圆柱形蛋白石和反蛋白石结构光子晶体的制备及其光学性质

研究了在圆柱曲面基底上自组装空心和实心的圆柱形蛋白石和反蛋白石结构光子晶体的方法. 用垂直沉积法在不同曲率半径的毛细管内自组装了空心圆柱形聚苯乙烯(PS)蛋白石结构光子晶体薄膜和二氧化硅 (SiO₂) 反蛋白石结构薄膜; 用类重力沉积法制得实心圆柱形蛋白石和反蛋白石结构光子晶体, 并讨论了这一生长方式中的状态变化过程及影响因素. 用扫描电子显微镜对样品内部结构进行了表征, 用光谱仪测试了光子晶体薄膜的反射光谱, 结果表明: 基底曲率半径和微球粒径的大小是影响空心蛋白石和反蛋白石薄膜质量的主要因素; 微球大小是影响实心结构有序性的主要因素. 关键词： 反蛋白石 空心圆柱 溶胶凝胶协同自组装     

Temperature dependences of the order parameter for sodium nitrite embedded into porous glasses and opals

The temperature dependences of the order parameter η(T) for sodium nitrite NaNO₂ embedded in porous glasses with average pore diameters of 320 and 20 nm, as well as in artificial opals, have been investigated. It has been demonstrated that the dependence η(T) for sodium nitrite in the porous glass almost coincides with that for the bulk material, whereas this dependence for NaNO₂ in opals differs substantially from that observed in the bulk material and from those previously determined for sodium nitrite in porous glasses with average pore diameters of 3 and 7 nm. It has been revealed that the dependence of the order parameter for sodium nitrite in opals exhibits a temperature hysteresis (approximately equal to 8 K). The temperature dependence η(T) has been described using a simple model, which takes into account the nanopore diameter distribution existing in artificial opals.     

Size effects upon phase transitions in vanadium oxide nanocomposites

A phenomenological model has been proposed for the formation of the major thermal hysteresis loop of optical parameters upon the semiconductor-metal phase transition in vanadium oxide nanocomposites. It has been demonstrated that the effects associated with the influence of nanocrystallite sizes on the phase transition temperature in an individual nanocrystallite, which is determined by the width of the elementary hysteresis loop and the position of the phase equilibrium temperature on the temperature scale, manifest themselves in the form of pronounced features in the loop shape. In particular, the size effects for VO₂ polycrystalline films are observed in the formation of a trapezoidal shape of the optical thermal hysteresis loop with a wide lower base, whereas these effects for nanocomposites based on porous glasses with VO₂ nanocrystals are revealed in the form of the optical hysteresis loop with a narrow lower base (wide upper base). The proposed model also explains the symmetric shape of the major hysteresis loop for vanadium oxide nanocomposites based on opals. The size effects in opal nanocomposites with strictly fixed sizes of pores and, therefore, nanocrystallite sizes manifest themselves in the form of well-defined steps in the heating and cooling branches of the major hysteresis loop.     

Optical characterization of natural and synthetic opals by Bragg reflection spectroscopy

The Bragg reflection of light from natural and synthetic opals was studied experimentally, and the samples were characterized by atomic-force microscopy. The reflection spectra were theoretically calculated within the model of a planar, periodically layered medium. A comparison of the experimental and calculated data made it possible to determine the parameters of the crystal structure of synthetic opals (lattice constants and sintering coefficients of a-SiO₂ particles). It was concluded that the pores in the structure of natural opals are filled by a material with a refractive index close to that of a-SiO₂.     

Determination of the real structure of artificial and natural opals on the basis of three-dimensional reconstructions of reciprocal space

The distribution of the scattering intensity in the reciprocal space for natural and artificial opals has been reconstructed from a set of small-angle X-ray diffraction patterns. The resulting three-dimensional intensity maps are used to analyze the defect structure of opals. The structure of artificial opals can be satisfactorily described in the Wilson probability model with the prevalence of layers in the fcc environment. The diffraction patterns observed for a natural opal confirm the presence of sufficiently long unequally occupied fcc domains.     

