Protection of silica-coated ZnO nanoparticles on pre-dyed polyester fabrics against photofading

This work was designed to investigate the ability of silica-coated ZnO (ZnO&SiO2) nanoparticles (NPs) as ultraviolet (UV) absorbers for protecting pre-dyed polyester fabrics against photofading. Despite that ZnO NPs are excellent UV absorbers, their strong photocatalytic activity limits the application in UV protection. In this study, a silica layer was coated onto ZnO NPs to form a physical barrier between the ZnO and a polyester substrate, which allowed effective UV shielding while minimising the harmful effects of photocatalytic activity on the substrate. The structure and optical proprieties of ZnO&SiO2 NPs were observed. The bare ZnO and ZnO&SiO2 NPs were, respectively, applied to polyester fabrics coloured with three kinds of dyes by a dip coating method. The photofading level of treated fabrics after exposure under simulated sunlight was evaluated. The ZnO&SiO2 NPs exhibited excellent protection on pre-dyed polyester fabrics against photofading.

Hermetically coated superparamagnetic Fe2O3 particles with SiO2 nanofilms

Magnetic nanoparticles are frequently coated with SiO2 to improve their functionality and biocom-patibility in a range of biomedical and polymer nanocomposite applications. In this paper, a scalable flame aerosol technology is used to produce highly dispersible, superparamagnetic iron oxide nanoparticles hermetically coated with silica to retain full magnetization performance. Iron oxide particles were produced by flame spray pyrolysis of iron acetylacetonate in xylene/acetonitrile solutions and the resulting aerosol was in situ coated with silicon dioxide by oxidation of swirling hexamethlydisiloxane vapor. The process allows independent control of the core Fe2O3 (maghemite) particle properties and the thickness of their silica coating film. This ensures that the nonmagnetic SiO2 layer can be closely controlled and minimized. The optimal SiO2 content for complete (hermetic) encapsulation of the magnetic core particles was determined by isopropanol chemisorption. The magnetization of Fe 2O3 coated with about 2 nm thin SiO2 layers was nearly identical to that of uncoated, pure Fe2O3 nanoparticles. © 2009 American Chemical Society.

Lanthanide oxide nanotubes and nanorods: synthesis, processing, luminescence and catalytic properties

Esta tese relata estudos de síntese, caracterização da estrutura e das propriedades de fotoluminescência e aplicações de nanotubos e nanobastonetes de óxidos de lantanídeos em pontas para microscopia de força atómica, catálise heterogénea e compósitos de base polimérica. Há um interesse crescente em compreender como o confinamento quântico decorrente da redução do tamanho de partícula pode influenciar a eficiência da luminescência, a dinâmica dos estados excitados, a transferência de energia e os efeitos de termalização de nanoluminóforos. Em nanocristais dopados com lantanídeos (Ln3+), e apesar da localização dos estados 4f, ocorrem efeitos de confinamento quântico via interacção com os modos vibracionais da rede. Em particular, a termalização anómala, descrita para uma variedade de nanocristais dopados com Ln3+, tem sido atribuída à ausência de modos vibracionais de menor frequência. Este nanoconfinamento pode ter impacto na dinâmica da luminescência, bem como na transferência de energia mediada por modos vibracionais e processos de upconversion. Nesta tese, relata-se o estudo deste efeito em nanotubos de Gd2O3:Eu3+. A influência de parâmetros como a concentração de európio e as condições de calcinação também foi investigada. Algumas aplicações destes óxidos de lantanídeos também foram exploradas, nomeadamente a modificação de pontas usadas em microscopia de força atómica com nanobastonetes de Gd2O3:Eu3+, lograda através de dielectroforese, técnica que não degrada a emissão de luz (rendimento quântico 0.47). As pontas modificadas são estáveis sob condições de trabalho, podendo ser aplicadas, por exemplo, em microscopia óptica de varrimento de campo próximo (SNOM). A oxidação em fase líquida do etilbenzendo foi investigada usando como catalisador nanotubos de CeO2, em presença dos oxidantes hidroperóxido de t-butilo e H2O2, e do solvente acetonitrilo, e temperaturas entre 55 e 105 ºC. Nanobastonetes de Gd2O3:Eu3+ recobertos com sílica foram preparados pelo método sol-gel. Esta cobertura resultou num aumento, quer do rendimento quântico de emissão, de 0.51 para 0.86 (excitação a 255 nm), quer dos tempos de vida,de 1.43 para 1.80 ms (excitação a 394.4 nm). A superfície dos nanotubos cobertos com sílica foi modificada com o agente de acoplamento metacrilato de 3-(trimetoxissilil)propilo que permitiu a preparação de compósitos através da subsequente polimerização in-situ do estireno por técnicas de miniemulsão e solução. ABSTRACT: This thesis reports on the synthesis, characterisation of the structure and photoluminescence properties, and applications of nanotubes and nanorods of lanthanides oxides in atomic force microscopy tips, heterogeneous catalysis and polymer-base composites. There is a growing interest in understanding how size-dependent quantum confinement affects the photoluminescence efficiency, excited-state dynamics, energy-transfer and thermalisation phenomena in nanophosphors. For lanthanide (Ln3+)-doped nanocrystals, and despite the localisation of the 4f states, confinement effects are induced mostly via electron-phonon interactions. In particular, the anomalous thermalisation reported for a handful of Ln3+-doped nanocrystals has been rationalised by the absence of lowfrequency phonon modes. This nanoconfinement may further impact on the Ln3+ luminescence dynamics, such as phonon-assisted energy transfer or upconversion processes. Here, this effect is investigated in Gd2O3:Eu3+ nanotubes. The influence of parameters such as europium concentration and calcination procedure is also studied. Some applications of these lanthanides oxides have been explored, for instance the modification of atomic force microscopy tips with photoluminescent Gd2O3:Eu3+ nanorods, using dielectrophoresis, a technique which preserves the red emission of the nanorods (quantum yield 0.47). The modified tips are stable under working conditions and may find applications in scanning near-field optical microscopy. The liquid-phase oxidation of ethylbenzene over CeO2 nanotubes has been investigated, using tert-butyl-hydroperoxide and H2O2 as the oxidising agents, and acetonitrile as the solvent, in the range 55-105 ºC. Gd2O3:Eu3+ nanorods have been coated with silica via a sol-gel approach. The silica coating increases both, the Eu3+ absolute emission quantum yields from 0.51 to 0.86 (255 nm excitation), and decay times from 1.43 to 1.80 ms (394.4 nm excitation). The silica coating was modified with 3- (trimethoxysilyl) propyl methacrylate and, subsequently, composites have been prepared by in-situ radical polymerisation of styrene via miniemulsion and solution routes.

