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1
Brayer, Marie-Ange. "Entre art et architecture : la maquette comme objet d'expérimentation au XXe siècle." Paris, EHESS, 2016. http://www.theses.fr/2016EHES0136.
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La maquette d'architecture est envisagée comme un objet d'expérimentation au confluent des pratiques artistiques et architecturales. Trois moments de rupture ont été circonscrits qui, à chaque fois, bouleversèrent la compréhension de la maquette : les avant-gardes historiques ; l'architecture radicale des années 1960-1970 ; l'architecture numérique. Si la maquette est appréhendée jusqu'au XXe siècle dans un rapport analogique à l'architecture, elle s'affirme comme un objet autonome d'expérimentation avec les avant-gardes historiques. L'œuvre se convertit alors en maquette d'architecture, en « construction spatiale » tandis que la maquette d'architecture acquiert un statut d'objet esthétique, interférant avec les autres champs de la création (sculpture, photographie, film, théâtre, etc). L'architecture expérimentale des années 1960-1970 ouvre une brèche utopique dans la notion de projet architectural. On assiste alors à l'effondrement du projet architectural comme langage codifié, qui se dissémine en multiples modes d'expression (performances, objets de design, environnements, etc. ) qui viendront se substituer aux outils projectuels. L'avènement des technologies numériques dans les années 1990 modifiera en profondeur le rôle de la maquette d'architecture qui se convertit au sein de l'espace digital en matrice numérique, code, image, prototype, objet générique. Comme dans les avant-gardes historiques et l'architecture radicale, la maquette est à nouveau un dispositif articulant différents plans de perception, dans une dimension physique et cognitive, où s'échangent les régimes de l'image et de l'objet, dans une « mutabilité » des langages et des échellesThe architectural model is envisaged as an object of experimentation, at the crossroads of artistic and architectural practices. Three moments of epistemological rupture have been identified, each of which has in turn shattered the understanding of the model: The historical avant-gardes; The radical architecture of the 1960s-1970s in Europe; Digital architecture. Although up to the beginning of the 20th century the model was grasped in its analogical relation to architecture, the practices of the historical avant-garde movements led to its being increasingly seen as an object of experimentation. The avant-gardes transformed the work into a model, into a "spatial construction" while the architectural model acquired the status of aesthetic object, interfering with the other fields of creation (sculpture, photography, film, theater, etc. ). The experimental architecture of the 1960s-1970s opened a utopian breach in the concept of the architectural project. This resulted in the collapse of the architectural project as the production of a codified language which was now disseminated though multiple modes of expression (performances, design objects, environments, etc. ), and which gradually began to replace the tools for planning. The advent of digital technologies in the 1990s profoundly transformed the role of the architectural model, which within digital space became a digital matrix, code, image, prototype, generic object. As with the historical avant-gardes and radical architecture, the model has once again become a device for joining different planes of perception, in a physical and cognitive dimension, where the rules governing the image and the object are interchangeable, in a "mutability" of languages and scales
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Fumanal, Quintana Maria. "Radical-Pair Formation in Organic π-Stacked Architectures." Doctoral thesis, Universitat de Barcelona, 2015. http://hdl.handle.net/10803/345173.
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Interest in organic molecule-based materials has extraordinarily grown in both the electronic and data storage industries. Specifically, research in the development of new plastic devices for technological proposes has emerged as they may provide lower manufacturing costs, more versatile synthetic processes and better mechanical properties (i.e. transparency, flexibility) than standard inorganic materials. However, in order to compete with these inorganic-based materials in terms of effectiveness, their conductive, magnetic and switchable characteristics must be improved, such that they can be applied as high-performance molecular conductors, magnets and memory devices. The physical properties of these organic materials not only depend on the nature of its constituent molecules (magnetic, biocompatible) but on how they organize in the solids (polymeric, amorphous, crystalline). Therefore, predicting and achieving a particular final behaviour is challenging and requires investigations on the structure-property relationships as well as on the nature of the chemical species. Over the last years, continuous effort has been done aimed at developing new purely organic-based materials with technologically relevant properties. Since Gomberg's synthesis of the triphenylmethyl neutral radical, a large variety of stable organic radicals have been reported, such as nitroxides, verdazyl-, phenoxyl-, phenalenyl-, dithiazolyl- and triazinyl-based compounds, as well as several functionalized radical ions based on tetracyanoethylene (TCNE), and tetrathiafulvalene (TTF+.) among others. These particular families of organic radicals can be used as versatile templates for the synthesis of new derivatives with improved characteristics by the introduction of different substituents into their basic skeleton. However, further progress in novel materials must be achieved through a rational design of new chemical structures. In this context, the available computational tools can substantially contribute to obtain the necessary knowledge of the factors controlling the final target physical properties, namely conductivity, magnetism and bistability, which are essentially dominated by the electronic structure of these materials. The work presented in this thesis is devoted to study different purely organic derivatives that have been shown to be promising for the development of new functional materials. In particular, the attention has been focused on three different families of organic radicals that present interesting physical properties as a consequence of a Tr-stacked radical-pair formation in the condensed phase, that is: (1) radical ions, (2) phenalenyl- and (3) triazinyl-based compounds. Overall, the present PhD thesis aims at contributing to the field of computational chemistry as well as to the understanding of the electronic properties that govern the Tr-dimerization of these systems, which, ultimately, determine their magnetic and switchable behaviour.En els últims anys, s'ha fet un esforç continu per desenvolupar materials nous purament orgànics amb propietats tecnològicament rellevants. Des de la síntesi de Gomberg del radical neutre trifenilmetil, s'ha reportat una gran varietat de radicals orgànics estables, com ara els nitròxids, verdazils, fenoxils, fenalenils, ditiazolils i compostos basats en triazinil, així com diversos ions radicals funcionalitzats basats en tetracianoetilè (TCNE-•), i tetratiafulvalè (TTF1-.), entre d'altres. Aquestes famílies de radicals orgànics s'utilitzen per a la síntesi de nous derivats amb característiques millorades a partir de la introducció de diferents substituents en el seu esquelet bàsic. No obstant això, els avenços en nous materials s'han d'aconseguir a través d'un disseny racional de les noves estructures químiques. En aquest context, les eines computacionals disponibles poden contribuir substancialment a obtenir els coneixements necessaris sobre els factors que controlen les propietats físiques desitjades, a saber, la conductivitat, el magnetisme i la biestabilitat, dominades fonamentalment per l'estructura electrònica d'aquests materials. El treball presentat en aquesta tesi està dedicat a estudiar diferents derivats purament orgànics que han demostrat ser prometedors per al desenvolupament de nous materials funcionals. En particular, l'atenció s'ha centrat en tres famílies de radicals orgànics que presenten propietats físiques interessants com a conseqüència de la formació de parells de radical Tr, aquests són: (1) els ions radicals, (2) els fenalenils i (3) els compostos basats en triazinil. En global, aquesta tesi doctoral té com a objectiu contribuir al camp de la química computacional, així com a la comprensió de les propietats electròniques que regeixen la dimerització Tr d'aquests sistemes, que, en última instància, determina el seu comportament magnètic i commutable.
