Conventional liquid lubricants are faced with limitations under extreme cyclic operating conditions, such as in applications that require lubrication when changing from atmospheric pressure to ultrahigh vacuum and ambient air to dry nitrogen (e.g., satellite components), and room to elevated (>500°C) temperatures (e.g., aerospace bearings). Alternatively, solid lubricant coatings can be used in conditions where synthetic liquid lubricants and greases are not applicable; however, individual solid lubricant phases usually perform best only for a limited range of operating conditions. Therefore, solid lubricants that can adequately perform over a wider range of environmental conditions are needed, especially during thermal cycling with temperatures exceeding 500°C. One potential material class investigated in this dissertation is lubricious oxides, because unlike other solid lubricant coatings they are typically thermodynamically stable in air and at elevated temperatures. While past studies have been focused on binary metal oxide coatings, such as ZnO, there have been very few ternary oxide and no reported quaternary oxide investigations. The premise behind the addition of the third and fourth refractory metals Ti and Zr is to increase the number of hard and wear resistant phases while maintaining solid lubrication with ZnO. Therefore, the major focus of this dissertation is to investigate the processing-structure-tribological property relations of composite ZnO, TiO2 and ZrO2 phases that form ternary (ZnTi)xOy and quaternary (ZnTiZr)xOy nanocrystalline coatings. The coatings were processed by atomic layer deposition (ALD) using a selective variation of ALD parameters. The growth structure and chemical composition of as-deposited and ex situ annealed ternary and quaternary oxide coatings were studied by combined x-ray diffraction/focused ion beam microscopy/cross-sectional transmission electron microscopy, and x-ray photoelectron spectroscopy/Auger electron spectroscopy, respectively. It was determined that the structure varied from purely nanocrystalline (ternary oxides) to composite amorphous/nanocrystalline (quaternary oxides) depending on ALD parameters and annealing temperatures. In particular, the ZnTiO3 ilmenite phase with (104) textured nanocolumnar grains, exhibiting high stacking fault/partial dislocation densities >1012/cm2, was responsible for the excellent tribological behavior. Steady-state sliding friction coefficients down to 0.12 in humid air and 0.2 in dry nitrogen were measured along with sliding and fretting wear factors in the range of 10-6 to 10-7 mm3/N·m, even after ex situ annealing to 550°C. Additionally, the quaternary oxide phase Zn(Ti,Zr)O3 in solid solution exhibited a low fretting wear rate of 1x10-6 mm3/N·m. In contrast, certain phases, such as Zn2TiO4 cubic spinel, that form at annealing temperatures >550°C were responsible for high friction and wear. Mechanistic studies using the above techniques revealed low friction and wear-reducing surfaces and subsurfaces were due to different velocity accommodation modes (VAM). In the case of the ternary system, sliding-induced plastic deformation was possible when ZnTiO3 (104) stacking faults, bordered by partial dislocations, serve as a pathway for the dislocations to glide parallel to the sliding direction and hence achieve low friction and wear via an intrafilm shear VAM. It was evident that the individual nanocolumnar ZnTiO3 grains were plastically sheared as opposed to being fractured during wear. Conversely for the quaternary system, an interfacial sliding VAM between the counterface and a mechanically mixed layer (tribofilm) composed of the refined coating and counterface material, that also served as a source for the formation of cylindrical rolls, was responsible for wear reduction. Therefore, these lubricious oxides are a potential candidate for solid lubrication at high temperatures (up to 550 °C) and in space environments.