Reducing the photocatalytic activity of zinc oxide quantum dots by surface modification

The use of zinc oxide (ZnO) nanoparticles as ultraviolet (UV) absorbers for many organic substrates is limited because of the high photocatalytic activity of ZnO. In this study, a facile and efficient technique for the preparation of a hybrid material of silica-coated ZnO nanoparticles was used to reduce the photocatalytic activity of ZnO. Monodispersed ZnO nanopartcles were prepared by wet chemistry and the particle surface was modified by tetraethylorthosilicate to form a silica coating via the Sto¨ ber method. ZnO samples, both before and after the coating process, were investigated by transmission electron microscopy, X-ray diffraction, dynamic light scanning, infrared, and UV-Vis absorption spectroscopy. The effect of the surface modification on the photocatalytic activity of ZnO was studied by monitoring the degradation of Rhodamine B caused by photo-generated free radicals. The results implied that the photo-generation of free-radicals was strongly quenched by the presence of silica on the particle surface.

Nano related research in fibres and textiles

With the increasing hype surrounding what nanotechnology can actually deliver, research emphasis in this area needs to be placed on how nanotechnology can bring tangible benefits to existing industries and ordinary consumers. This paper gives selected examples of real world applications of nano-structured materials, including nano fibrous and particulate materials. It reviews recent research into nano-structured surface coating of textile substrates for enhanced functionalities, and the development of fine and uniform nanofibres for advanced applications. Emphasis has been placed on relevant research activities in the Centre for Material and Fibre Innovation at Deakin University, Australia. In the nano-structured surface coating area, several examples of enhancing fabric performance and functionality are provided, including silica coating for photochromic textiles, superhydrophobic surface coating and transparent ZnO coating to reduce colour fading of textiles exposed to UV radiation. In the nanofibre area, these activities include: elimination of beaded fibres without increasing the average diameter of the electrospun nanofibres, electrospinning of side-by-side bi-component nanofibres, new insight into the evolution of fibre morphology in electrospinning and the electrospinning technology itself.

