Made available in DSpace on 2016-12-08T17:19:37Z (GMT). No. of bitstreams: 1 1_Introducao.pdf: 64784 bytes, checksum: a1b19b41bade65db44f4ab7b4a5561dc (MD5) Previous issue date: 2011-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Polyamide-imide (PAI) is a polymer widely used in magnet wires for electrical applications due to combination of their mechanical, electrical and thermal properties. This polymer can be improved by the addition of inorganic moieties, among them silsesquioxanes, forming organic/inorganic hybrids. This dissertation presents the preparation of hybrid polymers PAI/copolysilsesquioxane (PAI/coPSQ), where the matrix of polyamide-imide (PAI) is prepared from the condensation of trimellitic anhydride (TMA) and diphenylmethane-4 ,4-diisocyanate (MDI), and the copolysilsesquioxane is prepared by the sol-gel method from alkoxide precursors, in this case, 3-aminopropyltriethoxysilane (APES) and phenyltrietoxisilane (PTES). The methods for obtaining the hybrid PAI/coPSQ by simple mixing and in situ reaction were evaluated. The hybrid polymers were characterized by their spectroscopic characteristics, morphology, electrical, mechanical and thermal properties. The PAI/coPSQs coatings prepared with APES-rich coPSQ presented gelatinization due to high crosslinking generated by the polymer chains of PAI and the amine groups of PSQ. The method of in situ reaction mixture was more efficient in the generation of hybrid PAI/coPSQ, minimizing the occurrence of gelatinization. The SEM and AFM confirmed the absence of separation between the organic and inorganic phases and the FTIR and NMR 13C and 29Si analysis confirmed the formation of a Si-O-Si network. PAI/coPSQ hybrid samples showed no significant changes of Tg, while PAI/PTES hybrid obtained by polycondensation of PTES presented a decrease of Tg. PAI/PSQs hybrids were analyzed by thermogravimetry and showed a small improvement in thermal resistance. The results of nanoindentation tests confirmed the influence of adding coPSQ to increase hardness and elastic modulus of PAI films, while the average performance of dielectric strength showed trends of increasement. / O polímero poliamida-imida (PAI) é amplamente utilizado em fios esmaltados para aplicações elétricas devido ao balanço de suas propriedades mecânicas, elétricas e térmicas. Este polímero pode ser melhorado pela adição de cargas inorgânicas em sua matriz, dentre elas os silsesquioxanos, formando híbridos orgânicos/inorgânicos. O presente trabalho apresenta o preparo de polímeros híbridos PAI/copolissilsesquioxano (PAI/coPSQ), onde a matriz de poliamida-imida (PAI) é preparada a partir da reação de condensação entre o anidrido trimelitico (TMA) e o difenilmetano-4,4-diisocianato (MDI), e o copolissilsesquioxano é preparado pelo método sol-gel a partir de precursores alcóxidos, neste caso o 3-aminopropiltrietoxissilano (APES) e o feniltrietoxissilano (PTES). Foram avaliadas as metodologias de obtenção do híbrido PAI/coPSQ por mistura simples e por reação in situ. Os polímeros híbridos foram caracterizados quanto às suas características espectroscópicas e morfológicas, propriedades elétricas, mecânicas e térmicas. Os vernizes de PAI preparados com coPSQs ricos em APES apresentaram gelatinização devido ao alto grau de reticulação gerado pelas ligações cruzadas entre as cadeias poliméricas do PAI e os grupos amínicos. O método de mistura por reação in situ mostrou-se mais eficiente na geração do híbrido PAI/coPSQ, minimizando a ocorrência de gelatinização. As análises morfológicas confirmaram a ausência de separação entre as fases orgânica e inorgânica e as análises de FTIR e NMR 13C e 29Si confirmaram formação da rede Si-O-Si. As amostras híbridas PAI/coPSQ não apresentaram alterações significativas de Tg, enquanto que o híbrido PAI/PTES obtido pela policondensação somente do PTES apresentou grande diminuição de Tg. Os híbridos PAI/PSQs apresentaram uma pequena melhoria na estabilidade térmica analisada por termogravimetria. Os resultados do ensaio de nanoindentação confirmaram a influência da adição do coPSQ para o aumento da dureza e do módulo de elasticidade dos filmes de PAI, enquanto que os resultados médios da propriedade de rigidez dielétrica apresentaram tendência de aumento.

