<p>The relationship between the amount and conformation of apolymer at the solid-liquid interface, and the resultinginteraction forces between two such surfaces has beeninvestigated. With a degree of control of the polymerconformation, by varying the temperature, solvent quality,polymer charge density etc, it has been possible to measure andinterpret the resulting changes in the surface interactions.The recurring themes of dynamics and hydrodynamics have beencontinually considered due to the large range and viscoelasticnature of the polymeric systems.</p><p>The polymeric systems investigated in this thesis are, poly(N-isopropylacrylamide), poly (12-hydroxystearate) and a seriesof AM-MAPTAC polyelectrolytes with variable chargedensities.</p><p>Adsorption and conformation of polymers have beeninvestigated by the novel QCM instrument. By comparison tosimultaneously measured energy loss information, a greaterunderstanding of the conformation of the polymer has beengained, both as a function of layer build-up during initialadsorption, and as a result of induced conformational changes.Comparing the results to<i>in situ</i>surface plasmon resonance and subsequent x-rayphotoelectron spectroscopy measurements, the relativeconcentration of polymer within the layer is determined. Inaddition, efforts have been made to extend the scope of thetechnique, in such ways as measuring with QCM as a function oftemperature and deriving viscoelastic properties. The later isstill to be achieved in absolute terms for polymer layers inliquid environments, yet both the principle and experimentalcapabilities have been shown.</p><p>Normal interaction forces have been measured as a functionof solvation of the polymer layer, for both adsorbed andgrafted polymer layers. For fully solvated (steric) polymerlayers, which can act as colloidal stabilisers, the dynamics ofthe repulsive force, including hydrodynamics have beeninvestigated. The same has been achieved for collapsed polymerlayers, in which the dynamic adhesion has also beeninvestigated. The effect on the adhesion of three differentdynamic mechanisms has been determined (which, like the surfaceforces, depend on the polymer conformation andviscoelasticity). These dynamic mechanisms are based onbridging forces, polymer entanglement and a viscoelastic‘bulk’response from the surface layers.</p><p>Lateral or friction measurements have also been completed.The effect of load and rate have been investigated as afunction of both the polymer charge density and the underlyingsubstrate, which result in a variable conformation and bindingstrength to the substrate. This has resulted in a complexaddition of numerous mechanisms, the dominant mechanism beingdetermined by the binding strength to the surface, polymerconformation and viscoelasticity. The results have shown thatadsorbed polymer layers can be used to both increase anddecrease friction, and to change the direction of the ratedependence.</p>

Current problems on the interaction of complex liquids (i.e. droplets or foams) with complex surfaces (i.e. soft deformable or porous surfaces) are addressed in the following areas: (1) wetting of deformable substrates and surface forces, (2) kinetics of wetting and spreading of non-Newtonian liquids over porous substrates, (3) kinetics of spreading of non-Newtonian solutions over hair, (4) free drainage of foams produced from non-Newtonian solutions, and (5) foam drainage placed on porous substrates. Equilibrium of liquid droplets on deformable substrates was investigated and the effect of disjoining pressure action in the vicinity of the apparent three phase contact line was taken into account. It was proven that the deformation of soft solids is determined by the action of surface forces inside the transition zone. Spreading/imbibition of blood, which is a power law shear thinning non-Newtonian liquid, over a dry porous layer was investigated from both theoretical and experimental points of view. It was found that blood droplet spreading/imbibition over porous substrates shows two different behaviours: (i) partial wetting case with three subsequent stages: initial fast spreading, constant maximum droplet base and the shrinkage of the droplet base; (ii) complete wetting case with only two stages: initial fast spreading and the shrinkage of the droplet base. The wetting of hair tresses by aqueous solutions of two commercially available polymers, AculynTM 22 (A22) and AculynTM 33 (A33) was investigated experimentally. Both A22 and A33 solutions demonstrate well pronounced shear thinning behaviour. Initial contact angle of the A22 and A33 solutions on hair tresses was about 100o. The A22 droplets remained on the hair tress after spreading for at least half an hour. However, a fast penetration of the A33 droplets inside the hair tresses was observed when advancing contact angle in the course of spreading reached a critical value of about 60o. This could be explained by Cassie-Wenzel wetting transition which is caused by filling the pores inside the porous media by liquid. The influence of non-Newtonian rheology of A22 and A33 solutions on foam drainage was also investigated experimentally and a new theory of foam drainage was presented for the case of free drainage. For lowly viscous polymeric solutions and under the assumption of rigid surface of the Plateau border, the predicted values of the time evolution of the foam height and liquid content were in good agreement with the experimental data. However, in the case of highly viscous solutions an interfacial mobility at the surface of the Plateau border has to be taken into account. A completely new theory of foam drainage placed on porous substrate was developed. It was found that there are three different regimes of the process: (i) a rapid imbibition, the imbibition into the porous substrate dominates as compared with the foam drainage; (ii) an intermediate imbibition, that is, the imbibition into the porous substrate and the rate of drainage are comparable; (iii) a slow imbibition, the rate of drainage inside the foam is higher than the imbibition into the porous substrate for a period of time and a free liquid layer is formed over the porous substrate.

