Neste trabalho, um polímero eletrólito derivado do poli(indeno) (PInd) foi desenvolvido como componente de membranas poliméricas a base de polibenzimidazol (PBI) para célula a combustível de média temperatura. Foi investigado o método de síntese, envolvendo a reação de fosfonação pelo método de Friedel-Crafts assistido por catalisador ácido de Lewis AlCl3. O polímero poli(indeno) fosfonado (PPInd) foi comparado com seu análogo sulfonado, o poli(indeno) sulfonado (SPInd), e usados nas blendas com 5, 7,5 e 10% em peso com o PBI. Os polímeros precursores foram caracterizados por espectroscopia de infravermelho, espectroscopia de ressonância magnética nuclear, espectroscopia de energia dispersiva, espectrometria de espalhamento Rutherford, análise termogravimétrica acoplada com espectrometria de massas e calorimetria exploratória diferencial. As blendas PPInd/PBI e SPInd/PBI foram caracterizadas por análise termogravimétrica, grau de dopagem e espectroscopia de impedância eletroquímica. A modificação realizada pelo método de Friedel-Crafts permitiu a obtenção do poli(indeno) fosfonado parcialmente solúvel em solventes orgânicos e água, com grau de modificação de 81%. Houve convergência dos teores de modificação encontrados pelas análises termogravimétrica, espectrometria de espalhamento Rutherford e espectroscopia de energia dispersiva. O polímero PPInd apresentou estabilidade química na temperatura de operação da célula a combustível de média temperatura, passando por processos de degradação típicos de sua estrutura aromática fosfonada. A degradação dos polímeros PInd, PPInd e SPInd ocorreu majoritariamente com cisão de unidades monoméricas de indeno não funcionalizado. A inserção dos polímeros modificados PPInd e SPInd no PBI resultou no aumento da condutividade iônica, tendo a blenda com 10% de PPInd apresentado o maior valor de condutividade protônica (0,015 S.cm-1), a 25 oC. O uso do poli(indeno) modificado com grupos ácido fosfônico visa aumentar a gama de eletrólitos para células a combustível de média temperatura. / In this work a polymer electrolyte derivated from the poly(indene) (PInd) was developed to be used as polymer electrolyte membrane in medium-temperature fuel cells. The modification method, based on the AlCl3 assisted Friedel-Crafts reaction, was investigated as fosfonation strategy. The phosphonated poly(indene) was compared to its similar sulphonated poly(indene) and they were used in blends of 5, 7.5 and 10wt% in polybenzimidazole (PBI). Pristine polymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, energy dispersive spectroscopy, Rutherford backscattering spectrometry, thermogravimetric analysis coupled with mass spectrometry and differential scanning calometry. The PPInd/PBI and SPInd/PBI blends were characterized by thermogravimetric analysis, doping level and electrochemical impedance spectroscopy. The modification by Friedel-Crafts reaction produced phophonated poly(indene) with degree of phosphonation of 81%, partially soluble in organic solvent and water. It was found convergence on the results for degree of phosphonation calculated by thermogravimetric analysis, Rutherford backscattering spectrometry and energy dispersive spectroscopy. PPInd presented chemical and thermal stabilities within the fuel cell operating temperature, passing by typical degradation processes of macromolecules made of phosphonated aromatic structures. The degradation of PPInd and SPInd occurred mainly by cleavage of monomeric units of non-funcionalized indene. Addition of modified polymers PPInd and SPInd resulted in increase of PBI’s ionic conductivity. 10PPInd/PBI blend presented the highest ionic conductivity (0.015 S.cm-1) at 25 oC. The use of phosphonated poly(indene) on PBI membranes enlarges the variety of available polymer electrolyte membranes for medium-temperature fuel cells.