非密堆积TiO2空心微球光子晶体的制备与能带分析

利用胶体自组装、高温烧结和HF酸刻蚀技术,制备了SiO₂微球非密堆积面心立方(FCC)结构的胶体晶体,并以此为模板,利用溶胶凝胶方法和NaOH湿法刻蚀技术制备了TiO₂空心微球非密堆积FCC结构光子晶体.利用电子显微镜分析了晶体的结构,用平面波展开法对该结构进行了能带计算与分析.计算结果表明,制备的TiO₂空心微球非密堆积FCC结构光子晶体在低能区的第二、第三能带之间除布里渊区的W点仍保持简并外,其余各点简并都已经消除. 关键词： 空心微球 非密堆积 光子晶体 光子带隙     

High Miller-index photonic bands in synthetic opals

We present a detailed study of high Miller-index (h k l) photonic bands in a-SiO₂ synthetic opals. Polarized light transmission spectra of opals were studied in a wide wavelength range for all high symmetry directions on the Brillouin zone (BZ) in the face-centered cubic (fcc) lattice. It is shown that under the conditions of low dielectric contrast the dispersion of high Miller-index photonic bands is described well by the calculated dependences of Bragg wavelengths diffracted from the (h k l) crystallographic planes of the fcc lattice.     

Modelling of 3D photonic crystals based on opals

The construction of 3D photonic crystals with gaps in the visible or the near-infrared frequency range requires engineering of complex microstructures which are very difficult to realize by etching and micro-fabrication. Consequently, self-ordered systems such as synthetic opals are very promising. Synthetic bare opals are constituted by SiO₂ spheres that organize themselves by a sedimentation process in a face centered cubic (fcc) arrangement. Using the plane wave method, we examine the photonic band structures of close-packed opal-based photonic crystals with an SiO₂ (n = 1.5) matrix. The incomplete photonic band gaps at the X- and L-points have been studied which correspond to normally incident plane waves onto the (100) and (111) crystal planes. With the transfer matrix method, we model the transmission properties. We find that the incomplete gap at the L-point fully inhibits the transmission of waves propagating in the [111] direction for opal sample thicknesses that are easily obtainable. This property shows that bare opals could be good candidates for complete inhibition of transmission in the near-infrared and visible frequency range for given orientations.     

Optical characterization of synthetic opals

The results of a structural-optical characterization of synthetic opals are presented. Information on the growth-induced features of the opal structure was derived from an analysis of the position and width of the one-dimensional photonic band gap. The structure of the samples was found to vary substantially along the growth axis coinciding with the [111] direction of the fcc lattice. It was shown that the regions corresponding to early stages in the opal structure growth are typically strongly disordered, which manifests itself, in particular, in the crystallites being misoriented relative to the sample growth axis. It was concluded that the regions of synthetic opals most suitable for application as photonic crystals are those corresponding to later growth stages.     

Photoluminescence properties of bare and ZnO infilled artificial opal

Photoluminescence of bare and ZnO infilled artificial opals was investigated. A presence of a photonic band gap results in distortion of the photoluminescence spectra of both the bare and ZnO infilled opal nanocomposite. Filling of the opal with ZnO resulted in a shift of the Bragg diffraction peak from 430 to 460 nm. The emission from ZnO infilled opal contains no UV photoluminescence from ZnO nanocrystals, while the ZnO nanocrystals deposited on substrate by the same method exhibit strong excitonic UV emission. Although a high temperature treatment in ambient air results in an increase in the photoluminescence intensity of the ZnO nanocrystals, the quenched behavior of the excitonic emission from ZnO nanocrystals embedded in the opal matrix remains. A domination of the artificial opal matrix intrinsic emission in the photoluminescence spectra from the untreated as well as heat treated ZnO filled opal nanocomposites is observed.     

Multiple Bragg diffraction in low-contrast photonic crystals based on synthetic opals

The phenomenon of multiple Bragg diffraction in low-contrast photonic crystals based on synthetic opals has been studied both experimentally and theoretically. The transmission and reflection spectra of opal films near the K point of the Brillouin zone of the face-centered cubic lattice in s-polarization exhibit the effect of anticrossing of dispersion curves corresponding to the (111) and ([`1]11)(\bar 111) photonic stop bands. The effect of quasi-Brewster suppression of stop bands is clearly pronounced in p-polarization. The experimental data are analyzed using the calculation of the band structure of opal with the inclusion of the polarization of incident light.     

