TiO2 films have attracted much attention because of their photoactivity and superhydrophilcity. For the superhydrophilicity studies, most research focused mainly on enhancing superhydrophilicity of Ti02 film under UV illumination. A hydrothermal-dip-coating superwetting TiO2 film was synthesised and found to preserve its superhydrophilicity up to 6 months. This non-UV superwetting TI02 film potentially opens an alternative application as bioactive layer for growing hydroxyapatite (HAP) coating, used extensively as prosthetic device medically. In this research, a systematic study was carried out, aiming to understand and optimise the hydrophilicity and superwetting properties of Ti O2 film without UV illumination. The effect of (i) PEG concentration, (ii) film thickness and (iii) agglomerate size of TiO2 on the wettability of TiO2 film was investigated. Although the presence of PEG does affect the porosity of the film, PEG concentration does not play significant role in retaining superhydrophilicity of the film. The evidence from AFM showed that surface roughness is the key parameter to control in order to retain the superhydrophilic wetting and antifogging behavior of the synthesised films, which can be tuned by simple manipulation of the multilayer assembled of TiO2 nanoparticles through varying the film thickness and agglomerate size. A film thickness of (????140nm) yielded the optimum roughness (rms =23nm) for the creation of the best superhydrophilic wetting behavior. Thicker films smoothened the film roughness, and therefore causing detrimental effects on their superhydrophilic wetting properties. Smaller agglomerate size was also found to be important in retaining the roughness film. The photoactivity of the "non UV illuminated"superhydrophilic film was found that be comparable with a Pilkington Activ??? in degrading methyl blue. The growth of Hydroxyapatite (HAP), synthesised via organic-inorganic hybrid method, and the mechanical stability of the HAP coating on the TiO2 films applied on titanium foil were studied. Homogenous HAP coating was found to grow only on the T O2 film with superhydrophilic properties. However the coating was of poor mechanical stability. Surface -OH was found to play an important role in aligning the phosphonate groups in HAP recursor during dip-coating.

Orientador: Mário Alexandre Coelho Sinhoreti / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-09-11T21:15:34Z (GMT). No. of bitstreams: 1 Brandt_WilliamCunha_D.pdf: 1998947 bytes, checksum: 914e15da8572efd8f5e7f4b69beb9370 (MD5) Previous issue date: 2010 / Resumo: O objetivo neste estudo foi analisar diferentes fontes de luz e fotoiniciadores e sua influência nas propriedades físicas e térmicas e na resistência da união (RU) de compósitos odontológicos experimentais contendo diferentes fotoiniciadores. Um compósito experimental contendo uma mistura de BisGMA, UDMA, BisEMA, TEGDMA e 65% em peso de partículas de carga silanizadas foi preparado com o uso dos fotoiniciadores CQ (Canforoquinona) e PPD (1-Fenil-1,2-Propanodiona). O co-iniciador usado foi a amina terciária dimetil amino etil metacrilato (DMAEMA). As fontes de luz utilizadas foram uma lâmpada halógena (XL 2500-3M/ESPE) e duas de diodo emissor de luz - LED (UltraBlue ISDMC e UltraLume LED 5-UltraDent). A mensuração da irradiância e do espectro de luz emitido pelos aparelhos foi realizada por meio de medidor de potência e espectrômetro (USB 2000), respectivamente. A curva de absorção dos fotoiniciadores foi aferida por um espectrofotômetro (Varian Cary 5G). As propriedades físicas e térmicas do material foram analisadas em Espectroscopia de Infravermelho Transformada de Fourier (FTIR), análise Termogravimétrica (TGA), análise Termo-Dinâmica-Mecânica (DMA), resistência à compressão (RC), resistência à compressão diametral (RCD) e módulo diametral (MD). Para o teste de RU, push-out foi realizado em cavidades cônicas preparadas em noventa incisivos bovinos. Porém, antes da realização do teste push-out, a dureza Knoop (DK) foi mensurada no topo e na base