In this thesis, geometry is used as a basis for conducting experiments aimed at growing and arranging inorganic minerals on curved interfaces. Mineralisation is directed using crystalline and liquid-crystalline metallic soaps and surfactant/water systems as templates.¶ A review of the history, syntheses, structure and liquid crystallinity of metallic soaps and other amphiphiles is presented as a foundation to understanding the interfacial architectures in mesostructured template systems in general.¶ In this study, a range of metallic soaps of varying chain length and cation type are synthesised and characterised to find potentially useful templates for mineral growth. These include alkaline-earth, transition metal, heavy metal and lanthanide soaps. These are systematically characterised using a variety of analytical techniques, including chemical analyses, x-ray diffraction (XRD) infrared spectroscopy (IR) and differential scanning calorimetry (DSC). Their molecular and crystal structures are studied using transmission electron microscopy (TEM), cryo-TEM, electron diffraction (ED), electron paramagnetic spin resonance (EPR), absorption spectroscopy (UV-VIS), high resolution laser spectroscopy, atomic force microscopy (AFM), nuclear magnetic resonance spectroscopy, scanning electron microscopy (SEM), electron dispersive x-ray analysis (EDXA), thermal gravimetric analysis (TGA) and magnetic measurements. Models for the molecular and crystal structures of metallic soaps are proposed. The soaps are predominantly lamellar crystalline or liquid crystalline lamellar rotor phases with tilted and/or untilted molecular constituents. These display evidence of varying degrees of headgroup organisation, including superstructuring and polymerisation. A single crystal structure is presented for a complex of pyridine with cobalt soap. Simple models for their structure are discussed in terms of their swelling properties in water and oils. Experiments are also presented to demonstrate the sorbent properties of aluminium soaps on oil spills.¶ The thermotropic liquid crystallinity of alkaline earth, transition metal, heavy metal and lanthanide soaps is investigated in detail. This is done to assess their suitability as templates, and to document their novel thermotropic behaviour, particularly the relatively unknown lanthanide soaps. Liquid crystalline behaviours are studied using high-temperature XRD (HTXRD), hot-stage optical microscopy and DSC. Models for a liquid crystalline phase progression from crystals to anisotropic liquids are discussed in terms of theories of self-assembly and interfacial curvature. The terminology required for this is drawn from various nomenclature systems for amphiphilic crystals and liquid crystals. General agreement with previous studies is reported for known soaps, while liquid crystallinity is demonstrated in the lanthanide and some non-lanthanide soaps for the first time. A general phase progression of crystalline lamellar through liquid crystalline lamellar to non-lamellar liquid crystalline is discussed in terms of models concerned with the molecular and crystal structures of the soaps and their phase transitions via headgroup and chain re-arrangements.¶ Experiments aimed at guiding growth of metal sulfides using metallic soaps as templates are described, and a model for this growth is discussed. Metal sulfides have been successfully grown by reacting crystalline and liquid crystalline transition metal and heavy metal soaps with H2S gas at room temperature and at elevated temperature. These have been characterised using XRD, TEM, ED and IR. Sulfide growth is demonstrated to be restricted and guided by the reacting soap template architecture. Zinc, cadmium, indium and lead soaps formed confined nanoparticles within the matrix of their reacting soap template. In contrast, curved and flat sheet-like structures, some resembling sponges were found in the products of sulfided iron, cobalt, nickel, copper, tin and bismuth soaps. A model to explain this behaviour is developed in terms of the crystal and liquid crystal structures of the soaps and the crystal structures of the metal sulfide particles.¶ Liquid crystalline iron soaps have been subjected to controlled thermal degradation yielding magnetic iron oxide nanoparticles. Some XRD and TEM evidence has been found for formation of magnetic mesostructures in heat-treated iron soaps. Models for the molecular and liquid crystalline structure of iron soaps, their thermotropic phase progression and eventual conversion to these magnetic products are discussed. Systematic syntheses of mesoporous silicates from sheeted clays are discussed.¶The templates that have been used are cationic surfactants and small, organic molecular salts. Experiments are reported where a cooperative self-assembly of surfactant/water/kanemite plus or minus salt and oils yields 'folded sheet materials' (FSM'S). Templating of kanemite has also been achieved using cobalt cage surfactants. A theoretical prediction of the specific surface areas and specific volumes of homologous sets of FSM's gave excellent agreement with measured values. The geometry and topology of the mesostructures are discussed. A theoretical model is also discussed regarding the curvature found in the sheets of natural clays , and results of templating clays and silica using metallic soaps are presented. Experiments and a model for low temperature nucleation and growth of microporous silicalite-1 are described in terms of silica templating by water clathrates.¶ Finally, the problem of finding minimal surface descriptions of crystal networks is addressed. Combinatoric methods are used to disprove the existence of possible embeddings of type I and II clathrate networks in non-self intersecting periodic minimal surfaces. The crystal network of the clathrate silicate, melanophlogite is successfully embedded in the WI-10 self-intersecting surface. Details of a previously unreported, genus-25 periodic surface with symmetry Im3m are discussed.

