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ABSTRACT: Amorphous titanium dioxide (TiO(2)) thin films exhibiting high refractive indices (n ≈ 2.1) and high transparency were fabricated by spin-coating titanium oxide liquid precursors having a weakly branched polymeric structure. The precursor solution was prepared from titanium tetra-n-butoxide (TTBO) via the catalytic sol-gel process with hydrazine monohydrochloride used as a salt catalyst, which serves as a conjugate acid-base pair catalyst. Our unique catalytic sol-gel technique accelerated the overall polycondensation reaction of partially hydrolyzed alkoxides, which facilitated the formation of liner polymer-like titanium oxide aggregates having a low fractal dimension of ca. (5)/(3), known as a characteristic of the so-called "expanded polymer chain". Such linear polymeric features are essential to the production of highly dense amorphous TiO(2) thin films; mutual interpenetration of the linear polymeric aggregates avoided the creation of void space that is often generated by the densification of high-fractal-dimension (particle-like) aggregates produced in a conventional sol-gel process. The mesh size of the titanium oxide polymers can be tuned either by water concentration or the reaction time, and the smaller mesh size in the liquid precursor led to a higher n value of the solid thin film, thanks to its higher local electron density. The reaction that required no addition of organic ligand to stabilize titanium alkoxides was advantageous to overcoming issues from organic residues such as coloration. The dense amorphous film structure suppressed light scattering loss owing to its extremely smooth surface and the absence of inhomogeneous grains or particles. Furthermore, the fabrication can be accomplished at a low heating temperature of <80 °C. Indeed, we successfully obtained a transparent film with a high refractive index of n = 2.064 (at λ = 633 nm) on a low-heat-resistance plastic, poly(methyl methacrylate), at 60 °C. The result offers an efficient route to high-refractive-index amorphous TiO(2) films as well as base materials for a wider range of applications.
Langmuir 07/2012; 28(33):12245-55. · 4.19 Impact Factor
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ABSTRACT: Titanium oxide polymers having a low-fractal dimension (d(f) < 2) were rapidly synthesized from titanium tetra-n-butoxide via a catalytic sol-gel process with a hydrazine monohydrochloride catalyst. Different from conventional sol-gel processes aimed at producing low-fractal dimension titanium oxide polymers, the present synthetic strategy needed neither organic ligand to enhance the stability of titanium alkoxides nor an extremely long reaction time in a strongly acidic solution condition, thanks to a drastically accelerated polycondensation reaction. We pursued the structure evolution of the titanium oxide polymers by means of time-resolved small-angle X-ray scattering (Tr-SAXS). The SAXS data unambiguously demonstrate the generation of the expanded polymer-like structure characterized by the fractal dimension of d(f) approximately equal 5/3. The results offer an efficient route to the synthesis of the weakly-branched titanium oxide polymers, which are expected to be used to create a wide range of optical materials having a high refractive index, such as anti-glare coating.
Journal of Nanoscience and Nanotechnology 05/2012; 12(5):3732-8. · 1.56 Impact Factor
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ABSTRACT: The so-called sol-gel technique has been shown to be a template-free, efficient way to create functional porous silica materials having uniform micropores. This appears to be closely linked with a postulation that the formation of weakly branched polymer-like aggregates in a precursor solution is a key to the uniform micropore generation. However, how such a polymer-like structure can precisely be controlled, and further, how the generated low-fractal dimension solution structure is imprinted on the solid silica materials still remain elusive. Here we present fabrication of microporous silica from tetramethyl orthosilicate (TMOS) using a recently developed catalytic sol-gel process based on a nonionic hydroxyacetone (HA) catalyst. Small angle X-ray scattering (SAXS), nitrogen adsorption porosimetry, and transmission electron microscope (TEM) allowed us to observe the whole structural evolution, ranging from polymer-like aggregates in the precursor solution to agglomeration with heat treatment and microporous morphology of silica powders after drying and hydrolysis. Using the HA catalyst with short chain monohydric alcohols (methanol or ethanol) in the precursor solution, polymer-like aggregates having microscopic correlation length (or mesh-size) < 2 nm and low fractal dimensions ∼2, which is identical to that of an ideal coil polymer, can selectively be synthesized, yielding the uniform micropores with diameters <2 nm in the solid materials. In contrast, the absence of HA or substitution of 1-propanol led to considerably different scattering behavior reflecting the particle-like aggregate formation in the precursor solution, which resulted in the formation of mesopores (diameter >2 nm) in the solid product due to apertures between the particle-like aggregates. The data demonstrate that the extremely fine porous silica architecture comes essentially from a gaussian polymer-like nature of the silica aggregates in the precursor having the microscopic mesh-size and their successful imprint on the solid product. The result offers a general but significantly efficient route to creating precisely designed fine porous silica materials under mild condition that serve as low refractive index and efficient thermal insulation materials in their practical applications.
The Journal of Physical Chemistry B 06/2011; 115(30):9369-78. · 3.70 Impact Factor
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ABSTRACT: A microporous silica thin film with low refractive index (low-n) of 1.27 and high Young's modulus of 19.5 GPa was obtained by sol-gel synthesis using hydroxyacetone catalyst with tetramethyl orthosilicate and water in ethanol. Transmission electron microscope images and nitrogen adsorption-desorption measurements showed that the pores in the synthesized silica were <1 nm in diameter. Unlike many other microporous synthesis methods, our method did not require sacrificial reagents as templates. This allowed low-temperature fabrication of high-strength low-n silica.
ACS Applied Materials & Interfaces 10/2010; 2(11):3128-33. · 4.53 Impact Factor