No estudo de sistemas híbridos orgânico-inorgânico, o uso de materiais como polímeros conjugados e óxidos de metal de transição tem despertado grande interes- se. Em particular, destacam-se sistemas compostos de tiofenos e óxido de titânio, que encontram uma importante aplicação em células solares. Para um melhor entendimento da interação entre os dois sistemas, torna-se necessário conhecer a organização do polímero sobre o substrato inorgânico. Desse modo, investigamos neste trabalho a formação da interface entre oligômeros de tiofeno e a superfície (101) de TiO2-anatase utilizando um enfoque de multiformalismo, que inclui simulações de dinâmica molecular clássica, e uma combinação de cálculos de primeiros princípios segundo Hartree-Fock e Teoria do Funcional da Densidade (DFT) para a determinação de propriedades estruturais e eletrônicas. A deposição de oligômeros de tiofeno sobre TiO2, constituindo sistemas de milhares de átomos, foi simulada por meio de dinâmica molecular clássica. Como requisito do cálculo clássico para estes sistemas, realizamos a reparametrização do campo de forças Universal tanto para os oligômeros, cujas estruturas não são bem descritas pelos campos de força padrões, como para o cristal e a superfície de TiO2. Foi observada a formação de filmes desordenados e densos de quatertiofeno, com a presença de uma maioria de moléculas de orientação quase perpendicular em relação ao plano superficial. Na camada de interface também se encontram moléculas dispostas paralelamente ao substrato, aumentando o contato entre os sistemas orgânico e inorgânico. A deposição de oligômeros isolados de quatertiofeno e de hexatiofeno mostra ainda que as moléculas se dispõem paralelas na superfície, alinhadas segundo direções de periodicidade dos átomos da superfície. Estudamos desta forma as propriedades eletrônicas de um sistema composto de politiofeno sobre TiO2, com o polímero paralelo na superfície e disposto na direção preferencial, através de um formalismo ab initio DFT. Apesar do tratamento DFT apresentar problemas conhecidos quanto na definição do gap, o que é mais relevante ainda no nosso caso de sistemas híbridos, os resultados revelam um deslocamento do topo da banda de valência do material orgânico em relação ao inorgânico. Isto possibilita o aprisionamento de um buraco no polímero, condição necessária para o uso deste tipo de sistema em células fotovoltaicas. Verifica-se ainda o acoplamento entre átomos de enxofre do politiofeno e de oxigênio do TiO2 através da presença de um estado associado a uma densidade eletrônica que se estende do polímero na superfície. Nossos resultados indicam assim um bom acoplamento eletrônico da superfície (101) de TiO2-anatase com politiofenos. / In the study of organic-inorganic hybrid systems, the use of materials such as conjugated polymers and transition metal oxides has attracted great interest. In particular, it is worth mentioning systems composed by thiophenes and titanium oxide, which have an important application in solar cells. For a better understand- ing of the interaction between these systems, it is necessary to know the polymer organization over the inorganic substrate. Therefore, we investigated in this work the formation of the interface between thiophene oligomers and the (101) surface of TiO2-anatase by means of a multi-formalism approach, which includes classical molecular dynamics simulations, and a combination of ¯rst principles calculations based on Hartree-Fock and Density Functional Theory (DFT) for structural and electronic properties. The simulation of deposition of thiophene oligomers on TiO2, which demands systems with thousands of atoms, was performed by classical molecular dynamics. As a prerequisite for the classical calculation for these systems, we performed a re-parameterization of the Universal force ¯eld for the oligomers, whose structures are not well described by standard force ¯elds, and for the TiO2 bulk and surface. We observed the formation of disordered and dense quaterthiophene ¯lms, with presence of a majority of molecules oriented almost perpendicularly to the surface plane. In the ¯rst interfacial layer we ¯nd also molecules oriented parallel to the sub- strate, which increases the contact between the organic and the inorganic systems. The deposition of isolated quaterthiophene and sexithiophene oligomers resulted in molecules disposed parallel to the surface and aligned along directions of periodicity of the surface atoms. We therefore studied the electronic properties of a system composed of poly- thiophene on TiO2, with the polymer parallel to the surface and oriented along a preferential direction, by means of DFT formalism. Although DFT treatments present known problems in the de¯nition of the energy gap, even of more relevance in our case of hybrid systems, the results for the occupied states revealed a sizeable displacement of the top of the valence band of one system with respect to the other. The misalignment will prevent the passage of a hole from the polymer to the oxide, providing in this way the necessary condition for the use of this type of system in solar cells. It was also seen electronic coupling between sulfur atoms from polythio- phene, and oxygen atoms from TiO2 through the presence of a state associated with an electronic density extended from the polymer to the surface. Our results thus indicate there is good electronic coupling between the (101) surface of TiO2-anatase and polythiophenes.