Le contrôle de la friction en régime limite s’effectue par le biais de lubrifiants qui, par l’adsorption de molécules sur les surfaces, réduisent les contacts directs entre aspérités. Dans ce contexte, l’objectif de cette thèse est de comprendre et de coupler les mécanismes, à la fois, d’adsorption et d’auto-organisation de différents acides gras sur des surfaces, et les mécanismes de friction interfaciale sous des conditions stationnaires et transitoires. L’effet de l’architecture moléculaire, modifiée par la présence et la conformation d’une insaturation dans la chaîne aliphatique des acides gras, a également été analysé. La caractérisation in-situ, à l’échelle moléculaire, a été réalisée avec le tribomètre moléculaire ATLAS développé au LTDS. Cet appareil permet des déplacements quasi-statiques et dynamiques, d’une sphère mise en regard d’un plan, suivant trois axes. Trois solutions d’acides gras, en faible concentration dans du dodécane, ont été analysées. Les déplacements et les forces, normaux et tangentiels, sont mesurés à l’aide de capteurs capacitifs d’une résolution respective de 0.015 nm et 10 nN. Des sollicitations dynamiques superposées permettent de caractériser simultanément la rhéologie de l’interface confinée en termes d’amortissement et de raideur, dans les deux directions. Les résultats montrent que les acides gras s’adsorbent par interaction physique sur les surfaces pour former des films visco-élastiques d’une épaisseur d’environ 15 Å sur chaque surface. Le taux de couverture et la cinétique d’adsorption de ces couches dépendent de l’architecture moléculaire des acides gras. Cette dernière gouverne également la friction interfaciale, qui a été qualifiée de supraglissement, et la rhéologie des monocouches auto-assemblées. Les différentes organisations de films conduisent ainsi à différentes évolutions de la friction en fonction de la vitesse de glissement et de la pression de contact. La réponse en friction transitoire et l’accommodation lors du glissement vers un nouvel état stationnaire ont de plus été décrites par des distances caractéristiques, de plusieurs nanomètres, reflétant le renouvellement statistique des spots de contact, et par des temps de relaxation, de l’ordre de la seconde, décrivant le réarrangement moléculaire au sein de l’interface. Enfin, une modélisation théorique de la friction limite a été proposée afin de comprendre l’origine moléculaire de la friction entre monocouches d’acides gras mettant ainsi en évidence le couplage fort de deux échelles spatiales et temporelles. / Friction in boundary lubrication can be controlled by the adsorption of molecules on surfaces that reduce direct contacts between asperities. In this context, the aim of this thesis is to understand and to couple the mechanisms of adsorption and self-organization of different fatty acids on surfaces, with the mechanisms of interfacial friction under steady-state regime and transient conditions. The effect of the molecular architecture, modified by the presence and conformation of one unsaturation in the aliphatic chain of fatty acids, was also analyzed. In-situ characterization, at the molecular level, was performed with the molecular tribometer ATLAS, developed at LTDS. This apparatus allows quasi-static and dynamic displacements, of a sphere in front of a plane in three directions. Three fatty acids solutions, in low concentration in dodecane, were analyzed. The displacements and the forces, normal and tangential, are measured using capacitive sensors with a resolution of 0.015 nm and 10 nN respectively. Dynamic superimposed measurements allow a simultaneous rheological characterization of the confined interface in terms of damping and stiffness in two directions. The results show that the fatty acids adsorb on the surfaces by weak interactions and form viscoelastic films with a thickness of about 15 Å on each surface. The coverage rate and adsorption kinetics of these layers depend on the molecular architecture of the fatty acids. This architecture also governs interfacial friction, which has been described as superlubricity, and the rheology of self-assembled monolayers. Various film organizations have thus led to different evolutions of the friction as a function of the sliding speed and the contact pressure. The transient friction response and its accommodation during slip to a new stationary state have also been described by characteristic distances of several nanometers, reflecting the statistic average renewal of the contact spots, and by relaxation times of the order of the second, describing the molecular rearrangement within the interface. Finally, theoretical modeling of boundary friction has been proposed to understand the molecular origin of the friction between monolayers of fatty acids and highlight the strong coupling between both spatial and temporal scales.