das restaurações. O monitoramento (tempo real) da reação de polimerização foi realizado utilizando FTIR (Prestige21) e o grau de conversão (GC) para cada segundo foi calculado e curvas GC x tempo obtidas. A taxa de conversão (TC) foi avaliada por meio de ajuste das curvas, utilizando regressão não-linear (Hill - 3 parâmetros). Todos os resultados (GC, TGA, DMA, RC, RCD, MD, DK e RU) foram submetidos à análise de variância dois fatores e as médias comparadas pelo teste de Tukey (5%). De acordo com os resultados de FTIR, que avaliou o DC (%), quando os compósitos foram fotoativados pelos LEDs, não existiu diferença nos valores de GC. Porém, quando o XL 2500 foi usado, o compósito com PPD mostrou valores de GC menores que os com CQ. Não existiram diferenças nas propriedades mecânicas (RC, RCD e MD) entre os compósitos quando fotoativados por qualquer fonte de luz. A análise termogravimétrica (TGA), usada para confirmar a quantidade de partículas de carga e a porcentagem de monômero residual, não mostrou nenhuma diferença estatisticamente significante desses dois fatores, independentemente do fotoiniciador ou fonte de luz utilizada. A análise Termo-Dinâmica-Mecânica (DMA) analisou a temperatura de transição vítrea (Tg) e a rigidez do material a 37°C. De acordo com os resultados, o fotoiniciador PPD e a fonte de luz UltraLume LED 5 produziram polímeros com maior densidade de ligações cruzadas, pois apresentaram os maiores valores de Tg. Nenhuma diferença foi encontrada na rigidez a 37°C. A avaliação da cinética e taxa de polimerização mostrou que o PPD produz reação de polimerização mais lenta, levando a maiores valores de RU. Os valores de DK mostraram que XL 2500 produziu os maiores valores tanto no topo como na base das restaurações, exceto para a fotoativação do PPD, que mostrou resultados de DK inferiores no topo das restaurações. Em geral, UltraBlue IS e UltraLume 5 não apresentaram diferenças entre si. Dessa forma, pode-se concluir que o PPD mostrou potencial para a iniciação da reação de polimerização, pois apresentou propriedades semelhantes às da CQ, aumentando a RU entre dente/restauração. Os LEDs, principalmente o UltraLume 5, produziram valores de GC semelhantes para todos os compósitos, enquanto o QTH produziu maior conversão para a CQ, comparado ao PPD. / Abstract: The aim of this study was to analyze the spectrum of different lightcuring units (LCUs) and photo-initiators and yours influence in the physical and thermal properties and bond strength (BS) of experimental resin composites with different photo-initiators. A blend with BisGMA, UDMA, BisEMA, TEGDMA and 65 wt% of silanated filler particles was prepared with CQ (Camphorquinone) and PPD (1-phenyl-1,2-propanedione) photo-initiator. Dimethylaminoethyl methacrylate (DMAEMA) was used as co-initiator. One quartz-tungsten-halogen - QTH (XL 2500, 3M/ESPE) and two light-emitting diode (LED) LCUs (UltraBlue IS, DMC and UltraLume LED 5, Ultradent) were used for photo-activation procedures. Irradiance (mW/cm²) was calculated by the ratio of the output power by the area of the tip, and spectral distribution with a spectrometer (USB 2000). The absorption curve of each photo-initiator was determined using a spectrophotometer (Varian Cary 5G). The physical and thermal properties were analyzed through of Fourier transformed infra-red spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), compression strength (CS), diametral tensile strength (DTS) and diametral modulus (DM). For BS, push-out test was accomplished in prepared conical cavities in ninety incisive bovine. However, before the accomplishment push-out test, Knoop hardness (KH) was made in the top and botton of the restorations. The real-time polymerization of the experimental resins was evaluated by Fourier transform infrared spectroscopy (Prestige21) and the degree of conversion (DC) for each second was calculated and a curve DC x time obtained. The rate of polymerization (RP) was calculated considering data fitting and Hill's 3 parameter non-linear regressions were used. The all results