Polymer – clay nanocomposites have improved thermal, mechanical, and barrier properties when compared with the pure polymer. The objective of this study was to examine if gas separation performance could be improved by introducing a layered nanopourous aluminum phosphate with a large aspect ratio into a polymeric matrix. The aluminum phosphate has eight membered rings, which could potentially serve as a size selective medium. A hexafluorinated polyimide, 6FDA-6FpDA-8%-DABA, was used as the polymeric matrix. The polyimide and the aluminum phosphate were synthesized separately according to well documented procedures. The two materials were blended and fabricated into nanocomposite membranes. The effect of mixing temperature and percentage of layered aluminum phosphate added to the polymer on the permeation properties were examined. These factors had a direct effect on the degree of intercalation and exfoliation of the nanocomposite structure. Transmission FTIR, TEM, DMTA, and X-ray diffraction were used to characterize the morphology, structure, and composition of these nanocomposite films. The permeation properties of the nanocomposite membranes were evaluated using pure gases (He, O₂, N₂, CH₄, CO₂) at 35°C and a feed pressure of 4 atm. In general, the permeability decreased and the selectivity coefficients increased when adding 10 wt% aluminum phosphate to the polyimide. Furthermore, the membranes showed size selectivity, consistent with the pore size in the layered aluminum phosphate. / Master of Science

No description available.

The purpose of this investigation was to study fundamentally the difference in structure of aluminum phosphates synthesized in various mediums. / Master of Science

O fósforo (P) tem sido um dos fatores mais limitantes da produção agrícola em solos de exploração recente, bem como nos solos há tempo utilizados e cuja fertilidade não é mantida. Tradicionalmente, o uso de fontes de P de elevada solubilidade tem auxiliado no aumento da fertilidade desses solos proporcionando acréscimos na produtividade das culturas. No entanto, o processo de fabricação desses fertilizantes requer o uso de rochas fosfáticas com baixa quantidade de impurezas metálicas como ferro e alumínio. Essa exigência tem levado as indústrias a descartarem quantidades elevadas de resíduo fosfático, no qual se encontram os minerais do grupo da crandallita. A busca de fontes alternativas de P para a produção agrícola encontra-se dentro do contexto de aproveitamento racional de recursos minerais existentes bem como de avançar no conhecimento de condições agronômicas que maximizem sua utilização pelas plantas. Para tanto, coletaram-se amostras do rejeito da mineração de depósitos fosfáticos de importância nacional (Catalão-GO, Juquiá-SP e Tapira-MG) contendo fosfatos aluminosos do grupo da crandallita, objetivando-se avaliar a capacidade desses minerais, após tratamento térmico, em disponibilizar P para plantas em solos sob condição de inundação e de pH próximo à neutralidade e determinar sua eficiência agronômica relativa em comparação à uma fonte padrão de P, relacionando-a com as suas características químicas e mineralógicas. O material coletado foi submetido ao tratamento térmico sob diferentes temperaturas para avaliar o efeito sobre a solubilidade e transformação morfológica. O material tratado foi: (i) misturado a amostras de terra com diferentes valores de pH para avaliar o comportamento de dissolução, (ii) submetido a teste de hidrólise em solução aquosa com valores de pH distintos e (iii) avaliado como fonte de P para as culturas do arroz-de-sequeiro e arroz inundado. De acordo com os resultados obtidos, concluiu-se que: (i) o tratamento térmico dos fosfatos aluminosos do grupo da crandallita com temperaturas ao redor de 500 ºC aumenta sua solubilidade em solução de citrato neutro de amônio e promove modificações na estrutura cristalina dos minerais, (ii) a liberação de P desses minerais é bastante reduzida em solução aquosa com valores de pH entre 4 e 8, (iii) a dissolução dos fosfatos aluminosos do grupo da crandallita calcinados em condição de solo é maior quando o valor de pH está próximo à neutralidade, comparado ao levemente ácido e (iv) que a adição dessas fontes de P ao solo promoveu resposta significativa na produção de matéria seca, na quantidade de P acumulado pela parte aérea das plantas e no rendimento de grãos de plantas de arroz-de-sequeiro e inundado, contudo não tão eficiente quanto a fonte padrão de P. / Phosphorus (P) has been one of the most limiting factors for crop production in recent cultivated soils as well as in old cropped soils in which fertility is not maintained. Traditionally, the application of high solubility P sources has helped to raise soil fertility providing increase of crop yield. However, the manufacturing process of water-soluble P fertilizers requires the use of phosphate rocks with low quantity of metal impurities as iron and aluminum. This requirement has forced the fertilizer industry to discard great amounts of phosphate residue, in which the aluminous phosphates of the crandallite group can be found. Searching alternative P sources for crop production meets the context of rational use of existing mineral resources as well as move forward on the knowledge of agronomic conditions to maximize P uptake by plants. Therefore, samples of the mine residue from phosphate deposits of great relevance (Catalão-GO, Juquiá-SP e Tapira-MG) with aluminous phosphates of the crandallite group were collected and thermal treated, aiming to evaluate their ability to provide P to plants in soils under flooding condition and with pH around neutrality, to determine their relative agronomic effectiveness compared to a standard P source, and relate it with their chemical and mineralogical properties. The material collected was submitted to a thermal treatment under different temperatures to evaluate its effect on solubility and morphology. Treated material was (i) mixed to soil samples with different pH values to evaluate its dissolution, (ii) submitted to a hydrolysis test in aqueous solution with distinct pH values, and (iii) evaluated as a P source to upland rice and flooded rice. According to the obtained results, it was concluded that: (i) the thermal treatment of aluminous phosphates of the crandallite group with temperatures around 500 ºC increase its solubility in neutral ammonium citrate solution and cause alterations on the crystalline structure of minerals, (ii) P released from these mineral is very low in aqueous solution with pH ranging from 4 to 8, (iii) dissolution of aluminous phosphates of the crandallite group under soil conditions is higher when soil pH is around neutrality, compared to low acidity, and (iv) the addition of these P sources to soil significantly increased dry matter yield, P uptake by plants, and grain yield of upland rice and flooded rice, however not as much as for the standard P source.