研究生：江雅文(1999) 論文題目：光電產業競爭優勢之研究--以國內LCD產業為例 研究所名稱：國立政治大學企業管理學系碩士班 論文摘要： 光電產業中的「光電顯示元件」在未來高度資訊化的時代中將扮演著重要的人機界面媒介，除了筆記型電腦及LCD監視器的應用之外，在「後PC時代」中，消費性電子產品及多媒體產品的應用範圍將擴大，對顯示元件之需求量將大增。現在的消費大眾對電子產品的要求傾向輕薄、省電、低輻射、環保性。傳統的CRT(Cathode Ray Tube, 陰極射線管)顯示器已無法滿足這方面的訴求，因而各類的平面顯示器正不斷地被研發中。包括液晶顯示器(LCD，Liquid Crystal Display)、電漿顯示器(PDP，Plasma Display Panel)、電激發光顯示器(ELD，Electron Luminescent Display)、真空螢光顯示器(VFD，Vacuum Fluorescent Display)、發光二極體(LED，Light Emitting Diode)、場發射顯示器(FED，Field Emission Display)等。 液晶顯示器(以下簡稱LCD)則因技術已趨成熟，其需求隨著全球筆記型電腦及LCD監視器市場的成長而迅速擴增，此外，液晶顯示技術的發展也刺激了其他電子產品的創新，其範圍涵蓋了資訊、通訊及消費性電子商品等。因此，LCD產業的發展被資訊界喻為本世紀末的產業革命之一，因為其具有輕薄、省電、無輻射、不佔空間及可攜性等優勢，隨著多元化應用的推廣及技術的發展，LCD的整體市場規模將急遽成長。 由於液晶顯示器產業是一個相當重要的高科技產業，對於國內相關產業的關鍵零組件自主性與促進產業升級都有重大的影響。尤其是這個產業在技術與市場上的變化仍相當快速。目前以日本及韓國對我國之威脅最大，我國廠商要如何在這個光電市場領域中建立競爭優勢，找到適當定位，是一個很重要的課題。此外，自1997年開始，國內各大廠商及集團紛紛集資興建大尺寸TFT-LCD廠，預計在1999年至2001年間投產。究竟這個產業有何吸引力，為何能夠讓各種不同型態的廠商爭相投入，是個有趣的問題。而在一陣投資熱潮之後，業者是否會因產能過剩，面臨殺價競爭的慘烈局面，投入的業者應如何在這樣不確定的環境前題之下建立競爭優勢，則是個應認真思考的嚴肅議題。 本研究希望透過研究的過程，廣泛地探討競爭優勢的觀念，從競爭優勢形成的條件、競爭優勢的來源，到競爭優勢最後表現出的市場競爭效果，做一觀念上的釐清，以便對競爭優勢的分析有一深入的認知。進而找出一套適用於光電顯示元件LCD產業之有系統的競爭優勢分析架構。在實務上則希望能夠作為業者擬定企業競爭策略及政府擬定產業政策的基礎。 研究首先確立研究背景。在釐清研究問題與目的之後，著手蒐集相關產業資訊，並據以界定研究範圍；並根據文獻探討擬定研究架構作為LCD產業分析之基本架構。競爭優勢分析之理論基礎主要係按照Porter(1980)的五力分析架構，於初步了解台灣LCD產業的優勢、劣勢、機會與威脅之後，再根據Porter(1990)國家優勢競爭之鑽石模型概念分析我國發展LCD產業之競爭優勢形成條件，最後，再針對台灣LCD產業的未來發展提出策略建議。 本研究為一探索性研究，為釐清LCD產業的環境及條件前提，必須建立產業分析的基本資料。首先廣泛地蒐集國內外相關的文獻、報告、期刊、雜誌、報紙及新聞等次級資料，採用Porter(1980)五力分析架構及Porter(1990)國家優勢競爭之鑽石模型概念將之整理、歸納。本著資訊收集網路化的原則，透過網際網路瀏覽器廣泛地蒐集相關網站資訊。接著，對國內廠商與相關專家進行訪談，以了解國內產業最新發展動態及其對產業競爭優勢之看法，期能提出我國LCD產業之競爭優勢狀況及可行策略，作為業者之參考。 目 錄 第一章 緒論 第一節 研究背景 1 第二節 研究問題與目的 4 第三節 研究範圍 5 第二章 文獻探討 第一節 競爭優勢的觀念 7 第二節 競爭優勢及其來源 8 第三節 價值鏈模型 22 第四節 鑽石模型 24 第五節 動態競爭理論 26 第三章 研究設計 第一節 研究流程及架構 30 第二節 分析方法及資料來源 31 第三節 研究限制 32 第四章 光電產業概述 第一節 世界光電產業概述 34 第二節 我國光電產業概述 36 第三節 結論 47 第五章 LCD產業之發展概述 第一節 LCD產業概述 50 第二節 整體LCD產業發展趨勢 71 第三節 我國LCD產業發展概況 83 第四節 LCD產業未來發展趨勢 105 第六章 我國LCD產業之競爭優勢分析 第一節 我國LCD產業結構分析 117 第二節 我國LCD產業之競爭優勢分析 121 第三節 LCD產業之鑽石模型分析模式 126 第四節 我國LCD產業未來發展策略建議 130 第七章 結論與建議 第一節 結論 135 第二節 建議 138 參考文獻 141 附錄一 145

This thesis, which contains fourteen chapters in two parts, presents theoretical and computer simulation studies of dynamics in supercooled liquids and thermotropic liquid crystals. These two apparently diverse physical systems are unified by a startling similarity in their complex slow dynamics. Part I consists of six chapters on supercooled liquids while Part II comprises seven chapters on thermotropic liquid crystals. The fourteenth chapter provides a concluding note. Part I starts with an introduction to supercooled liquids given in chapter 1. This chapter discusses basic features of supercooled liquids and the glass transition and portrays some of the theoretical frameworks and formalisms that are widely recognized to have contributed to our present understanding. Chapter 2 introduces a new model of binary mixture in order to study dynamics across the supercooled regime. The system consists of an equimolar mixture of the Lennard-Jones spheres and the Gay-Berne ellipsoids of revolution, and thus one of its components has orientational degrees of freedom (ODOF). A decoupling between trans-lational diffusion and rotational diffusion is found to occur below a temperature where the second rank orientational correlation time starts showing a steady deviation from the Arrhenius temperature behavior. At low temperatures, the optical Kerr effect (OKE) signal derived from the system shows a short-to-intermediate time power law decay with a very weak dependence on temperature, if at all, of the power law exponent as has been observed experimentally. At the lowest temperature investigated, jump motion is found to occur in both the translational and orientational degrees of freedom. Chapter 3 studies how the binary mixture, introduced in the previous chapter, explores its underlying potential energy landscape. The study reveals correlations between the decoupling phenomena, observed almost universally in supercooled molecular liquids, and the manner of exploration of the energy landscape of the system. A significant deviation from the Debye model of rotational diffusion in the dynamics of ODOF is found to begin at a temperature at which the average inherent structure energy of the system starts falling as the temperature decreases. Further, the coupling between rotational diffusion and translational diffusion breaks down at a still lower temperature, where a change occurs in the temperature dependence of the average inherent structure energy. Chapters 4-6 describe analytical and numerical approaches to solve kinetic models of glassy dynamics for various observables. The β process is modeled as a thermally activated event in a two-level system and the a process is described as a β relaxation mediated cooperative transition in a double-well. The model resembles a landscape picture, conceived by Stillinger [Science 267, 1935 (1995)], where the a process is assumed to involve a concerted series of the β processes, the latter being identified as elementary relaxations involving transitions between contiguous basins. For suitable choice of parameter values, the model could reproduce many of the experimentally observed features of anomalous heat capacity behavior during a temperature cycle through the glass transition as described in chapter 4. The overshoot of the heat capacity during the heating scan that marks the glass transition is found to be caused by a delayed energy relaxation. Chapter 5 shows that the model can also predict a frequency dependent heat capacity that reflects the two-step relaxation behavior. The high-frequency peak in the heat capacity spectra appears with considerably larger amplitude than the low-frequency peak, the