The adsorption of cationic and zwitterionic surfactants is studied in aqueous electrolyte solutions. A Maxwell relation is applied to Atomic Force Microscopy (AFM) data to obtain changes in surfactant adsorption as a function of the separation between two glass surfaces. In addition, self-consistent field theory (SCF) is used to calculate the adsorption profiles and interaction energies when two solid surfaces are brought into close proximity. Addition of surfactant is shown to affect the surface forces when lateral surfactant chain interactions are significant. The surfactant adsorbs and desorbs in response to over-lapping electric double-layers, with the adsorption being affected at larger solid-solid separations when the double-layer force is longer ranged. Furthermore, elimination off the surface charge or net surfactant charge eliminates adsorption with decreased solid-solid separation. The magnitude of the changes in surfactant adsorption at decreased separations is shown to scale with the chain length of the surfactant. Surfactant adsorption exceeds that required to regulate the surface charge according to the constant potential boundary condition in Poisson-Boltzmann theory. An equation of state including short-ranged (contact) tail interactions is proposed to describe both the adsorption of surfactant and the surface forces at small separations, where the double-layers overlap. Furthermore, SCF calculations show confinement-induced phase transitions when the surfactant layers on opposite surfaces merge. These phase transitions lead to further surfactant adsorption and a corresponding attractive force. / Ph. D.

Although enormous potential benefits are envisioned with the application of nanotechnology in conjunction with biological systems, interactions of nano particulate materials with biological materials is not well understood. The focus of this dissertation is to determine the mathematical relationships of the forces between nanoparticles and biological agents. The systems under investigation are the alpha-SiC/H2O/LGG polar based systems. The mathematical analysis for the surface forces, based on the attractive van der Waals forces for the alpha-SiC/H2O/alpha-SiC and alpha-SiC/H2O/LGG polar solvent based systems are presented and discussed. The rheological parameters including pH, zeta potential, shear rate, shear stress and viscosity that alter the dispersion mechanisms are also presented and discussed. The concurrence of the experimental analysis with the mathematical modeling is also presented. The rheological analysis in these systems for determining of the optimum amounts of dispersant, binder, plasticizer and solids loading using the Krieger-Dougherty fit and Liu's model are presented and discussed. Alpha-SiC/H2O/alpha-SiC and alpha-SiC/H2O/LGG polar solvent based samples were also fabricated to test for an application area of nano-bio technology: A novel nano and micro porous materials fabrication process. Porous materials are used for a variety of applications including insulation, filtration, catalytic substrates, textiles and consumer goods and accounts for billions of dollars in sales annually. Results from the alpha-SiC/H2O/alpha-SiC and alpha-SiC/H2O/LGG polar solvent based slip and freeze cast samples and their characterization using digital and electron microscopy are presented and discussed. Finally, the green and sintered density, porosity and strength of the alpha-SiC/H2O/alpha-SiC and alpha-SiC/H2O/LGG polar solvent based dispersion samples are determined and discussed. / Ph. D.

