Entrapping homogeneous catalysts by sol-gel methods: the bottom-up synthesis of catalysts that recycle and cascade

Perspective and front cover article: Homogeneous catalysts entrapped in silica matrices, including ionic liquid containing 'ionogels', exhibit high selectivity, unexpected activity and excellent recyclability.

Active corrosion protection of AA2024 by sol-gel coatings with corrosion inhibitors

A indústria aeronáutica utiliza ligas de alumínio de alta resistência para o fabrico dos elementos estruturais dos aviões. As ligas usadas possuem excelentes propriedades mecânicas mas apresentam simultaneamente uma grande tendência para a corrosão. Por esta razão essas ligas necessitam de protecção anticorrosiva eficaz para poderem ser utilizadas com segurança. Até à data, os sistemas anticorrosivos mais eficazes para ligas de alumínio contêm crómio hexavalente na sua composição, sejam pré-tratamentos, camadas de conversão ou pigmentos anticorrosivos. O reconhecimento dos efeitos carcinogénicos do crómio hexavalente levou ao aparecimento de legislação banindo o uso desta forma de crómio pela indústria. Esta decisão trouxe a necessidade de encontrar alternativas ambientalmente inócuas mas igualmente eficazes. O principal objectivo do presente trabalho é o desenvolvimento de prétratamentos anticorrosivos activos para a liga de alumínio 2024, baseados em revestimentos híbridos produzidos pelo método sol-gel. Estes revestimentos deverão possuir boa aderência ao substrato metálico, boas propriedades barreira e capacidade anticorrosiva activa. A protecção activa pode ser alcançada através da incorporação de inibidores anticorrosivos no prétratamento. O objectivo foi atingido através de uma sucessão de etapas. Primeiro investigou-se em detalhe a corrosão localizada (por picada) da liga de alumínio 2024. Os resultados obtidos permitiram uma melhor compreensão da susceptibilidade desta liga a processos de corrosão localizada. Estudaram-se também vários possíveis inibidores de corrosão usando técnicas electroquímicas e microestruturais. Numa segunda etapa desenvolveram-se revestimentos anticorrosivos híbridos orgânico-inorgânico baseados no método sol-gel. Compostos derivados de titania e zirconia foram combinados com siloxanos organofuncionais a fim de obter-se boa aderência entre o revestimento e o substrato metálico assim como boas propriedades barreira. Testes industriais mostraram que estes novos revestimentos são compatíveis com os esquemas de pintura convencionais actualmente em uso. A estabilidade e o prazo de validade das formulações foram optimizados modificando a temperatura de armazenamento e a quantidade de água usada durante a síntese. As formulações sol-gel foram dopadas com os inibidores seleccionados durante a primeira etapa e as propriedades anticorrosivas passivas e activas dos revestimentos obtidos foram estudadas numa terceira etapa do trabalho. Os resultados comprovam a influência dos inibidores nas propriedades anticorrosivas dos revestimentos sol-gel. Em alguns casos a acção activa dos inibidores combinou-se com a protecção passiva dada pelo revestimento mas noutros casos terá ocorrido interacção química entre o inibidor e a matriz de sol-gel, de onde resultou a perda de propriedades protectoras do sistema combinado. Atendendo aos problemas provocados pela adição directa dos inibidores na formulação sol-gel procurou-se, numa quarta etapa, formas alternativas de incorporação. Na primeira, produziu-se uma camada de titania nanoporosa na superfície da liga metálica que serviu de reservatório para os inibidores. O revestimento sol-gel foi aplicado por cima da camada nanoporosa. Os inibidores armazenados nos poros actuam quando o substrato fica exposto ao ambiente agressivo. Numa segunda, os inibidores foram armazenados em nano-reservatórios de sílica ou em nanoargilas (halloysite), os quais foram revestidos por polielectrólitos montados camada a camada. A terceira alternativa consistiu no uso de nano-fios de molibdato de cério amorfo como inibidores anticorrosivos nanoparticulados. Os nano-reservatórios foram incorporados durante a síntese do sol-gel. Qualquer das abordagens permitiu eliminar o efeito negativo do inibidor sobre a estabilidade da matriz do sol-gel. Os revestimentos sol-gel desenvolvidos neste trabalho apresentaram protecção anticorrosiva activa e capacidade de auto-reparação. Os resultados obtidos mostraram o elevado potencial destes revestimentos para a protecção anticorrosiva da liga de alumínio 2024.

