Fabrication of synthetic opals composed of mesoporous SnO2 spheres with an anodization-assisted double template process

Synthetic opals composed of mesoporous SnO₂ spheres were successfully fabricated from anodization of Sn opals, double templated from polystyrene opals. The mesoporous SnO₂ spheres were 440 nm in diameter containing mesopores of 20–40 nm. The resultant mesoporous SnO₂ opals possessed a high specific surface area of 196 m²/g and a grain size of 12 nm as estimated from XRD patterns. Such a hierarchical structure of SnO₂ is a promising candidate for applications in gas sensors, catalysts, and electrode materials since the regularity of the sub-micron opal structure eases transfers of relevant chemical species within the structure while the mesoporosity of the constituent SnO₂ spheres offers sufficient functioning surfaces for targeted applications.     

A Raman, infrared and XRD analysis of the instability in volcanic opals from Mexico

A series of natural volcanic opal samples with the destabilization phenomena from Mexican deposits (states of Queretaro and Jalisco) was investigated by Raman microprobe (RMP), infrared spectrometry and XRD analysis. These techniques show that at low and room temperatures the unaltered transparent opals may be transformed into destabilized white opals, which are a mixture of different polymorphs of tridymite and alpha-cristobalite with various degrees of crystallinity. We found systematic changes in frequencies of both the Raman and the infrared bands, caused by increasing regularities of bond-lengths and bond-angles Si-O-Si groups under the effect of stability. Micro-Raman spectrometry confirms that in the destabilized opal the principal mineral phases are MC (monoclinic ordered)- and MX (incommensurate monoclinic)-tridymites that are characterized by more structural order in comparison with other structural modification of this phase in unaltered opal (POn pseudo-orthorhombic disordered tridymite). XRD investigations show that in the sequence from unaltered to destabilized opal the position of principal maximum (4.30, 4.10 and 2.50 A) shifts towards higher d-spacing. This XRD shifting to higher d-spacing can largely be explained by an increasing amount of tridymite stacking and unresolved superposition of cristobalite and tridymite reflections. The destabilization phenomena in volcanic opals is due to the structural ordering/disordering that is characterized mainly by the formation of the different tridymite polymorphs (MC and MX) in the destabilized opal-CT as well as the decreasing content of molecular water in the structure.     

TMA and SEM characterization of the thermal dehydration of australian sedimentary opal

The dehydration of samples of a Coober Pedy, South Australian sedimentary white opal, displaying play of colour, was investigated using TMA by heating the samples of the specimen to a range of temperatures between room temperature and 1000 at 200°C intervals followed by cooling to room temperature. Etched fracture surfaces of the samples were then examined using SEM. The samples showed the typical expansion at low temperature up to 210°C before contraction was observed. The contraction of the opals was ascribed to both sintering, supported by morphological change observed in the SEM micrographs, and dehydroxylation of the silanol groups producing silicon-oxygen-silicon bridges resulting in a more dense silica network.     

Fabrication and characterization of cerium-doped barium titanate inverse opal by sol-gel method

Cerium-doped barium titanate inverted opal was synthesized from barium acetate contained cerous acetate and tetrabutyl titanate in the interstitial spaces of a polystyrene (PS) opal. This procedure involves infiltration of precursors into the interstices of the PS opal template followed by hydrolytic polycondensation of the precursors to amorphous barium titanate and removal of the PS opal by calcination. The morphologies of opal and inverse opal were characterized by scanning electron microscope (SEM). The pores were characterized by mercury intrusion porosimetry (MIP). X-ray photoelectron spectroscopy (XPS) investigation showed the doping structure of cerium, barium and titanium. And powder X-ray diffraction allows one to observe the influence of doping degree on the grain size. The lattice parameters, crystal size and lattice strain were calculated by the Rietveld refinement method. The synthesis of cerium-doped barium titanate inverted opals provides an opportunity to electrically and optically engineer the photonic band structure and the possibility of developing tunable three-dimensional photonic crystal devices.     