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Long, David. "Waste City: alternative architecture for radical change." Master's thesis, University of Cape Town, 2010. http://hdl.handle.net/11427/19086.
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This thesis is an exploration into the possible creation of radically alternative ways of dwelling within the city, whereby inhabitants would construct their own environments through the use of waste as a building resource. The project challenges and contests the status quo of architectural production, market driven planning and a societal structure which is governed by the continuous consumption of 'stuff', while simultaneously attempting to address the ever-increasing social inequality experienced within Cape Town. Given our present conditions of crisis born out of modernity and the processes of modernization, the research brings foreword the utopian debate, questioning how we might begin to envision a better future. To this end the research begins with an exploration into the conditions of modernity and the implications these conditions have had on human existence. The modern social project of architecture forms the basis of this study, unpacking the complexities it faced when confronting the social conditions of modernity and its attempts to bring about social transformation. The conclusions drawn from this study formed the development of a personal philosophical position and the development of a series of propositions presented in the form of cartoons. The study thus formed the basis and genesis of ideas for the design project. This ideological response comes in the form of self-sufficiency support structures, whereby inhabitants would construct their own environment to meet their own desires. Free from the constraints of capital labour, people could engage in free play, creativity and celebrate collective life, thus potentially overcoming the alienating and fragmenting forces associated with the conditions of modernity. This thesis is an exploration into the possible creation of radically alternative ways of dwelling within the city, whereby inhabitants would construct their own environments through the use of waste as a building resource. The project challenges and contests the status quo of architectural production, market driven planning and a societal structure which is governed by the continuous consumption of 'stuff', while simultaneously attempting to address the ever-increasing social inequality experienced within Cape Town. Given our present conditions of crisis born out of modernity and the processes of modernization, the research brings foreword the utopian debate, questioning how we might begin to envision a better future. To this end the research begins with an exploration into the conditions of modernity and the implications these condition~ have had on human existence. The modern social project of architecture forms the basis of this study, unpacking the complexities it faced when confronting the social conditions of modernity and its attempts to bring about social transformation. The conclusions drawn from this study formed the development of a personal philosophical position and the development of a series of propositions presented in the form of cartoons. The study thus formed the basis and genesis of ideas for the design project. This ideological response comes in the form of self-sufficiency support structures, whereby inhabitants would construct their own environment to meet their own desires. Free from the constraints of capital labour, people could engage in free play, creativity and celebrate collective life, thus potentially overcoming the alienating and fragmenting forces associated with the conditions of modernity.
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Carlmark, Anna. "Complex Macromolecular Architectures by Atom Transfer Radical Polymerization." Doctoral thesis, KTH, Fibre and Polymer Technology, 2004. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3740.
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Controlled radical polymerization has proven to be a viableroute to obtain polymers with narrow polydispersities (PDI's)and controlled molecular weights under simple reactionconditions. It also offers control over the chain-]ends of thesynthesized polymer. Atom transfer radical polymerization(ATRP) is the most studied and utilized of these techniques. Inthis study ATRP has been utilized as a tool to obtain differentcomplex macromolecular structures.
In order to elaborate a system for which a multitude ofchains can polymerize in a controlled manner and in closeproximity to one another, a multifunctional initiator based onpoly(3-ethyl-3-(hydroxymethyl)oxetane was synthesized. Themacroinitiator was used to initiate ATRP of methyl acrylate(MA). The resulting dendritic-]linear copolymer hybrids hadcontrolled molecular weights and low PDI's. Essentially thesame system was used for the grafting of MA from a solidsubstrate, cellulose. A filter paper was used as cellulosesubstrate and the hydroxyl groups on the cellulose weremodified into bromo-]ester groups, known to initiate ATRP.Subsequent grafting of MA by ATRP on the cellulose made thesurface hydrophobic. The amount of polymer that was attached tothe cellulose could be tailored. In order to control that thesurface polymerization was -eliving-f and hence that thechain-]end functionality was intact, a second layer of ahydrophilic monomer, 2-hydroxyethyl methacrylate, was graftedonto the PMA- grafted cellulose. This dramatically changed thehydrophilicity of the cellulose.
Dendronized polymers of generation one, two and three weresynthesized by ATRP of acrylic macromonomers based on2,2-bis(hydroxymethyl)propionic acid. In the macromonomerroute, macromonomers of each generation were polymerized byATRP. The polymerizations resulted in polymers with low PDI's.The kinetics of the reactions were investigated, and thepolymerizations followed first-order kinetics when ethyl2-bromopropionate was used as the initiator. In the-egraft-]onto-f route dendrons were divergently attached to adendronized polymer of generation one, that had been obtainedby ATRP.
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Marraccini, Marco. "Radical reuse : from the superfluous to the exquisite." Thesis, Massachusetts Institute of Technology, 2006. http://hdl.handle.net/1721.1/35613.
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Thesis (M. Arch.)--Massachusetts Institute of Technology, Dept. of Architecture, 2006.Leaves 73-74 blank.
Includes bibliographical references (leaves 68-69).
This thesis focuses on the systematic possibilities for the intricate architectural reuse and reconfiguration of the radial tire and the PET plastic bottle. Both waste products demonstrate significant structural and phenomenological potential and are abundantly available at the global scale. Through the specific exploration of these systems, reuse will be introduced to America's high-end architectural client base. Work in this well-established field has been typically associated with squatter settlements, ecological housing, and low-income developments. The objective is to demonstrate the elegance and sophistication that this strategy can yield. It is through the attention to the detail and the specific aggregation of waste materials that the exquisite and desirable can be created out of the unwanted, thus demonstrating the possibilities for future reuse in the larger construction market.
by Marco Marraccini.