Conventional studies of ionomers have focused on ionomers bearing monovalent carboxylate or sulfonate pendant ions. There are relatively fewer studies on ionomers containing multivalent pendant ions, such as divalent phosphonate. In this dissertation, poly(ethylene terephthalate) (PET) and polystyrene ionomers with divalent phosphonate pendant ions have been synthesized, and the influence of divalent phosphonate pendant ions on the structure-morphology-property relationship has been compared to the ionomers with monovalent sulfonate pendant ions. The phosphonate groups generated a stronger physically crosslinked network in phosphonated ionomers as compared to sulfonated analogues. Higher plateau modulus, longer relaxation time, and significantly higher zero-shear viscosity were noted for phosphonated ionomers by a dynamic melt rheology study. Compared to the ionic aggregates generated from sulfonate groups, larger ionic aggregates with associated phosphonate groups have been observed. Furthermore, phosphonated ionomers displayed significantly higher glass transition temperatures than sulfonated ionomers. Ionomers have proven to be attractive, interfacially active compatibilizers for a number of polymer blend systems because of specific interactions that may develop between the ionic groups and complementary functional groups on other polar polymers within the blends. The successful compatibilization of polyester/polyamide blends (prepared by solution mixing and melt blending methods) using phosphonated PET ionomers as a minor-component compatibilizer has been demonstrated. The phase-separated polyamide domain dimension decreased with increasing mol % phosphonated monomers and this decrease was attributed to the specific interactions between the ionic phosphonate groups on the polyester ionomer and the amide linkages of polyamide. More importantly, the divalent phosphonate pendant ions are more effective at compatibilizing polyester/polyamide blends in comparison to the monovalent sulfonate pendant ions. Phosphonated PET ionomer-compatibilized polyester/polyamide blends required 6 times fewer ionic monomers to achieve domain dimension < 1 μm as compared to sulfonated PET-containing blends. Deep eutectic solvents (DES) have been reported to be the next generation solvents due to the superior biocompatibility, biodegradability, and sustainability as compared to ionic liquids. Two types of deep eutectic solvents, choline chloride : malic acid (ChCl:MA) and L-arginine : levulinic acid (Arg:LA), have been demonstrated as effective plasticizers for poly(vinyl alcohol) (PVOH) films. The plasticization effects on the properties of PVOH films were evidenced by lower crystallizability and improved film ductility. In addition, ChCl:MA deep eutectic solvent was more effective in plasticizing PVOH as compared to propylene glycol, one of the most widely studied alcohol-type plasticizers. From an applied perspective, DES-plasticized PVOH film is a promising candidate in the packaging market of heath-related products. / Doctor of Philosophy / Non-covalent interactions play an important role on the structure-morphology-property relationship of polymeric materials. Divalent phosphonate pendant ions provide interesting effects on the properties of ionomer and polymer blends as compared to the monovalent sulfonate pendant ions. Ionomers containing phosphonate pendant ions exhibit a significantly stronger physically crosslinked network as compared to sulfonated ionomers. Compared to monovalent sulfonate groups, the divalent phosphonate groups are more effective at compatibilizing polymer blends. Furthermore, the compatibilized poly(ethylene terephthalate)-based blends exhibit improved optical and oxygen barrier properties compared to the base blend without compatibilizer, signifying potential benefits in packaging industry. Poly(vinyl alcohol) is one of the most widely used packaging materials for food, medicine, detergent, etc. The incorporation of deep eutectic solvents as plasticizers significantly improved film ductility. In addition, the plasticization effect for choline chloride-based deep eutectic solvent is more profound than one of the most widely studied alcohol-type plasticizers, propylene glycol. The effective plasticization of poly(vinyl alcohol) using deep eutectic solvents confirmed the potential for future applications in the packaging market of health-related product.

Segmented copolymers are important polymers with attractive properties and wide applications. In this dissertation, segmented polyurethanes containing triptycene units and multiblock copolymers containing poly(arylene ether sulfone) (PAES) and poly(1,4-cyclohexyldimethylene terephthalate) (PCT) segments were synthesized and systematically studied. Investigation of the influence of the bulky triptycene structure on the morphologies and properties of segmented polyurethanes was carried out by using triptycene-1,4-hydroquinone bis(2-hydroxyethyl)ether (TD) as the chain extender. Segmented polyurethanes based on poly(tetramethylene glycol) (PTMG) of 1000 g/mol were synthesized using a two-step polymerization procedure. Hydroquinone bis(2-hydroxyethyl)ether (HQEE) was used for the purpose of comparison. Hard segments with different bulkiness and flexibility were prepared with hexamethylene diisocyanate (HDI) and 4,4'-methylenebis(phenyl isocyanate) (MDI), and HQEE or TD as chain extenders. The incorporation of bulky TD and less flexible MDI significantly inhibited hydrogen bonding based on the Fourier transform infrared (FTIR) results. In addition, the microphase separation was also disturbed by the bulky and less flexible hard segments with confirmation from tapping mode atomic force microscopy (AFM) and small angle X-ray scattering (SAXS). The flexible HDI can be used to overcome the bulkiness of triptycene, promote microphase separation, and enhance mechanical properties. Novel PTMG based soft segments containing triptycene units were also prepared with number average molecular weight (Mn) around 2500 g/mol. Then this soft segment was reacted with MDI and HQEE to prepare segmented polyurethanes. Soft segments such as hydroquinone (HQ) containing PTMG (Mn = 2100 g/mol), and pure PTMGs (Mn = 1000 and 2000 g/mol) were used for comparison. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) results demonstrated that triptycene units led to an increased glass transition temperature (Tg) and an elimination of the crystallization of the soft segments. The absence of strain hardening for the triptycene-containing sample suggested a suppressed strain induced crystallization of soft segments, which was also confirmed by the analysis of wide-angle X-ray diffraction (WAXD) on the films strained to 370 %. Crystallizable PCT segments were copolymerized with PAESs to enhance solvent resistance and mechanical properties. PAES oligomers (Mn = 2000 g/mol) were first synthesized, and then reacted with dimethyl terephthalate (DMT) and 1,4-cyclohexanedimethanol (CHDM). Weight percentages of PCT segments were gradually changed from 20 wt% to 80 wt%. With PCT content greater than 50 wt%, crystallinity was observed by DSC, DMA, and WAXD. The extent of crystallinity of the copolymers was dependent on the wt% of PCT. Furthermore, crystallization behavior of copolymers based on two CHDMs with different isomer ratios (cis/trans 30/70 and all trans) were studied. Due to their more symmetric structure, copolymers based on all trans CHDM exhibited a higher extent of crystallization. / Ph. D.