Cette thèse a pour objectif d'étudier les réactions des alcools en conditions hydrothermales. Dans une phase préliminaire, le phényl-éthanediol a été étudiés. Après aldolisation, cyclisation intramoléculaire et aromatisation sont suivi en formant 1-phénylnaphthalène. L'aldolisation et la cyclisation du type de Friedel et Crafts ont été mise en œuvre.Les transformations de l'éthylène glycol et du 1,2-propanediol sont fortement dépendantes des conditions de réaction (température, durée de réaction et nature du solvant). La réaction de transformation du 1,2-propanediol permet de synthètiser les composés suivants : mésitylène, 2-méthyl-pentènal et 2-éthyl-3,5-diméthyl-cyclopent-2-ènone. Ces produits peuvent être utilisés comme biocarburant ou solvant ou peuvent constituer des matières premières pour des synthèses organiques.Les alkylations du naphthalène et du phénol ont été étudiées en détails en fonction de la nature du solvant. L'emploi d'acide chlorhydrique en concentration de 0.05mol/L à 180°C permet l'alkylation des aromats par l'alcool benzylique. D'autres solvants (acide acétique, acide formique à 1mol/L) permettent d'obtenir ces composés avec des rendements d'alkylation inférieurs. Par ailleurs, le recyclage de ces solvants est réalisable. Notons enfin que l'alcool benzylique peut polymériser et cette polymérisation est fortement influencée par la température utilisée. La polymérisation de l'alcool benzylique a été appliquée avec succès à la séparation des platinoïdes d'une solution modèle d'effluents issue du traitement du combustible nucléaire. / This thesis aims to study and to apply reactions of alcohols under hydrothermal conditions.Studies on 1-phenyl-ethanediol show an aldolisation, followed by an intramolecular Friedel-Crafts type reaction and an aromatisation. Finally, it ends up by as 1-phenyl-naphthalene.Ethylene glycol reacts on itself with a strong dependence on the temperature and the solvent. The conversion of 1,2-propanediol showed similar dependences and obtained even the aromatic compound mesitylene and especially the amount of products proves dependence on the temperature and the duration of the reaction. The main compounds can be used as solvents, as biofuel and for syntheses, whereas the byproducts might be biocarburants after hydrogenation.The Friedel-Crafts type reaction is transferred to an intermolecular one. Naphthalene and phenol are studied in more detail. 0.05mol/L HCl are enough in order to benzylate an aromatic compound at 180°C. HCl can be replaced by acetic acid or formic acid, but even concentrations of 1.0mol/L do not achieve results as good as 0.05mol/L HCl. The recycling of the aqueous phase of these reactions is advantageous. Additionally, benzyl alcohol alkylates benzyl alcohol and thus it can polymerize. Higher temperatures lead to longer polymers. This polymerization can be used in the domain of nuclear fuel recycling in order to separate platinum group metals out of a model solution.

Thesis (MTech (Interior Design))--Cape Technikon, Cape Town,1996 / This research project has endeavoured to analyse the extent to which craft ideas and techniques are combining with technological skills in order to formulate an identity for Western Cape furniture design. This identity has been shown to be strongly linked to the determinants of style". which include the national striving for a South African zeitgeist. a sense of unified spirit. The problems of eclecticism are discussed in the light of superficial ethnic cooption. The new craft of the Western Cape (and more specifically Cape Town) of South Africa. is represented against the background of the old craft of the Arts and Crafts Movement in Britain at the turn of the century. Those old methods and ideas influenced the Cape Colony especially when it was under British rule. This dissertation shows that the new craft ideas and methods are synonymous with the new ideology of South Africa. a new craft for a new South Africa. The designers and practical work selected to be part of this research all share a common approach in their positive attitude towards experimenting with new techniques and using available resources to produce quality furniture which is accessible to most consumers. The work of four design groups: Greenspace. Metropolis. Flying Cow and the Montebel70 Smithy are discussed in terms of the objectives of this research which are essentially linked to the unravelling of the determinants of style and their relation to the concept identity in the South Africa which has succeeded the first free and fair general elections of April 1994.