Orientador : Celia Marina de Alvarenga Freire / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-06T16:45:17Z (GMT). No. of bitstreams: 1 Souza_MariaElizianePiresde_D.pdf: 6548696 bytes, checksum: a583e3d7f5ab6c842a79ec6878142db1 (MD5) Previous issue date: 2006 / Resumo: As características protetoras das superfícies de aços galvanizados são geralmente intensificadas através da passivação por cromo hexavalente (Cr+6). Porém, por ser este um elemento tóxico, vários estudos visando a substituição do procedimento de cromatização vêm sendo realizados. As resinas de polissiloxanos e materiais híbridos organo-inorgânicos preparados pelo processo sol-gel, podem vir a ser um excelente substituinte ao processo de cromatização. Neste trabalho, filmes híbridos organo-inorgânico e filmes de silicone foram aplicados em aço galvanizado e em camadas de Zn-Fe. Os revestimentos foram então avaliados através de Espectroscopia de Impedância Eletroquímica. Os dados obtidos pela Espectroscopia foram modelados através de um circuito equivalente, permitindo a obtenção dos parâmetros eletroquímicos para os sistemas avaliados. Além disso, o potencial em circuito aberto, para os diferentes sistemas, foi monitorado durante processo de desgaste em sistema pino-disco em solução de NaCI 3%. Os revestimentos foram comparados em termos de resistência à corrosão e coeficiente de fricção. Os resultados mostram um bom desempenho para os revestimentos como protetores de corrosão e o comportamento destes mostraram-se dependente do tipo de revestimento metálico que foi aplicado no aço / Abstract: Chromating pre-treatments have been widely used to improve galvanized steel corrosion resistance. However, due to the high toxicity of chromate ions, chromatation pre-treatments tend to be banned and, in last years, alternative coating systems are under investigation. Recently, polysiloxanes and hybrids materiais by the sol-gel process have been extensively investigated. These materiais may be considered as promising substitutes for chromatation pre-treatments. In this work organic-inorganic hybrid materiais and silicone films have been prepared and applied on galvanized steel and on steeJ electroplated with a Zn-Fe alloy. Electrochemical Impedance Spectroscopy (EIS) was used as a technique for the evaluation of the corrosion mechanisms of the coating systems and the EIS data was fitted to an equivalent circuit from which the electrochemical parameters were obtained. Additionally, the evolution of open circuit potential, for samples, was monitored during alternative reciprocating sliding against an alumina pin in a 3% NaCl solution. The behaviour of the coatings has been compared in terms of corrosion potential and friction coefficient. Results show the protective character of the hybrid films and silicon resin films, when compared with uncovered specimens. The overall performance of the coating systems appears to be highly dependent on the type of metallic coating applied to the steel / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Atualmente com o advento da nanociência e nanotecnologia, as nanopartículas magnéticas têm encontrado inúmeras aplicações nos campos da biomedicina, diagnóstico, biologia molecular, bioquímica, catálise, etc. As nanopartículas magnéticas funcionalizadas são constituídas de um núcleo magnético, envolvido por uma camada polimérica com sítios ativos, que podem ancorar metais ou compostos orgânicos seletivos. Estas nanopartículas são consideradas materiais híbridos orgânico-inorgânicos de grande interesse em aplicações comerciais devido à particularidade das propriedades obtidas. Entre as aplicações importantes podemos citar: tratamento por magnetohipertermia, carregadores de fármacos para áreas específicas do corpo, seleção de moléculas específicas, biossensores, melhoria da qualidade de imagens por RMN, etc. O trabalho foi desenvolvido em duas partes: 1) a síntese do núcleo constituído de nanopartículas