La firme est un ensemble de contrats conclus entre les différentes parties prenantes, actionnaires, créanciers, salariés, dirigeants, clients, fournisseurs, pouvoirs publics, etc. Les conflits d‟intérêts naissent lors de la répartition de la valeur ajoutée et chacun des parties procède à augmenter sa part au détriment des autres. Les salariés réclament une augmentation de salaire ou un intéressement aux résultats, les actionnaires, apporteurs du capital financier, désirent un part élevé des bénéfices afin de rémunérer le risque financier. D‟un autre côté, les créanciers souhaitent le remboursement de leurs crédits avec des taux d‟intérêt plus élevés alors que l‟objectif de l‟entreprise est de garder une partie des bénéfices afin de financer de nouveaux investissements. Suite aux différents conflits, les dirigeants agissent afin de modifier la répartition de la valeur ajoutée entre les différentes parties prenantes. Ils réduisent la richesse des salariés afin de créer de la valeur au profit des actionnaires. De ce fait, plusieurs mécanismes sont mis en place afin de protéger les salariés et assurer une meilleure répartition de la valeur ajoutée. Sur la base d‟un échantillon de 85 firmes françaises durant la période 2000-2005, notre étude montre que les droits accordés aux actionnaires et aux salariés ainsi que les mécanismes de gouvernance affectent leurs parts dans la valeur ajoutée. A partir des résultats, nous concluons des différences selon la structure de propriété de la firme. / The firm is represented as a set of contracts concluded between the various stakeholders, the shareholders, but also, creditors, employees, leaders, customers, suppliers, public authorities, etc. conflicts of interests are born during the distribution of the added value and each proceeds to increase his part to the detriment of the others. The employees demand a pay rise or a profit-sharing in the results, the shareholders, the contributors of the financial capital, wish one part raised by profits to pay the financial risk. Of other one quoted, the creditors wish a better payment for their credits with higher interest rates while the purpose of the company is to constitute a reserve to finance new investments. Further to the various conflicts, the leaders act to modify the distribution of the added value between the various stakeholders. They reduce the wealth of the employees for the benefit of the shareholders they reduce the wealth of the employees for the benefit of the shareholders. Therefore, several mechanisms are set up to protect the employees and assure a better distribution of the added value. On the basis of a sample of 85 French firms during period 2000-2005, our study shows that the rights of the shareholders and employees as well as the characteristics of property and governance affect their parts in the added value. From the results, we conclude differences according to the structure of property of the firm.