Ultrasmall-angle X-ray scattering analysis of photonic crystal structure

The results of an ultrasmall-angle X-ray scattering study of iron(III) oxide inverse opal thin films are presented. The photonic crystals examined are shown to have fcc structure with amount of stacking faults varying among the samples. The method used in this study makes it possible to easily distinguish between samples with predominantly twinned fcc structure and nearly perfect fcc stacking. The difference observed between samples fabricated under identical conditions is attributed to random layer stacking in the self-assembled colloidal crystals used as templates for fabricating the inverse opals. The present method provides a versatile tool for analyzing photonic crystal structure in studies of inverse opals made of various materials, colloidal crystals, and three-dimensional photonic crystals of other types.     

Effect of Compatibilizer Content on the Shear and Extensional Rheology of Polypropylene/Clay Nanocomposites

The shear and extensional rheology of polypropylene (PP)/organoclay nanocomposites in the presence of various maleic anhydride grafted polypropylene (PP-g-MA) compatibilizer concentrations were investigated. The PP nanocomposites were prepared via direct melt intercalation in an internal mixer. The structures of the nanocomposites were characterized by X-ray diffraction (XRD) and scanning electron microscopy. It was found that both the compatibilized and uncompatibilized nanocomposites could form an intercalated structure. However, the organoclay particles can disperse well only in the compatibilized systems. The linear viscoelastic properties, including the storage modulus G′ and complex viscosity η* were very sensitive to the microstructure of the nanocomposites. The extensional viscosities of PP nanocomposites were enhanced under a low deformation rate with increasing compatibilizer content and displayed a lack of superposition for different strain rates. It was proposed that the lack of superposition might originate from the formation of a three-dimensional organoclay network, which decreased in its complexity and strength as the deformation rate increased.     

Synthesis and Characterization of Novel Poly(1‐Naphthylamine)‐Montmorillonite Nanocomposites Intercalated by Emulsion Polymerization

Nanocomposites of montmorillonite (MMT) with poly(1‐naphthylamine) (PNA) is investigated for the first time by emulsion polymerization using three different oxidants. Polymerization of PNA was confirmed by Fourier transformation infrared (FT‐IR) as well as UV‐visible spectra. The in situ intercalative polymerization of PNA within MMT layers was confirmed by FT‐IR, X‐ray diffraction, conductivity; scanning electron microscopy (SEM) as well as transmission electron microscopy studies. X‐ray diffraction revealed intercalated as well as exfoliated structures of PNA/MMT nanocomposites, which were compared with the reported polyaniline‐MMT nanocomposites. It was found that the increase in the concentration of PNA in the interlayer galleries of MMT led to destruction of the layered clay structure resulting in exfoliation of the nanocomposite. Conductivity of the nanocomposites was found to be in the range of 10^?3 to 10^?2 S cm^?1 which was found to be higher than the ones reported for polyaniline‐clay nanocomposites as well as PEOA‐OMMT nanocomposites at similar concentrations of intercalated species. The morphology of PNA/MMT nanocomposites was found to be governed by the nature of the oxidant used.     

Effects of Modifier Concentration on Structure and Viscoelastic Properties of Copolyester/Clay Nanocomposites

Abstract

Poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate)(PETG)/clay nanocomposites were prepared via melt intercalation technique. The effects of concentration of the organic modifier in the clay on the properties of the nanocomposites were studied. Three clays modified using the same alkyl ammonium modifier, but differing in modifier concentration, are used for this purpose. The nanocomposites are characterized using wide‐angle x‐ray diffraction for their structure. Dynamic mechanical analysis of these nanocomposites is also studied to investigate their viscoelastic behaviors. The x‐ray diffraction study shows an increase in the interlayer spacing of organically modified clays as compared to that of Na⁺ clay. The extent of increase in the interlayer spacing is dependent on the concentration of organic modifier used to modify the montmorillonite. The presence of well‐defined diffraction peaks and the observed increase in the interlayer spacing in the nanocomposites imply the formation of an intercalated hybrid. Dynamic mechanical properties show an increase in the storage modulus of the nanocomposite over the entire temperature range studied, as compared to the pristine polymer. Investigation of the rubbery plateau modulus confirms the reinforcing effect of organically modified clay. The observed enhancement in the modulus was greater for the clay with the lowest content of the organic modifier. These results indicate that in nanocomposites, apart from the compatibility of the organic modifier with the polymer, its concentration in the interlayer also plays a critical role in the structure development and thus in the enhancement of the properties. The nanocomposites showed reduced damping, which was governed by the modifier concentration in the clay.     