O fósforo (P) tem sido um dos fatores mais limitantes da produção agrícola em solos de exploração recente, bem como nos solos há tempo utilizados e cuja fertilidade não é mantida. Tradicionalmente, o uso de fontes de P de elevada solubilidade tem auxiliado no aumento da fertilidade desses solos proporcionando acréscimos na produtividade das culturas. No entanto, o processo de fabricação desses fertilizantes requer o uso de rochas fosfáticas com baixa quantidade de impurezas metálicas como ferro e alumínio. Essa exigência tem levado as indústrias a descartarem quantidades elevadas de resíduo fosfático, no qual se encontram os minerais do grupo da crandallita. A busca de fontes alternativas de P para a produção agrícola encontra-se dentro do contexto de aproveitamento racional de recursos minerais existentes bem como de avançar no conhecimento de condições agronômicas que maximizem sua utilização pelas plantas. Para tanto, coletaram-se amostras do rejeito da mineração de depósitos fosfáticos de importância nacional (Catalão-GO, Juquiá-SP e Tapira-MG) contendo fosfatos aluminosos do grupo da crandallita, objetivando-se avaliar a capacidade desses minerais, após tratamento térmico, em disponibilizar P para plantas em solos sob condição de inundação e de pH próximo à neutralidade e determinar sua eficiência agronômica relativa em comparação à uma fonte padrão de P, relacionando-a com as suas características químicas e mineralógicas. O material coletado foi submetido ao tratamento térmico sob diferentes temperaturas para avaliar o efeito sobre a solubilidade e transformação morfológica. O material tratado foi: (i) misturado a amostras de terra com diferentes valores de pH para avaliar o comportamento de dissolução, (ii) submetido a teste de hidrólise em solução aquosa com valores de pH distintos e (iii) avaliado como fonte de P para as culturas do arroz-de-sequeiro e arroz inundado. De acordo com os resultados obtidos, concluiu-se que: (i) o tratamento térmico dos fosfatos aluminosos do grupo da crandallita com temperaturas ao redor de 500 ºC aumenta sua solubilidade em solução de citrato neutro de amônio e promove modificações na estrutura cristalina dos minerais, (ii) a liberação de P desses minerais é bastante reduzida em solução aquosa com valores de pH entre 4 e 8, (iii) a dissolução dos fosfatos aluminosos do grupo da crandallita calcinados em condição de solo é maior quando o valor de pH está próximo à neutralidade, comparado ao levemente ácido e (iv) que a adição dessas fontes de P ao solo promoveu resposta significativa na produção de matéria seca, na quantidade de P acumulado pela parte aérea das plantas e no rendimento de grãos de plantas de arroz-de-sequeiro e inundado, contudo não tão eficiente quanto a fonte padrão de P. / Phosphorus (P) has been one of the most limiting factors for crop production in recent cultivated soils as well as in old cropped soils in which fertility is not maintained. Traditionally, the application of high solubility P sources has helped to raise soil fertility providing increase of crop yield. However, the manufacturing process of water-soluble P fertilizers requires the use of phosphate rocks with low quantity of metal impurities as iron and aluminum. This requirement has forced the fertilizer industry to discard great amounts of phosphate residue, in which the aluminous phosphates of the crandallite group can be found. Searching alternative P sources for crop production meets the context of rational use of existing mineral resources as well as move forward on the knowledge of agronomic conditions to maximize P uptake by plants. Therefore, samples of the mine residue from phosphate deposits of great relevance (Catalão-GO, Juquiá-SP e Tapira-MG) with aluminous phosphates of the crandallite group were collected and thermal treated, aiming to evaluate their ability to provide P to plants in soils under flooding condition and with pH around neutrality, to determine their relative agronomic effectiveness compared to a standard P source, and relate it with their chemical and mineralogical properties. The material collected was submitted to a thermal treatment under different temperatures to evaluate its effect on solubility and morphology. Treated material was (i) mixed to soil samples with different pH values to evaluate its dissolution, (ii) submitted to a hydrolysis test in aqueous solution with distinct pH values, and (iii) evaluated as a P source to upland rice and flooded rice. According to the obtained results, it was concluded that: (i) the thermal treatment of aluminous phosphates of the crandallite group with temperatures around 500 ºC increase its solubility in neutral ammonium citrate solution and cause alterations on the crystalline structure of minerals, (ii) P released from these mineral is very low in aqueous solution with pH ranging from 4 to 8, (iii) dissolution of aluminous phosphates of the crandallite group under soil conditions is higher when soil pH is around neutrality, compared to low acidity, and (iv) the addition of these P sources to soil significantly increased dry matter yield, P uptake by plants, and grain yield of upland rice and flooded rice, however not as much as for the standard P source.