A turn away from language and the human mind as the dominant (or only) determinants of reality can be identified within many disciplines, including anthropology, philosophy and literature, reflecting a growing acceptance of human and non-human, living and non-living entities as real, complex and partially withdrawn agents in the world. In Object Oriented Ontology the definition of object is extended to include humans, who have no special ontological status. Timothy Morton proposes rhetoric as a means of drawing closer to other objects, of contacting the ‘strange stranger’; objects cannot be known directly, or fully, but can be explored through imaginative speculation. Drawing on Object Oriented Ontology, my project explores making - an intimate engagement between body and material - as a means of thinking the body as a (strange) object within a mesh of strange objects. Facture is documented as image and language, prompting a series of shifting, speculative questions: • Can writing be brought to making to generate new new approaches to craft production? • How might writing in response to making, or objects, be reintroduced into a making process as a form of feedback? • Can writing_making methods generate new approaches to writing (about) making and materials? • How might a combination of production, documentation and reflection be displayed as artwork/research? • Can making be seen as a means for contacting the ‘strange stranger’?

Des complexes NHC du gallium(III) et de l’indium(III) ont été préparés. Ces composés, simples à synthétiser, se sont révélés être beaucoup plus stables que les sels commerciaux de type MX₃ (M = Ga, In ; X = Cl, Br, I). Ces complexes, une fois activés par AgSbF₆, présentent un fort caractère acide de Lewis. [IPr-GaCl₂][SbF₆] s’est ainsi montré très actif en tant qu’acide de Lewis π et a été utilisé comme catalyseur dans différentes réactions impliquant l’activation de fonctions carbonées insaturées. Il a ainsi permis d’effectuer des hydroarylations inter- et intramoléculaires d’alcynes, d’alcènes et d’allènes. La généralité de cette transformation a pu être démontrée dans une réaction tandem de cycloisomérisation/Friedel-Crafts entre un arényne et un nucléophile aromatique. La capacité des complexes cationiques de gallium et d’indium à activer des alcènes a également pu être mise à profit pour la réduction de dérivés styréniques en présence de cyclohexa-1,4-diène comme source d’hydrogène. Et parce que ces complexes permettent la génération de dérivés du styrène par hydroarylation d’alcynes, une cyclisation réductrice d’arénynes sans précédent a pu être développée. Enfin le complexe [IPr-GaCl₂][SbF₆] a été utilisé dans des réaction impliquant l’eau en tant que réactif. Quelques alcynes ont ainsi pu être hydratés et des esters γ,δ-insaturés ont été transformés en lactones. En résumé, nos complexes cationiques de gallium et d’indium peuvent être utilisés dans des réactions généralement considérées comme relevant du domaine des métaux de transition nobles (Au, Pt, Ru…). / NHC complexes of gallium(III) and indium(III) have been prepared. These compounds, easy to synthesize, proved to be much more stable than the commercially-available salts MX₃ (M = Ga, In ; X = Cl, Br, I). These complexes, once activated by AgSbF₆, show a strong Lewis acid character. For instance, [IPr-GaCl₂][SbF₆] showed a high activity as π-Lewis acid and was used as catalyst in several reactions triggered by the activation of unsaturated C-C bonds such as inter- and intramolecular hydroarylations of alkynes, alkenes and allenes. The versatility of this transformation was demonstrated in a cycloisomerization/Friedel-Crafts tandem reaction between an arenyne and an aromatic nucleophile. The ability of cationic complexes of gallium and indium to activate alkenes was also used for the reduction of styrene derivatives with 1,4-cyclohexadiene as hydrogen source. Also, because these complexes are able to generate styrene derivatives by hydroarylation of alkynes, an unprecedented reductive cyclization of arenynes could be developped. Moreover, [IPr-GaCl₂][SbF₆] was used in reactions involving water as reagent. Several alkynes were hydrated and γ,δ-unsaturated esters were transformed into lactones. In summary, our cationic complexes of gallium and indium can be used in reactions generally catalyzed by noble metals (Au, Pt, Ru…).