M.Arch.
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Liu, Tengjia. "Preserving bad architecture : radicaL preservation in the post-disaster era." Thesis, Massachusetts Institute of Technology, 2016. http://hdl.handle.net/1721.1/103477.
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Thesis: M. Arch., Massachusetts Institute of Technology, Department of Architecture, 2016.Cataloged from PDF version of thesis.
Includes bibliographical references (pages 126-127).
The essence of trauma is precisely that it is too horrible to be remembered, to be integrated into our symbolic universe. All we have to do is to mark repeatedly the trauma as such. - Slavoj Žižek This thesis re-examines the role of ruins preservation by speculating on the inherent tension between disaster ruins, psychological interventions and collective memorialization. It challenges the misconception of architectural preservation which is against human interaction as well as possibilities for future change. In other words, the historicization of past events should not only be manifested as the physical integrity of artifacts, but rather shape and be shaped by the present and future of a place. The thesis seeks to rethink the act of preservation as a means of integrating memorialization into the everyday experience of the inhabitants. Sited in the 2008 Wenchuan Earthquake in China, the thesis proposes an alternative way to restore and memorialize the aftermath of the Beichuan town. By establishing a live memorial versus a frozen ghost town, the thesis positions the quake aftermath in a direct relationship with the contemporary citizens and thus projects the site towards its future. The thesis traces the frozen ruins in both geographical and ideological terms. It explores preservation through memorialization by embracing future collapse, growth or transformation. After analyzing the existing urban context, the thesis welcomes change as a positive element in the preservation process. The project adapts and recycles building waste; transforms physical memories into resilient infrastructure; utilize the secondary disaster to reshape the landscape: and celebrates the tectonic rubbles together with natural or sub-natural elements, such as debris, dust, mud, as well as annual flooding.
by Tengjia Liu.
M. Arch.
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Berríos, Negrón Luis Rafael 1971. "The Turtle : an American school of architecture : a radical mediocracy." Thesis, Massachusetts Institute of Technology, 2006. http://hdl.handle.net/1721.1/34649.
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Thesis (M. Arch.)--Massachusetts Institute of Technology, Dept. of Architecture, 2006.Vita.
Includes bibliographical references (p. 98-103).
This thesis evolves as a curatorial exercise with three phases: revisiting the practical and aesthetic position of the architecture thesis, structuring a design environment within MIT for fellow thesis candidates, leading to the development of a 1:1 test case - the Turtle. The Turtle will transport past student theses while also serving as a remote "pin-up" review space. The unit travels through and out of campus, in order to place greater publicity on the output of MIT both within and beyond the Institute. This provides theses candidates with a prop for their respective presentations allowing for more informed contributions to the MIT School of Architecture. The Turtle ultimately aims to serve as cultural equipment towards informing a broader sphere of knowledge that becomes more accessible to the contemporary architecture student, their critics/consultants, and their respective audiences. Considering MIT's digital thesis search engine, D-Space, these additional terms are addressed: a new type of specialist, authorship, collaboration, collective imagination, communication, digital, Venturi's duck, education, endless, fact, faction, fear, fiction, Gehry's fish, hegemony, human, infinite, interference, knowledge, lack of knowledge, learning, material, mode of production, movement, myth, need, open source, optimism, party, political imagination as risk society, practice, propaganda, property, public programs, Goulthorpe's rabbit, relations, research, reticulation, rhinoceros, scale, simulation, spiritual, student tools, students as medium, teaching, technological, truth, turtle, variation.
by Luis Rafael Berríos Negrón.
M.Arch.
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Shooter, Andrew James. "Living free radical polymerisation." Thesis, University of Warwick, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.263817.
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Lee, Sang-Hun. "Supramolecular architectures : macrocycles, catenanes and polyrotaxanes /." Diss., This resource online, 1996. http://scholar.lib.vt.edu/theses/available/etd-08232007-112703/.
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Ellis, Charles. "Direct Radical Intuition: toward an 'Architecture of Presence' through Japanese ZEN Aesthetics." University of Cincinnati / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1306498199.
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Bertin, Denis. "Polymérisation radicalaire contrôlée : synthèses de copolymères à architecture contôlée." Montpellier 2, 1997. http://www.theses.fr/1997MON20058.
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Wong, Benjamin. "Novel star-shaped polymeric architectures by copper (I) mediated living radical polymerisation." Thesis, University of Warwick, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.397276.
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Park, Sangwoo. "Electrochemically Controlled Atom Transfer Radical Polymerization and Synthesis of Polymers with Complex Architectures." Research Showcase @ CMU, 2016. http://repository.cmu.edu/dissertations/1031.
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Atom transfer radical polymerization (ATRP) is one of the most broadly applied reversible deactivation radical polymerization (RDRP) technique that provide well-defined polymers with predetermined molecular weight (MW) and narrow molecular weight distribution (MWD). The functional polymers synthesized by ATRP showed a potential promise in the fields of biomedical applications such as smart drug delivery, tissue engineering, and diagnostic sensors. In general, conventional ATRP requires a large amount of transition metal catalysts (> 1000 parts per million (ppm) versus molar ratio of monomers) and removal of the residual catalysts is necessary for use of advanced materials in bio-applications. The advent of catalysts (re)generation from the oxidized transition metal/ligand catalysts allows for the use of ppm level of catalysts in an ATRP, and offers more environmentally benign and industrially favorable reaction conditions for the synthesis of polymers. This work mainly explores electrochemically controlled atom transfer radical polymerization (eATRP) with diminished catalysts conditions as one of many catalysts regeneration ATRP systems being examined in the past decade. This dissertation is composed of nine chapters. Chapter I reviews recent progress in electrochemically controlled chemical reaction and polymerization. Chapter II provides an in-depth study of eATRP and serves as a basis for the discussions in Chapter III on developing a simplified eATRP reaction (seATRP). Chapters II and III cover six appendices, which include related collaborations, explanations on catalysts development and characterization, polymerization mechanism, and evaluation of new polymerization procedures. Chapter IV and V address related aqueous eATRP techniques. Chapter IV details optimization of polymerization conditions for acrylamides and minimization of side reactions. Chapter V explores miniemulsion polymerization of n-butyl acrylate which requires optimization of aqueous-organic phase catalyst communication. Chapter VI addresses development of electrochemically mediated reversible addition-fragmentation chain transfer (eRAFT) polymerization of methyl methacrylate. Chapters VII to IX discuss the synthesis of copolymers with complex polymeric architectures, i.e., star polymers. Specifically in Chapter VII procedures for achieving high yield for the synthesis of stars by combining arm-first methods and eATRP to reduce initial intermolecular termination reactions. Chapter VII also contains an appendix on star synthesis by the core-first method via eATRP. Chapter VIII and IX elucidate applications of the functional star polymers. In Chapter VIII, the preparation and application of light induced crosslinkable star polymers in surface patterning are discussed and extended to biomedical applications. Lastly, Chapter IX encompasses temperature responsive surfaces, that were prepared by star polymers upon UV irradiation, as smart cell cultivate substrates.