都市的發展隨著時間而不斷地演變，都市內會不斷產生不能適應今日都市生活活動需求的地區，所以需要更新之地區會不斷的產生。從都市有限的土地資源來看，都市更新是要促進土地使用的合理化與使用強度的提高，所以都市更新是土地資源的一種再生型態。都市更新為現代台灣不動產開發之主流，為改善都市早期發展的舊城市，及促進都市的永續發展，都市更新將是未來都市發展政策的必然趨勢。然而，「都市更新不是目標，而是工具」。增進都市機能，改善生活環境，促進都市健全發展，才是都市更新的主要目的，惟應經由何種方式(工具)，方能順利達成上述目標，厥為都市更新所應關注之重點。而權利變換是實施都市更新的方式之一，本研究是從產權理論之產權結構的觀點出發來探討它在權利變換制度實務操作上的影響。 本論文主要在說明，從都市更新條例(以下簡稱本條例)第3條有關權利變換的定義來看，更新單元內之土地所有權人、合法建築物所有權人、他項權利人及實施者是一種「合夥」的關係，但依本條例第30、31條的規定，實施者則又成了代工者，然而在實務操作上實施者掌握了整個權利變換的控制權，在實施者追求利潤或利益極大化的前題下，實施者只好隱藏利潤於費用之中，以獲取剩餘利益。本研究以產權結構的理論為基礎，用已完成之案例來分析，以說明上述現象的存在事實，以為後續修法的參考。 本研究的論述重點，主要是在說明權利變換的生產要素經整合後組成了一個新的產權，而這個新產權是由參與權利變換的權利人所共有，而產權結構裡的控制權與剩餘收入權，是由實施者掌握了控制權，而土地所有權人則擁有剩餘收入權，在實施者與土地所有權人不能同時控制權與剩餘收入權的情形下，所產生的利益衝突現象，以致造成實施者與土地所有權人的利益目標或利益函數不一致，制度的設計應該是將資源分配的私下協議的障礙降至最低，換言之，應該要設計成實施者與土地所有權人的利益目標或利益函數一致，才會使實施者與土地所有權人為這個事業共同去努力，這樣才有助於都市更新事業的推動。 本研究透過理論與實證只是證明目前權利變換存在的不合理現象，至於權利變換的性質或定性應該是屬何種，例如：合夥、代理(承攬)或互易，則非本研究的範圍，有待後續的先進繼續探討。 / The development of urban is proceeding with the time, there are areas that can not accommodate the needs of urban life activities nowadays in the urban, thus those areas need to renew are continually generated. We could see from the view that land resource in the urban are limited, urban renewal help forward rationalize land use and raise the use intensity, thus urban renewal is one kind of revive types of land resource. Urban renewal is the mainstream in the development of modern Taiwan real estate; in order to improve the old town in the early urban development, and promote the sustainable urban development, urban renewal will be the consequential trend in the urban development policy in the future. However, “Urban renewal is not a goal, it is a tool.” The main goals of urban renewal shall be building up urban function, improving living environment and advancing well-balanced urban development. The emphasis of urban renewal shall be in which way (tool) to achieve the above goals. Right transformation is one kind of ways to improve urban renewal, in this study we use the view from the structure of property rights in Property Theory to discuss its effects in the Right transformation system manipulation. This essay is mean to explain that form the Urban Renewal Act (The Act for short) clause 3 about right transformation definition, the land owner, legal building owner, other owner and implementer are kind of “partnership” relation in renewal unit, but according to the rules in The Act 30 and 32 clauses, implementer become OEM command the control right in the whole rights transformation in manipulation process, implementer pursuits benefit or in the premise of maximize profit, implementer has to hide the benefit behind the cost, to obtain the residual benefit. Property right structure theory is the basis of this study, analyzed by the finished case study to explain the above exist fact for the reference of amendment hereafter. The emphasis of this study is to explain there is a new property right generated after integrating the produce factors in rights transformation, and this new property right is co-owned by the oblige who participated the right transformation. As the control right and the residual income right in the right structure, the implementer command the control right and the land owner command the residual income right, when implementer and the land owner can not command the control right and the residual income right at the same time, the benefit conflict will make the different profit goal or the different profit function between the implementer and the land owner. The system should be designed to minimize the obstacle of private negotiated resource allocation. In other words, it should be designed as a same profit goal or function to make the implementer and the landowner to exert themselves for this career, thus make for the advance of the urban renewal career. Through the theory and real demonstration in this study is only to prove the existing unreasonable phenomena in rights transformation, as for the character or the qualitative of right transformation shall be, for example, partnership, agent（to take full charge of responsibility）or trade, is not in the study range, and need the fellow successor to discuss about .