latter being due to the a relaxation. The model, when simplified with a modified description of the a process that involves an irreversible escape from a metabasin, can be solved analytically for the relaxation time. This version of the model captures salient features of the structural relaxation in glassy systems as described in chapter 6. In Part II, thermotropic liquid crystals are studied in molecular dynamics simulations using primarily the family of the Gay-Berne model systems. To start with, chapter 7 provides a brief introduction to thermotropic liquid crystals, especially from the perspective of the issues discussed in the following chapters. This chapter ends up with a detail description of the family of the Gay-Berne models. Chapter 8 demonstrates that a model system for calamitic liquid crystal (comprising rod-like molecules) could capture the short-to-intermediate time power law decay in the OKE signal near the isotropic-nematic (I-N) phase transition as observed experimentally. The single-particle second rank orientational time correlation function (OTCF) for the model liquid crystalline system is also found to sustain a power law decay regime in the isotropic phase near the I-N transition. On transit across the I-N phase boundary, two power law decay regimes, separated by a plateau, emerge giving rise to a step-like feature in the single-particle second rank OTCF. When the time evolution of the rotational non-Gaussian parameter is monitored as a diagnostic of spatially heterogeneous dynamics, a dominant peak is found to appear following a shoulder at short times, signaling the growth of pseudonematic domains. These observations are compared with those relevant ones obtained for the supercooled binary mixture, as discussed in chapter 2, in the spirit of the analogy suggested recently by Fayer and coworkers [J. Chem. Phys. 118, 9303 (2003)]. In chapter 9, orientational dynamics across the I-N transition are investigated in a variety of model systems of thermotropic liquid crystals. A model discotic system that consists of disc-like molecules as well as a lattice system have been considered in the quest of a universal short-to-intermediate time power law decay in orientational relaxation, if any. A surprisingly general power law decay at short to intermediate times in orientational relaxation is observed in all these systems. While the power law decay of the OKE signal has been recently observed experimentally in calamitic systems near the I-N phase boundary and in the nematic phase by Fayer and coworkers [J. Chem. Phys. 116, 6339 (2002), J. Phys. Chem. B 109, 6514 (2005)], the prediction for the discotic system can be tested in experiments. Chapter 10 presents the energy landscape view of phase transitions and slow dynamics in thermotropic liquid crystals by determining the inherent structures of a family of one-component Gay-Berne model systems. This study throws light on the interplay between the orientational order and the translational order in the mesophases the systems exhibit. The onset of the growth of the orientational order in the parent phase is found to induce a translational order, resulting in a smectic-like layer in the underlying inherent structures. The inherent structures, surprisingly, never seem to sustain orientational order alone if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. The Arrhenius temperature dependence of the orientational relaxation time breaks down near the I-N transition and this breakdown is found to occur at a temperature below which the system explores increasingly deeper potential energy minima. There exists a remarkable similarity in the manner of exploration of the potential energy landscape between the Gay-Berne systems studied here and the well known Kob-Andersen binary mixture reported previously [Nature, 393, 554 (1998)]. In search of a dynamical signature of the coupling between orientational order and translational order, anisotropic translational diffusion in the nematic phase has been investigated in the Gay-Berne model systems as described in chapter 11. The translational diffusion coefficient parallel to the director D// is found to first increase and then decrease as the temperature drops through the nematic phase. This reversal occurs where the smectic order parameter of the underlying inherent structures becomes significant for the first time. The non-monotonic temperature behavior of D// can thus be viewed from an energy landscape analysis as a dynamical signature of the coupling between orientational and translational order at the microscopic level. Such a view is likely to form the foundation of a theoretical framework to explain the anisotropic translation diffusion. Chapter 12 investigates the validity of the Debye model of rotational diffusion near the I-N phase boundary with a molecular dynamics simulation study of a Gay-Berne model system for calamitic liquid crystals. The Debye model is found to break down near the I-N phase transition. The breakdown, unlike the one observed in supercooled molecular liquids where a jump diffusion model is often invoked, is attributed to the growth of orientational pair correlation. A mode-coupling theory analysis is provided in support of the explanation. Chapter 13 presents a molecular dynamics study of a binary mixture of prolate ellipsoids of revolution with different aspect ratios interacting with each other through a generalized Gay-Berne potential. Such a study allows to investigate directly the aspect ratio dependence of the dynamical behavior. In the concluding note, chapter 14 starts with a brief summary of the outcome of the thesis and ends up with suggestion of a few relevant problems that may prove worthwhile to be addressed in future.