Neste trabalho foram realizadas análises estruturais de dois conjuntos de vidros metafosfatos ternários relevantes em potenciais aplicações: aluminofosfatos e álcalis mistos. Para os aluminofosfatos a análise estrutural tem por objetivo verificar a existência de comportamentos preferenciais da conectividade entre os grupos fosfatos e os átomos de Al, e verificar a possível extensão a estes sistemas ternários de princípios de ligação química e ordem local inferidos em fosfatos binários, sendo os sistemas estudados K(1-x)Alx(PO3)(2x+1) e Na(1-x)Alx(PO3)(2x+1) . Para os vidros de álcalis mistos, a análise estrutural tem por objetivo identificar se existe segregação ou mistura aleatória das duas espécies de cátions, e determinar quais modificações na ordem local de cada álcali são induzidas pela troca de espécies, sendo os sistemas estudados LixNa(1-x)(PO3), KxNa(1-x)(PO3, RbxNa(1-x)(PO3), RbxLi(1-x)(PO3) e CsxLi(1-x)(PO3). As informações estruturais nestes vidros foram obtidas através de técnicas de Ressonância Magnética Nuclear (RMN) de estado sólido de 7Li, 23Na, 27Al, 31P, 87Rb e 133Cs. A conectividade entre a rede de fosfatos e os átomos de Al foi estudada utilizando informações a respeito da distribuição de espécies tetraédricas de fosfatos Q2m , sendo m = 0,1, 2 o número de pontes P-O-Al por tetraedro, obtidas através de RMN de 31P, e do número de coordenação médio do Al obtido através de RMN de 27Al. Da análise quantitativa da evolução das diferentes populações Q2m com a concentração de Al, juntamente com o número de coordenação médio do Al, foi possível verificar a existência de comportamentos preferenciais na organização estrutural: tetraedros fosfatos compartilham um vértice único (oxigênio não-ponte) com os poliedros de coordenação do Al. Esta organização de médio alcance é mantida até uma determinada concentração de Al, onde todo tetraedro forma uma ponte P-O-Al . A distribuição das espécies Q2m resultante é do tipo binária em função da concentração de Al: { Q20, Q21 } até concentrações intermediárias e { Q21, Q22 } para concentrações altas. Para os metafosfatos de álcalis mistos, o comportamento do desvio químico de 23 Na e 133Cs revela um efeito sistemático de aumento/decréscimo no tamanho do ambiente de coordenação ao redor dos álcalis em função da substituição. O ambiente de O dos álcalis de menor raio iônico resulta comprimido quando ocorre a substituição deste por uma espécie de raio iônico maior, e vice-versa. Com relação à distribuição dos álcalis na rede vítrea, as evoluções dos desvios químicos em função da substituição excluem a possibilidade de segregação dos álcalis ou separação de fase. A análise do acoplamento dipolar homonuclear de 23 Na, através da medida do segundo momento, revelou que a mistura de Na com o segundo álcali não é aleatória, existindo uma maior probabilidade de um Na ter outro Na como próximo vizinho. A correlação entre o grau de não-aleatoriedade na dispersão do Na e o incremento na magnitude do efeito de álcalis mistos na condutividade DC dos metafosfatos de Rb-Na, K-Na e Li-Na sugere que os fenômenos estão fundamentalmente relacionados. Esta seria a primeira evidência de vínculo entre uma propriedade estrutural da distribuição dos álcalis e o efeito de álcalis mistos de uma propriedade dinâmica. / In this work, the structure of two ternary metaphosphate glass systems was analyzed: aluminum-phosphates and mixed-alkali. The aim of the study in aluminum-phosphates is to determine the existence of preferential structural connectivities between phosphate groups and Al, and to verify the possible extension to these ternary glasses of principles of structural organization valid in binary phosphates. The aluminum metaphosphates studied here were K(1-x)Alx(PO3)(2x+1) and Na(1-x)Alx(PO3)(2x+1) . In mixed-alkali metaphosphates the goal of the structural analysis is the identification of the way in which alkali cations are distributed in the glass network (segregation versus random mixture), and to determine what kind of modification in the local order around the alkalis are induced by the substitution of species. The mixed-alkali metaphosphate studied here were LixNa(1-x)(PO3), KxNa(1-x)(PO3, RbxNa(1-x)(PO3), RbxLi(1-x)(PO3) and CsxLi(1-x)(PO3). The structural information was obtained using solid-state Nuclear Magnetic Resonance (NMR) techniques of 7Li, 23Na, 27Al, 31P, 87Rb and 133Cs. The connectivity between the phosphate groups and Al was analyzed studying the populations of phosphate species Q2m, with m=0,1,2 being the number of P-O-Al bridges per tetrahedron, obtained using 31P-NMR, and considering the average coordination number of Al obtained by 27Al-NMR. Through the quantitative analysis of the evolution of the Q2m population with the Al concentration, it was possible to identify the existence of a preferential structural behavior: phosphate tetrahedra share only one common corner (non-bridging oxygen) with the coordination polyhedra around Al. This medium-range organization can be sustained up to a certain concentration