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Heibeck, Felix. "Augmented material interfaces : exploring bidirectional microinteractions enabled by radical elements." Thesis, Massachusetts Institute of Technology, 2015. http://hdl.handle.net/1721.1/101839.
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Thesis: S.M., Massachusetts Institute of Technology, School of Architecture and Planning, Program in Media Arts and Sciences, 2015.Cataloged from PDF version of thesis.
Includes bibliographical references (pages 124-130).
Advances in material science and miniaturization of electromechanical devices are liberating the surface of the embedded device from its rigid shell. These new modes of dynamic expression have to be coupled with sensing capabilities in order to create comprehensible interactions. This thesis explores the space of augmented materials that are bidirectional transducers, called radical elements. We present currently available radical elements that facilitate embodied interactions through sensing and actuation methods on the same modality. To exemplify how a radical element can be fabricated with simple materials, we present a thin film shape-changing composite uniMorph. It is based on a flexible circuit composite that is able to actuate its own shape by combining the thermo- electric characteristics of copper with the high thermal expansion rate of ultra-high molecular weight polyethylene. Finally, a taxonomy for augmented materials is presented that explores how new material capabilities can extend the perceived behavior of materials in the context of microinteractions. This thesis concludes with a survey of tangible interface projects in the design space of radical element enabled augmented materials.
by Felix Heibeck.
S.M.
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Hsu, Shu-Yao. "Fabrication of Well-Defined Architectures of Ultrahigh-Molecular-Weight Polymers by Living Radical Polymerization." 京都大学 (Kyoto University), 2016. http://hdl.handle.net/2433/215574.
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Lang, Andreas [Verfasser], and Mukundan [Akademischer Betreuer] Thelakkat. "Semiconductor Polymer Architectures using Click Chemistry and Controlled Radical Polymerization / Andreas Lang. Betreuer: Mukundan Thelakkat." Bayreuth : Universitätsbibliothek Bayreuth, 2011. http://d-nb.info/101923458X/34.
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Sebra, Robert P. "Design and application of chemically and biologically active surface graft architectures using living radical photopolymerization chemistry." Diss., Connect to online resource, 2005. http://wwwlib.umi.com/cr/colorado/fullcit?p3190353.
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Luo, Yan. "Radical Architecture, Collective Mindfulness, and Information Technology: A Dialectical Analysis of Risk Control in Complex Socio-Technical Systems." online version, 2009. http://rave.ohiolink.edu/etdc/view.cgi?acc%5Fnum=case1228450166.
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Thesis (Ph. D.)--Case Western Reserve University, 2009.Department of Information Systems, Weatherhead School of Management. Includes bibliographical references. Available online via OhioLINK's ETD Center.
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Sweeting, R. B. "Architecture and undecidability : explorations in there being no right answer : some intersections between epistemology, ethics and designing architecture, understood in terms of second-order cybernetics and radical constructivism." Thesis, University College London (University of London), 2014. http://discovery.ucl.ac.uk/1443544/.
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In this thesis I have explored some of the ways in which the contexts of epistemology, ethics and designing architecture are each concerned with undecidable questions (that is, with those questions that have no right answers). Drawing on design research, second‐order cybernetics and radical constructivism, I have understood this undecidability to follow in each case from our being part of the situation in which we are acting. This idea is primarily epistemological (being part of the world we observe, we cannot verify the relationship between our understanding and the world beyond our experience as it is impossible to observe the latter) but can also be interpreted spatially and ethically. From this starting point I have developed connections between questions in architecture, epistemology and ethics in two parallel investigations. In the first, I have proposed a connection between design and ethics where design is understood as an activity in which ethical questioning is implicit. Rather than the usual application of ethical theory to practice, I have instead proposed that design can inform ethical thinking, both in the context of designing architecture and also more generally, through (1) the ways designers approach what Rittel (1972) called “wicked problems” (which, I argue, have the same structure as ethical dilemmas) and (2) the implicit consideration of others in design’s core methodology. In parallel to this I have explored the spatial sense of the idea that we are part of the world through a series of design investigations comprising projects set in everyday situations and other speculative drawings. Through these I have proposed reformulating the architectural theme of place, which is usually associated with phenomenology, in constructivist terms as the spatiality of observing our own observing and so as where the self‐reference of epistemology (that we cannot experience the world beyond our experience) becomes manifest.
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Destarac, Mathias. "Etude des mécanismes de la polymériation radicalaire contrôlée. Application à la synthèse de copolymères à architecture contrôlée." Montpellier 2, 1997. http://www.theses.fr/1997MON20147.
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Jones, Jason William. "Enhanced Architectural and Structural Regulation Using Controlled Free Radical Polymerization Techniques; Supramolecular Assemblies: Pseudorotaxanes and Polypseudorotaxanes." Thesis, Virginia Tech, 2001. http://hdl.handle.net/10919/31766.