Bioactivating the surfaces of titanium by sol-gel process

In the present study, titanium (Ti) samples were surface-modified by titania (TiO₂), silica (SiO₂) and hydroxyapatite (HA) coatings using a sol-gel process. The bioactivity of the film-coated Ti samples was investigated by cell attachment and morphology study using human osteoblast-like SaOS-2 cells. Results of the cell attachment indicated that the densities of cell attachment on the surfaces of Ti samples were significantly increased by film coatings; the density of cell attachment on HA film-coated surface was higher than those on TiO₂ and SiO₂ film-coated surfaces. Cell morphology study showed that the cells attached, spread and grew well on the three kinds of film-coated surfaces. It can be concluded that the three kinds of film coatings can bioactivate the surfaces of Ti samples effectively. Overall, Ti sample with HA film-coated surface exhibited the best bioactivity.

A study on the photostability of photochromic fabrics from hybrid organosilica coatings

Photochromic fabrics were prepared using a coating solution containing photochromic dyes and silica sol-gel. The photochromic effect was rapid. The effect of three different post treatments on the optical and durability of the photochromic fabrics was evaluated. These included incorporating a UV stabilizer, increasing the surface hydrophobicity by fluorinating the pores, and blockading the dye-containing pores with additional silica coating. All the treatments improved photostability, without significantly affecting response/fading speeds.

Fabrication of ZnO/SiO2 composite nanospheres with high core-loading levels

Monodispersed silica shell / zinc oxide core composite nanospheres were prepared in an oil-in-water microemulsion system. By using cyclohexane as the oil phase and Triton X-100 as the surfactant, nanospheres with a high core loading level and high monodispersity were obtained. The silica coating greatly reduced the photoactivity of ZnO nanoparticles, offering safe and durable applications of ZnO as UV screening agents.

Photochromic fabrics with improved optical performance

In this PhD project, the photostability and colour depth of photochromic fabrics prepared by a hybrid silica coating were improved and the relationship between the pore structure of the silica coatings and the photochromic properties of the coated fabrics was investigated.

Efficacy of Air-abrasion Technique and Additional Surface Treatment at Titanium/Resin Cement Interface

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

Effect of Static and Cyclic Loading on Ceramic Laminate Veneers Adhered to Teeth with and Without Aged Composite Restorations

Purpose: Existing composite restorations on teeth are often remade prior to the cementation of fixed dental prostheses. The aim of this study was to evaluate the effect of static and cyclic loading on ceramic laminate veneers adhered to aged resin composite restorations.Materials and Methods: Eighty sound maxillary incisors were collected and randomly divided into four groups: group 1: control group, no restorations; group 2: two Class III restorations; group 3: two Class IV restorations; group 4: complete composite substrate. Standard composite restorations were made using a microhybrid resin composite (Anterior Shine). Restored teeth were subjected to thermocycling (6000 cycles). Window preparations were made on the labial surface of the teeth for ceramic laminate fabrication (Empress II). Teeth were conditioned using an etch-and-rinse system. Existing composite restorations representing the aged composites were silica coated (CoJet) and silanized (ESPE-Sil). Ceramic laminates were cemented using a bis-GMA-based cement (Variolink Veneer). The specimens were randomly divided into two groups and were subjected to either static (groups 1a, 2a, 3a, 4a) or cyclic loading (groups 1b, 2b, 3b, 4b). Failure type and location after loading were classified. Data were analyzed using one-way ANOVA and Tukey's test.Results: Significantly higher fracture strength was obtained in group 4 (330 +/- 81 N) compared to the controls in group 1 (179 +/- 120 N) (one-way ANOVA, p < 0.05). Group lb survived a lower mean number of cyclic loads (672,820 cycles) than teeth of groups 2b to 4b (846x10(3) to 873x10(3) cycles). Failure type evaluation after the fracture test showed predominantly adhesive failures between dentin and cement, but after cyclic loading, more cohesive fractures in the ceramic were seen.Conclusion: Ceramic laminate veneers bonded to conditioned aged composite restorations provided favorable results. Surface conditioning of existing restorations may eliminate the necessity of removing aged composite restorations.