of Al, to the point where every phosphate establishes a P-O-Al bridge. The resulting distribution of Q2m species can be identified as binary, as a function of the Al content: { Q20, Q21} up to intermediate concentrations and { Q21, Q22} for higher concentrations. In the mixed-alkali metaphosphates, the behavior of the 23Na and 133Cs chemical shift reveals a systematic increase/decrease in the average size of the coordination environment around the alkalis as a function of the substitution. The O environment around cations with the smaller ionic radius is compressed as this species is substituted by another alkali with bigger ionic radius, and vice-versa. With respect to the alkali distribution in the glass network, the observed evolution of the chemical shift as a function of the cation substitution excludes the possibility of segregation of alkalis or phase separation. The analysis of the 23Na homonuclear magnetic dipolar coupling, through the measurement of the second moment, revealed that the mixture at atomic scale of Na with the second alkali is not random, having a higher probability of a Na being close to other Na than to other alkali. The correlation between the degree of non-random dispersion of Na and the increment in the magnitude of the mixed alkali effect in the dc conductivity of Rb-Na, K-Na and Li-Na metaphosphates indicates a fundamental connection between both phenomena. This may be the first evidence of a relation between a structural property of the alkali distribution and the mixed alkali effect of a dynamical property.

Neste trabalho foram realizadas análises estruturais de dois conjuntos de vidros metafosfatos ternários relevantes em potenciais aplicações: aluminofosfatos e álcalis mistos. Para os aluminofosfatos a análise estrutural tem por objetivo verificar a existência de comportamentos preferenciais da conectividade entre os grupos fosfatos e os átomos de Al, e verificar a possível extensão a estes sistemas ternários de princípios de ligação química e ordem local inferidos em fosfatos binários, sendo os sistemas estudados K(1-x)Alx(PO3)(2x+1) e Na(1-x)Alx(PO3)(2x+1) . Para os vidros de álcalis mistos, a análise estrutural tem por objetivo identificar se existe segregação ou mistura aleatória das duas espécies de cátions, e determinar quais modificações na ordem local de cada álcali são induzidas pela troca de espécies, sendo os sistemas estudados LixNa(1-x)(PO3), KxNa(1-x)(PO3, RbxNa(1-x)(PO3), RbxLi(1-x)(PO3) e CsxLi(1-x)(PO3). As informações estruturais nestes vidros foram obtidas através de técnicas de Ressonância Magnética Nuclear (RMN) de estado sólido de 7Li, 23Na, 27Al, 31P, 87Rb e 133Cs. A conectividade entre a rede de fosfatos e os átomos de Al foi estudada utilizando informações a respeito da distribuição de espécies tetraédricas de fosfatos Q2m , sendo m = 0,1, 2 o número de pontes P-O-Al por tetraedro, obtidas através de RMN de 31P, e do número de coordenação médio do Al obtido através de RMN de 27Al. Da análise quantitativa da evolução das diferentes populações Q2m com a concentração de Al, juntamente com o número de coordenação médio do Al, foi possível verificar a existência de comportamentos preferenciais na organização estrutural: tetraedros fosfatos compartilham um vértice único (oxigênio não-ponte) com os poliedros de coordenação do Al. Esta organização de médio alcance é mantida até uma determinada concentração de Al, onde todo tetraedro forma uma ponte P-O-Al . A distribuição das espécies Q2m resultante é do tipo binária em função da concentração de Al: { Q20, Q21 } até concentrações intermediárias e { Q21, Q22 } para concentrações altas. Para os metafosfatos de álcalis mistos, o comportamento do desvio químico de 23 Na e 133Cs revela um efeito sistemático de aumento/decréscimo no tamanho do ambiente de coordenação ao redor dos álcalis em função da substituição. O ambiente de O dos álcalis de menor raio iônico resulta comprimido quando ocorre a substituição deste por uma espécie de raio iônico maior, e vice-versa. Com relação à distribuição dos álcalis na rede vítrea, as evoluções dos desvios químicos em função da substituição excluem a possibilidade de segregação dos álcalis ou separação de fase. A análise do acoplamento dipolar homonuclear de 23 Na, através da medida do segundo momento, revelou que a mistura de Na com o segundo álcali não é aleatória, existindo uma maior probabilidade de um Na ter outro Na como próximo vizinho. A correlação entre o grau de não-aleatoriedade na dispersão do Na e o incremento na magnitude do efeito de álcalis mistos na condutividade DC dos metafosfatos de Rb-Na, K-Na e Li-Na sugere que os fenômenos estão fundamentalmente relacionados. Esta seria a primeira evidência de vínculo entre uma propriedade estrutural da distribuição dos álcalis e o efeito de álcalis mistos de uma propriedade dinâmica. / In this work, the structure of two ternary metaphosphate glass systems was analyzed: aluminum-phosphates and mixed-alkali. The aim of the study in aluminum-phosphates is to determine