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Due in large part to the growth and development of reliable surface characterization techniques, as well as to advances in the physical and chemical techniques used to modify surfaces, the technology of surface modification has seen rapid expansion over the past two decades. A major thrust of this research is the growth of controlled/"living" polymeric brushes from the surface of various substrates, an advance that promises to be a facile and reproducible way of altering surface properties. A unique initiator bearing ATRP (atom transfer radical polymerization), cleavage, and condensation functionalities was prepared and attached to the hydrolyzed surface of silica gel. Preliminary results indicate that control of reversibly terminated grafts of varying degrees of polymerization with polydispersity indices approaching 1.5 can be readily achieved-significant findings in the quest to design desired surface characteristics.
Important physical characteristics may also be altered by way of varying molecular topologies. In the second major research thrust, the use of self-assembly to construct such topologies in the form of pseudorotaxanes fashioned from diverse macrocycles with multifarious guest ions is discussed. While the underlying goal was to investigate and understand the mode of complexation based on such environmental factors as substituent affects and neighboring group influences, new insight was gained on the synthetic manipulation of cooperative events-events that freely occur in nature. The complexation behavior of several functionalized bis-(meta-phenylene)-32-crown-10 macrocycles with various paraquat guest moieties was. As expected, studies indicated that electron-donating substituents on the crown ether drive association, a likely result of increased p -p interactions among host and guest species. The association between a bicyclic macrocycle and dimethyl paraquat was also investigated. Not surprisingly, binding of paraquat by the bicyclic was much stronger than the binding found in analogous macrocycles. Lastly, the endgroup functionalization of poly(propyleneimine) dendrimers with two crown ether macrocycles was performed and the complexation with host-specific guests studied. Curiously, two extreme binding regimes were found: the larger 32-membered crown ether assembly displayed anti-cooperative behavior upon complexation with paraquat, while the smaller 24-membered macrocyclic system exhibited cooperative effects with 2o ammonium ions. These cooperative results are among the very first described for non-biological systems and hint at their potential use in developing highly efficient, synthetically designed supramolecular systems.Master of Science
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Wright, Peter. "The use of controlled radical techniques to form polymer architectures suitable for use as Gear Oil Viscosity Modifiers." Thesis, University of Warwick, 2008. http://wrap.warwick.ac.uk/2735/.
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This project is concerned with the synthesis of Viscosity Modifiers (VMs) for use in gear box oils. The use of amines as precursors for initiators is also of interest due to their dispersant properties. Atom transfer radical polymerisation (ATRP) was used to prepare statistical copolymers of n-Butyl methacrylate and C12/15 methacrylate for use as VMs. These copolymers were first of a linear nature demonstrating that ATRP could be used to polymerise this monomer combination to give well defined polymers with a high degree of control. Thereafter, multi-functional initiators were used to synthesise core first stars with differing numbers of arms. Three, four, five and eight arm stars were successfully synthesised giving well defined polymers. These polymers were tested by Lubrizol for their viscometric properties. All were found to give significant improvements versus Lubrizol’s existing linear polymers in almost all respects. Although the core first stars gave a significant improvement in viscometric properties the costs of the core are relatively high for the application. Therefore the synthesis of arm first stars via ATRP was carried out. Design of experiment (DoE) was used to aid in the optimisation process and to interrelate any factors used in the design. The DoE process indicated two relationships between input factors, one of which was defined numerically. A range of polymers were synthesised on a larger scale for testing by Lubrizol for their viscometric properties. The polymers were found to have exceptional viscosity properties, compared to the baseline sample. The use of amines as precursors for initiators (forming amide initiators) was investigated. 4-Aminodiphenylamine (ADPA) was synthesised into an initiator suitable for ATRP and used in several polymerisations. It was found to have very low initiator efficiency. For this reason Single Electron Transfer Living Radical Polymerisation (SET-LRP) was employed to polymerise methyl acrylate from this initiator with near 100% initiator efficiency. A range of other amide initiators were also successfully used in polymerisations. A new solvent system for SET-LRP was also demonstrated. The addition of phenol to toluene promoted the disproportionation of Cu(I) allowing SETLRP to take place. Polymers were synthesised in this solvent mixture with high degrees of control over molecular weight with narrow Polydipersity indexs (PDI).
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Wilkerson, Lonnie Otto. "A radical embodied model of language and mind in a swarm-based system: Coaxing deep structure out of shallow architecture." OpenSIUC, 2010. https://opensiuc.lib.siu.edu/theses/260.
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While a symbol based system externally, there is evidence that, internally the realization of language is much different. Through revisiting the foundations of our perceptions and assumptions about language and cognition, the presented argument will coalesce into an illustration of the unsuitability of symbolic systems for recreating the functions which we call "mind". Simply stated, computational models of mind are the latest arguments of the Cartesian paradigm. The thesis concludes with an argument for the exploration of a symbol-less architecture of cognition based upon a model found repeatedly throughout nature: swarms. Discussions of some of the impacts are presented.
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Diaz, Thierry. "Macro-amphiphiles cationiques à architecture contrôlée : synthèse par PRCN et étude de leur organisation en milieu aqueux." Nancy 1, 2004. http://www.theses.fr/2004NAN10010.
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Le développement récent de nouveaux nitroxydes, conçus pour contrôler notamment la polymérisation de monomères polaires, a conduit notre équipe à utiliser le N-t-butyl-N-(1-diéthylphosphono-2,2-diméthyl)propyl-nitroxyde (DEPN) pour préparer des copolymères amphiphiles cationiques riches en motifs hydrophiles ayant une structure bien définie et évolutive. Nos travaux ont montré que la 4-vinylpyridine (4VP) et le N,N-diméthylacrylamide (DMAA) peuvent polymériser de façon contrôlée en présence de DEPN et qu'il est possible de synthétiser des diblocs présentant de faibles indices de polymolécularité en polymérisant le DMAA avec une alcoxyamine macromoléculaire poly(4VP)-DEPN. Après quaternisation, ces diblocs ont conduit à une série de macro-amphiphiles de composition variable. Des études par viscosimétrie et par spectroscopie de fluorescence ont révélé que, dans des milieux riches en eau, ces composés forment des micro-domaines hydrophobes par le biais d'associations intramoléculairesThe ability of b-hydrogenated nitroxides to polymerize polar monomers according to a controlled process led our team to use the N-t-butyl-N-(1-diethylphosphono-2,2-dimethyl)propyl nitroxide (DEPN) to prepare new amphiphilic cationic diblock copolymers with a well-defined and variable structure. In this work, we have shown that the polymerization of 4-vinylpyridine (4VP) and N,N-dimethylacrylamide (DMAA) are controlled in the presence of DEPN, and that well-defined diblock copolymers of these two monomers can easily be achieved by polymerizing DMAA with a macromolecular alcoxyamine poly(4VP)-DEPN. The quaternization of these diblocks with different alkyl bromides led to a series of comb-like copolymers, and the behaviour of these products in aqueous medium was investigated by viscosimetry and fluorescence spectroscopy. Long alkyl chains were proved to form hydrophobic microdomains by intramolecular agregations
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Khoukh, Abdelouahed. "Apport de la RMN diffusionnelle à l’étude des systèmes polymères : extrémités de chaîne, contrôle des architectures et auto-assemblage." Thesis, Pau, 2014. http://www.theses.fr/2014PAUU3055/document.