Dendrimers are a class of monodisperse polymeric macromolecules with a well defined and highly branched three-dimensional architecture. Their well-defined structure and structural precision makes them outstanding candidates for the development of new types of multifunctional super-molecules and materials with applications in medicine and pharmacy, catalysis, electronics, optoelectronics, etc. Liquid Crystalline Dendrimers (LCDrs) are a relatively new class of super-molecules which are based on the functionalization of common dendrimers with mesogenic (liquid crystalline) units. The combination of the fascinating molecular properties of the common dendrimers with the directionality of the mesogenic units have produced a novel class of liquid crystal forming super-mesogens (LCDRs) with unique molecular properties that allow novel ways of supramolecular self-assembly and self-organisation. This work is mainly concerned with the computational modelling of LCRs. A coarse grain strategy is adopted for the development of computational tractable models which take explicitly into account the specific architecture, the extended flexibility and the shape anisotropy of the mesogenic units of LCDRs. The developed force field applies easily to a variety of dendritic architectures. Utilizing Monte Carlo computer simulations we study the structural and conformational behavior of single LCDrs and of systems of LCDrs either in confined geometries or in the bulk. Special emphasis is given on the modeling of the response of LCDRS on externally applied alignment fields. External fields might be fictitious aligning potentials which mimic electric or magnetic fields or fields induced by the confining substrates. The surface alignment of liquid crystalline dendrimers (LCDrs) is a key factor for many of their potential applications. We present results from Monte Carlo simulations of LCDrs adsorbed on flat, impenetrable aligning substrates. A tractable coarse-grained force field for the inter-dendritic and the dendrimer-substrate interactions is introduced. The developed force field is based on modifications of well-known interaction potentials that can be used either with MC or with molecular dynamics simulations. We investigate the conformational and ordering properties of single, end-functionalized LCDrs under homeotropic, random (or degenerate) planar and nidirectional planar aligning substrates. Depending on the anchoring constrains to the mesogenic units of the LCDr and on temperature, a variety of stable ordered LCDr states, differing in their topology, are observed and analyzed. The influence of the dendritic generation and core functionality on the surface-induced ordering of the LCDrs are examined. The study has been extended to system of LCDrs confined in nano-pores of different shapes and sizes under several anchoring conditions. Two basic confining geometries (pores) considered in this work: slit and cylindrical pores. In each confining geometry, different anchoring conditions are imposed. The Isobaric-Isothermal (NPT) Monte Carlo Simulation is used to investigate the thermodynamic and structural properties of these nano-confined systems. The ransmission of orientational and positional ordering from the surface to the middle region of the pore depends on the size of the pore as well as on temperature and on anchoring strength. In the case of cylindrical pore, alignment propagation is short ranged compared to that of slit-pore. As a benchmark of our coarse-grained modelling strategy, we have extended and tested our coarse grained Force Field for the study of Janus-like dendrimers confined on planar substrates. The obtained results indicate the capability of our model to capture successfully the highly amphipilic nature of these class dendrimers and their self-organisation properties. / Τα δενδριμερή είναι μία