No description available.

A variety of organometallic-fused heterocycles and acene quinones were prepared and characterized. This work was divided into three parts: first, the synthesis of 5,5-fused heterocyclic complexes of tricarbonylmanganese and (1’,2’,3’,4’,5’-pentamethylcyclopentadienyl)ruthenium; second, the synthesis of 1,2-diacylcyclopentadienyl p-cymene complexes of ruthenium(II); and third, synthesis of cyclopentadienyl-fused polyacenequinone complexes of ruthenium, iron and manganese. The first examples of the convenient, versatile and symmetric cyclopentadienyl-fused heterocycle complexes of (1’,2’,3’,4’,5’-pentamethylcyclopentadienyl)ruthenium(II) and tricarbonylmanganese(I) were synthesized starting from (1,2-dicarbophenoxycyclopentadienyl)sodium. The sodium salt was transmetalated using [MnBr(CO)5] and 1/4 [Ru(μ3-Cl)(Cp*)]4 to give [Mn(CO)3{η5-C5H3(CO2Ph)2-1,2}] and [Ru{η5-C5H3(CO2Ph)2-1,2}(Cp*)]. The diester complexes were saponified under basic conditions to obtain the corresponding dicarboxylic acids. The dicarboxylic acids were used to synthesize unique cyclopentadienylmetal complexes including diacyl chlorides, anhydrides, thioanhydrides and p-tolyl imides of ruthenium and manganese. Similarly, a series of 1,2-diacylcyclopentadienyl-p-cymene cationic complexes of ruthenium were synthesized using thallium salt of 2-acyl-6-hydroxyfulvene and [Ru(η6-p-cymene)(μ-Cl)Cl]2 in a 2:1 ratio with an intension of converting them into heterocycle-fused cationic sandwich complexes. However, our attempts of ring closing on 1,4-diketons with sulfur or selenium were unsuccessful. A methodology involving the synthesis of metallocene-fused quinone complexes was employed starting from pentamethylruthenocene-1,2-dicarboxylic acids. The diacyl chloride was prepared in situ from the dicarboxylic acids and used for Friedel-Crafts acylation. We observed single-step room-temperature diacylation of aromatics, including benzene, o-xylene, toluene, 1,4-dimethoxybenzene and ferrocene with pentamethylruthenocene-1,2-diacyl chloride to obtain the corresponding quinone complexes. Similarly, we synthesized mononuclear and binuclear γ-quinones by aldol condensation of 1,2-diformylcyclopentadienylmetal complexes with cyclohexane-1,4-dione or 1,4-dihydroxyarenes. The third methodology involves the Friedel-Crafts acylation of ferrocene with 2-carbomethoxyaroyl chlorides followed by saponification, carbonyl reduction, and ring closing by second Friedel-Crafts acylation to give Ferrocene-capped anthrone-like tricyclic and tetracyclic ketones. The oxidation of the ketones gave [3,4-c]-fused α-quinone complexes of iron. The oxidative and reductive coupling, enolization and C-alkylation of the anthrone complex were studied. Solvolysis of α-carbinol gave α-ferrocenylcarbenium salt, which underwent dimerization on treatment with non-nucleophilic base. We were successful to trap the in situ generated trimethylsilylenol ether of ferrocene-anthrone using dienophiles like N-phenylmaleimide or dimethylacetylenedicarboxylate under Diels-Alder conditions.