the existence of preferential structural connectivities between phosphate groups and Al, and to verify the possible extension to these ternary glasses of principles of structural organization valid in binary phosphates. The aluminum metaphosphates studied here were K(1-x)Alx(PO3)(2x+1) and Na(1-x)Alx(PO3)(2x+1) . In mixed-alkali metaphosphates the goal of the structural analysis is the identification of the way in which alkali cations are distributed in the glass network (segregation versus random mixture), and to determine what kind of modification in the local order around the alkalis are induced by the substitution of species. The mixed-alkali metaphosphate studied here were LixNa(1-x)(PO3), KxNa(1-x)(PO3, RbxNa(1-x)(PO3), RbxLi(1-x)(PO3) and CsxLi(1-x)(PO3). The structural information was obtained using solid-state Nuclear Magnetic Resonance (NMR) techniques of 7Li, 23Na, 27Al, 31P, 87Rb and 133Cs. The connectivity between the phosphate groups and Al was analyzed studying the populations of phosphate species Q2m, with m=0,1,2 being the number of P-O-Al bridges per tetrahedron, obtained using 31P-NMR, and considering the average coordination number of Al obtained by 27Al-NMR. Through the quantitative analysis of the evolution of the Q2m population with the Al concentration, it was possible to identify the existence of a preferential structural behavior: phosphate tetrahedra share only one common corner (non-bridging oxygen) with the coordination polyhedra around Al. This medium-range organization can be sustained up to a certain concentration of Al, to the point where every phosphate establishes a P-O-Al bridge. The resulting distribution of Q2m species can be identified as binary, as a function of the Al content: { Q20, Q21} up to intermediate concentrations and { Q21, Q22} for higher concentrations. In the mixed-alkali metaphosphates, the behavior of the 23Na and 133Cs chemical shift reveals a systematic increase/decrease in the average size of the coordination environment around the alkalis as a function of the substitution. The O environment around cations with the smaller ionic radius is compressed as this species is substituted by another alkali with bigger ionic radius, and vice-versa. With respect to the alkali distribution in the glass network, the observed evolution of the chemical shift as a function of the cation substitution excludes the possibility of segregation of alkalis or phase separation. The analysis of the 23Na homonuclear magnetic dipolar coupling, through the measurement of the second moment, revealed that the mixture at atomic scale of Na with the second alkali is not random, having a higher probability of a Na being close to other Na than to other alkali. The correlation between the degree of non-random dispersion of Na and the increment in the magnitude of the mixed alkali effect in the dc conductivity of Rb-Na, K-Na and Li-Na metaphosphates indicates a fundamental connection between both phenomena. This may be the first evidence of a relation between a structural property of the alkali distribution and the mixed alkali effect of a dynamical property.

The main goal of this dissertation was to show that the principle of atomic layer deposition (ALD) can be applied to “endless” fibers. A reactor of atomic layer deposition has been designed, especially for coating depositions onto meter long bundles of fibers. Aluminum oxide (alumina), titanium oxide (titania), double layers of alumina and titania, as well as aluminium phosphate have been deposited onto bundles of carbon fibers using the home-built reactor. Scanning electron microscopic (SEM) and transmission electron microscopic (TEM) images indicate that the coatings were uniform and conformal onto fiber surface. There was a good adhesion of the coatings to the fibers. Alumina has been deposited using two separate aluminum sources (aluminum trichloride and trimethylaluminum), and water as a source of oxygen. In case of alumina deposition using aluminum trichloride and water, initial deposition temperature was 500 °C. In these conditions, a part of the fiber bundle has been damaged. Thus, the deposition temperature was decreased to 300 °C and the fibers were unaffected. In addition, during this process hydrochloric acid is formed as a byproduct which is a corrosive substance and affects the reactor and there was a chloride impurity in the coatings. Thus, aluminum trichloride precursor was replaced by trimethylalumium. Alumina deposition onto carbon fibers using trimethylaluminum and water was carried out at a temperature of 77 °C. SEM images revealed that the fibers were unaffected and the coatings were uniform and conformal. Oxidation resistance of the carbon fibers was improved slightly after alumina deposition. Oxidation onset temperature of the uncoated fibers was about 630 °C. The resistance was linearly increased with the coating thickness (up to 660 °C) and getting saturated over a thickness of 120 nm. Titania coatings have been deposited using titanium tetrachloride