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.

Approved for public release, distribution is unlimited / Warfare planners and tacticians are seeking ways to leverage information technology to gain advantage on the battlefield. With the advent of Internet technologies, complex systems are becoming more networked, and access to information is more critical than ever. The increasing utilization of special operations forces in ad hoc, dynamic operations poses a need for adaptable communications to support the unit. Effective communication within the unit and critical information exchange with the command center affect the overall outcome of the mission. An adaptive, mobile network with UAV relays is well-suited to support the ad hoc nature of special operations. The area of research for this thesis is the role of the tactical network operations communication coordinator in mobile UAV networks. The coordinator's purpose is to oversee the management and status of the network and provide feedback to network participants, thus resulting in an effective and well-functioning environment. The tactical network coordinator is an important and integral part of network operations by establishing what is known as network awareness. This thesis will be a model for sharing network awareness, and it will explore the potential benefits of incorporating network performance as a planning objective rather than a constraint. / First Lieutenant, United States Air Force

Approved for public release; distribution is unlimited / A historical analysis of the Iraqi military suggests that certain actions should be taken if the state building process of the United States led coalition is to be successful. The fulcrum of power in Iraq has always been the internecine ethnic, religious, and tribal relationships and interactions. This thesis studies the recently constructed security structure of Iraq, particularly the new Iraqi Armed Forces, by focusing on likely influences of the ethnic and sectarian factions and social structure of the country on security and reconstruction/reintegration of the new Iraqi Military. The thesis brings into sharp focus a singular fact that the military of Iraq has always been used in one way or another against one section of the population or another by the prevailing political power using the time-honored virtues of patronage and corruption. The use of the military in Iraq as an internal political tool more than anything else contributed to the lack of national identity, the prerequisite for a sound military structure. The thesis presents some situational operating methodologies that if followed should provide a structurally sound modern Iraqi military rather than a supernumerary police force. The recommendations would not only provide a military as a strong basis for national unity and identity, but they would create a military contributing to regional stability. / Major, Turkish Army

La République Centrafricaine, 622 984 km2 pour 4,525 millions d’habitants en 2012, est une ancienne colonie française, indépendante le 13 août 1960. Durant les premières décennies post-indépendance, un État faiblement structuré a été mis en place. Au moment où les efforts conjugués des bailleurs de fonds commençaient à inscrire une nouvelle dynamique de stabilité, la rébellion de la Séléka conduite par Michel Djotodia, a pris le pouvoir le 24 mars 2013. Depuis lors, le pays est confronté à l’une de ses crises majeures, caractérisée par l’intermittence de la violence, la pluralité des acteurs et la complexité des facteurs belligènes. Le défi de sécurité étant un déterminant incompressible, ce travail est construit autour de l’impact irréversiblement positif de la refonte des Forces de défense et de sécurité dans la construction de la paix, de la stabilité et du développement. / The Central African Republic, 622,984 km2 area for 4.525 million inhabitants in 2012, is a former French colony that became independent on August 13, 1960. During the first decades of post-independence, a weakly structured state was established. At the time when the combined efforts of the donors were beginning to introduce a new dynamic of stability, the Séléka rebellion led by Michel Djotodia took power on March 24, 2013. Since then, the country has faced one of its major crisis, characterized by the intermittent violence, the plurality of actors and the complexity of the belligerent factors. The security challenge is an incompressible means, this academic work is built around the positive irreversibly impact of the armed forces and security in the building of peace, stability and development in Central African Republic.

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

Hydraulic spool valves are found in most hydraulic circuits in which flow is to be modulated. Therefore their dynamic performance is critical to the overall performance of the circuit. Fundamental to this performance is the presence of flow reaction forces which act on the spool. These forces can result in the necessity of using two stage devices to drive the spool and in some cases have been directly linked to valve and circuit instabilities. As such, a great deal of research and design has concentrated on ways to reduce or compensate for flow forces. In one particular series of studies conducted on flow divider valves, it was established that a rim machined into the land of the spool reduced the flow dividing error by approximately 70-80%, and it was deduced that the main contribution to this error was flow forces. Direct verification of the claim regarding flow force reduction was not achieved and hence was the motivation for this particular study. <p> This thesis will consider the reaction (flow) force associated with a conventional spool land and one with a rim machined into it, and a modified form of the rimmed land referred to as a sharp edge tapered rim spool land. The rim and the sharp edge tapered rim were specially designed geometrical changes to the lands of the standard spool in order to reduce the large steady state flow forces (SSFF) inherent in the standard spool valve. In order to analyze the flow field inside the interior passages of the valve, three configurations of the spool were considered for orifice openings of 0.375, 0.5, 0.75 and 1.05 mm. Computational Fluid Dynamics (CFD) analysis was used to describe the fluid mechanics associated with the steady state flow forces as it provided a detailed structure of the flow through the valve, and to identify the flow mechanism whereby flow forces are reduced by the machining of a rim and tapered rim on the land of the spool. For all openings of the spool, the sharp tapered rim valve provides the largest reduction in SSFF. It was also observed that for all cases studied, the inflow SSFFs were smaller than for the outflow conditions. <p>The prediction of the steady state flow force on the rim spool was investigated in a flow divider valve configuration, and the results from the CFD analysis indicated a reduction by approximately 70%.

University of Macau / Faculty of Law

Hydraulic spool valves are found in most hydraulic circuits in which flow is to be modulated. Therefore their dynamic performance is critical to the overall performance of the circuit. Fundamental to this performance is the presence of flow reaction forces which act on the spool. These forces can result in the necessity of using two stage devices to drive the spool and in some cases have been directly linked to valve and circuit instabilities. As such, a great deal of research and design has concentrated on ways to reduce or compensate for flow forces. In one particular series of studies conducted on flow divider valves, it was established that a rim machined into the land of the spool reduced the flow dividing error by approximately 70-80%, and it was deduced that the main contribution to this error was flow forces. Direct verification of the claim regarding flow force reduction was not achieved and hence was the motivation for this particular study. <p> This thesis will consider the reaction (flow) force associated with a conventional spool land and one with a rim machined into it, and a modified form of the rimmed land referred to as a sharp edge tapered rim spool land. The rim and the sharp edge tapered rim were specially designed geometrical changes to the lands of the standard spool in order to reduce the large steady state flow forces (SSFF) inherent in the standard spool valve. In order to analyze the flow field inside the interior passages of the valve, three configurations of the spool were considered for orifice openings of 0.375, 0.5, 0.75 and 1.05 mm. Computational Fluid Dynamics (CFD) analysis was used to describe the fluid mechanics associated with the steady state flow forces as it provided a detailed structure of the flow through the valve, and to identify the flow mechanism whereby flow forces are reduced by the machining of a rim and tapered rim on the land of the spool. For all openings of the spool, the sharp tapered rim valve provides the largest reduction in SSFF. It was also observed that for all cases studied, the inflow SSFFs were smaller than for the outflow conditions. <p>The prediction of the steady state flow force on the rim spool was investigated in a flow divider valve configuration, and the results from the CFD analysis indicated a reduction by approximately 70%.