Hybrid Zirconium Sol-Gel Thin Films With High Refractive Index

We describe the synthesis of optical quality thin film materials with high refractive index, employing zirconium based hybrid sol-gel precursors. As the zirconium propoxide precursor is unstable in the presence of a strong nucleophilic agent such as water, two synthesis routes have been performed employing a chelating agent and an organosilane precursor to avoid the formation of any undesired ZrO2 agglomerates, leading to organo-zirconate complexes and silicato-zirconate copolymers, respectively. The prepared hybrid sol-gel materials were deposited by spin-coating to form a transparent thin film on silicon substrates, and heat treated at 100 °C for the final stabilisation of the layer. The effect of the two synthesis routes on the optical properties of zirconium based hybrid sol-gel material is discussed. It was found that the nature and concentration of the organosilane precursor can significantly affect the structural properties of the deposited films. A correlation was also demonstrated between the concentration of the organosilane precursor and the refractive index of the material. By reducing the concentration of organosilane precursor, high refractive index materials were obtained. Similar behaviour was observed for the materials synthesised via chelating agent. The synthesis employing an organosilane precursor produces films with higher refractive index. A maximum refractive index of 1.746 was measured at 635nm for the deposited thin films

Hybrid Solar Thermophotovoltaic-Biomass/Gas Power Generation System with a Spectrally Matched Emitter for Lower Operating Temperatures

Three conceptual designs have been developed for hybrid solar-biomass/gas thermophotovoltaic (TPV) system for a non-intermittent power generation which can operate at relatively low TPV operating temperatures. TPV cells with lower band gap has been chosen for this conceptual hybrid device. The low band TPV cell generates electricity at longer photonic wavelength which corresponds a lower operating temperature. The development methodology is presented for a spectrally matched emitter which emits maximum photonic energy in the 600°C -1000°C temperature range with correspondingly lower photonic energy emission in the 0°C -600°C range. This approach for spectral control in TPV systems requires fewer system components

Waveguide Fabrication In UV-Photocurable Sol–Gel Materials: Influence Of The Photoinitiating System

In this paper we identify and explain the different chemical interactions involved between a sol–gel matrix and photoinitiators used in the fabrication of optical waveguides. A well-established sol–gel matrix composed of 3-methacryloxypropyltrimethoxysilane, zirconium n-propoxide and methacrylic acid was developed, and two different photoinitiators (Irgacure® 819 and 1800) were added to the host matrix. Optical microscopy was used to characterise the structure of the waveguides as a function of the photoinitiator nature and concentration, and aging of the hybrid sol–gel material. It is clearly demonstrated that the width of the waveguides is strongly influenced by the sol aging. Furthermore, it is shown that degradation of photoinitiators occurs during the sol–gel process. Oxidation of the phosphonyl groups by the zirconium complex accounts for this results

The effect of curing and zirconium content on the wettability and structure of a silicate hybrid sol-gel material

Functional hybrid sol-gel coatings have been developed for numerous applications with a wide range of wettabilities. This study proposes to investigate the relationship between the structure and the wetting properties of a zirconium modified silicate hybrid sol-gel coating. The structures of the coatings were altered by varying the content of zirconium, and the curing process, while keeping the sol-gel preparation conditions identical. The structure of the materials was characterized by FTIR, 29Si NMR and SEM. The thermal properties and the wettability are identified by DSC and contact angle measurements, respectively. By corroborating the structural and wettability analyses, it is shown that the transition metal minimizes the thermally-assisted condensation of the silicate network and enables to stabilize the wetting properties at higher hydrophilic values. This article highlights that the wettability of hybrid sol-gel coatings can be controlled by both the curing process and transition metal content

Application of Niobium Enriched Ormosils as Thermally Stable Coatings for Aerospace Aluminium Coatings

The aim of this experimental research is to study the ability of niobium rich sol-gel coatings to withstand thermal stress, while remaining impermeable to corrosive agents for the protection of aerospace alloys. The coating material is developed via polymeric sol-gel synthesis employing 3-(trimethoxysilyl)propylmethacrylate (MAPTMS) and niobium ethoxide precursors as a source of silicon and niobium, respectively. The beneficial effect of niobium inclusion within coating was characterised spectroscopically, calorimetrically and electrochemically. The thermal cycling effects of the coating were studied using microscopic and accelerated test methods. Electrochemical tests showed that corrosion current of the material was 2 orders lower in magnitude than MAPTMS coating. The neutral salt spray test results of thermal stressed samples prove that inclusion of niobium nanoparticles within the silane matrix considerably improves the corrosion resistance performances in salt spray test resulting in better ability to resist thermal shock failure when compared to the MAPTMS coating alone

Effect of the Condensation of Hybrid Organic–Inorganic sol–gel Materials on the Optical Properties of Tripan Blue