and water. The physical appearances of the titania coatings were similar to the alumina coatings. The oxidation onset temperature of the titania coated carbon fibers was similar to the uncoated fibers but the rate of oxidation was decreased than the uncoated fibers. Two double layer coatings were deposited, alumina followed by titania (alumina/titania), and titania followed by alumina (titania/alumina). If the fibers were coated with the double layer of alumina/titania, they had almost same oxidation onset as alumina coated fibers but the rate of oxidation was decreased significantly compared to alumina coated fibers. This feature is independent of the thickness of the titania layers, at least in the regime investigated (50 nm alumina followed by 13 nm and 40 nm titania). On the other hand, the oxidation onset temperature of fibers coated with titania/alumina (20 nm titania /30 nm alumina) was approximately 750 °C. The fibers were burned completely when temperature was further increased to 900 °C and held another 60 minutes at 900 °C. This is significantly better than any other coating used in this dissertation. ALD of titania and alumina in principle was known beforehand, this dissertation here applies this knowledge for the first time to endless fibers. Furthermore, this dissertation shows for the first time that one can deposit aluminum phosphate via ALD (planar surface as well as fibers). Aluminum phosphate might be special interest in the fiber coating because it is a rather soft material and thus might be used to obtain a weak coupling between fiber and matrix in composites. Aluminum phosphate was deposited using trimethylaluminum and triethylphosphate as precursors. Energy dispersive X-ray spectroscopy and solid state nuclear magnetic resonance spectra confirmed that the coating comprises aluminum phosphate (orthophosphate as well as other stoichiometries). Scanning electron microscopic images revealed that coatings are uniform and conformal. In cases of alumina and titania, it was observed that the coatings were delaminated from the ends of cut fibers and thus formed of clear steps. On the other hand, for aluminum phosphate coating it was observed that the border between coating and underlying fiber often being smeared out and thus formed an irregular line. It seems in case aluminum phosphate cohesion is weaker than adhesion, thus it might be act a weak interface between fiber and matrix. Alumina, titania, and double layer microtubes have been obtained after selective removal of the underlying carbon fibers. The carbon fibers were selectively removed via thermal oxidation in air at temperatures exceeding 550 °C. SEM and TEM images indicate that the inner side of the tube wall has the same morphology like the fibers. In addition, it was observed that the individual microtubes were separated from their neighbors and they had almost uniform wall thicknesses. The longest tubes had a length of 30 cm. / Das Hauptziel dieser Dissertation bestand darin nachzuweisen, dass die Atomlagenabscheidung (engl. atomic layer deposition (ALD)) auf „endlose“ Fasern angewendet werden kann. Es wurde ein Reaktor zur Atomlagenabscheidung gestaltet, der speziell für die Beschichtung meterlanger Faserbündel geeignet ist. Aluminiumoxid, Titanoxid, Doppelschichten aus Aluminiumoxid und Titanoxid sowie Aluminiumphosphat wurden mit Hilfe des selbstgebauten Reaktors auf Kohlefaserbündel abgeschieden. Rasterelektronenmikroskopische (REM) und transmissionselektronenmikroskopische (TEM) Aufnahmen zeigten, dass die Beschichtung auf den Fasern einheitlich und oberflächentreu war. Des Weiteren wurde eine gute Adhäsion zwischen Beschichtung und Fasern beobachtet. Das Prinzip der Beschichtung mit Titanoxid und Aluminiumoxid mit Hilfe der ALD war bereits vorher bekannt und im Rahmen dieser Dissertation jedoch erstmals auf "endlose" Fasern angewendet. Des Weiteren wird in dieser Dissertation erstmals gezeigt, dass es möglich ist, Aluminiumphosphat mittels ALD abzuscheiden (sowohl auf planaren Oberflächen als auch auf Fasern). Aluminiumphosphat könnte von besonderem Interesse in der Faserbeschichtung sein, da es ein relativ weiches Material ist und könnte daher als eine Art „schwacher“ Verbindung zwischen Faser und Matrix in Kompositen dienen. Die Oxidationsbeständigkeit von beschichten Kohlefasern wurde im Vergleich zu unbeschichteten Fasern bis zu einem gewissen Grad erhöht. Monoschichten von Aluminiumoxid und Titanoxid waren dafür wenig effektiv. Aluminiumphosphatbeschichtete Fasern waren deutlich besser geeignet als die beiden anderen. Eine Doppelschicht aus Titanoxid gefolgt von Aluminiumoxid verbesserte die Oxidationsbeständigkeit nochmals deutlich gegenüber allen anderen Beschichtungen, die in dieser Dissertation verwendet wurden. Mikroröhren aus Aluminiumoxid, Titanoxid und Doppelschichten wurden durch die selektive Entfernung der zugrunde liegenden Kohlefasern erhalten. Einzelne Mikroröhren waren von benachbarten Röhren getrennt und sie weisen eine nahezu einheitliche Wanddicke auf.