obtained (DC, TGA, DMA, CS, DTS, DM, KH and BS) were evaluated using a two-way analysis of variance (ANOVA) and Tukey's test (5%). The FTIR results, which analyzed the DC (%), when the resin composites were photo-activated with the LEDs LCUs, there aren't differences in the DC values. However, when XL 2500 was used for photo-activation, the PPD-containing resins showed lower DC values that CQ-containing resins. There are not differences in the mechanical properties (CS, DTS and DM) among the composite resins, regardless LCU used. The TGA, used to confirm the weight percent filler and the lost residual monomer (%) in each composite resin, didn't show any difference, regardless photo-initiator or LCU used. The DMA analyzed the glass transition temperature - Tg (°C) and the storage modulus (E' - MPa) in 37°C. In agreement with the results, the photo-initiator PPD and the UltraLume LED 5 LCU produced polymers with higher cross-link density, because they presented the highest Tg values. No difference was found in the E' in 37°C. The evaluation of the kinetics and rate of polymerization showed that PPD produces a slower reaction of polymerization, taking to highest BS values. The KH values showed that XL 2500 produced the highest values in the top and botton of the restorations, except for PPD, that showed lower KH values in the top of the restorations. In general, UltraBlue IS and UltraLume 5 didn't present differences amongst themselves. In that way, it can be concluded that PPD showed potential for the initiation of the polymerization reaction, because it presented similar properties to CQ; however it increased the BS between tooth/restoration. The LEDs, mainly the UltraLume 5, produced similar DC values for all composite resins, while QTH produced higher conversion for CQ, compared to PPD. / Doutorado / Materiais Dentarios / Doutor em Materiais Dentários

Orientador: Claudia Longo / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T02:32:28Z (GMT). No. of bitstreams: 1 Miranda_BarbaraSantosde_M.pdf: 1864005 bytes, checksum: 098b7327374f16552656f05bf9aef20f (MD5) Previous issue date: 2009 / Resumo: As propriedades de eletrodos de filmes finos e porosos dos titanatos, H2Ti2O5; H2Ti4O9 e H2Ti8O17 foram investigadas, visando sua aplicação em dispositivos para conversão de energia solar. Os titanatos foram sintetizados por reações de estado sólido, pelo aquecimento de misturas de TiO2 e K2CO3 seguida por tratamento com HCl para a troca iônica e lavagem com água. Análises por Difração de Raios-X indicaram a presença dos precursores, sugerindo que a reação de estado sólido não foi completa. Dependendo das condições de síntese, obtiveram-se produtos com estrutura e morfologia muito distintos. O aquecimento de TiO2:K2CO3 2:1 a 640 °C por 8 horas resultou na mistura H2Ti2O5/H2Ti4O9, constituido por bastoes (100 nm de diâmetro, 500 nm de comprimento) e partículas esféricas. Bastões com mesmo diâmetro e comprimento de 5 mm foram observados para H2Ti4O9 (razão molar de reagentes 4:1, 800 °C por 20 horas). Para o H2Ti8O17, sintetizado a partir da razão 8:1 sob 1100 °C por 4 horas, observaram-se predominantemente folhas. A Energia de band gap foi estimada em 3,5 eV para o H2Ti2O5 e 3,2 eV para os outros titanatos. Filmes porosos dos titanatos foram depositados em eletrodos transparentes. Na ausência de irradiação, em solução aquosa de Na2SO4 0,1 M, os eletrodos apresentaram corrente capacitiva baixa e reações de desprendimento de hidrogênio e de oxigênio em -0,1 V e 1,3V; em K4Fe(CN)6, observou-se a reversibilidade da reação redox apenas em velocidades de varredura < 10mV.s. Sob irradiação policromática, os eletrodos apresentaram fotocorrente positiva e potencial de circuito aberto negativo, comportamento típico de semicondutor de tipo-n. No estudo de possíveis aplicações para o eletrodo de H2Ti4O9, observou-se baixa atividade fotocatalítica para a degradação de fenol. Este eletrodo apresentou, porém, alta adsorção para um corante de rutênio, resultado promissor para aplicação em células solares de semicondutor