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La Résonance Magnétique Nucléaire RMN DOSY (Diffusion Ordered SpectroscopY) 1H est une technique permettant de mesurer les coefficients de diffusion des espèces en solution. Elle permet ainsi d’obtenir des informations structurales de par sa dimension RMN conventionnelle mais également des informations physico-chimiques telles que la taille de la (macro)molécule ou encore la formation d’agrégats. L’objectif de ces travaux a été d’examiner comment les méthodes de RMN (RMN 1D ,2D et DOSY), permettent de fournir des informations sur la caractérisation des matériaux polymères. La première partie de ce travail souligne l’intérêt de la RMN pour la caractérisation de la microstructure de quelques matériaux polymères en s’attardant plus particulièrement sur l’exploration de leurs extrémités de chaînes. La RMN s’est en effet révélée très performante pour établir le lien entre extrémité de chaîne et méthode de polymérisation appliquée. Le deuxième volet de ces travaux concerne l’étude de quelques architectures complexes (type dibloc et tribloc) et la mise en évidence du caractère contrôlé d’une copolymérisation radicalaire grâce à la RMN diffusionnelle. Nous avons également vu comment déterminer la masse moyenne en poids (Mw) par une simple mesure du coefficient d’autodiffusion. Finalement, l’ensemble des travaux présentés dans ce manuscrit a été valorisé grâce à l’étude des interactions par RMN diffusionnelle. Plus particulièrement la RMN DOSY 1H a permis d’observer des phénomènes de micellisation, d’agrégation, d’encapsulation et de relargage de molécules de principe actifDiffusion Ordered Spectroscopic Nuclear Magnetic Resonance (DOSY NMR 1H) makes it possible to determine physicochemical data such diffusion coefficients. While typical NMR data on the structure of molecules can be obtained, this technique also permits determinations of the physicochemical characteristics, such as molecular sizes or aggregate formation. The objective of this work was to examine how various NMR methodologies, specifically, 1 and 2 dimensional DOSY NMR, can be applied to the characterization of polymers. The first part of the manuscript relates the NMR characterization of some polymeric materials with a special interest in chain-end groups. In particular, we demonstrate the relationships between chain-ends and the polymerization methods employed. In a second part, the potential of the DOSY technique is used to determine controlled features of a radical polymerization resulting in di- and triblock architectures. Molecular weights are also determined by self-diffusion coefficient measurements. The results presented herein demonstrate that diffusional NMR can be effectively employed to understand interactions in polymeric structures. Indeed, DOSY 1H-NMR provides new interesting results concerning micellization, aggregation, encapsulation phenomena and the release of active molecules
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Zhang, Wenjing. "Auto-assemblage de copolymères à blocs amphiphiles induit par la polymérisation : vers des édifices polymères à architecture, morphologie et propriétés contrôlées." Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10222/document.
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L’objectif principal de ce travail de thèse est de synthétiser par polymérisation RAFT en milieux homogène et hétérogène des copolymères à blocs amphiphiles de structure bien contrôlée. Un procédé simplifié, « ont pot » a donc été développé pour synthétiser ces copolymères et les auto-assembler en particules dans l’eau. Cette méthode dite de « l’auto-assemblage induit par la polymérisation » (PISA) permet de synthétiser en quantité des copolymères à blocs amphiphiles en milieux aqueux sans aucune étape de purification intermédiaire. Dans ce procédé, deux étapes successives sont effectuées dans le même réacteur. La 1ère étape a pour but de synthétiser des agents RAFT macromoléculaires hydrophiles (macroRAFTs) par polymérisation en solution dans l’eau. Ces macroRAFTs fonctionnalisés par un groupement trithiocarbonate sont ensuite utilisés dans le même réacteur comme agents de contrôle etprécurseurs de stabilisants pour la polymérisation en émulsion du monomère hydrophobe directement dans l’eau. Lors de cette 2nde étape, des copolymères à blocs amphiphiles sont formés et s’auto-assemblent sous forme de particules aux morphologies variées (sphères, filaments et vésicules). Nous avons alors étudiés les différents paramètres (pH, température de polymérisation en émulsion, nature des monomères hydrophobe et hydrophile, taux de solide, masses molaires des blocs hydrophobe et hydrophile, etc)gouvernant la formation de morphologies spécifiques. Un objectif supplémentaire a été l’étude du comportement viscoélastique linéaire des suspensions de ces nano-fibres polymère à une température inférieure (25°C) ou supérieure (130°C) à la température de transition vitreuse (Tg) du coeur polystyrène des nano-fibres. A T < Tg, les nano-fibres sont parfaitement rigides et obéissent à une dynamique brownienne de bâtonnets. En effet, les lois d’échelles déduites du comportement viscoélastique de ces suspensions obéissent aux lois prédites par Doi-Edwards. En revanche, ces nano-fibres sont flexibles pour T > Tg et ont une dynamique Brownienne de chaînes polymères en solutionThe aim of this work was synthesis of well-defined amphiphilic block copolymers in homogenous and heterogenous media using RAFT polymerization (Reversible Addition-Fragmentation Chain Transfer) and to study their self-assemblies in water. A one-pot process in water was developed for the synthesis of amphiphilic block copolymers that simultaneously to their growth self-assembled into nano-particles. This method called “polymerization-induced self-assembly” (PISA) allows the synthesis of large quantities of amphiphilic block copolymers in aqueous media without any intermediate purification step. During this process, two successive polymerization steps are performed in the same reactor. The first step consists in the synthesis of the hydrophilic macromolecular RAFT agents (macroRAFT agents) possessing a trithiocarbonate reactive group via RAFT in water. Without purification, these macroRAFT agents are reactivated for the polymerization of a hydrophobic monomer in the same reactor via RAFT emulsion polymerization. The resulting amphiphilic block copolymers self-assembled into nano-objects with various morphologies (spherical micelles, nanofibers and vesicles). Different parameters (pH, temperature, natureof hydrophilic and hydrophobic monomers, solids contents, molar masse of hydrophilic and hydrophobic blocks, etc) control these morphologies. Besides, the viscoelastic properties of polymeric nanofibers suspensions were studied as a function of the temperature. Below the Tg of polystyrene core at 25°C, the scaling law from viscoelastic behavior of these nanofiber suspensions the Doi−Edwards theory on the Brownian dynamics of rigid rods. Above Tg at 130°C, the nanofibers are flexible and it observed that their dynamics obey the power laws for polymer chains in solution
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Dinis, Cati Oliveira. "Cork oak (Quercus suber L.) root system: a structural-functional 3D approach." Doctoral thesis, Universidade de Évora, 2014. http://hdl.handle.net/10174/14573.