Στην παρούσα διδακτορική διατριβή έγινε μελέτη πολυμερικών βουρτσών που διαμορφώνονται από συμπολυμερή πολυστυρενίου-πολυβουταδιενίου που φέρουν στην άκρη τους ομάδες ικανές να προσροφηθούν (PS-PB-Zw) Η μελέτη έγινε κυρίως με την τεχνικής της μέτρησης δυνάμεων (SFA) και της ανάκλασης νετρονίων. Ιδιαίτερο ενδιαφέρον παρουσιάζουν οι γραμμικές πολυμερικές αλυσίδες όπου ένα μεγάλου μοριακού βάρους πολυμερές φέρει στην άκρη του μια μόνο ακραία ομάδα. Τα γραμμικά αυτά συμπολυμερή είχαν μελετηθεί και στο παρελθόν. Το ζητούμενο όμως ήταν να μεταβάλλουμε την αρχιτεκτονική αυτή και να παρατηρήσουμε τις πιθανές μεταβολές στα ποιοτικά χαρακτηριστικά των προσροφημένων πολυμερικών στρωμάτων που διαμορφώνουν. Ως μέτρο σύγκρισης μελετήσαμε αρχικά τις ήδη μελετημένες γραμμικές αλυσίδες και στη συνέχεια προχωρήσαμε στη μελέτη των νέων δειγμάτων. Προσθέσαμε δύο και τρεις ακραίες ομάδες στο άκρο της πολυμερικής αλυσίδας μεγάλου μοριακού βάρους και αναμέναμε σύμφωνα με θεωρητικές προβλέψεις αύξηση στο προσροφημένο ποσό. Η αύξηση αυτή θα ήταν εμφανής μέσω της αύξησης του πάχους του πολυμερικού στρώματος που εύκολα μπορεί να μετρηθεί με την τεχνική της μέτρησης των δυνάμεων αλληλεπίδρασης. Επίσης μετρήσαμε άμεσα το προσροφημένο ποσό και με την τεχνική της ανάκλασης νετρονίων για πολυμερή τριών διαφορετικών μοριακών βαρών (25000, 70000 και 150000). Το σημαντικότερο αποτέλεσμά μας είναι ότι δεν παρατηρήσαμε αύξηση στο προσροφημένο ποσό σε σχέση με τις γραμμικές αλυσίδες και σε χρόνους ενός τυπικού πειράματος. Υπήρχε ωστόσο η υποψία ότι σε βάθος χρόνου μπορεί να αυξάνεται το προσροφημένο ποσό. Για το λόγο αυτό διεξαγάγαμε μια σειρά από μετρήσεις «κινητικής» με την τεχνική της ανάκλασης νετρονίων, αλλά και με συμπληρωματικές τεχνικές (διέγερση επιφανειακών πλασμονίων). Καμία μεταβολή δεν παρατηρήσαμε στο προσροφημένο ποσό, ούτε σε βάθος χρόνου αλλά ούτε και με την προσθήκη επιπλέον ακραίων ομάδων ικανών να προσροφώνται σε επιφάνειες. Στη συνέχεια επεκτείναμε τη μελέτη μας στην «αντίστροφη» αρχιτεκτονική. Διατηρήσαμε μια ακραία ομάδα και προσθέσαμε δύο και τρεις πολυμερικές αλυσίδες μεγάλου μοριακού βάρους (Μr=70000). Η αρχιτεκτονική που διαμορφώσαμε με τον τρόπο αυτό ήταν ουσιαστικά αρχιτεκτονική αστεροειδών πολυμερών με μικρό αριθμό πλοκαμιών. Στη περίπτωση αυτή παρατηρήσαμε μια σταδιακή μείωση του προσροφημένου ποσού με την προσθήκη επιπλέον βραχιόνων στο αστέρι. Η μείωση αύτη έχει παρατηρηθεί τόσο από μετρήσεις δυνάμεων, όσο και από μετρήσεις με ανάκλαση νετρονίων. Στα προφίλ δυνάμεων παρατηρούμε διαφοροποιήσεις σε σχέση με την γενική εικόνα που εμφανίζουν οι πολυμερικές βούρτσες. Αυτές οι διαφοροποιήσεις μπορούν να ερμηνευτούν με τη βοήθεια θεωρητικών προβλέψεων για τη συμπεριφορά των αστεροειδών πολυμερών. Η μείωση του προσροφημένου ποσού με αύξηση του αριθμού των πλοκαμιών μπορεί να αποδοθεί είτε σε λόγους κινητικής, είτε σε λόγους αλληλεπίδρασης μεταξύ των πολυμερικών αλυσίδων και μεταξύ των πλοκαμιών ενός μακρομορίου. Επίσης στη παρούσα διδακτορική διατριβή μελετήσαμε τη συμπεριφορά προσροφημένων ασθενών πολυ-ηλεκτρολυτών. Οι πολυ-ηλεκτρολύτες συγκεντρώνουν σταδιακά την προσοχή όλο και περισσότερων ερευνητών καθώς εμφανίζουν αρκετές σημαντικές εφαρμογές και είναι συμβατοί με βιολογικά συστήματα. Μέχρι πριν λίγο καιρό οι ασθενείς πολυ-ηλεκτρολύτες, όπως είναι το πολυακρυλικό οξύ που μελετούμε στη παρούσα εργασία, δεν είχαν μελετηθεί εκτενώς. Η μελέτη τους παρουσιάζει δυσκολίες, λόγω της πολυπλοκότητας στη συμπεριφορά τους. Αυτή εξαρτάται τόσο από τη συγκέντρωση άλατος του διαλύματος, όσο και από το pH. Μεταβάλλαμε τόσο τη συγκέντρωση άλατος του διαλύματος, όσο και το pH του διαλύματος εξετάζοντας πως αυτά επηρεάζουν το πάχος του προσροφημένου στρώματος και τα ποιοτικά χαρακτηριστικά των πολυ-ηλεκτρολυτικών προσροφημένων στρωμάτων. Παρατηρήσαμε λοιπόν μείωση του πάχους της πολυ-ηλεκτρολυτικής βούρτσας με αύξηση της συγκέντρωσης άλατος. Το αποτέλεσμα αυτό είναι πλήρως συμβατό με θεωρητικές προβλέψεις. Στη συνέχεια εξετάσαμε τη συμπεριφορά των ασθενών πολυ-ηλεκτρολυτών μεταβάλλοντας το pH του διαλύματος. Παρατηρήσαμε ότι με αύξηση του pH οι πολυμερικές αλυσίδες εκτείνονταν αυξάνοντας το πάχος της πολυμερικής βούρτσας. Αυτή