sensibilizado por corante / Abstract: Thin porous films electrodes of titanates H2Ti2O5, H2Ti4O9 and H2Ti8O17 were prepared and investigated. The titanates were synthesized through solid state reactions by heating mixtures of TiO2 and K2CO3; after HCl treatment for ion exchange, the samples were rinsed with water. X-ray diffraction and scanning electron microscopy indicated that, depending on the synthesis conditions, different titanates were obtained. Also, precursors were identified, meaning the solid state reaction was not complete. Heating of TiO2:K2CO3 2:1 at 640 °C for 8 hours resulted on the mixture H2Ti2O5/H2Ti4O9, composed by rods (100 nm diameter, 500 nm length) and spherical particles. Rods with the same diameter and 5 mm length were observed for H2Ti4O9 (molar ratio of reagents 4:1, 800 °C for 20 hours). For H2Ti8O17, synthesized from ratio 8:1 at 1100 °C for 4 hours, mainly sheets were observed. Band gap energy was estimated at 3,5 eV for H2Ti2O5/H2Ti4O9 and 3,2 eV for the others titanates. Thin porous films of titanate were deposited on transparent electrodes. In the dark, the electrodes presented low capacitive current and hydrogen and oxygen evolution reactions at -0,2V and 1,4V (vs. Ag/AgCl) in Na2SO4 0,1 M aqueous solution; also, the reversibility of redox reaction in K4Fe(CN)6, was observed only at slow scanning rates. Under polychromatic irradiation, the electrodes presented positive photocurrents and negative open circuit potential, a typical behavior of n-type semiconductor. Studies of possible applications for the H2Ti4O9 electrode revealed low activity for phenol photocatalytic degradation. Nevertheless, this electrode showed high adsorption of a ruthenium-based dye, a promising result for application on dye-sensitized solar cells / Mestrado / Físico-Química / Mestre em Química

No description available.

Cette thèse porte sur les complexes de coordinations basés sur les métaux de transitions et les lanthanides en tant qu'éléments clés pour créer des matériaux fonctionnels. Précisément, des matériaux contenant des propriétés de détection, d'auto assemblage et optique ont été conçus et optimisés. En plus d'une brève introduction sur la photophysique, les gels supramoléculaires et les nanoparticules métalliques, un résumé sur les différents instruments et techniques employés pour ces travaux est inclus. Le chapitre 3 décrit la synthèse et la caractérisation de complexe de lanthanide anionique. Des techniques analytiques, tels que la spectroscopie d'émission ou la cristallographie à rayon X ont été employé pour caractériser ces différents complexes. Dans le chapitre 4, l'étude de complexes métalliques luminescents se focalise sur les complexes de métaux de transition, et plus précisément sur les complexes d'iridium(lll). Une famille de complexes d'iridium(lll) bi-cyclométallés neutres qui montre une intense émission rouge sous photo ou electro excitation est étudié. Le chapitre 5 présente la conception et le développement d'une nouvelle famille de gelators à faible poids moléculaire, basée sur des terpyridines perfluorés.La morphologie ainsi que les propriétés mécaniques et thermodynamique de ces metallogels sont étudiées. Le chapitre 6 présente une nouvelle sonde colorimétrique, composée de nanoparticules d'or fonctionnalisées avec des complexes de Zn aminoterpyridinique via des liaisons thiol est décrite pour la détection de pyrophosphate. / This thesis deals with coordination compounds based on transition metals and lanthanides as key components of functional materials. Besides a brief summary of photophysics, supramolecular gels and metal nanoparticles, an overview of the instruments and techniques employed in this work is included. This thesis is further divided into four chapters focused on optically active metalcomplexes (chapters 3 and 4), stimuli responsive metallogels (chapter 5) and functionalized nanomaterials for sensing applications (chapter 6). In chapter 3, the synthesis and characterization of anionic lanthanide complexes is reported. Analytical techniques, emission