Bond strength durability of a resin composite on a reinforced ceramic using various repair systems

Objectives. This study compared the durability of repair bond strength of a resin composite to a reinforced ceramic after three repair systems.Methods. Alumina-reinforced feldspathic ceramic blocks (Vitadur-alpha(R)) (N=30) were randomly divided into three groups according to the repair method: PR-Porcelain Repair Kit (Bisco) [etching with 9.5% hydrofluoric acid + silanization + adhesive]; CJ-CoJet Repair Kit (3M ESPE) [(chairside silica coating with 30 mu m SiO2 + silanization (ESPE(R)-Sil) + adhesive (Visio(TM)-Bond)]; CL-Clearfil Repair Kit [diamond surface roughening, etching with 40% H3PO4 + Clearfil Porcelain Bond Activator + Clearfil SE Bond)]. Resin composite was photo-polymerized on each conditioned ceramic block. Non-trimmed beam specimens were produced for the microtensile bond strength (mu TBS) tests. In order to study the hydrolytic durability of the repair methods, the beam specimens obtained from each block were randomly assigned to two conditions. Half of the specimens were tested either immediately after beam production (Dry) or after long-term water storage (37 degrees C, 150 days) followed by thermocyling (12,000 cycles, 5-55 degrees C) in a universal testing machine (1 mm/min). Failure types were analyzed under an optical microscope and SEM.Results. mu TBS results were significantly affected by the repair method (p=0.0001) and the aging conditions (p=0.0001) (two-way ANOVA, Tukey's test). In dry testing conditions, PR method showed significantly higher (p < 0.001) repair bond strength (19.8 +/- 3.8 MPa) than those of CJ and CL (12.4 +/- 4.7 and 9.9 +/- 2.9, respectively). After long-term water storage and thermocycling, CJ revealed significantly higher results (14.5 +/- 3.1 MPa) than those of PR (12.1 +/- 2.6 MPa) (p < 0.01) and CL (4.2 +/- 2.1 MPa) (p < 0.001). In all groups when tested in dry conditions, cohesive failure in the composite accompanied with adhesive failure at the interface (mixed failures), was frequently observed (76%, 80%, 65% for PR, CJ and CL, respectively). After aging conditions, while the specimens treated with PR and CJ presented primarily mixed failure types (52% and 87%, respectively), CL group presented mainly complete adhesive failures at the interface (70%).Significance. Hydrolytic stability of the repair method based on silica coating and silanization was superior to the other repair strategies for the ceramic tested. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effect of surface conditioning methods on the microtensile bond strength of resin composite to composite after aging conditions

Objectives. This study evaluated the effect of two different surface conditioning methods on the repair bond strength of a bis-GMA-adduct/bis-EMA/TEGDMA based resin composite after three aging conditions.Methods. Thirty-six composite resin blocks (Esthet X, Dentsply) were prepared (5 mm x 6 mm x 6 mm) and randomly assigned into three groups for aging process: (a) immersion in citric acid (pH 3.0 at 37 degrees C, 1 week) (CA); (b) boiling in water for 8h (BW) and (c) thermocycling (x5000, 5-55 degrees C, dwell time: 30s) (TC). After aging, the blocks were assigned to one of the following surface conditioning methods: (1) silica coating (30 mu m SiOx) (CoJet, 3M ESPE) + silane (ESPE-Sil) (CJ), (2) phosphoric acid + adhesive resin (Single Bond, 3M ESPE) (PA). Resin composite (Esthet.X (R)) was bonded to the conditioned substrates incrementally and light polymerized. The experimental groups formed were as follows: Gr1:CA + PA; Gr2:CA + CJ Gr3:BW + PA; Gr4: BW + CJ; Gr5:TC + PA; Gr6: TC + CJ. The specimens were sectioned in two axes (x and y) with a diamond disc under coolant irrigation in order to obtain non-trimmed bar specimens (sticks, 10 mm x 1 mm x 1 mm) with 1 mm(2) of bonding area. The microtensile test was accomplished in a universal testing machine (crosshead speed: 0.5 mm min(-1)).Results. The means and standard deviations of bond strength (MPa +/- S.D.) per group were as follows: Gr1: 25.5 +/- 10.3; Gr2: 46.3 +/- 10.1; Gr3: 21.7 +/- 7.1; Gr4: 52.3 +/- 15.1; GrS: 16.1 +/- 5.1; Gr6, 49.6 +/- 13.5. The silica coated groups showed significantly higher mean bond values after all three aging conditions (p < 0.0001) (two-way ANOVA and Tukey tests, alpha = 0.05). The interaction effect revealed significant influence of TC aging on both silica coated and acid etched groups compared to the other aging methods (p < 0.032). Citric acid was the least aggressive aging medium.Significance. Chairside silica coating and silanization provided higher resin-resin bond strength values compared to acid etching with phosphoric acid followed by adhesive resin applications. Thermocycling the composite substrates resulted in the lowest repair bond strength compared to citric acid challenge or boiling in water. (C) 2006 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Non-leachable highly luminescent ordered mesoporous SiO2 spherical particles

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)