Nanostructured polymer gels

A brief review of our recent work on polymer gel opals is given in memory of late Professor Tanaka. The central idea is to first synthesize monodisperse polymer gel nanoparticles, then self-assemble them into a 3D network, and eventually covalently bond them. The covalent bonding contributes to the structural stability, while self-assembly provides them with crystal structures that diffract light, resulting in colors. N-isopropylacrylamide (NIPA) gel has been used as a model system for this study. The nanostructured NIPA gel, which contain up to 97 wt% water, displays a striking iridescence like precious opal but are soft and flexible like gelatin.     

Preparation and characterization of Pb<Subscript>0.56</Subscript>Sr<Subscript>0.44</Subscript>Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>O<Subscript>3</Subscript> inverse opal

Pb_0.56Sr_0.44Zr_0.52Ti_0.48O₃ (PSZT) inverse opal photonic crystals (PCs) have been synthesized by a process of self-assembly in combination with a sol–gel procedure. PSZT inverse opals show pure perovskite structure with good orders in three dimensions. The evident photonic band gaps have been observed in the transmittance spectra with a blue-shift phenomenon due to the decrease of opal template periods. PSZT inverse opals also exhibit the reflection peaks in basic agreement with the calculated results. This three-dimensional (3D) ordered PSZT inverse opals have shown interesting optical characteristics and potential applications in optoelectronic and photonic devices.     

From planar defect in opal to planar defect in inverse opal

We demonstrate a facile method of fabricating opal and inverse opal structures with a planar defect. A single layer of silica beads was embedded into polystyrene opals by combining an inward-growing self-assembly method with spin-coating technique. After the infiltration of silica followed by the removal of the polystyrene beads by calcination, an inverted structure was obtained. The silica beads were connected together by the infiltrated silica, thus a solid silica phase with the silica beads as a planar defect embedded in the inverse silica opal was obtained. The thickness of the defect layer can be adjusted by changing the size of the silica beads. Scanning electron microscope images showed the good quality of the crystal and the uniformity of the defect layer. Optical transmission spectra indicated the existence of a defect state induced by the defect layer in both the opal and inverse opal structures. High-cost techniques such as lithography and chemical vapor deposition are not involved in the fabrication of inverse opals with planar defects.     

三维SiO2欧泊模板溶剂热法制备硫化锌光子晶体

以单分散二氧化硅微球在重力场下自组装得到的三维有序欧泊(opal)为模板，采用溶剂热法在模板空隙内生长ZnS晶体，从而制备高质量的硫化锌基光子晶体. 通过X射线衍射(XRD)和Raman光谱证明ZnS晶体为闪锌矿结构且晶体质量较好，并对其生长机理进行了讨论. 通过场发射扫描电子显微镜(FESEM)和紫外-可见分光光度计对所合成的ZnS/opal复合物与ZnS反欧泊结构进行了表征，结果表明两种结构都保持了欧泊三维有序性，并且在Г-L方向(垂直于(111)方向)上出现了布拉格衍射峰，说明其具有良好的光子晶体特性.     

Phase transitions of octamethylcyclotetrasiloxane confined inside aluminosilicate and silicate nanoporous matrices

We report the melting behaviour of a dipolar cyclic siloxane liquid: octamethylcyclotetrasiloxane (OMCTS) confined in three mesoporous silica matrices: Al-SBA-15, SBA-15 and CPG glasses, using differential scanning calorimetry and dielectric spectroscopy. We investigate the influence of acid sites on the adsorptive properties of mesoporous silica materials, which were synthesized by applying Pluronic-type polymers as pore-creating agents. Aluminosilicate matrices have been synthesized by direct synthesis procedure using aluminium chloride. These materials characterized by N₂ sorption measurements, and the small-angle X-ray scattering data exhibit the same hexagonal P6 mm structure with a mean mesopores size of 4.6 nm (Al-SBA-15) and 4.9 nm (SBA-15). The controlled pore glasses used in this experiment have pores of mean diameter of 7.5 nm. For all systems studied, the OMCTS melting point in pores has been found to decrease with decreasing pore diameter. This result is in qualitative agreement with that obtained in molecular simulation where the adsorbate-wall interactions are weak compared to the adsorbate–adsorbate interactions.     