η συμπεριφορά είναι άμεσο αποτέλεσμα της αύξησης του βαθμού διάστασης των πολυμερικών αλυσίδων. Αυξάνοντας το pH περισσότερα φορτία αποσπώνται από την πολυμερική αλυσίδα φορτίζοντάς την έτσι ισχυρότερα. Οι απωστικές ηλεκτροστατικές αλληλεπιδράσεις μεταξύ των φορτίων εξαναγκάζουν την αλυσίδα σε έκταση επιμηκύνοντας την πολυμερική βούρτσα. Τα αποτελέσματα αυτά είναι επίσης σε πλήρη συμφωνία με θεωρητικές προβλέψεις. / Flexible polymer chains end-tethered to a surface in good solvent tend to extend away from the surface due to excluded volume interactions. At sufficiently high grafting densities the chains become elongated normal to the surface, this extension being opposed by an elastic restoring force of entropic origin to form a layer of stretched chains referred to as a “polymer brush”. These systems have been studied extensively in recent years by numerous experimental techniques and theoretical methods. In the present investigation we have studied asymmetric star-shaped polymers whereby the different arms are either non-adsorbing PS chains or short PB chains terminating in a zwitterionic end-group known to adsorb strongly on surfaces such as mica or quartz. In this manner, it is possible on the one hand to form brushes with a single PS chain, but multiple zwitterionic stickers, and on the other to study the reverse case of multiple non-adsorbing arms attached to a surface via a single zwitterions. We have used the surface force balance technique to determine the interaction between such brush-layers formed on mica and neutron scattering to determine the absorbed amount and interanchor distance. Interactions between polymer brushes formed by highly asymmetric star-like polymers with a long PS arm and one, two or three short PB arms each terminating in a zwitterionic end-group were studied in order to explore the effect of the sticking energy on the brush structure. Polystyrene stars with two and three tails bearing a single end group were also studied to investigate how the height of the adsorbed layer and the grafting density are affected. Our measurements show no significant differences between PS with 1, 2 and 3 end groups. This may be due to kinetic reasons since additional polymer chains are hindered from attaching to a brush-bearing surface. The behavior of two PS chains with one end-group ((PS)2-PB-X) seems not to differ appreciably from that of PS-PB-X copolymer. On the other hand three PS chains with one end-group ((PS)3-PB-X) appeared to form layers with smaller brush height and greater interanchoring distance, relative to PS-PB-X layers. We can attribute this to the extra stretching that the three-chain architecture imposes on the adsorbed brush. In the present investigation we have also studied weak polyelectrolytes. Polyelectrolytes (charged polymer chains) remain among the least understood materials despite their importance in biology (proteins, DNA) and materials science. Their behavior and characteristics are not yet fully understood because of complicated correlations due to their charged nature that gives rise to long-range interactions. The counterplay of their properties as polymers and electrolytes with counterions around polyelectrolyte chains imposes additional difficulties on explaining their behavior. The association of counterions around polyelectrolytes and the pH of the solution are two parameters than can affect the properties of such systems. Especially weak polyelectrolytes (like poly-acrylic acid) are even sensitive to pH changes because of the alterable degree of dissociation. We measured forces between two charged polymer layers of Poly (isoprene-acrylic acid) diblock copolymers adsorbed on mica surfaces. Poly (isoprene-acrylic acid) diblock copolymers can be adsorbed from one end (poly-isoprene) which is sorter than the poly-(acrylic acid) part. The properties of the polymer layer at various salt concentrations and different pH of the solutions were measured by Surface Forces Apparatus. Information about the height of the polymer layer, and the adsorbed amount were extrapolated. The extracted results were compared with theoretical predictions showing well fit.