κατηγορία μονοδιάσπαρτων πολυμερικών μακρομορίων με δενδρόμορφη τρισδιάστατη αρχιτεκτονική. Η μοριακή αρχιτεκτονική τους και η μονοδιασπορά τους καθιστούν τα δενδριμερή ιδανικά ως πολυλειτουργικά υπερ-μόρια με εφαρμογές στην ιατρική και τη φαρμακολογία, την κατάλυση, την ηλεκτρονική και οπτοηλεκτρονική κλπ. Τα Υγρό-Κρυσταλλικά Δενδριμερή (ΥΚΔ) είναι μια σχετικά νέα κατηγορία υπερ-μορίων που βασίζονται στη χημική τροποποίηση των κοινών δενδριμερών με μεσογόνες (υγρόκρυσταλλικές) μοριακές μονάδες. Ο συνδυασμός των ιδιαίτερων μοριακών ιδιοτήτων των κοινών δενδριμερών με την κατευθυντικότητα των μεσογόνων έχουν οδηγήσει σε μια νέα κατηγορία υπερ-μεσογόνων (ΥΚΔ) με μοναδικές μοριακές ιδιότητες που επιτρέπουν νέους τρόπους (υπερ)μοριακής αυτο-συναρμολόγησης και αυτο-οργάνωσης. Η εργασία αυτή ασχολείται με τη μοντελοποίηση και την υπολογιστική προσομοίωση ΥΚΔ. Εισάγονται οι αρχές για μια αδροποιημένη μοντελοποίηση ΥΚΔ που να λαμβάνει ρητά υπόψη την ειδική αρχιτεκτονική, την εκτεταμένη μοριακή ευκαμψία και την ανισοτροπία σχήματος των μεσογόνων του ΥΚΔ. Τα δυναμικά αλληλεπιδράσεων που εισάγονται επιτρέπουν τη μοντελοποίηση ποικίλων δενδριτικών αρχιτεκτονικών. Με την χρήση υπολογιστικών προσομοιώσεων Monte Carlo μελετώνται οι μοριακές ιδιότητες απλών ΥΚΔ διαφόρων γενεών και αρχιτεκτονικών καθώς και η θερμοδυναμική συμπεριφορά και οι μετατροπές φάσεων συστημάτων ΥΚΔ. Ιδιαίτερη έμφαση δίνεται στην μοντελοποίηση της απόκρισης των LCDRS σε εξωτερικά πεδία που μπορούν να προκαλέσουν ευθυγράμμισης των μεσογόνων ομάδων του ΥΚΔ. Τα εξωτερικά εφαρμοζόμενα πεδία μπορεί να είναι δυναμικά ευθυγράμμισης που μιμούνται τα ηλεκτρικά ή μαγνητικά πεδία ή πεδία που επάγονται από τους γεωμετρικούς περιορισμούς (συνοριακές συνθήκες) που επιβάλλονται στο υλικό όταν βρίσκεται κοντά σε επιφάνειες ή περιορισμένο εντός πόρων. Η δυνατότητα επίτευξης κοινού μοριακού προσανατολισμού στις μεσοφάσεις από ΥΚΔ αποτελεί βασικό παράγοντα για πολλές από τις πιθανές εφαρμογές τους. Παρουσιάζονται αποτελέσματα προσομοιώσεων Monte Carlo Μόντε ΥΚΔ σε επαφή με επίπεδο, αδιαπέραστο υπόστρωμα που έχει τη δυνατότητα προσρόφησης (αγκύρωσης) των μεσογόνων μονάδων του ΥΚΔ υπό επιθυμητό προσανατολισμό. Τα αποτελέσματα βασίζονται σε κατάλληλα αδροποιημένο πεδίο δυνάμεων για την περιγραφή των αλληλεπιδράσεων μεταξύ των δενδριμερών καθώς και του δενδριμερούς με το υπόστρωμα. Ανάλογα με τον τύπο μοριακής αγκύρωσης στην επιφάνεια και τη θερμοκρασία, μια ποικιλία από διαφορετικούς τρόπους οργάνωσης του ΥΚΔ στην επιφάνεια παρατηρούνται και αναλύονται. Η μελέτη έχει επεκταθεί επίσης σε συστήματα ΥΚΔ περιορισμένα σε νανο-πόρους διαφόρων σχήματα και μεγεθών κάτω από διάφορες συνθήκες μοριακής αγκύρωσης. Οι δύο βασικές γεωμετρίες περιορισμού (πόροι) που μελετούνται αναφέρονται σε παραλληλεπίπεδους και κυλινδρικούς πόρους. Σε κάθε γεωμετρία επιβάλλονται διαφορετικές συνθήκες αγκύρωσης. Οι προσομοιώσεις Monte Carlo έγιναν στην ισοβαρή συλλογή (ΝΡΤ) και διερευνήθηκε η θερμοδυναμική συμπεριφορά καθώς και η μοριακή οργάνωση των συστημάτων υπό νανο-εγκλεισμό. Τα συστήματα αυτά παρουσιάζουν πλούσια θερμοδυναμική συμπεριφορά. Η μοριακή οργάνωση καθώς και η μετάδοση του προσανατολισμού και της τάξης θέσεων από την επιφάνεια προς την μεσαία περιοχή των πόρων εξαρτάται το σχήμα και τι μέγεθος του πόρου, από τη θερμοκρασία καθώς και από τις συνθήκες μοριακής αγκύρωσης στις επιφάνειες του πόρου. Για έλεγχο της αποτελεσματικότητας της στρατηγικής αδροποιημένης μοντελοποίησης που αναπτύχθηκε μελετήθηκαν επίσης αμφίφυλα δενδριμερή τύπου Janus περιορισμένα σε επίπεδη επιφάνεια. Τα αποτελέσματα των προσομοιώσεων έδειξαν την ικανότητα του μοντέλου μας να αποτυπώσει με επιτυχία το την αμφίφυλη φύση αυτών των δενδρομερών και να περιγράψει με επιτυχία διαφορετικούς τύπους αυτοργάνωσης που σχετίζονται με την αμφιφυλικότητα αυτών των μορίων και τον συνεπαγόμενο νανο-φασικό διαχωρισμό τους.