The work reported in this paper highlights the effect of sol–gel structures on the optical properties of a typical organic dye (Trypan Blue, TB). Three transition-metal-based hybrid sol–gel materials with different structures and morphologies were developed and characterised by TEM. The optical properties of TB were investigated by incorporating it in the different sol–gel materials and the UV–Visible spectra recorded in both liquid and solid state, in thin-coatings cured at temperatures in the range 100– 150 [1]C. These studies revealed two relevant results. First, the sol–gel morphology plays a critical role in the optical properties of the dye. The effect of the sol–gel host matrix on the optical properties of the dye is attributed to the steric hindrance of the nanostructures, themselves intimately dependant on the reactivity of the transition metal. For instance, the less condensed system showed the highest reactivity with the dye, while the more condensed system exhibited limited interaction with the dye, symbolised by a significant change or quasi-unchanged UV–Visible spectra, respectively. It is also shown that the increase of the condensation degree of the sol–gel coatings by heat-curing can dramatically alter the optical properties of the dye especially for the most condensed sol–gel systems. This has been attributed to proximity effects enabled by the further increase of the materials densities. The results reported here aim to provide a better understanding of how material formulations can influence the optical properties of organic dyes and suggest that the structure of the host matrix along with the applied curing process have to be fully considered and assessed in the choice of organic dyes for a given application

Corrosion Protection Properties of Various Ligand Modified Organic Inorganic Hybrid Coating on AA 2024-T3

The inclusion of zirconium precursors to prepare organosilane solgel coatings improves the corrosion protection performance of the coatings on aluminium and steel. The inherent differences in the hydrolysis rates of the silane and zirconium precursors, various ligands were used to control the hydrolysis by decreasing the number of reactive alkoxide group. Hybrid sols were synthesised using 3-(trimethoxysilyl) propylmethacrylate (MAPTMS) and zirconium n-propoxide chelated with organic ligands including different organic acids, acetyl acetone and 2 2’ bipyridyl. The effects of zirconia inclusion on the properties of the coatings were compared on the aerospace alloy AA 2024-T3. Electrochemical analysis and salt spray exposure characterized the corrosion protective properties. The results indicate that acid chelated systems possess better corrosion protection when compared to the other ligands, due to smaller zirconium nanoparticles being formed. In particular superior performance was displayed by the coatings involving 3,4 diaminobenzoic acid (DABA) due to inherent anticorrosive properties

Improving the Holographic Recording Characteristics of a Water-Resistant Photosensitive Sol–Gel for Use in Volume Holographic Optical Elements

Continual improvements to holographic recording materials make the development of volume holographic optical elements increasingly more attainable for applications where highly efficient, lightweight diffractive optical elements can replace conventional optics. A fast-curing, water resistant photosensitive sol–gel capable of volume holographic recording has recently drawn attention for its extreme environmental and physical robustness, in particular its water/moisture and scratch resistance. However, to date, the refractive index modulation has been limited. While water-resistant properties are invaluable in the face of the weathering which many practical systems for outdoor applications will endure, high refractive index modulation is also important in order to facilitate high diffraction efficiency holograms recorded in relatively thin layers. Lower grating thickness ensures a large angular and wavelength range of operation-properties that are critical for many applications of holographic optical elements such as solar light harvesting, optical displays and illumination management. For any application where low-cost mass production is envisaged, sensitivity/writing speed is also a crucial factor. In this research, we studied the recording properties of these water resistant photosensitive sol–gel layers at two different recording wavelengths (532 and 476 nm) and investigated methods for improving these properties. We report more than two-fold improvement of the refractive index modulation from 1.4 10 3 to 3.3 10 3 in layers of thickness ranging from 40–100 m and more than an order of magnitude increase in photosensitivity/recording speed through better matching between recording wavelength and layer absorption, chemical alterations and thermal post-processing techniques

Correlation between the structure and the anticorrosion barrier properties of hybrid sol–gel coatings: application to the protection of AA2024-T3 alloys

Hybrid sol–gel materials have been extensively studied as viable alternatives to toxic chromate (VI)-based coatings for the corrosion protection of AA2024-T3 in the aerospace industry, due to the wide range of available chemistries they offer and the tremendous development potential of innovative functional coatings. However, so far, little work has been performed in identifying the effect of the employed chemistries on the structure and anticorrosion properties of the coatings. This work proposes to contribute to a better understanding of the relationship existing between the structure, morphology and anticorrosion properties of hybrid sol–gel coatings deposited on AA2024- T3 aluminium surfaces, the most widely used alloy in the aerospace industry. The sol–gels are prepared employing two hybrid precursors; an organosilane, 3-trimethoxysilylpropylmethacrylate, and a zirconium complex prepared from the chelation of zirconium n-propoxide, and methacrylic acid. The structure of the hybrid sol–gel formulation is modified by altering the concentration of the transition metal complex. The structure and morphology of the coatings are characterised by dynamic light scattering, fourier transform infrared spectroscopy, silicon nuclear magnetic resonance spectroscopy, differential scanning calorimetry, scanning electron microscopy, atomic-force microscopy and the anticorrosion barrier properties characterised by electrochemical impedance spectroscopy and neutral salt-spray. It is found that the transition metal concentration affected the morphology and structure, as well as the anticorrosion performances of the hybrid sol–gel coatings. A direct correlation between the morphology of the coatings and their final anticorrosion barrier properties is demonstrated, and the optimum material amongst this series is determined to be comprised of a concentration of between 20 and 30% of transition metal