No description available.

L'hydrate de méthane est un cristal non-stœchiométrique dans lequel les molécules d'eau forment des cages liées par liaison hydrogène qui piégent des molécules de méthane. Des ressources abondantes en hydrate de méthane peuvent être trouvées sur Terre, en particulier dans les roches poreuses minérales (par exemple, l'argile, le permafrost, les fonds marins, etc.). Pour cette raison, la compréhension de la thermodynamique et de la cinétique de formation de l'hydrate de méthane confiné dans des milieux poreux suscite beaucoup d'attention. Dans cette thèse, nous combinons la modélisation moléculaire et des approches théoriques pour déterminer la thermodynamique et la cinétique de formation de l'hydrate de méthane confiné dans des milieux poreux. Tout d'abord, l'état de l'art en matière de thermodynamique et de cinétique de formation de l'hydrate de méthane est présenté. Deuxièmement, différentes stratégies de simulation moléculaire, y compris des calculs d'énergie libre utilisant l'approche de la molécule d'Einstein, la méthode de coexistence directe et la technique textit{hyperparallel tempering}, sont utilisées pour évaluer la stabilité de l'hydrate de méthane à différentes températures et pressions. Troisièmement, parmi ces stratégies, la méthode de coexistence directe est choisie pour déterminer le déplacement du point de fusion lors du confinement dans des pores, $Delta T_m = T_m^{pore} - T_m^{bulk} $ où $ T_m^{pore}$ et $T_m^{bulk}$ sont les températures de fusion d'hydrate de méthane non confiné et confiné. Nous avons constaté que le confinement diminue la température de fusion, $T_m^{pore} < T_m^{bulk} $. Le changement de température de fusion en utilisant la méthode de la coexistence directe est cohérent avec l'équation de Gibbs-Thompson qui prédit que le décalage de la température de fusion dépend linéairement de l'inverse de la taille des pores, $Delta T_m/T_m^{bulk} sim k_{GT}/ D_p$. La validité quantitative de cette équation thermodynamique classique pour décrire de tels effets de confinement et de surface est également abordée. Les tensions de surface des interfaces hydrate-substrat et eau-substrat sont déterminées à l'aide de la dynamique moléculaire pour valider quantitativement l'équation de Gibbs-Thompson. Des simulations de dynamique moléculaire sont également effectuées pour déterminer les propriétés thermodynamiques importantes de l'hydrate de méthane non confiné et confiné: (a) conductivité thermique $lambda$ en utilisant le formalisme de Green-Kubo et la fonction d'autocorrélation du flux thermique; (b) expansion thermique $alpha_P$ et compressibilité isotherme $kappa_T$. Enfin, des conclusions et perspectives pour des travaux futurs sont présentées. / Methane hydrate is a non-stoichiometric crystal in which water molecules form hydrogen-bonded cages that entrap methane molecules. Abundant methane hydrate resources can be found on Earth, especially trapped in mineral porous rocks (e.g., clay, permafrost, seafloor, etc.). For this reason, understanding the thermodynamics and formation kinetics of methane hydrate confined in porous media is receiving a great deal of attention. In this thesis, we combine computer modeling and theoretical approaches to determine the thermodynamics and formation kinetics of methane hydrate confined in porous media. First, the state-of-the-art on the thermodynamics and formation kinetics of methane hydrate is presented. Second, different molecular simulation strategies, including free energy calculations using the Einstein molecule approach, the direct coexistence method, and the hyperparallel tempering technique, are used to assess the phase stability of bulk methane hydrate at various temperatures and pressures. Third, among these strategies, the direct coexistence method is chosen to determine the shift in melting point upon confinement in pores, $Delta T_m = T_{m}^{pore} - T_{m}^{bulk}$ where $T_m^{pore}$ and $T_m^{bulk}$ are the melting temperatures of bulk and confined methane hydrate. We found that confinement decreases the melting temperature, $T_m^{pore}<T_m^{bulk}$. The shift in melting temperature using the direct coexistence method is consistent with the Gibbs-Thompson equation which predicts that the shift in melting temperature linearly depends on the reciprocal of pore width, i.e., $Delta T_m/T_m^{bulk} sim k_{GB}/D_p$. The quantitative validity of this classical thermodynamic equation to describe such confinement and surface effects is also addressed. The surface tensions of methane hydrate-substrate and liquid water-substrate interfaces are determined using molecular dynamics to quantitatively validate the Gibbs-Thompson equation. Molecular dynamics simulations are also performed to determine important thermodynamic properties of bulk and confined methane hydrate: (a) thermal conductivity $lambda$ using the Green-Kubo formalism and the autocorrelation function of the heat-flux and (b) the thermal expansion $alpha_P$ and isothermal compressibility $kappa_T$. Finally, some conclusions and perspectives for future work are given.