A considerable amount of mineral particles are found to have a plate-like shape. The work in this thesis concerns theoretical investigations, using a Monte Carlo method, of the properties of such particles in aqueous solutions. The objectives were first to create a model that could capture the essential physics of clay suspensions and also to understand the role of thermodynamics in certain chemical processes. For all investigations, the results are related to experimental studies. The acid-base behavior of clays have been studied, using the primitive model, and an excellent agreement between simulated and experimental results was found. The formation of gel phases as a function of the charge anisotropy have also been investigated. Liquid-gel and sol-gel transitions are found to occur for high and moderate charge anisotropy, respectively. These transitions were also found to be size and salt dependent. In absence of charge anisotropy, a liquid-glass transition is reported. The formation of smectic and columnar liquid crystals phases with plate-like particles has been found to be favored by a strong charge anisotropy, in opposition to what was observed for nematic phases. New liquid-crystal phases were also reported. The stability and growth of nanoplatelets is discussed. It was found that the internal Coulombic repulsion could be the cause of the limited growth of C-S-H platelets. The influence of thermodynamics on the agregation mode of such platelets was also investigated

在台灣，未來很有可能帶領台灣高科技產業向上突破的新英雄---薄晶電晶體液晶顯示器（TFT-LCD），已逐漸為人所重視，近來，TFT-LCD產業的更是利多頻傳，不但在股票成交量創下新高，股價更是一再突破新高。本文則是希望以資料包絡分析法(DEA)來比較分析台灣各家廠商（友達、華映、奇美電、廣輝、彩晶）的相對經營績效，研究範圍從2001年第四季一直到2004年的第一季，所採用的投入變數即為資產總額、營業成本、營業費用和員工人數，產出變數我們則採用營業收入和營業淨利。 總結來看，廠商在CCR和BCC模式下，雖然在平均排名上，兩個模式並不盡相同，但由時間趨勢來看，五家廠商在趨勢變動上，大致是一樣的；效率值表現較好的時期為2002Q1、和2002Q2和2004Q1，較差的則為2002Q4和2003Q1，推測其原因，一部分當然是和景氣的波動有關，但也和面板的價格波動有一定程度的相關。 藉由Tobit 迴歸分析，意味著廠商可藉由提高每人配備率、總資產週轉率、流動比率、研發費用率及經營年限等變數，可提昇廠商的整體技術效率，提供了一些政策方向供廠商參考。 以Malmquist生產力指數來看，總要素生產力的變動（Tfpch）大部分的因素，是來自於生產技術的變動(Tech）；彩晶在總要素生產力的變動上，平均有16.8%的成長，是第1名，其他的廠商則呈現不大的差別；但若以時間趨勢來看，2001Q4到2002Q1和2003Q1到2003Q2兩各階段都有滿大的成長，但在2002Q2到2002Q3和2002Q3到2002Q4兩個階段卻呈現衰退的表現。 / In Taiwan, TFT-LCD, which is likely to lead high-tech to strive upward in the future, has been receiving more and more attention. Recently, TFT-LCD industry has come into great blossom. Not only does the stock transaction amount achieve a record-breaking peak, but the stock price also makes breakthroughs at all times. This research is to use Data Envelopment Analysis(DEA) to compare and analyze the relative operating efficiency of chief leaders in the high-tech industry, including AUO, CPT, CMO, QDI to HannStar. The research ranges from the 4th quarter in 2001 to the 1st quarter in 2004. The researcher adopts input variables, which include total assets, business costs, business expenses and employees, and output variables, business revenues and business net profits, as well. On the whole, in spite of CCR and BCC model, the average order is different, but approximately similar. The quarters, which perform well, are the 1st quarter in 2002 and the 1st quarter in 2004; the bad quarters are the 4th quarter in 2002 and the 1st quarter in 2003. To speculate reasons, it has to do with the business cycle and panel board price fluctuation. Under the frame, by use of Tobit analysis, factories can strengthen total technology efficiency by raising equipment per employee, total asserts turnover, current ratio, R & D ratio, and the period of operating. It provides these factories a referential direction. In conclusion, according to Malmquist index analysis, the Tfpch is the better part from the tech. HannStar, with 16.8% average growth in Tfpch, is the top one. The other factories are nearly close. In the time period, from the 4th quarter in 2001 to the 1st quarter in 2002, and from the 1st quarter in 2003 to the 2nd quarter in 2003, the other factories has a high growth, but from the 2nd quarter in 2002 to the 3rd quarter in 2002 and from the 3rd quarter in 2002 to the 4th quarter in 2002, there is a decline in growth.

Dans le cadre de cette thèse, on s'intéresse à la dynamique de quelques fluides complexes. D'une part on étudie la dynamique des cristaux liquides nématiques, en utilisant les modèles proposés par Ericksen et Leslie, Beris et Edwards, Qian et Sheng. D'autre part, on analyse un fluide complexe dont la dynamique dépend de la température et qui est modélisée par le système de Boussinesq. Les cristaux liquides sont des matériaux avec une phase de la matière intermédiaire entre les liquides et les solides qui sont des phases plus connues. Dans cette thèse, on s'intéresse à l'étude du problème de Cauchy associé à chaque système modélisant leurs hydrodynamiques. Tout d'abord on obtient des résultats d'existence et d'unicité de solutions faibles ou classiques, solutions qui sont globales en temps. Ensuite, on analyse la propagation de la régularité des données initiales pour ces solutions. Le cadre fonctionnel adopté pour les données initiales est celui des espaces de Besov homogènes, généralisant des classes d'espaces mieux connues : les espaces de Soboloev homogènes et les espaces de Hölder. Le système Ericksen-Leslie est considéré dans la version simplifiée proposée par F. Lin et C. Liu, version qui préserve les principales difficultés du système initial. On étudie ce problème en dimension supérieure ou égale à deux. On considère le système dans le cas inhomogène, c'est-à dire avec une densité variable. De plus, on s'intéresse au cas d'une densité de faible régularité qui est autorisée à présenter des discontinuités. Donc, le résultat que l'on démontre peut être mis en relation avec la dynamique des mélanges de nématiques non miscibles. On démontre l'existence globale en temps de solutions faibles de régularité invariante par changement d'échelle, en supposant une condition de petitesse sur les données initiales dans des espaces de Besov critiques. On démontre aussi l'unicité de ces solutions si de plus on suppose une condition supplémentaire de régularité pour les données initiales. Le système Beris-Edwards est analysé dans le cas bidimensionnel. On obtient l'existence et l'unicité de solutions faibles globales en temps, lorsque les données initiales sont dans des espaces de Sobolev spécifiques (sans condition de petitesse). Le niveau de régularité de ces espaces fonctionnels est adapté pour bien définir les solutions faibles. L'unicité est une question délicate et demande une estimation doublement logarithmique pour une norme sur la différence entre deux solutions dans un espace de Banach convenable. Le lemme d'Osgood permet alors de conclure à l'unicité de la solution. On obtient également un résultat de propagation de régularité d'indice positif. Afin de prendre en compte l'inertie des molécules, on considère