Síntese sol-gel de biomateriais à base de água de fontes hidrotermais para otimização do comportamento celular e regeneração dos tecidos ósseos

Dissertação de Mestrado, Ciências Biomédicas, 18 de Março de 2016, Universidade dos Açores.

Elaboration and optimization of (Y,Er)Al(3)(BO(3))(4) glassy planar waveguides through the sol-gel process

In this work, a sol-gel route was used to prepare Y(0.9)Er(0.1)Al(3)(BO(3))(4) glassy thin films by spin-coating technique looking for the preparation and optimization of planar waveguides for integrated optics. The films were deposited on silica and silicon substrates using stable sols synthesized by the sol-gel process. Deposits with thicknesses ranging between 520 and 720 nm were prepared by a multi-layer process involving heat treatments at different temperatures from glass transition to the film crystallization and using heating rates of 2 degrees C/min. The structural characterization of the layers was performed by using grazing incidence X-ray diffraction and Raman spectroscopy as a function of the heat treatment. Microstructural evolution in terms of annealing temperatures was followed by high resolution scanning electron microscopy and atomic force microscopy. Optical transmission spectra were used to determine the refractive index and the film thicknesses through the envelope method. The optical and guiding properties of the films were studied by m-line spectroscopy. The best films were monomode with 620 nm thickness and a refractive index around 1.664 at 980 nm wavelength. They showed good waveguiding properties with high light-coupling efficiency and low propagation loss at 632.8 and 1550 nm of about 0.88 dB/cm. (C) 2009 Elsevier B.V. All rights reserved.

External polyacrylate-coating as alternative material for preparation of photopolymerized sol-gel monolithic column

Photopolymerized sol-gel monolithic columns for use in capillary electrochromatography were prepared in 125 mu m i.d. polyacrylate-coated fused-silica capillaries. The polyacrylate-coating, unlike the polyimide one, is transparent to the radiation used (approximate to 370 nm), and thus, no coating removal is necessary. This is a very important particularity since intrinsic capillary column characteristics, such as flexibility and mechanical resistance, are unchanged. A mixture containing metacryloxypropyltrimethoxysilane (MPTMS) as the polymeric precursor, hydrochloric acid as the catalyst, toluene as the porogen and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819) as the photoinitiator was irradiated at 370 nm for 20 min inside the capillaries to prepare the columns through sol-gel approach. The versatility and viability of the use of polyacrilate as a new capillary external coating were shown through preparation of two columns under different conditions, which were tested in electrochromatography for separation of standard mixture containing thiourea (marker compound), propylbenzene, phenanthrene and pyrene. (C) 2008 Elsevier B.V. All rights reserved.

NiTiO3 nanoparticles encapsulated with SiO2 prepared by sol-gel method

NiTiO3 (NTO) nanoparticles encapsulated with SiO2 were prepared by the sol-gel method resulting on core-shell structure. Changes on isoelectric point as a function of silica were evaluated by means of zeta potential. The NTO nanoparticles heat treated at 600 degrees C were characterized by X-ray diffraction, transmission electron microscopy (TEM) and energy dispersive X-ray analysis. TEM observations showed that the mean size of NTO is in the range of 2.5-42.5 nm while the thickness of SiO2 shell attained 1.5-3.5 nm approximately.