In this thesis the interactions in cellulose systems havebeen studied with emphasis on surface forces and adsorptionphenomenon. The study was limited to surfaces and polymers ofinterest for papermaking. During papermaking both therunability of the paper machine as well as the properties ofthe final paper will depend on the molecular interactionsbetween the components present in the suspension. The objectiveof this work was to gain a better understanding of theseinteraction forces and how they are affected by solutionconditions like pH and electrolyte concentration. The maintechniques employed for this purpose were direct surface forcemeasurements using both the interferometric surface forceapparatus (SFA) and the atomic force microscopy (AFM)colloidal-probe technique. In addition, both electronspectroscopy for chemical analysis (ESCA) and AFM imaging wereused for surface characterisation and to study adsorptionbehaviour. Since a smooth and transparent surface is needed forsurface force studies using SFA, Langmuir-Blodgett films ofcellulose were employed. The interactions between cellulose surfacesand xylansurfaces were studied. Cellulose is the main constituent of thewood fibre. In close association with cellulose in the cellwall are the hemicelluloses, xylan being a commonhemicellulose. Steric forces were found to dominate theinteractions between these substances in aqueous solutions.Still factors like charge density, solution pH and electrolyteconcentration were important. The adhesion between cellulosesurfaces in air depended on the contact area. The effect of acationic polyelectrolyte on the forces between cellulosesurfaces and between cellulose and mineral surfaces wasinvestigated to obtain a better understanding of the effects ofcationic retention and strength additives. In the presence of acationic polyelectrolyte the forces at large distances weredominated by double-layer repulsion. Bridging attraction was insome cases observed, but the presence and magnitude of thisforce was dependent on the properties of the substratesurface. Lignin on the fibre surface affects brightness, swelling andstrength of paper. In addition, dissolved lignin interfereswith added polymers during papermaking. For this reason theadsorption of lignin on cellulose fibre surfaces was explored.The adsorption of lignin was influenced by the concentration oflignin in solution and by the electrolyte composition of thesolution. The retention of lignin was affected by the presenceof a cationic polyelectrolyte and particularly by how thepolyelectrolyte was added. The AFM imaging revealed thestructure of the adsorbed lignin, which varied with the way ofadding the polyelectrolyte, and gave an idea about theadsorption mechanism. The effect of lignin on strengthproperties of paper sheets was also evaluated. Keywords: cellulose, hemicellulose, xylan, lignin, surfaceforces, adsorption, polyelectrolyte, SFA, AFM, ESCA,Langmuir-Blodgett films, chitosan, steric forces,bridging,adhesion

The main objective for the work described in this PhD thesiswas to formulate a friction model to characterize thefrictional behavior of paper. More specifically, the modelshould explain a phenomenon that is typical for paper grades,viz.: that the level of paper-to-paper friction is dependent onthe direction and the number of previous slides. The modelshould also explain the lubricating effect oflow-molecular-mass lipophilic compounds (LLC) that occur inpaper on paper-to-paper friction. Furthermore, the model shoulddescribe the types of forces that influence paper-to-paperfiction and explain the mechanism by which the LLC decreasepaper-to-paper friction. This thesis consists of a literature review of the basicconcepts of tribology and a summary of the main results andconclusions from four studies on the frictional characteristicsof paper and a study on the friction and adhesion of cellulosesurfaces together with some unpublished material. The purpose of the investigation described in the firstpaper was to explain a phenomenon that is typical for papergrades, viz.: the level of paper-to-paper friction is dependenton the direction and the number of previous slides. Thisbehavior is called“friction hysteresis”by theauthors, and it has its origin in the reorientation of thefibers on the surface of a paper and their alignment relativeto the sliding direction. The second paper describes a study that was aimed atidentifying lubricants that occur natively in paper. Filterpapers were impregnated with model compounds representing woodextractives, i.e. low-molecular-weight