spectroscopy and X-ray crystallography were employed to characterize these complexes. ln chapter 4, the study of light emitting metal complexes is extended to transition metal complexes, in particular to iridium (lll) complexes. A family of neutral bis-cyclometallated iridium (lll) complexes that exhibit an intense red emission under photo- or electro-excitation is studied. ln chapter 5 the design and investigation of a new family of low molecular weight gelators based on perfluorinated terpyridines is reported. The morphology and mechanical and thermodynamical properties of these metallogels is studied. Chapter 6 studies the excellent cooperation between coordination compounds and nanomaterials to yield optical sensors. A new colorimetric sensor for pyrophosphate consisting of gold nanoparticles acting as reporting units functionalized with a thiol-modified aminoterpyridine-Zn complex is described.

Diploma thesis Iron Functionalized Nanoparticles of Titanium Dioxide Lenka Volfová 2017, ABSTRACT Iron-functionalized TiO2 were obtained by hydrolysis of aqueous solutions of titanyl sulfate with addition of ferric nitrate with ammonium hydroxide and the reaction filtered and washed with hydrogen peroxide. The colloid solutions thus prepared were lyophilized and the products were subsequently annealed at three different temperatures of 650 řC, 800 řC and 950 řC. The prepared doped materials were characterized by powder X-ray diffractometry, electron microscopy, infrared spectroscopy, Mössbauer spectroscopy, UV/VIS spectroscopy, thermogravimetric analysis and differential thermal analysis, and measurement of the specific surface area. Photocatalytic activity was determined by measuring of the decomposition of kinetics of 4-chlorophenol in an aqueous solution in the ultraviolet and visible area. For comparison of activity in the UV area and in the visible area were used a previously prepared highly photoactive specimen and standard TiO2 from Kronos, respectively. Keywords: Doped titanium dioxide, nanostructure, X-ray diffraction, electron microscopy, Mössbauer spectroscopy, suppression of photoactivity

Les solides hybrides poreux ou les « MOFs » sont l'une des classes les plus récentes de polymères de coordination poreux cristallins. En raison de la variété de leur structure et leur composition, Ils sont actuellement considérés comme des candidats prometteurs dans divers domaines (le stockage de gaz, la séparation des fluides, la catalyse, la biomédecine…). Cependant, la littérature sur l'activité photocatalytique de ces solides n’a commencé à s’exploser que très récemment, bien que l’utilisation de ces matériaux comme photocatalyseurs hétérogènes soit avantageux en comparaison avec les semi-conducteurs classiques. Compte tenu des propriétés photocatalytiques bien établies de TiO2, il semble logique de se concentrer sur le titane(IV) pour la conception de nouveaux MOFs pour de telles applications. Néanmoins, en raison de la difficulté de contrôler la réactivité de cet ion métallique en solution (en particulier hors des conditions très acides), très peu de MOFs à base de titane ont été décrits, parmi les MOFs nombreux connus dans la littérature. Ainsi, l'obtention de solides cristallins à base de titane dans l'eau et en milieu basique reste un défi majeur dans ce domaine. Dans nos travaux, certaines stratégies ont été suivies afin de bénéficier des avantages de l’utilisation des cations Ti4+ et parallèlement confronter leurs limitations en se focalisant sur l'exploration de la chimie de ces cations (alcoxydes de titane, complexes et oxo-clusters) avec divers ligands polytopiques, en particulier les dérivés hydroxycarboxylates et polycatécholates pour la conception de nouveaux solides hybrides poreux stables à base de titane. Ces ligands présentent des avantages importants par rapport aux carboxylates purs, tels que la diversité structurale potentiellement plus élevée, les liaisons Ti-O plus fortes conduisant à une stabilité chimique améliorée en milieu basique, et une large absorption dans le