The main goal of this dissertation was to show that the principle of atomic layer deposition (ALD) can be applied to “endless” fibers. A reactor of atomic layer deposition has been designed, especially for coating depositions onto meter long bundles of fibers. Aluminum oxide (alumina), titanium oxide (titania), double layers of alumina and titania, as well as aluminium phosphate have been deposited onto bundles of carbon fibers using the home-built reactor. Scanning electron microscopic (SEM) and transmission electron microscopic (TEM) images indicate that the coatings were uniform and conformal onto fiber surface. There was a good adhesion of the coatings to the fibers. Alumina has been deposited using two separate aluminum sources (aluminum trichloride and trimethylaluminum), and water as a source of oxygen. In case of alumina deposition using aluminum trichloride and water, initial deposition temperature was 500 °C. In these conditions, a part of the fiber bundle has been damaged. Thus, the deposition temperature was decreased to 300 °C and the fibers were unaffected. In addition, during this process hydrochloric acid is formed as a byproduct which is a corrosive substance and affects the reactor and there was a chloride impurity in the coatings. Thus, aluminum trichloride precursor was replaced by trimethylalumium. Alumina deposition onto carbon fibers using trimethylaluminum and water was carried out at a temperature of 77 °C. SEM images revealed that the fibers were unaffected and the coatings were uniform and conformal. Oxidation resistance of the carbon fibers was improved slightly after alumina deposition. Oxidation onset temperature of the uncoated fibers was about 630 °C. The resistance was linearly increased with the coating thickness (up to 660 °C) and getting saturated over a thickness of 120 nm. Titania coatings have been deposited using titanium tetrachloride and water. The physical appearances of the titania coatings were similar to the alumina coatings. The oxidation onset temperature of the titania coated carbon fibers was similar to the uncoated fibers but the rate of oxidation was decreased than the uncoated fibers. Two double layer coatings were deposited, alumina followed by titania (alumina/titania), and titania followed by alumina (titania/alumina). If the fibers were coated with the double layer of alumina/titania, they had almost same oxidation onset as alumina coated fibers but the rate of oxidation was decreased significantly compared to alumina coated fibers. This feature is independent of the thickness of the titania layers, at least in the regime investigated (50 nm alumina followed by 13 nm and 40 nm titania). On the other hand, the oxidation onset temperature of fibers coated with titania/alumina (20 nm titania /30 nm alumina) was approximately 750 °C. The fibers were burned completely when temperature was further increased to 900 °C and held another 60 minutes at 900 °C. This is significantly better than any other coating used in this dissertation. ALD of titania and alumina in principle was known beforehand, this dissertation here applies this knowledge for the first time to endless fibers. Furthermore, this dissertation shows for the first time that one can deposit aluminum phosphate via ALD (planar surface as well as fibers). Aluminum phosphate might be special interest in the fiber coating because it is a rather soft material and thus might be used to obtain a weak coupling between fiber and matrix in composites. Aluminum phosphate was deposited using trimethylaluminum and triethylphosphate as precursors. Energy dispersive X-ray spectroscopy and solid state nuclear magnetic resonance spectra confirmed that the coating comprises aluminum phosphate (orthophosphate as well as other stoichiometries). Scanning electron microscopic images revealed that coatings are uniform and conformal. In cases of alumina and titania, it was observed that the coatings were delaminated from the ends of cut fibers and thus formed of clear steps. On the other hand, for aluminum phosphate coating it was observed that the border between coating and underlying fiber often being smeared out and thus formed an irregular line. It seems in case aluminum phosphate cohesion is weaker than adhesion, thus it might be act a weak interface between fiber and matrix. Alumina, titania, and double layer microtubes have been obtained after selective removal of the underlying carbon fibers. The carbon fibers were selectively removed via thermal oxidation in air at temperatures exceeding 550 °C. SEM and TEM images indicate that the inner side of the tube wall has the same morphology like the fibers. In addition, it was observed that the individual microtubes were separated from their neighbors and they had almost uniform wall thicknesses. The longest tubes had a length of 30 cm.:Bibliographische Beschreibung und Referat 2 Abstract 4 List of abbreviations 10 1. General introduction and outline of this dissertation 12 1.1 References 20 2. Atomic layer deposition: Process and reactor 25 2.1 Introduction 25 2.2 Principle of atomic layer deposition 26 2.3 Materials and methods 29 2.3.1 Precursors 29 2.3.2 Precursors transportation 31 2.3.3 Carrier and purge gas 32 2.3.4 ALD reactors 32 2.4 Flow-Type ALD reactor for fiber coating 33 2.5 Conclusion 35 2.6 References 35 3. Single layer oxide coatings 38 3.1 State of the art 38 3.2 Alumina coating using non-flammable precursors 39 3.2.1 Introduction 39 3.2.Result