Spectroscopy of stop bands in artificial opals filled with an alcohol solution of potassium iodide

The spectral position of the stop bands in photonic crystals based on artificial opals filled with an alcohol solution of potassium iodide is investigated. The energy-band structure of samples with quartz globules 230 nm in diameter is modeled based on the dispersion equation. The spectral position of the stop bands in the [111] direction at different solution concentrations is determined. The conditions for forbidden-band ??collapse?? are established. The possibility of applying artificial opals in optical cavities of lasers of different types is analyzed.     

Specific features in the thermal conductivity of synthetic opals

Data on the thermal conductivity ϰ _ph of the cluster lattice of synthetic opals are analyzed. All opals are divided into two groups according to the temperature dependence of their ϰ _ph. These are opals-1, whose thermal conductivity behaves like ϰ _ph(T) of quasi-crystalline materials, and opals-2, with a ϰ _ph(T) dependence typical of classical amorphous solids. Possible reasons for this difference are considered. An attempt is made to explain the complex temperature hysteresis in ϰ _ph(T) observed earlier in opals-2. Fiz. Tverd. Tela (St. Petersburg) 39, 392–398 (February 1997)     

Effect of sodium alginate modification of graphene (by ‘anion-π’ type of interaction) on the mechanical and thermal properties of polyvinyl alcohol (PVA) nanocomposites

Layered aligned dispersion of graphene in graphene/polyvinyl alcohol (PVA) nanocomposites is prepared in the form of films through simple solution processing route. The results indicate that there exist an interfacial interaction between PVA and graphene because of hydrogen bonding. This is responsible for the change in structure of PVA (such as decrease in the level of crystallization) and exhibiting ductile PVA nanocomposite film with improved tensile modulus, tensile strength, and thermal stability. Moreover, to improve the mechanical properties of PVA nanocomposites, graphene is successfully modified using a non-covalent modifier, sodium alginate (SA) and there exist an ‘anion-π’ type of interaction in between SA and graphene. The modification results in finer dispersion of the graphene in PVA/SA-m-graphene nanocomposites. In addition, there exist a hydrogen bonding in between PVA and SA. This has resulted in the remarkable improvement in mechanical properties of PVA/SA-m-graphene nanocomposites as compared to pure PVA and PVA/graphene nanocomposites. The increase in mechanical properties of PVA/SA-m-graphene nanocomposites is achieved through better load transfer from graphene to polymer matrix, despite decrease in crystallinity of PVA. Improvement in tensile modulus and tensile strength is highest at 0.5 wt.% of SA-modified graphene in PVA/SA-m-graphene nanocomposites because of finer dispersion of graphene and is 62 and 40% higher than that of pure PVA. Addition of SA-modified graphene also improves the thermal stability of PVA/SA-m-graphene nanocomposites remarkably as compared to unmodified graphene PVA nanocomposites.     

Epoxy/Silica Nanohybrids or Nanocomposites: Atomic Force Microscopy and X-ray Photoelectron Spectroscopy Investigation of the Processing–Structure–Property Relationships

The structural and morphological features influencing the glass transition temperature of epoxy/silica nanohybrid and nanocomposite materials containing 25–30 phr of nanoscale silica phases are discussed in this letter to answer the questions related to the processing–structure–property relationships. X-ray photoelectron spectroscopy and atomic force microscopy are used to study the surface chemical structure and morphology of epoxy/silica nanohybrids and nanocomposites. Nanohybrids are synthesized via in situ sol-gel process, while the respective nanocomposites are prepared by mechanical blending of preformed silica nanoparticles into epoxy resin. Differential scanning calorimetry is used to determine glass transition temperature of different materials. The surface analytical characterizations reveal that in situ sol-gel process is more suitable for producing organic–inorganic hybrid materials with superior glass transition temperature owing to the achievement of stronger interfacial compatibility and greater crosslink density. A number of other factors affecting glass transition temperature are explored and discussed with reference to surface chemistry, microstructure, and morphology of epoxy/silica nanohybrids and nanocomposites, respectively.     

One-dimensional opal photonic crystals

One-dimensional opals are 1D self-assembled close packed colloidal crystals consisting of monodisperse colloidal globules. Polystyrene globules with sizes in the 1.9–10 μm range sit on a flat substrate and touch two neighbors in diametrally opposite contact points. These opals are quasi-1D photonic crystals. Optical modes, including whispering gallery modes of individual globules, coupled collective modes, and nanojet-induced modes, are visualized in 1D opals.