Full textAbstract:
The last decades have witnessed the decline and sudden death of the cork oak (Quercus suber L.) in Montado. The complexity of this production system management has lead to a large set of solutions which have been absent by scientific based research findings (such as those related with the cork oak root system) deriving mainly from empirical knowledge application. The present integrated research approach permits a better understanding of the production system vulnerabilities that can result in management modification proposals which will be useful in a near future. To contribute to a more realistic and integrated forest management and planning, a study relying on a morphological evaluation of cork oak root system in a Cambissoil soil, using a 3D digitizing method was performed. Cork oak showed a dimorphic root system with a relative high quantity of sinkers distributed all over the soil profile, one root subsystem at a superficial level until 40 cm depth and another at a deeper level, around 1.20 m depth. Tree biomass allocation was similarly distributed between aerial and root systems. Previously, a study on methodologies for roots excavation - profile washing with water and excavation through high pressure air jet – was carried out. Results showed that for sandy soils the most suitable method is the excavation by high pressure air jet. Both methods showed to be inadequate for clayed soils. Following the evidence that soil compaction could be an important factor for root growth, a study was conducted, in a greenhouse, with cork oak seedlings. Results showed that tap root length and total root biomass (coarse and fine roots) are negatively affected by soil compaction in depth. In regard to the low survival rate of cork oaks regeneration that has been observed in Montado, another complementary study was conducted in a greenhouse where fertilisation, inoculation with mycorrhizal fungi and aminoacids supply were tested. It was concluded that seedlings subjected to fertilisation and inoculation had a more equilibrated growth between shoot and root components. It is expected that the research developed in the present thesis can provide an essential tool for future forest planning and management and for the natural and artificial regeneration processes in cork oak stands, ensuring the maintenance of the typical Montado landscape; Sistema Radical do Sobreiro (Quercus suber L.): Uma Abordagem Estrutural Funcional 3D
Resumo:
Desde as últimas décadas que se tem vindo a testemunhar o declínio e a morte súbita do sobreiro (Quercus suber L.) no Montado. A complexidade da gestão deste sistema de produção engloba um grande conjunto de soluções que, por terem sido ausentes de validação científica (tal como a relacionada com o sistema radical do sobreiro), tem vindo a ser suportado, principalmente, pela aplicação do conhecimento empírico. A presente abordagem integrada permite uma melhor compreensão das vulnerabilidades deste sistema que pode resultar em propostas de alteração de gestão que serão úteis num futuro próximo. De forma a contribuir para uma gestão e planeamento florestal mais realistas e integrados, foi realizado um estudo acerca da avaliação morfológica do sistema radical do sobreiro num cambissolo, usando o método de digitalização 3D. O sobreiro mostrou um sistema radicular dimórfico com uma elevada quantidade relativa de sinkers distribuídos por todo o perfil do solo. Foi observado um subsistema à superfície, até aos 40 cm de profundidade e outro mais profundo, a cerca de 1.20 m. Observou-se também que a biomassa da árvore foi distribuída de forma similar entre os sistemas aéreo e radical. Anteriormente foi conduzido um estudo sobre as metodologias de escavação de raízes - lavagem de perfil com água e escavação por meio de jato de ar de alta pressão. Os resultados mostraram que para solos arenosos, o método mais adequado é o método por meio de jato de ar de alta pressão e, que ambos os métodos mostraram ser inadequados para os solos argilosos. Após a observação de que a compactação do solo pode ser um fator importante para o crescimento das raízes, um estudo foi realizado em ambiente de estufa com plântulas de sobreiro. Os resultados mostraram que o comprimento da raiz principal e a biomassa total de raízes (raízes grossas e finas) foram negativamente afetados pela compactação do solo em profundidade. No que diz respeito à baixa taxa de sobrevivência da regeneração dos sobreiros, outro estudo complementar foi realizado em ambiente de estufa onde a fertilização, a inoculação com fungos micorrizos e o suplemento de aminoácidos foram testados. Concluiu-se que as plântulas submetidas à fertilização e inoculação tiveram um crescimento mais equilibrado entre as componentes aéreas e radicais. Espera-se que a investigação apresentada nesta tese possa proporcionar uma ferramenta essencial para o planeamento e gestão florestal futuros e, contribuir para o sucesso da regeneração natural e artificial dos povoamentos de sobreiro, garantindo a manutenção da paisagem típica do Montado.
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フアン, モントヤ セバスチャン, and Sebastian Juan Montoya. "New understandings of disruptive innovation : micro- and macro-level studies." Thesis, https://doors.doshisha.ac.jp/opac/opac_link/bibid/BB13060307/?lang=0, 2018. https://doors.doshisha.ac.jp/opac/opac_link/bibid/BB13060307/?lang=0.