Mesoporous titania photocatalyst: effect of relative humidity and aging on the preparation of mesoporous titania and on its photocatalytic activity performance

Mesoporous TiO₂ has been synthesized by the sol–gel method, using a nonionic triblock copolymer P123 as surfactant template under acidic conditions. The as-prepared samples were characterized by thermogravimetry–differential thermal analysis (TG–DTA), nitrogen absorption–desorption (BET), field emission scanning electron microscopy, and transmission electron microscopy. The photocatalytic activity of the mesoporous TiO₂ was evaluated by degradation of methylene blue under high-intensity UV light irradiation; the amount of methylene blue was measured by UV–visible spectroscopy. TG–DTA analysis revealed that the surfactant had been removed partly in as-synthesized samples. BET analysis proved that all the samples retained mesoporosity with a narrow pore-size distribution (4.5–6.3 nm) and high surface area (103–200 m²/g). All calcined mesoporous TiO₂ had high photocatalytic activity in the photodegradation of methylene blue.     

Effect of disorder on the optically amplified photocatalytic efficiency of titania inverse opals

Optically amplified photochemistry with slow photons has been realized in our previous work when a photoactive material such as TiO(2) was molded into a photonic crystal and the corresponding energy of photonic bands overlapped with the electronic excitation. While numerous applications of photonic crystals have been proposed, the real practicality depends on the extent of structural imperfection that can be tolerated before significant deterioration in the optical response deems it unrealistic to use. As a result, it is important to evaluate the amount of structural disorder that can be tolerated in inverse TiO(2) opals if they are to be used as amplified photocatalysts for photolytic degradation of organics in environmental remediation and water purification. We present a systematic study on the effect of disorder with relation to the photocatalytic efficiency of oxidizing methylene blue dye adsorbed on inverse TiO(2) opals by introducing different fractions and sizes of guest spheres into the opal template. Our results show that half of the enhancement originally achieved by the inverse opal made from monodispersed 150-nm spheres is conserved when the domain size of the host spheres remains above a critical threshold. The substitution fraction can be as high as 0.4 when the guest spheres are 1.2 times larger than the host spheres. Such a high tolerance to structural disorder provides strong support for the potential use of inverse TiO(2) opals in environmental cleanup and water treatment applications.     

Chemically modified opals as thin permselective nanoporous membranes

Thin-film opals comprising three layers of 440 nm diameter SiO2 spheres were assembled on Pt electrodes and modified with amino groups on the silica surface. Diffusion of anionic, cationic, and neutral redox species through the opals was studied by cyclic voltammetry. The chemically modified opal membranes demonstrate high molecular throughput and, at low pH, selectively block transport of a cationic redox species relative to that of anionic and neutral redox species. This permselective behavior is attributed to the electrostatic interactions that are enhanced by the tortuous pathway within the opal and by the high surface area of the chemically modified spheres.     

Trace elements in coloured opals using neutron activation analysis

Neutron activation analysis was used to determine the concentration of trace elements in 50 samples of orange, yellow, honey, green, blue and pink opals as well as 18 samples of colourless opals taken from a number of recognised fields in Australia, Peru, Mexico and USA. The results were evaluated to determine the relationship between trace element content and opal colour.     

Process optimization of sol–gel derived colloidal photonic crystals

Three-dimensional photonic bandgap structures have been synthesized by a colloidal/sol–gel route, starting with the self-organization of polystyrene microspheres into opals by dip-coating, sedimentation or vertical convective self-assembly, followed by sol–gel infiltration of the interstices with silica, titania or a silica-titania mixture, by dip-coating and removal of the polymeric template. The structural and optical properties of the opals and inverse opals prepared by this method have been studied by scanning electron microscopy and visible infra-red spectroscopies to assess the relationship between their structure and the photonic properties obtained. The optical transmission and reflection spectra of the opal and inverse opal structures have also been simulated by the Translight Software code, using the Transfer Matrix method, for different numbers of stacked layers, showing reasonable agreement with the experimental results. By optimizing the fabrication parameters, colloidal photonic crystals of good quality have been obtained, with reduced defect concentrations and increased mechanical strength.     