lipophilic compounds,which are present in wood, pulp and paper, and thepaper-to-paper friction was determined. The results of thatstudy show that a wood extractive must fulfill severalstructural criteria in order to lubricate a paper surface: Itmust have a hydrophilic group that can attach to the papersurface and a linear hydrocarbon backbone of sufficientlength. Although it is not specifically stated in the second paper,the authors proposed a type of lubrication by which woodextractives decrease paper-to-paper friction that is, ineffect, boundary lubrication. The purpose of the investigationdescribed in the third paper was to clarify whether woodextractives and other low-molecular-mass lipophilic compoundsthat occur in paper can act as boundary lubricants on papersurfaces. The main objective of that study was to investigatethe role of chemical structure of LLC for their orientationrelative to the paper surface, which is an important criterionfor boundary lubrication. Filter papers were impregnated withmagnesium salts of different lipophilic acids, which were usedfor model compounds for the LLC. The deposited layers ofmagnesium salts were characterized by X-ray photoelectronspectroscopy (XPS) and contact angle goniometry and thefriction of the impregnated paper sheets was determined. Theresults show that the degree of lubrication and the resistanceto wear of the layers of a magnesium salt increased withincreasing chain length and increasing degree of linearity ofthe lipophilic acid. Based on the results of that study and ofearlier studies, it is concluded that boundary lubrication isthe type of lubrication by which low-molecular-mass lipophiliccompounds that occur natively in paper decreasepaper-to-paper-friction. In boundary lubrication, surfaces are covered withmonolayers of lubricant molecules that comprise an active headgroup that can attach to the surface, e.g. a carboxyl group,and an inert linear backbone, such as a long saturatedhydrocarbon chain. Such compounds form ordered monolayers onsurfaces, so that the backbone points vertically out of planeof the surface. The friction is then determined by theinteractions between the monolayers, which are weaker than theinteractions between the clean surfaces and this gives a lowerfriction. The fourth paper describes a study on the origin of thedifferences in friction levels between different linerboardsbased on recycled fiber (old corrugated container, OCC). Thesheets were subjected to two extraction stages and analyzedwith respect to surface roughness and their content oflow-molecular-mass lipophilic compounds (LLC). The resultsshowed that a high amount of LLC in the sheets lead to lowfriction, due to lubrication. The fifth paper describes a study that was aimed atdetermining the types of forces that influence the frictionbetween the surfaces of hydrophilic polymers and explaining themechanism by which boundary lubricants decrease the friction.The adhesion and the friction of model systems was measuredwith atomic force microscopy (AFM) using regenerated cellulosefilms and functionalised AFM tips and the effect of fatty acidsand humidity was investigated. The friction significantlyincreased with increasing humidity and that there was a strongcorrelation between the ability of a fatty acid to form ahydrophobic surface and its lubricating performance. Measuredadhesion forces at high humidity were well predicted bytheoretical models that took into account the effect of theLaplace pressure acting in a water meniscus formed aroundcontact regions due to capillary condensation. The resultsindicated that the degree of capillary condensation may beeffectively suppressed by increasing the hydrophobicity of thecontacting surfaces, causing adhesion and friction to decrease.These results suggest that friction between paper surfacesunder ambient conditions is greatly influenced by the degree ofcapillary condensation. Furthermore, lubrication by fatty acidsis achieved by the formation of a vertically oriented,hydrophobic monolayer that can withstand the stresses duringsliding and increase the hydrophobicity of the paper surfaceand thereby suppress capillary condensation. <b>Keywords:</b>Friction, paper-to-paper friction, frictionhysteresis, fibers, orientation, sliding direction, woodextractives, low-molecular-mass lipophilic compounds, boundarylubrication, adhesion, capillary condensation, Laplacepressure, surface forces, JKR theory, gas chromatography-massspectroscopy, X-ray photoelectron spectroscopy, contact angle,atomic force microscopy