Full textAbstract:
本論文は破壊的イノベーションの微視的・巨視的構造に関する研究だ。クリステンセンによって提唱された破壊的イノベーション理論の基礎を明らかにし、破壊的イノベーション現象の原因と結果を明確に区別する。破壊的イノベーション理論が先行研究で直面した批判に取り組み、イノベーションのジレンマの原因メカニズムに関する問題を浮上する。This thesis is a comprehensive study about disruptive innovation, its patterns, and the mechanisms that cause it. This research tests Christensen's disruption theory, the main theory proposed today as an explanation of this phenomenon. In order to do so, this research identifies the strengths and weaknesses of Christensen's theory, and builds upon it to propose an improved theory of disruption that takes into account the differences between the micro and macro perspectives of disruption.
博士(技術・革新的経営)
Doctor of Philosophy in Technology and Innovative Management
同志社大学
Doshisha University
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Cheng, Irene. "The Shape of Utopia: The Architecture of Radical Reform in Nineteenth-Century America." Thesis, 2014. https://doi.org/10.7916/D8KW5D6T.
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In the tumultuous atmosphere of the decades leading up to the Civil War, the combined effects of religious millennialism, technological revolutions, and the growth of a capitalist economy led numerous Americans to propose radical schemes for transforming their society. At least a hundred cooperative colonies were founded in the 1830s to 50s, leading Ralph Waldo Emerson to famously observe that it seemed every "reading man" had a "draft of a new community in his waistcoat pocket." This dissertation explores a unique strain of mid-nineteenth-century utopianism that featured geometrically distinct architectural and urban plans. These schemes include a square land reform grid and radial republican village proposed by the National Reform Association, phrenologist Orson Fowler's octagon house, Henry Clubb's anti-slavery vegetarian Octagon Settlement Company, a hexagonal city published by the anarchist Josiah Warren, and an ovoid house and circular institution of Equitable Commerce proposed by the Spiritualist John Murray Spear and his followers. I also analyze Thomas Jefferson's octagonal houses and square land grids as precedents for the nineteenth-century utopian projects.
The creators of these plans were motivated to embrace geometric forms in part because of an emerging functionalist view that regarded the built environment as capable of not just representing but also directly shaping bodies and minds. At the same time that the geometric utopians spoke a language of functional effects, however, they also, consciously and unconsciously, used their plans as aesthetic and rhetorical devices to convince and inspire potential converts. Social reformers employed geometric diagrams to convey an affect of transparency at a time when many antebellum Americans saw the levers of political and economic power as increasingly mediated and remote. By exploring the links between utopians' ideas about architecture and causes such as phrenology, Spiritualism, anarchism, land reform, abolitionism, vegetarianism, and spelling and writing reform, I construct a deeper context for these geometric utopian projects that recovers some of their radical, imaginative, and critical spark, while shedding new interpretive light on the visual culture of mid-nineteenth-century radical reform movements.
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Annan, Jessica. "An uncomfortable city: a community-based investigation of hostile architecture." Thesis, 2021. http://hdl.handle.net/1828/13299.
Full textAbstract:
Hostile architecture is a medium through which social exclusion is enacted in the public and common areas of our cities. By limiting who is allowed to occupy space, and how they may do so, it functions to define the contours of inclusion in urban space-- all of which is predicated on one’s engagement with the zones of consumerism that have overtaken the cities’ commons. As a result, those without the means to partake are pushed aside, despite the inner-cities’ historical relationships with the poor, unhoused, and marginalized.
The purpose of this study is to explore how lived experiences and knowledge of discriminatory architecture can inform a sociological analysis of hostile architecture. By exploring hostile architecture in Calgary, this thesis addresses a specific question: How do people with lived experience of homelessness understand hostile architecture? Through Community-Based Participatory Research and Photovoice, this question is addressed through collaboration with community members with lived experience of homelessness.
Collectively, we conclude that those with lived experiences of homelessness understand hostile architecture in a multitude of ways. Amongst these understandings is the notion that hostile architecture not only excludes and displaces the unhoused and marginalized, but that it is also part and parcel of the wider range of hostilities against those experiencing homeless. One key theoretical concept grounds the research. Henri Lefebvre’s ‘Right to the City’ is used as a starting point in discussing what an equitable city might look like. I maintain that the lived experiences and knowledge held by those with experiences of homelessness can sensitize the public, and inform regional and national policymakers about this exclusionary mechanism.Graduate
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Coady, Daniel Joseph. "The use of new reactions for novel polymerizations, polymers and architectures." 2008. http://hdl.handle.net/2152/20145.
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The design, synthesis and characterization of novel conjugated polymers are described. Using a coupling reaction recently developed within our labs, polymers were constructed through triazene linkages generated by joining N-heterocyclic carbenes (NHCs) with organic azides. This triazene reaction produced polymer of sufficiently high molecular weight as to be spin-coated and rendered conductive upon doping with iodine. The reaction also has potential for executing post-polymerization modifications. This was evidenced through rapid functionalization of poly(4-methylazido-styrene) via triazene formation using a commercially available N-heterocyclic carbene (NHC). A formal anion metathesis of benzobis(imidazolium)s was used to transform neutral block copolymers into block ionomers. Further investigation of the block ionomers revealed their solvent mediated self assembly. The gradual change of organic to aqueous media caused the adoption of a three-dimensional micelle conformation as determined by transmission electron microscopy and dynamic light scattering. Through the exploitation of carbene-carbon disulfide adducts, new chain transfer agents were generated. After 2-dithiocarboxylate-imidazolium adduct formation, alkylation was performed with benzyl bromide. The resulting charged chain transfer agent was tested for its ability to moderate radical addition fragmentation (RAFT) polymerizations of styrene. A considerable increase in transfer kinetics as compared to that of commonly used RAFT agents was observed whilst retaining low polydispersity and molecular weight control. The rate enhancement is presumably due to the electron withdrawing imidazolium activating the thionyl towards the nucleophilic radical while retaining effective fragmentation. Ion coordinating macrocycles were affixed to a poly(methacrylate) scaffold for employment as electrolyte extractants. Polymer bound calix[4]pyrrole was found to complex fluoride and chloride with sufficient strength as to extract tetrabutylammonium salts from water. Enhanced extraction abilities were observed when calix[4]pyrrole was used in conjunction with benzo-15-crown-5. Methacrylate polymers containing both macrocycles affected the removal of aqueous potassium fluoride from a biphasic water/dichloromethane mixture. To provide evidence for the presence of potassium fluoride within the dichloromethane layer, ¹⁹F NMR and flame emission spectroscopy were used.text