superparamagnéticas de ferrita de cobalto e, 2) o recobrimento do núcleo por um polímero bifuncional o 3-aminopropiltrietoxissilano. Os parâmetros estudados na primeira parte da pesquisa foram: pH, concentração molar da base, tipo de base, ordem de adição dos reagentes, modo de adição dos reagentes, velocidade de agitação, concentração inicial dos metais, fração molar de cobalto e tratamento térmico. Na segunda parte estudou-se: o pH, a temperatura, o catalisador, a concentração do catalisador, o tempo de reação, a relação H2O/silano, o tipo de meio, o agente umectante e a eficiência do recobrimento em relação ao pH. Os produtos obtidos foram caracterizados pelas técnicas de difratometria de raios-X (DRX), microscopia eletrônica de transmissão (MET), microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva (EDS), espectroscopia de emissão atômica (ICP-AES), espectroscopia por infravermelho (FTIR), análises termogravimétricas (TGA/DTGA), calorimetria exploratória diferencial (DSC) e curvas de magnetização (MAV) / Nowadays with the appear of nanoscience and nanotechnology, magnetic nanoparticles have been finding a variety of applications in the fields of biomedicine, diagnosis, molecular biology, biochemistry, catalysis, etc. The magnetic functionalized nanoparticles are constituted of a magnetic nucleus, involved by a polymeric layer with active sites, which ones could anchor metals or selective organic compounds. These nanoparticles are considered organic-inorganic hybrid materials and have great interest as materials for commercial applications due to the specific properties. Among the important applications it can be mentioned: magnetohyperthermia treatment, drugs delivery in specific local of the body, molecular recognition, biossensors, enhancement of nuclear magnetic ressonance images quality, etc. This work was developed in two parts: 1) the synthesis of the nucleus composed by superparamagnetic nanoparticles of cobalt ferrite and, 2) the recovering of nucleus by a polymeric bifunctional 3-aminepropyltriethoxysilane. The parameters studied in the first part of the research were: pH, hydroxide molar concentration, hydroxide type, reagent order of addition, reagent way of addition, speed of shake, metals initial concentrations, molar fraction of cobalt and thermal treatment. In the second part it was studied: pH, temperature, catalyst type, catalyst concentration, time of reaction, relation ratios of H2O/silane, type of medium and the efficiency of the recovering regarding to pH. The products obtained were characterized using the following techniques X-ray powder diffraction (DRX), transmission electronic microscopy (MET), scanning electronic microscopy (MEV), spectroscopy of scatterbrained energy spectroscopy (DES), atomic emission spectroscopy (ICP-AES), themogravimetric analysis (TGA/DTGA), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and magnetization curves (VSM)

Novel highly functionalized hybrid organic-inorganic materials were synthesized by polycondensation of bis[3-(trimethoxysilyl)propyl]amine in presence of cationic and anionic surfactants. Reaction media strongly affected gelation time. Thus, in basic media gelation occurred immediately while acid increased gelation time. Material structures were studied by IR spectroscopy, porosimetry, XRD, and SAXS methods. In spite of the absence of an inorganic linker, obtained bridged silsesquioxanes had mesoporous structure. A material prepared in the presence of dodecylamine as a template had higher surface area and narrow pore size distribution while the use of sodium dodecylbenzene sulfate resulted in formation of mesopores with wide size ranges. Accessibility of surface amine groups in silsesquioxanes was studied for molecules of acidic nature and different sizes: HCl, CO2 and picric acid. High contents of accessible amine groups in these materials make them prospective adsorbents for post-combustion CO2 capture.