visible assurée par un transfert de charge ligand-métal. D'autre part, l'utilisation des complexes moléculaires ou des oxo-clusters de titane sera une opportunité prometteuse dans le but de contrôler l'hydrolyse spontanée et la réactivité élevée des ions Ti4+. En privilégiant la synthèse solvo- et hydrothermale à l'aide du « système haut-débit », ces stratégies ont conduit à l’obtention de nouveaux solides cristallins (composés moléculaires et polymériques 1D /2D /3D). La synthèse, la caractérisation structurale au travers de la combinaison de différentes techniques (diffraction des rayons X, analyse thermogravimétrique, spectroscopie IR, RMN du solide, mesure de sorption...), l'étude de certaines propriétés et l’étude préliminaire de l’activité photocatalytique (production de dihydrogène de l’eau) de ces nouveaux solides seront ainsi discutées dans ce manuscrit. / Crystalline Metal-Organic Frameworks MOFs are one of the most recent classes of crystalline porous coordination polymers. Due to the variety of their structure and composition, they are currently considered as promising candidates in various domains (gas storage, fluid separation, catalysis, biomedicine…). However, the literature on the photocatalytic activity of these solids has exploded only very recently, although the many advantages of using these materials as heterogeneous photocatalysts in comparison with classical semiconductors. Considering the well-established photocatalytic properties of TiO2, it seems logical to focus on titanium in order to design new MOFs for such applications. Nevertheless, because of the difficulty in controlling the reactivity of these ions in solution (especially out of the very acidic conditions), very few crystalline titanium-based MOFs have been described, among the numerous MOFs known in the literature. Thus, obtaining titanium-based MOFs in water and basic medium remains a big challenge. In our work, some strategies has been followed in order to benefice from the advantages of the titanium ions and at the same time confront their limitations by focusing on the exploration of the chemistry of Ti4+ ions (titanium alkoxides, complexes and oxo-clusters) with various polytopic ligands, especially hydroxycarboxylate and polycatecholate derivatives in order to design new stable titanium-based MOFs. Such ligands provide important advantages in comparison with pure carboxylates, such as a potentially higher structural diversity, stronger Ti-O bonds leading to an enhanced chemical stability in basic medium, and a strong absorption in the visible range ensured by ligand to metal charge transfer. On the other hand, the use of titanium molecular complexes or oxo-clusters will be a promising opportunity in order to control the spontaneous hydrolysis and the high activity of Ti4+ ions. By privileging the solvo- and hydrothermal synthesis using the «high-throughput system», these strategies lead to obtain new crystalline solids (molecular and 1D/2D/3D polymeric compounds). The synthesis, the structural characterization by a combination of different technics (X-ray diffraction, TGA analysis, IR spectroscopy, Solid State NMR, sorption measurement…), the study of some properties and the preliminary photocatalytic experiments (water splitting reaction) of these new solids will be discussed in this manuscript.

No description available.

This thesis describes the synthesis and characterisation of titania photocatalysts for incorporation into a polyethylene film. Monodisperse, anatase-phase titania nanoparticles are prepared and the synthesis conditions necessary for attraction to a laponite clay support are determined. Methods of preventing agglomeration of the laponite system such as the use of a polyethylene oxide surfactant or chemical modification of the laponite plate edges with a dimethyloctyl methoxysilane are also explored. Finally, photocatalytic studies on the laponite-supported titania nanoparticles are performed, and the compatibility and photoactivity of these materials in the polyethylene film are examined.