Synthesis and photochemical properties of zinc–aluminum layered double hydroxide/organic UV ray absorbing molecule/silica nanocomposites

Organic ultraviolet (UV) ray absorbents have been used as sunscreen materials, but may pose a safety problem when used at high concentration. In order to prevent direct contact of organic UV ray absorbent to the human skin several organic UV absorbents such as 4-hydroxy-3-methoxybenzoic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 4-hydroxy-3-methoxycinnamic acid, 4,4′-diaminostilbene-2,2′-disulfonic acid, p-aminobenzoic acid and urocanic acid were intercalated into Zn₂Al layered double hydroxides (Zn₂Al-LDHs) by anion-exchange and/or co-precipitation reaction. Thereafter, the obtained nanocomposites were coated with amorphous silica. Significant amounts (20–40 mass%) of organic UV absorbers were intercalated as univalent and/or divalent anions. The UV ray absorption ability of the organic UV absorbents increased and their catalytic activity for the air oxidation of castor oil greatly decreased when they were intercalated into the interlayer spaces of the Zn₂Al-LDHs. The deintercalation of organic molecules from LDHs by the anion exchange reaction with carbonate ion could be greatly depressed by coating the nanocomposite powder with amorphous silica.     

Benzisoxazole 2‐oxides as novel UV absorbers and photooxidation inhibitors

Compounds with strong absorptions in the ultraviolet (UV) region of the spectrum, particularly the UVA and UVB, have seen much interest as UV screeners or absorbers in a wide variety of commercial products. A series of benzisoxazole 2‐oxides have been synthesized and characterized by UV–vis spectroscopy. A number of derivatives have been shown to posses moderate to strong molar absorption coefficients in the UVB range (ca. 300 nm), the strongest being those derived from benzophenones. Three other derivatives containing additional electron withdrawing groups showed strong molar absorption coefficients in the UVA (ca. 340 nm). Solvent effects on the parent derivatives show changes in the molar absorption coefficients with little changes in the λ_max values. Preliminary studies of these compounds as potential additives to prevent photooxidation of polystyrene showed considerable inhibition of polymer degradation with the parent unsubstituted benzisoxazole 2‐oxide compounds being the most effective. Copyright © 2013 John Wiley & Sons, Ltd.     

ZnO:CeO2-based nanopowders with low catalytic activity as UV absorbers

Ultrafine systems of zinc oxide and cerium oxide for use as ultraviolet filter were synthesized by a non-alkoxide sol–gel process at different temperatures, to obtain solid materials (40 and 70 °C), that were characterized by X-ray diffraction, scanning electron microscopy, UV–vis reflectance. Their catalytic and photocatalytic activities were also evaluated. ZnO:CeO₂ systems present higher UV absorption and transparency in the visible region. The photocatalytic activity of ZnO:CeO₂ systems for the oxidation of organic materials is much smaller than that of titania, ceria and zinc oxide, suggesting that ZnO:CeO₂ systems are promising candidates for use as optical materials in UV-filters.     

The general linear theory of dynamic vibration absorbers

It is shown that vibrations of an elastic platform, induced by an external force \(f\left( t \right) = \sum\limits_{j = 0}^n {{A_j}} \sin \left( {{\omega _j}t + {\varphi _j}} \right)\), can be suppressed using n dynamic vibration absorbers with eigenfrequencies ω _j .     

Synthesis and coating methods of biocompatible iron oxide/gold nanoparticle and nanocomposite for biomedical applications

This detailed review presents an overview of current research on the synthesis, surface modification, and applications of Iron oxide (Fe₃O₄) nanoparticles and iron oxide/gold (Fe₃O₄/Au) nanocomposites. The different synthesis techniques of Fe₃O₄ with various basic organic and inorganic modifications are presented. The applicability and role of inorganic and organic coating on iron oxide/gold core/shell schemes were explored. The trade-off between choices for surface functionalization related to specific applications such as imaging contrast agent, drug delivery carrier and therapeutic device using iron oxide/gold core/shell was also elaborated. The versatility of combining iron oxide/ and gold as nanocomposite as the choice for biomedical application is demonstrated in MRI, CT scan, drug delivery, biosensors, and hyperthermia application.     