Background: Bioadhesion and surface interactions on enamel are of essential relevance for initiation, progression and prevention of caries and erosions. Salivary proteins on and within initial carious and erosive lesions can facilitate or aggravate de- and remineralization. This applies for the pellicle layer, the subsurface pellicle and for proteins within initial carious lesions. Little is known about these proteinaceous structures related to initial caries and erosion. Accordingly, there is a considerable demand for an understanding of the underlying processes occurring at the interface between the tooth surface and the oral cavity in order to develop novel agents that limit and modulate caries and erosion. Objectives and findings: The present paper depicts the current knowledge of the processes occurring at the interface of the tooth surface and the oral fluids. Proteinaceous layers on dental hard tissues can prevent or aggravate demineralization processes, whereas proteins within initial erosive or carious lesions might hinder remineralization considerably and restrict the entry of ions into lesions. Conclusions: Despite the fact that organic–inorganic surface interactions are of essential relevance for de- and remineralization processes at the tooth surface, there is limited knowledge on these clinically relevant phenomena. Accordingly, intensive research is necessary to develop new approaches in preventive dentistry.

Organisch-anorganische Perowskite sind attraktiv für Dünnschichtsolarzellen. Die Übertragung laborbasierter Herstellungsverfahren, typischerweise Rotationsbeschichtung, auf industrielle Prozesse erfordert ein tiefgehendes Verständnis der physikalisch-chemischen Auswirkungen auf die Schichtqualität. Diese Arbeit zeigt, dass die Effizienz-Reproduzierbarkeit von Perowskit-Solarzellen (PSCs) nicht primär durch Unterschiede zwischen Laboren, sondern durch interne Prozessschwankungen beeinflusst wird. Verglichen wurden PSCs mit PEDOT und PTAA als Lochleiter auf den beiden Perowskiten, MAPI und 3CAT. PEDOT-basierte PSCs zeigten neben geringerer Reproduzierbarkeit eine niedrigere Effizienz, bedingt durch Voc- und FF-Verluste, schlechtere energetische Angleichung und morphologische Grenzflächenprobleme. Im Vergleich zu 3CAT, war die Effizienz von MAPI-basierten Zellen schlechter reproduzierbar, was durch eine stärkere Abhängigkeit der MAPI-Schichten von Prozessschwankungen erklärt werden kann. Die Anwendung eines Anti-Lösungsmittel-Tropfens (AS-Tropfen) während des in dieser Rotationsbeschichtungsprozesses beeinflusst die Morphologie und Effizienz der Solarzellen erheblich. Das optimale Zeitfenster für den AS-Tropfen ist für MAPI (~10 s) kleiner als für 3CAT (~50 s). Ein falsches Timing führt zu morphologischen Hohlräumen und vermindert die Effizienz. Optische In-situ-Studien zeigten, dass der AS-Tropfen vor Beginn der natürlichen Perowskit-Kristallisation appliziert werden sollte. Für MAPI beginnt diese nach 20 Sekunden, für 3CAT nach 100 Sekunden. Ein zu später AS-Tropfen reduziert die Verfügbarkeit von Lösungsmittel für die Rekristallisation und verschlechtert die Morphologie der Perowskit-Phase. 3CAT toleriert zeitliche Variationen besser, da es während der natürlichen Kristallisation sowohl lösungsmittelhaltige Vorphasen als auch Perowskit-Phasen bildet, während MAPI hauptsächlich lösungsmittelhaltige Vorphasen bildet, was die Prozessanfälligkeit erhöht. / Organic-inorganic perovskites are promising materials for thin-film solar cells, with potential for industrial-scale production through scalable manufacturing. The transition from laboratory-based spin-coating to scalable processes requires understanding the factors affecting perovskite film quality. High-performance reproducibility is essential for commercializing perovskite solar cells (PSCs), currently challenging for certain perovskite combinations. Reproducibility issues are evident from performance variations in published PSC results fabricated from different laboratories. Even within a single laboratory, process fluctuations can lead to efficiency irreproducibility, as this study shows. Different PSC stack combinations were compared using two hole conductors, PEDOT and PTAA, with two perovskite compositions, MAPI and 3CAT. PEDOT solar cells showed low reproducibility and lower efficiency due to poor energetic alignment and morphological issues. MAPI and 3CAT with PTAA achieved higher efficiencies. However, MAPI is more sensitive to process variations, leading to lower reproducibility. This hypothesis is supported by in-situ measurements, which show that the timinng window for the addition of an anti-solvent drip (AS-drip) during spin-coating is narrower for MAPI (~10 s) than for 3CAT (~50 s). AS-drip outside this window causes morphological voids, reducing efficiency. The optical in-situ studies show that AS-drip timing is crucial: crystallization onset occurs earlier for MAPI (20s) than for 3CAT (100s). Late AS-drip results in solvate phase formation, reducing solvent availability and negatively impacting morphology. MAPI forms solvate exclusively during crystallization, while 3CAT forms both solvate and perovskite phases, increasing tolerance to timing variations.