Mitt examensarbete har till syfte att undersöka lärares erfarenheter av hur elever dokumenterar och reflekterar över sin arbetsprocess och sitt färdiga slöjdföremål på textilslöjden i grundskolan. Den metod jag valt är den kvalitativa forskningsintervjun med öppna frågor för att få veta hur intervju personerna upplever att elever reflekterar och dokumenterar över sitt arbete. De personer jag valt att intervjua är fyra textilslöjdslärare. Jag har kommit fram till resultatet att de fyra lärarna anser att dokumentation och reflektion är viktigt, de upplever att muntlig reflektion pågår under större delen av lektionen. Undersökningen visar att eleverna dokumenterar i loggbok eller genom skriftliga utvärderingar, där de beskriver arbetsprocessen och visar vad de lärt sig. Lärarna i intervjuerna kommer fram till att den muntliga och skriftliga dokumentationen är lika viktiga för lärandeprocessen.

This thesis contributes towards the knowledge of post conflict crafts of Kashmir and the role women play in this sector. It proposes crafts to be a culturally relevant activity which could generate income for people living in Kashmir. It analyses the impact of the conflict on the crafts of Kashmir from the perspective of the craftspeople. The research is based on fieldwork conducted in Srinagar, Kashmir (2003-2006). Here craftsmen’s groups were studied and a craftswomen’s organisation – Zanana Dastakari was used as a case study. Fieldwork techniques allowed the voices of crafts people to be heard, allowing this study to be conducted from their perspective. Supporting literature was used to place Kashmir within the larger context of crafts, gender and conflict. The research found the crafts of Kashmir to have changed in response to the conflict, the most significant shift being of women joining the crafts sector as stakeholders. Women have selected the area of crafts due to their subjective preferences, which often stem from their identity as Muslim women. This work proposes links between poverty, unemployment and conflict and suggests that culture can play a role in economic development. In Kashmir economic development and reconstruction could be boosted through promotion of this sector. The implications of this research in light of other research indicates a need for deeper understanding of identities and needs of women in conflict zones and the evolution of coping mechanisms used by them to generate sustainable incomes.

During the Indian Residential School period (1867-1960) in the Mackenzie River area of the Northwest Territories, Indigenous students at several schools administered by the Order of the Grey Nuns produced crafts and art items that were then exported to the Order’s motherhouse in Montréal. This collection of 275 pieces, ranging from garments and footwear to paintings and drawings, was repatriated at the request of the Fort Providence Métis Council to the Prince of Wales Northern Heritage Centre (PWNHC), in Yellowknife, Northwest Territories in 2001. While locationally repatriated, the Grey Nuns collection has to date remained in storage at the PWNHC until 2015 when, in cooperation of PWNHC staff, I was able to carry out a preliminary examination of the collection. The objective of this examination was to: (1) temporally and spatially trace the movement of the pieces across Canada, situating the PWNHC collection within the residential school history in Canada; (2) to explore if the making of these pieces by the children who attended residential schools in the Mackenzie River Valley perpetuated Indigenous artistic traditions; (3) to determine whether the materiality of the collection exposes the complex interrelations between children’s crafting knowledge and the colonial structure; (4) to explore the potential and challenges of reconnecting this collection now at the PWNHC with its source communities today. This thesis reports on the analysis of a small subset of the collection’s contents. This sample, consisting of two pairs of moccasins, one pair of mittens and a single souvenir object, was analyzed for information pertinent to my main objectives, and especially what they indicate about hybridity and materiality regarding the different cultural influences, Métis, Dene and Euro-Canadian, that met in the Indian Residential school setting. The objects, made at the behest of the Grey Nuns in order to meet the demands of the Canadian tourism industry, and provide badly needed income to support their Northwest Territories schools, exhibit a combination of two, and even three, of these influences, notably in the items’ styles, decorative motifs and the materials employed in their creation. Of particular note, these sample objects portray distinct Métis and Dene artistic knowledge and traits. Their making speaks to the continuance of important Indigenous women’s traditions, knowledge that did not disappear despite the often hostile institutional environment around their creators. The collections offers another window on student-colonizer relations within some Indian Residential schools in the Lower Mackenzie region in the early twentieth century. / Graduate / 0326 / abra.wenzel@gmail.com