aussi le modèle proposé par Qian et Sheng, et on étudie le cas de la dimension supérieure ou égale à deux. Ce système montre une caractéristique structurale spécifique, plus précisément la présence d'un terme inertiel, ce qui génère des difficultés significatives. On démontre l'existence d'une fonctionnelle de Lyapunov et l'existence et l'unicité de solutions classiques globales en temps, en considérant des données initiales petites. Enfin, on analyse le système de Boussinesq et on montre l'existence et l'unicité de solutions globales en temps. On considère la viscosité en fonction de la température en supposant simplement que la température initiale soit bornée, tandis que la vitesse initiale est dans des espaces de Besov avec indice de régularité critique. Les données initiales ont une composante verticale grande et satisfont à une condition de petitesse spécifique sur les composantes horizontales: elles doivent être exponentiellement petites par rapport à la composante verticale. / The present thesis is devoted to the dynamics of specific complex fluids. On the one hand we studythe dynamics of the so-called nematic liquid crystals, through the models proposed by Ericksen and Leslie, Beris and Edwards, Qian and Sheng.On the other hand we analyze the dynamics of a temperature-dependent complex fluid, whose dynamics is governed by the Boussinesq system.Nematic liquid crystals are materials exhibiting a state of matter between an ordinary fluid and a solid. In this thesis we are interested in studying the Cauchy problem associated to eachsystem modelling their hydrodynamics. At first, we establish some well-posedness results, such asexistence and uniqueness of global-in-time weak or classical solutions. Moreover we also analyzesome dynamical behaviours of these solutions, such as propagations of both higher and lowerregularities.The general framework for the initial data is that of Besov spaces, which extend the most widelyknown classes of Sobolev and Hölder spaces.The Ericksen-Leslie system is studied in a simplified form proposed by F. Lin and C. Liu,which retains the main difficulties of the original one. We consider both a two-dimensional and athree-dimensional space-domain. We assume the density to be no constant, i.e. the inhomogeneouscase, moreover we allow it to present discontinuities along an interface so that we can describe amixture of liquid crystal materials with different densities. We prove the existence of global-in-timeweak solutions under smallness conditions on the initial data in critical homogeneous Besov spaces.These solutions are invariant under the scaling behaviour of the system. We also show that theuniqueness holds under a tiny extra-regularity for the initial data.The Beris-Edwards system is analyzed in a two-dimensional space-domain. We achieve existenceand uniqueness of global-in-time weak solutions when the initial data belongs to specific Sobolevspaces (without any smallness condition). The regularity of these functional spaces is suitable inorder to well define a weak solution. We achieve the uniqueness result through a specific analysis,controlling the norm of the difference between to weak solutions and performing a delicate doublelogarithmicestimate. Then, the uniqueness holds thanks to the Osgood lemma. We also achieve aresult about regularity propagation.The Qian-Sheng model is analyzed in a space-domain with dimension greater or equal than two.In this case, we emphasize some important characteristics of the system, especially the presence ofan inertial term, which generates significant difficulties. We perform the existence of a Lyapunovfunctional and the existence and uniqueness of classical solutions under a smallness condition forthe initial data.Finally we deal with the well-posedness of the Boussinesq system. We prove the existence ofglobal-in-time weak solutions when the space-domain has a dimension greater or equal than two.We deal with the case of a viscosity dependent on the temperature. The initial temperature is justsupposed to be bounded, while the initial velocity belongs to some critical Besov Space. The initialdata have a large vertical component while the horizontal components fulfil a specific smallnessconditions: they are exponentially smaller than the vertical component.

La tectonique moléculaire est l’étude de la construction d’architectures cristallines périodiques par l’auto-assemblage de tectons. L’objectif de ces travaux fut d’associer les principes de la tectonique moléculaire à la possibilité de fonctionnalisation du macrocycle porphyrinique dans l’optique de générer des assemblages fonctionnels.Dans une première partie, la fonctionnalisation de surface avec des porphyrines a été réalisée. La synthèse de porphyrines originales dissymétriques méso-substituées par des groupes coordinants de type pyridine, éthynylpyridine ou éthynylterpyridine a été mise au point. Ces porphyrines ont conduit à la formation de réseaux mono- ou bi-dimensionnels sur différentes surfaces.La seconde partie s’intéresse à la formation de réseaux de coordination à l’état cristallin. De nouvelles porphyrines ont été synthétisées dans le but de générer des réseaux chiraux, directionnels ou encore flexibles à l’état cristallin.Enfin, dans une dernière partie, la fonctionnalisation de porphyrines par des groupements pyrogallates a été réalisée. Une porphyrine et son complexe de zinc ont ainsi conduit à la formation de mésophases colonnaires rectangulaires. Dans cette partie, l’introduction de groupements isomérisables à la périphérie du macrocycle porphyrinique a également été réalisée dans le but de générer des mésophases photo-commutables. / Molecular tectonic studies the construction of periodic crystalline architectures through self-assembly of tectons. The objective of this work was to associate the principles of molecular tectonic to the possibility of functionalization of the porphyrin macrocycle to generate functional assemblies.In the first part, the surface functionalization with porphyrins was performed. The synthesis of novel meso-substituted asymmetric porphyrins with several coordinating groups such as pyridine, ethynylpyridine or ethynylterpyridine was carried. These porphyrins have allowed the formation of mono- or bi-dimensional networks on surfaces.The second part focuses on the formation of coordination networks in the crystalline state. Different porphyrins were synthesized in order to generate chiral, directional or flexible networks in the solid state.Finally, in a last part, the functionalization of porphyrins with pyrogallate groups was performed. One porphyrin and it zinc complex have shown the formation of rectangular columnar mesophases. In this part, the functionalization of the porphyrin with isomerizable groups was also performed in order to generate photo-commutable mesophases.