External polyacrylate-coating as alternative material for preparation of photopolymerized sol-gel monolithic column

Photopolymerized sol-gel monolithic columns for use in capillary electrochromatography were prepared in 125 mu m i.d. polyacrylate-coated fused-silica capillaries. The polyacrylate-coating, unlike the polyimide one, is transparent to the radiation used (approximate to 370 nm), and thus, no coating removal is necessary. This is a very important particularity since intrinsic capillary column characteristics, such as flexibility and mechanical resistance, are unchanged. A mixture containing metacryloxypropyltrimethoxysilane (MPTMS) as the polymeric precursor, hydrochloric acid as the catalyst, toluene as the porogen and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819) as the photoinitiator was irradiated at 370 nm for 20 min inside the capillaries to prepare the columns through sol-gel approach. The versatility and viability of the use of polyacrilate as a new capillary external coating were shown through preparation of two columns under different conditions, which were tested in electrochromatography for separation of standard mixture containing thiourea (marker compound), propylbenzene, phenanthrene and pyrene. (C) 2008 Elsevier B.V. All rights reserved.

Erbium and ytterbium co-doped SiO2 : GeO2 planar waveguide prepared by the sol-gel route using an alternative precursor

The sol-gel method combined with a spin-coating technique has been successfully applied for the preparation of rare-earth doped silica:germania films used for the fabrication of erbium-doped waveguide amplifiers (EDWA), presenting several advantages over other methods for the preparation of thin films. As with other methods, the sol-gel route also shows some drawbacks, such as cracks related to the thickness of silica films and high hydrolysis rate of certain precursors such as germanium alkoxides. This article describes the preparation and optical characterization of erbium and ytterbium co-doped SiO2:GeO2 crack-free thick films prepared by the sol-gel route combined with a spin-coating technique using a chemically stable non-aqueous germanium oxide solution as an alternative precursor. The non-crystalline films obtained are planar waveguides exhibiting a single mode at 1,550 nm with an average thickness of 3.9 mu m presenting low percentages of porosity evaluated by the Lorentz-Lorenz Effective Medium Approximation, and low stress, according to the refractive index values measured in both transversal electric and magnetic polarizations. Weakly confining core layers (0.3% < Delta n < 0.75%) were obtained according to the refractive index difference between the core and buffer layers, suggesting that low-loss coupling EDWA may be obtained. The life time of the erbium I-4(13/2) metastable state was measured as a function of erbium concentration in different systems and based on these values it is possible to infer that the hydroxyl group was reduced and the formation of rare-earth clusters was avoided.

Influência da catálise ácida e básica na preparação da sílica funcionalizada pelo método sol-gel

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis of hybrid silicates containing porphyrins incorporated by a sol-gel process and their properties

Porphyrin was incorporated in a silicate network, via a covalent bond, by grafting a functional group with 3-aminopropyltriethoxysilane, using a sol-gel process. We have carried out the synthesis and measured the absorption spectra, nuclear magnetic resonance spectra, infrared (IR) spectra, luminescence spectra and lifetime of these hybrid silicates, porphyrinosilicas. These samples contained the following free-base porphyrins: meso-tetrakis-p-chlorobenzoylporphyrin, meso-tetrakis-2,6-dichloro-3-chlorosulfonylphenylporphyrin. The obtained porphyrinosilicas have similar absorption and luminescence spectra to the free base porphyrins in solution. IR spectra confirm the formation of monomeric species. Lifetime measurement for porphyrinosilica reveals that 32% +/- 2% of porphyrin is covalently bonded to the silica network. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Electroluminescence of zinc oxide thin-films prepared via polymeric precursor and via sol-gel methods