and discussion 39 3.3 Alumina coating using organometallic precursor 46 3.2.1 Introduction 46 3.2.2 Results and discussion 46 3.4 Titania coating using titanium tetrachloride and water 59 3.4.1 Introduction 59 3.4.2 Results and discussion 59 3.5 Experimental Part 67 3.5.1 General experiments 67 3.5.2 Alumina coating using aluminum chloride and water 69 3.5.3 Alumina coating using trimethylalumium and water 69 3.5.4 Titania coating 72 3.6 Conclusions 72 3.7 References 74 4. Coating thickness and morphology 78 4.1 Introduction 78 4.2 Results and discussion 80 4.2.1 Purge time 15 s 81 4.2.2 Purge time 30 s 85 4.2.3 Purge time 45 s to 100 s 85 4.3 Experimental part 88 4.4 Conclusions 89 4.5 References 89 5. Alumina and titania double layer coatings 91 5.1 Introduction 91 5.2 Results and discussion 92 5.3 Experimental part 102 5.4 Conclusions 103 5.5 References 103 6. Atomic layer deposition of aluminum phosphate 105 6.1 Introduction 105 6.2 Results and discussion 106 6.3 Experimental part 113 6.4 Conclusions 114 6.5 References 115 7. Alumina microtubes 117 7.1 Introduction 117 7.2 Results and discussion 118 7.2.1 Fibers before coating deposition 118 7.2.2 Coatings on the carbon fibers 118 7.2.3 Microtubes 121 7.3 Experimental part 127 7.4 Conclusions 128 7.5 References 128 8. Conclusions 131 Acknowledgements 136 Curriculum Vitae 138 Selbständigkeitserklärung 142 / Das Hauptziel dieser Dissertation bestand darin nachzuweisen, dass die Atomlagenabscheidung (engl. atomic layer deposition (ALD)) auf „endlose“ Fasern angewendet werden kann. Es wurde ein Reaktor zur Atomlagenabscheidung gestaltet, der speziell für die Beschichtung meterlanger Faserbündel geeignet ist. Aluminiumoxid, Titanoxid, Doppelschichten aus Aluminiumoxid und Titanoxid sowie Aluminiumphosphat wurden mit Hilfe des selbstgebauten Reaktors auf Kohlefaserbündel abgeschieden. Rasterelektronenmikroskopische (REM) und transmissionselektronenmikroskopische (TEM) Aufnahmen zeigten, dass die Beschichtung auf den Fasern einheitlich und oberflächentreu war. Des Weiteren wurde eine gute Adhäsion zwischen Beschichtung und Fasern beobachtet. Das Prinzip der Beschichtung mit Titanoxid und Aluminiumoxid mit Hilfe der ALD war bereits vorher bekannt und im Rahmen dieser Dissertation jedoch erstmals auf "endlose" Fasern angewendet. Des Weiteren wird in dieser Dissertation erstmals gezeigt, dass es möglich ist, Aluminiumphosphat mittels ALD abzuscheiden (sowohl auf planaren Oberflächen als auch auf Fasern). Aluminiumphosphat könnte von besonderem Interesse in der Faserbeschichtung sein, da es ein relativ weiches Material ist und könnte daher als eine Art „schwacher“ Verbindung zwischen Faser und Matrix in Kompositen dienen. Die Oxidationsbeständigkeit von beschichten Kohlefasern wurde im Vergleich zu unbeschichteten Fasern bis zu einem gewissen Grad erhöht. Monoschichten von Aluminiumoxid und Titanoxid waren dafür wenig effektiv. Aluminiumphosphatbeschichtete Fasern waren deutlich besser geeignet als die beiden anderen. Eine Doppelschicht aus Titanoxid gefolgt von Aluminiumoxid verbesserte die Oxidationsbeständigkeit nochmals deutlich gegenüber allen anderen Beschichtungen, die in dieser Dissertation verwendet wurden. Mikroröhren aus Aluminiumoxid, Titanoxid und Doppelschichten wurden durch die selektive Entfernung der zugrunde liegenden Kohlefasern erhalten. Einzelne Mikroröhren waren von benachbarten Röhren getrennt und sie weisen eine nahezu einheitliche Wanddicke auf.:Bibliographische Beschreibung und Referat 2 Abstract 4 List of abbreviations 10 1. General introduction and outline of this dissertation 12 1.1 References 20 2. Atomic layer deposition: Process and reactor 25 2.1 Introduction 25 2.2 Principle of atomic layer deposition 26 2.3 Materials and methods 29 2.3.1 Precursors 29 2.3.2 Precursors transportation 31 2.3.3 Carrier and purge gas 32 2.3.4 ALD reactors 32 2.4 Flow-Type ALD reactor for fiber coating 33 2.5 Conclusion 35 2.6 References 35 3. Single layer oxide coatings 38 3.1 State of the art 38 3.2 Alumina coating using non-flammable precursors 39 3.2.1 Introduction 39 3.2.Result and discussion 39 3.3 Alumina coating using organometallic precursor 46 3.2.1 Introduction 46 3.2.2 Results and discussion 46 3.4 Titania coating using titanium tetrachloride and water 59 3.4.1 Introduction 59 3.4.2 Results and discussion 59 3.5 Experimental Part 67 3.5.1 General experiments 67 3.5.2 Alumina coating using aluminum chloride and water 69 3.5.3 Alumina coating using trimethylalumium and water 69 3.5.4 Titania coating 72 3.6 Conclusions 72 3.7 References 74 4. Coating thickness and morphology 78 4.1 Introduction 78 4.2 Results and discussion 80 4.2.1 Purge time 15 s 81 4.2.2 Purge time 30 s 85 4.2.3 Purge time 45 s to 100 s 85 4.3 Experimental part 88 4.4 Conclusions 89 4.5 References 89 5. Alumina and titania double layer coatings 91 5.1 Introduction 91 5.2 Results and discussion 92 5.3 Experimental part 102 5.4 Conclusions 103 5.5 References 103 6. Atomic layer deposition of aluminum phosphate 105 6.1 Introduction 105 6.2 Results and discussion 106 6.3 Experimental part 113 6.4 Conclusions 114 6.5 References 115 7. Alumina microtubes 117 7.1 Introduction 117 7.2 Results and discussion 118 7.2.1 Fibers before coating deposition 118 7.2.2 Coatings on the carbon fibers 118 7.2.3 Microtubes 121 7.3 Experimental part 127 7.4 Conclusions 128 7.5 References 128 8. Conclusions 131 Acknowledgements 136 Curriculum Vitae 138 Selbständigkeitserklärung 142