Evaluation of nanoparticle emission for TiO<Subscript>2</Subscript> nanopowder coating materials

In this study, nanoparticle emission of TiO₂ nanopowder coated on different substrates including wood, polymer, and tile, was evaluated in a simulation box and measured with a Scanning Mobility Particle Sizer (SMPS) for the first time. The coating process for the substrate followed the instructions given by the supply company. In the simulation box, UV light, a fan, and a rubber knife were used to simulate the sun light, wind, and human contacting conditions. Among the three selected substrates, tile coated with TiO₂ nanopowder was found to have the highest particle emission (22 #/cm³ at 55 nm) due to nanopowder separation during the simulation process. The UV light was shown to increase the release of particle below 200 nm from TiO₂ nanopowder coating materials. The results show that, under the conditions of UV lamps, a fan and scraping motion, particle number concentration or average emission rate decreases significantly after 60 and 90 min for TiO₂/polymer and TiO₂/wood, respectively. However, the emission rate continued to increase after 2 h of testing for TiO₂/tile. It is suggested that nanoparticle emission evaluation is necessary for products with nanopowder coating.     

UV plasmonic-based sensing properties of aluminum nanoconcave arrays

For several decades the plasmonic behavior of materials has been almost exclusively studied in visible region. Emerging applications require, however, the development of efficient materials operating in UV range. In UV nanoplasmonics aluminum (Al) can play a leading role due to its advantageous electronic properties. Yet, there is still lack of reproducible method to obtain Al nanostructures with desired parameters. Al nanoconcaves can provide a way to overcome these limitations. Here, two different periodicities of the Al nanoconcaves arrays were analyzed. It was observed that the Al concaves can dramatically reduce the optical reflectivity as compared to flat, unstructured Al. At the same time pronounced reflectivity dips were discernible, which were ascribed to (0,1) plasmonic mode. The positions of the dips were at around 250 nm and 350 nm for Al concaves with interpores distance (D_c) of 246.3 nm and 456.7 nm, respectively. The refractive index sensitivity (RIS) was: ∼191 nm/RIU for the Al concaves with D_c = 246.3 nm, and ∼291 nm/RIU for the Al nanoconcaves arrays with D_c = 456.7 nm.     

Intercalative route to heterostructured nanohybrids

We have successfully synthesized inorganic–inorganic, organic–inorganic and bio-inorganic nanohybrids by applying an intercalation technique systematically to layered titanate, molybdenum disulfide (MoS₂), Bi-based cuprate superconductors (Bi₂Sr₂Ca_m−1Cu_mO_y (m=1, 2, and 3; BSCCO)), and to layered double hydroxides (LDHs), those which are of high importance in terms of basic understanding of intercalation reactions and of their practical applications. The inorganic–inorganic systems such as TiO₂-pillared titanate, TiO₂-pillared MoS₂, and CdS–MoS₂ hybrids were synthesized by exfoliation–restacking method. A novel pillaring process using an osmotic swelling was developed to prepare TiO₂-pillared layered titanate with a large surface area, high thermal stability, and enhanced photocatalytic activity. And the intercalation of TiO₂ and/or CdS nanocluster into the two dimensional MoS₂ lattice could be also realized by exfoliating and reassembling the lithiated molybdenum disulfide (LiMoS₂) in the presence of cationic TiO₂ and/or CdS nanocluster in an aqueous solution, respectively, to obtain the semiconductor–semiconductor hybrids. On the other hands, the organic–inorganic hybrids were achieved via intercalative complexation of iodine intercalated BSCOO with organic salt of Py–C_nH_2n+1I (Py=pyridine). The high-T_c superconducting intercalate with its remarkable lattice expansion can be applied as a precursor for superconducting colloids when dispersed in an appropriate solvent. This superconducting hybrid material had an unique structural feature of a superconducting-insulating-superconducting multilayer with atomically clean interfaces. Especially, this organic–inorganic nanohybrid is expected to be a promising precursor for preparing the superconducting colloidal suspension, which could be applied to the fabrication of superconducting films or wires. Recently, we were very successful in demonstrating in which the formation of bio-inorganic hybrids stabilized in the interlayer space of LDH retain their chemical and biological integrity. If necessary, LDH, as a reservoir, can be intentionally removed by dissolving it in an acidic media in such a way the interlayer biomolecules can be recovered or the intercalated biomolecules can be released from the LDH via ion-exchange reaction in electrolyte. It is, therefore, concluded that the inorganic LDH can play a role as a gene reservoir or carrier for various unstable organic or bio-molecules such as drugs and genes.     