L'objectif de cette thèse est de mener une étude fondamentale et expérimentale des propriétés physiques des cristaux liquides discotiques colonnaires (CLDCs) confinés dans des matrices poreuses templates hautement ordonnées à l'échelle nanométrique. Les molécules des CLDCs de forme plane, composées de noyaux polyaromatiques rigides entourées de chaînes aliphatiques flexibles fonctionnalisables, sont susceptibles de s'auto-assembler dans des colonnes favorisant ainsi le recouvrement de leurs orbitales électroniques π. Ce qui fait de ces matériaux de véritables candidats pour des applications dans l'électronique moléculaire et la photovoltaïque grâce à la possibilité de migration des porteurs de charges le long de leurs colonnes. Cependant, ces applications nécessitent une bonne maîtrise des paramètres influant sur les mécanismes d'alignement dans les phases colonnaires, sur de grands monodomaines, et de préférence à température ambiante. Une méthode très prometteuse visant à optimiser les longueurs de diffusion des porteurs de charge a été récemment proposée, basée sur la formation de nanofils orientés de CLDCs par auto-assemblage dans des matrices dites « templates » (de moulage). Toutefois, les propriétés structurales, dynamiques et les effets de confinement sur ces technologies restent aujourd'hui mal connus et morcelés et pourraient constituer un véritable verrou scientifique pour leur réalisation. Notre étude s'est portée sur les CLDCs commerciaux (HPT) et le Py4CEH (moins connus) qui sont confinés dans des alumines poreuses (AAO) et du silicium poreux (Sip) de diamètres de pores de quelques dizaines de nm. Les diagrammes de phase ont été d'abord étudiés par DSC puis les effets structuraux ont été approfondis grâce à la diffusion de neutrons. Dans les géométries confinées, nous observons une dépression des températures de transition, un élargissement du domaine de stabilité de la phase colonnaire et l'ouverture d'une hystérèse amplifiée dans les pores de plus petite taille. Un ordre orientationnel très élevé a été trouvé dans les phases colonnaires bulk par la RMN du solide et la structure des systèmes confinés colonnaires, dominée par une distribution radiale avec un ancrage homéotrope a été déterminée. La dynamique moléculaire a été étudiée par diffusion quasiélastique de neutrons. Elle est affectée par le confinement : la dynamique de grande amplitude est fortement ralentie, tandis que la dynamique rapide locale devient régie par une distribution très large de temps caractéristiques. / The aim of this work is to conduct fundamental and experimental studies of the physical properties of columnar discotic liquid crystal (CDLCs) confined in highly ordered porous templates at the nanoscale. CDLC molecule of planar shape, consist in rigid polyaromatic nuclei surrounded by functionalizable flexible aliphatic chains, and are capable of self-assembly in columns, thereby promoting overlap of their π electron orbitals. This makes these materials real candidates for applications in molecular electronics and photovoltaics due to the possibility of migration of the charge carriers along their columns. However, these applications require a good control of the parameters affecting the alignment mechanisms in the columnar phases of large single domains, preferably at room temperature. A very promising approach to optimize the diffusion lengths of charge carriers has been recently proposed, based on the formation of oriented CDLC nanowires by self-assembly in so-called "templates". However, structural and dynamical proprieties and confinement effects are still scarce, and could be a real scientific lock to their implementation. Our study is focused on commercial CDLCs (HPT) and Py4CEH which are confined in porous alumina and porous silicon membranes with pore diameters of c.a. tens of nm. The phase diagram was first studied by DSC and more deeply characterized by neutron scattering. In confined geometries, we observe a depression of the phase transition temperatures, a broadening of the columnar phase stability domain and an opening of hysteresis loops amplified by smaller pore size. A high orientational order was found in the bulk columnar phases by solid-state NMR, and the structure of confined columnar systems, dominated by a radial distribution with homeotropic anchoring was observed. The molecular dynamics was studied by quasielastic neutron scattering. It is affected by confinement: large lengthscale motions are massively slowed down, whereas the rapid and local dynamics becomes submitted to large distributions of correlation times.

Gegenstand der vorliegenden Arbeit ist die Herstellung und Charakterisierung neuer sternförmiger Mesogene. Bei den aufgeführten Sternverbindungen, handelt es sich um Oligobenzoate, bestehend aus aromatischen Hydroxy- oder Aminocarbonsäuren, die durch Kupplungsreaktionen mit Dicylohexycarbodiimid, in einer konvergenten Synthesestrategie verknüpft wurden. Das besondere Augenmerk der Arbeit richtete sich auf die Charakterisierung der von den neuen Substanzen gebildeten Mesophasen, die mit Hilfe von Polarisationsmikrokopie, dynamischer Differenzialkalorimetrie und Röntgenstreuung erfolgte. Zur Aufklärung spezieller dreidimensionaler Strukturen wurden als zusätzliche Methoden die Rasterkraftmikroskopie angewandt und der Zirkulardichroismus untersucht.