Zinc oxide (ZnO) is an electroluminescent (EL) material that can emit light in different regions of electromagnetic spectrum when electrically excited. Since ZnO is chemically stable, inexpensive and environmentally friendly material, its EL property can be useful to construct solid-state lamps for illumination or as UV emitter. We present here two wet chemical methods to prepare ZnO thin-films: the Pechini method and the sol-gel method, with both methods resulting in crystalline and transparent films with transmittance > 85% at 550 nm. These films were used to make thin-film electroluminescent devices (TFELD) using two different insulator layers: lithium fluoride (LiF) or silica (SiO2). All the devices exhibit at least two wide emission bands in the visible range centered at 420 nm and at 380 nm attributed to the electronic defects in the ZnO optical band gap. Besides these two bands, the device using SiO2 and ZnO film obtained via sol-gel exhibits an additional band in the UV range centered at 350 nm which can be attributed to excitonic emission. These emission bands of ZnO can transfer their energy when a proper dopant is present. For the devices produced the voltage-current characteristics were measured in a specific range of applied voltage. (C) 2007 Elsevier B.V. All rights reserved.

EXAFS, SAXS and Eu3+ luminescence spectroscopy of sol-gel derived siloxane-polyethyleneoxide hybrids

Hybrid Eu3+-doped silica-poliethyleneoxide (PEO) nanocomposites with covalent bonds between the inorganic (siloxane) and organic (PEO) phases have been obtained by sol-gel process. These materials are transparent, flexible and present high Eu3+ luminescence output. Their luminescence properties, local environment around europium ions and structure have been investigated as a function of europium content. EXAFS measurements indicate that the increase in Eu-doping induces a decrease in Eu3+ coordination number. An increase in symmetry degree around the metal ion is also observed for increasing Eu3+ concentration, while non radiative decay paths from the D-5(0) excited state become more important. SAXS results suggest the preferential interaction of europium ions with ether-type oxygens of the polymer chains. However, the existence of interactions between the cations and the carbonyl groups from urea bridges located at the siloxane-PEO interface can not be excluded.

Sol-gel Er-doped SiO(2)-HfO(2) planar waveguides: A viable system for 1.5 mu m application

70SiO(2)-30HfO(2) planar waveguides, doped with Er(3+) concentrations ranging from 0.3 to 1 mol %, were prepared by sol-gel route, using dip-coating deposition on silica glass substrates. The waveguides show high densification degree, effective intermingling of the two components of the film, and uniform surface morphology. Propagation losses of about 1 dB/cm were measured at 632.8 nm. When pumped with 987 or 514.5 nm continuous-wave laser light, the waveguides show the (4)I(13/2)-->(4)I(15/2) emission band with a bandwidth of 48 nm. The spectral features are found independent both on erbium content and excitation wavelength. The (4)I(13/2) level decay curves presented a single-exponential profile, with a lifetime between 2.9 and 5.0 ms, depending on the erbium concentration. (C) 2002 American Institute of Physics.

Preparation and characterization of erbium and ytterbium co-doped sol-gel SiO2 : HfO2 films for planar waveguides

This work reports on the preparation of erbium and ytterbium co-doped SiO2:HfO2 single mode planar waveguides using the sol-gel method. Silica nanoparticles were prepared from tetraethylorthosilicate in basic media and the films were characterized by transmission electron microscopy, scanning electron microscopy, mechanical profilometry, M-lines spectroscopy based on prism coupling technique, X-ray diffractometry, infrared spectroscopy and photoluminescence spectroscopy. The film thicknesses and the refractive indexes were adjusted in order to satisfy a future efficient coupling to single mode optical fiber. Films suitable for both weak and strong light confinement were prepared varying hafnia concentration into the silica matrix. The lifetime values of erbium I-4(13/2) state were measured in order to investigate the influence of clustering and hydroxyl groups on the fluorescence quantum efficiency of the I-4(13/2) level, responsible for the emission at 1.55 mu m attributed to the I-4(13/2) -> I-4(15/2) transition. The high lifetime values suggest the absence of erbium clusters and the elimination of hydroxyl groups by rapid thermal process. (c) 2007 Elsevier B.V. All rights reserved.

Active planar waveguides based on sol-gel Er3+-doped SiO2-ZrO2 for photonic applications: Morphological, structural and optical properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)