The germylenes, germanium(II) 2-(oxidomethyl)phenolate (1), germanium(II) 4-methyl-2-(oxidomethyl)phenolate (2) and germanium(II) 4-bromo-2-(oxidomethyl)phenolate (3) were synthesized and their thermally induced twin polymerization to give organic–inorganic hybrid materials was studied. The compounds 1–3 form oligomers including dimers, trimers and tetramers as a result of intermolecular coordination of the benzylic oxygen atom to germanium. The structural motifs were studied by single crystal X-ray diffraction analysis and DFT-D calculations. Thermally induced twin polymerization of these germylenes gave hybrid materials based on germanium-containing phenolic resins. Carbonization of these resins under reductive conditions resulted in porous materials that are composed of germanium and carbon (Ge@C materials), while oxidation with air provided non-porous germanium dioxide. The porous Ge@C materials were tested as potential anode materials for rechargeable Li-ion batteries. Reversible capacities of 540 mA h g−1 were obtained at a current density of 346 mA g−1 without apparent fading for 100 cycles, which demonstrates that germanium is well accessible in the hybrid material. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Amino-functionalized organic–inorganic hybrid materials with a narrow distributed nanostructure of 2–4 nm in size were obtained by means of a template-free and non-aqueous procedure. Simultaneous twin polymerization of novel amino group containing twin monomers with 2,2′-spirobi[4H-1,3,2-benzodioxasiline] has been applied for this purpose. The amino groups of the organic–inorganic hybrid material are useful for post derivatization. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Four molecular germanates based on salicyl alcoholates, bis(dimethylammonium) tris[2-(oxidomethyl)phenolate(2-)]germanate (1), bis(dimethylammonium) tris[4-methyl-2-(oxidomethyl)phenolate(2-)]germanate (2), bis(dimethylammonium) tris[4-bromo-2-(oxidomethyl)phenolate(2-)]germanate (3) and dimethylammonium bis[2-tert-butyl-4-methyl-6-(oxidomethyl)phenolate(2-)][2-tert-butyl-4-methyl-6-(hydroxymethyl)phenolate(1-)]germanate (4), were synthesized and characterized including single crystal X-ray diffraction analysis. In the solid state, compounds 1 and 2 exhibit one-dimensional hydrogen bonded networks, whereas compound 4 forms separate ion pairs, which are connected by hydrogen bonds between the dimethylammonium and the germanate moieties. The potential of these compounds for thermally induced twin polymerization (TP) was studied. Germanate 1 was converted by TP to give a hybrid material (HM-1) composed of phenolic resin and germanium dioxide. Subsequent reduction with hydrogen provided a microporous composite containing crystalline germanium and carbon (Ge@C – C-1, germanium content ∼20%). Studies on C-1 as an anode material for Li-ion batteries revealed reversible capacities of ∼370 mA h gGe@C−1 at a current density up to 1384 mA g−1 without apparent fading for 500 cycles. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.