Ce travail a consisté en la synthèse et la caractérisation de nouveaux polycondensats poly(urée-imide)s (PUIs) greffés par une réaction de chimie "click" avec des nombres de greffons variables. Deux familles de matériaux ont été obtenues à partir d'un même PUI et de greffons de structures différentes mais de mêmes masses molaires : poly(méthoxy (diéthylène glycol) méthacrylate) (PMDEGMA) synthétisé par polymérisation radicalaire par transfert d’atome (ATRP) ; poly(hydroxyéthyl acrylate) (PHEA) préparé par Single Electron Transfer Living Radical Polymerization (SET-LRP). Ces matériaux ont ensuite été étudiés pour la purification du biocarburant éthyl tert-butyl éther (ETBE) par le procédé membranaire de pervaporation. Pour la séparation correspondante du mélange azéotropique ETBE/éthanol, les polycondensats avec des greffons PMDEGMA ont conduit à d’excellentes performances en extrayant l’éthanol de manière très sélective. La stratégie de greffage a permis d’augmenter fortement le flux tout en maintenant une excellente sélectivité et de pallier ainsi la limitation classique des polycondensats linéaires pour lesquels flux et sélectivité varient fortement de manière opposée. Les propriétés de ces polycondensats greffés ont été corrélées à leur morphologie particulière étudiée par MDSC et Synchrotron SAXS. Les greffons PHEA avec des groupes hydroxyle ont permis d'augmenter encore l'affinité pour l'éthanol. Cette affinité ayant dépassé les espérances avec des membranes trop gonflées par le mélange cible, les propriétés de sorption et de perméation de la seconde famille de copolymères greffés ont finalement étudiées pour le transport de l'eau, autre domaine de la perméabilité à forts enjeux industriels / This work deals with the synthesis and characterization of new graft step-growth copolymers poly(urea-imide)s (PUIs) by ‘click’ chemistry with variable graft amounts. Two families of materials were obtained from the same PUI and polymer grafts with different structures and the same molecular weights : poly(methoxy (diethylene glycol) methacrylate) (PMDEGMA) prepared by Atom Transfer Radical Polymerization (ATRP); poly(hydroxyethyl acrylate) (PHEA) obtained by Single Electron Transfer Living Radical Polymerization (SET-LRP). These materials were then investigated for the purification of the ethyl tert-butyl ether (ETBE) biofuel by the pervaporation membrane process. For the corresponding separation of the azeotropic mixture ETBE/ethanol, the copolymers with the PMDEGMA grafts showed excellent performances with very selective ethanol extraction. The grafting strategy enabled to increase the flux strongly while maintaining an excellent selectivity and thus overcame the classical limitation of linear step-growth copolymers, for which flux and selectivity strongly vary in opposite ways. The properties of the graft copolymers were correlated to their particular morphology characterized by MDSC and Synchrotron SAXS. The PHEA grafts with their hydroxyl groups enabled to further increase affinity for ethanol. This affinity having gone beyond expectation with a too strong membrane swelling in the targeted mixture, the sorption and permeability properties of the second series of graft copolymers were finally investigated for water transport, i.e. another permeability field with strong industrial stakes

A balance between strength and ductility has been one of the most important considerations in the steel industry. Austenitic steel or multi-phase steel with retained austenite has plasticity-enhancing mechanisms, which can make it achieve high strength and good formability. Due to the occurrence of twinning-based mechanisms in high Mn steels, they have improved strength without sacrificing ductility. However, high Mn steels with extraordinary mechanical properties has not been used in mass production because of its high material cost together with welding problems and so on. As a consequence, many researchers have attempted to decrease the Mn concentration of high Mn twinning-induced plasticity steels without significant sacrifice of the mechanical properties. In the present work, a novel medium Mn steel with high C is designed with the aim of obtaining comparable mechanical properties as high Mn TWIP steel. In addition to Mn, C is also common effective austenite stabilizing element. C and Mn both increase the SFE of austenite. It should be possible to substitute at least some of the Mn in high Mn steels with C and still retain the TWIP effect. If the reduction in Mn content is not compensated for by the addition of other alloying elements, the microstructure will additionally contain some ferrite or martensite. The problem with C concentration is that it will result in the formation of carbide during the cooling process. As long as the carbide formation is suppressed, the formation of ferrite/martensite in medium Mn steels can be inhibited by an increase in the C concentration. In such cases, a soft and formable austenitic microstructure can be achieved by quenching from high austenitization temperatures to retain austenite with appropriate mechanical stability. The precipitation and dissolution of cementite in austenitic medium Mn high C steels capable of deformation-induced twinning were analyzed based on the associated length changes. Al addition was found to significantly retard the kinetics of cementite precipitation, indicating its usefulness in the design of cementite-free austenitic medium Mn steels with high C concentrations. Furthermore, Al addition changes the morphology of intragranular cementite from plate-shaped to equiaxed. The tensile properties of alloy were also examined in the present study. The present contribution discusses the mechanical properties of a bulk medium Mn high C steel with special alloying additions to oppose the precipitation of cementite. In particular, it aims to justify the mechanical properties based on crack nucleation and growth mechanisms. The reported mechanical properties enable a comparison with those of the well-known high Mn and Hadfield steels.

Diploma thesis “Property valuation type of summer camp” is focused on recording and valuation of all the immovable property, which are parts and outbuildings of summer camp near the Vranov dam. Theoretical part of this thesis deals with basic terminology and utilized valuation methods. Short locality characterization and relevant real estate market are described in the practical part. Main focus of the practical part is actual valuation of immovable property using methods described in theoretical part. After that, calculated and estimated prices are evaluated and analyzed.