Diffusion of n-alkanes in mesoporous 5A zeolites by ZLC method

Diffusion properties of mesostructured zeolite 5A were investigated by employing n-alkanes as probe molecules using the zero length column (ZLC) method. The mesopores were found to enhance molecule diffusion. Moreover, the effective diffusion time constant (D _eff/R ²) increased with mesoporosity in the zeolites between 308 K and 393 K, whereas the activation energy decreased with increasing mesopore volume. The effective diffusivity values of n-alkanes in mesoporous zeolite 5A were generally higher than that the microporous zeolite 5A sample. This clearly implied the important role of the mesopore in zeolites crystals in facilitating the transport of reaction molecules due to shorter average diffusion path length and less steric hindrance.     

Three regimes of water adsorption in annealed silica opals and optical assessment

Physisorbed and structurally bound (surface and internal) water in silica opals are distinguished and quantified by thermogravimetry. By controlled dehydroxylation with thermal annealing, we correlate these forms of water with the silica chemistry. In particular, we find that the silica capability to physically adsorb water from ambient moisture exhibits three regimes, associated with the distinct condensation behavior of bonded and unbonded surface silanols. Features in both opal IR absorbance and photonic band gap reproduce the physisorbed water regimes. This allows direct assessment of the water content and its evolution just by routine optical spectroscopy, being a useful tool for local and nondestructive analysis of colloidal silica. Besides, this provides a simple recipe for accurate tuning of the opal photonic band gap (about 10% in position and width) by just selecting the annealing temperature.     

Bound water restrained by nanocellulose fibres

The higher-order structure of natural cellulose fibres changes in the presence of water. In order to investigate the effect of molecular level fibre structure, melting behaviour of water restrained by nano- and microcellulose fibre was measured by differential scanning calorimetry. Fibre size was measured by scanning electron microscopy and atomic force microscopy. It was found that the melting peak of water restrained by microcellulose fibre started at 250–260 K in a W _c (=mass of water/mass of dry sample) range from 0.5 to 1.2, whereas that of nanocellulose fibre was 230–237 K. Furthermore, peak temperature of melting of water restrained by nanocellulose was observed at around 270 K, in contrast, that of water restrained by microcellulose fibre was observed at ca. 275 K. Bound water content was calculated from melting enthalpy. Both non-freezing and freezing bound water of nanocellulose fibre was far larger than that of microcellulose. The above results suggest that a large amount of freezing bound water is restrained in nanocellulose fibres. It is thought that a larger number of isolated hydroxyl groups exist on the fibre surface.     

Functional Opals from Reactive Polymers: Complex Structures,Sensors, and Modified Photoluminescence

Summary: This paper describes the synthesis and properties of functional opal structures, so-called colloidal photonic crystals (CPCs), from a variety of reactive polymers. Photoprocessable opals are presented as well as opals with incorporated “smart” defect layers that can be actively addressed by external stimuli. In addition, opals with functional bio-macromolecular defects have been developed. They present a new class of materials for optical biomonitoring through shifts of the induced photonic defect mode. Strong modification of photoluminescence according to the photonic bandstructure is observed from opals with embedded exclusively luminescent defect layer.     

Post‐Deposition Opal Evolution

The formation of artificial opal films consists of wet opal deposition, drying, and possible transformations in the dry state. The processes after deposition, before the crystals lattice reaches its final equilibrium state, are studied herein. We follow the time evolution of the optical transmission spectra for polystyrene opals with different thicknesses. The evolution of the spectra shows pronounced changes in the Bragg peak position, width and height, as well as changes in the background and, in the beginning of the process, a band related to residual water in the sample. Therefore, a wet and a dry phase can be distinguished in the opal transformations. They are all connected to shrinkage and we associate one of them with a possible new sintering mechanism.     

Integration of self-assembled three-dimensional photonic crystals onto structured silicon wafers

We report on the fabrication of high-quality opaline photonic crystals from large silica spheres (diameter of 890 nm), self-assembled in hydrophilic trenches of silicon wafers by using a novel technique coined a combination of "lifting and stirring". The achievements reported here comprise a spatial selectivity of opal crystallization without special treatment of the wafer surface, a filling of the trenches up to the top, leading to a spatially uniform film thickness, particularly an absence of cracks within the size of the trenches, and finally a good 3D order of the opal lattice even in trenches with a complex confined geometry, verified using optical measurements. The opal lattice was found to match the pattern precisely in width as well as depth, providing an important step toward applications of opals in integrated optics.