase gas hydrate formation rate. Memory water was used and the experiments were carried out at three different degrees of undercooling and two different surfactant concentrations. In addition, the effect of the surfactant on storage capacity of gas into hydrate was assessed. The morphology of the growing crystals and the gas consumption were observed during the experiments. The results show that branches of porous fibre-like crystals are formed instead of dendritic crystals in the absence of any additive. Finally, the addition of 2200 ppm of SDS was found to increase the mole consumption for hydrate formation by 4.4 times.

Enormous amount of latent heat generates/absorbs at the formation/dissociation process of gas hydrates and controlls their thermal condition themselves. In this paper we investigated the effect of ethane concentration on dissociation heat of mixed-gas (methane and ethane) hydrate. It has been reported by researchers that a structure II gas hydrate appears in appropriate gas composition of methane and ethane. We confirmed by using Raman spectroscopy that our samples had the following three patterns: structure I only, structure II only and mixture of structures I and II. Dissociation heats of the mixed-gas hydrates were within the range between those of pure methane and ethane hydrates and increased with ethane concentration. In most cases two peaks of heat flow appeared and the dissociation process was divided into two parts. This can be understood in the following explanation that (1) the sample contained both crystal structures, and/or (2) ethane-rich gas hydrate formed simultaneously from dissociated gas and showed the second peak of heat flow.

Crystallization of water or water-encaged gas molecules occurs when nuclei reach a critical size. Certain antifreeze proteins (AFPs) can inhibit the growth of both of these, with most representations conceiving of an embryonic crystal with AFPs adsorbing to a preferred face, resulting in a higher kinetic barrier for molecule addition. We have examined AFP-mediated inhibition of ice and clathrate hydrate crystallization, and these observations can be both explained and modeled using this mechanism for AFP action. However, the remarkable ability of AFPs to eliminate „memory effect‟ (ME) or the faster reformation of clathrate hydrates after melting, prompted us to examine heterogeneous nucleation. The ubiquitous impurity, silica, served as a model nucleator hydrophilic surface. Quartz crystal microbalance-dissipation (QCM-D) experiments indicated that an active AFP was tightly adsorbed to the silica surface. In contrast, polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap), two commercial hydrate kinetic inhibitors that do not eliminate ME, were not so tightly adsorbed. Significantly, a mutant AFP (with no activity toward ice) inhibited THF hydrate growth, but not ME. QCM-D analysis showed that adsorption of the mutant AFP was more similar to PVCap than the active AFP. Thus, although there is no evidence for „memory‟ in ice reformation, and the structures of ice and clathrate hydrate are distinct, the crystallization of ice and hydrates, and the elimination of the more rapid recrystallization of hydrates, can be mediated by the same proteins.

No
Solvent influences on the crystallization of polymorph and hydrate forms of the nootropic drug piracetam (2-oxo-pyrrolidineacetamide) were investigated from water, methanol, 2-propanol, isobutanol, and nitromethane. Crystal growth profiles of piracetam polymorphs were constructed using time-resolved diffraction snapshots collected for each solvent system. Measurements were performed by in situ energy dispersive X-ray diffraction recorded in Station 16.4 at the synchrotron radiation source (SRS) at Daresbury Laboratory, CCLRC UK. Crystallizations from methanol, 2-propanol, isobutanol, and nitromethane progressed in a similar fashion with the initial formation of form I which then converted relatively quickly to form II with form III being generated upon further cooling. However, considerable differences were observed for the polymorphs lifetime and both the rate and temperature of conversion using the different solvents. The thermodynamically unstable form I was kinetically favored in isobutanol and nitromethane where traces of this polymorph were observed below 10°C. In contrast, the transformation of form II and subsequent growth of form III were inhibited in 2-propanol and nitromethane solutions. Aqueous solutions produced hydrate forms of piracetam which are different from the reported monohydrate; this crystallization evolved through successive generation of transient structures which transformed upon exchange of intramolecular water between the liquid and crystalline phases