Accurate method for the measurement of absorption cross sections of solid-state saturable absorbers

A rigorous approach taking into account both the temporal and spatial distributions of the pulsed probe beam used for transmission measurements of solid-state saturable absorbers is applied to characterise these absorbers accurately. The use of this method can significantly influence the resulting value for the ground-state absorption cross section. It also permits us to avoid the introduction of an artificial excited-state absorption in systems where, according to energy-level diagrams, no such loss should occur. This is illustrated in the case of passive Q-switchers for 1.5-μm lasers such as Co²⁺-doped LaMgAl₁₁O₁₉ and MgAl₂O₄ and Co²⁺- or Cr²⁺-doped ZnSe and ZnS. Received: 21 November 2001 / Revised version: 22 January 2002 / Published online: 14 March 2002     

Preparation and Characterization of an Organic/Inorganic Composite Based on Ferrospinel with Poly(Methyl Methacrylate) and Polyaniline

A novel organic/inorganic composite based on LiNi–ferrospinel with poly(methyl methacrylate) (PMMA) and polyaniline (PANI), PANI/PMMA/LiNi_0.5Fe₂O₄ composite, was synthesized via a facile in-situ polymerization process. The structures of the resulting samples were investigated by X-ray diffraction, Fourier transform infrared spectroscopy, and atomic force microscopy. The optical and thermal properties of the PANI/PMMA/LiNi_0.5Fe₂O₄ composite were studied by fluorescent spectroscopy and thermogravimetry analysis. It was indicated that the existence of LiNi_0.5Fe₂O₄ (LFNO) in the PANI/PMMA/LFNO composite resulted in changes in the fluorescence spectra. The as-obtained composite may have potential for electrical and electromagnetic applications in antistatic materials, electromagnetic shields, radar absorbers, and so forth.     

Robust non-fragile dynamic vibration absorbers with uncertain factors

In this paper, the design problem for non-fragile dynamic vibration absorbers (DVAs) is investigated. Due to the imprecision of the manufacturing process or the variation during the operation, uncertainty in the parameters of the DVA is unavoidable. The uncertainty may degrade the performance of the designed DVA or even deteriorate the system. Hence, it is practically demanding to propose a design method for a non-fragile DVA, i.e., when the parameters of the DVA vary in an admissible range, an expected vibration suppression level should be guaranteed. The uncertainty of the DVA is feasibly assumed to be norm-bounded. Then, the design problem for the DVA is converted into a static output feedback (SOF) control problem. Sufficient condition for the existence of the non-fragile DVA with a prescribed H_∞ level is derived by using a bilinear matrix inequality (BMI). An iterative linear matrix inequality (ILMI) method is employed to solve the BMI condition. Finally, a design example is given to show the effectiveness of the proposed approach.     

Optimization and improvement of TIPS–pentacene transistors (OTFT) with UV–ozone and chemical treatments using an all-step solution process

We fabricated an organic thin-film transistor (OTFT) using an all-step solution process. The printed layers, in which the electrode (silver), dielectric layer (BaTiO₃–PMMA), source–drain layer, and semiconductor 6,13-Bis(triisopropylsilylethynyl)pentacene(TIPS–pentacene), were optimized using roll-to-roll, an inkjet printer, and drop-casting. After coating the source–drain layer, we applied ultraviolet (UV)–ozone and self-assembled monolayer (SAM) treatments to the composite layer. The OTFTs treated with the UV–ozone and SAM treatments were found to exhibit excellent performance and good properties in comparison to silicon-based OTFTs.     

A facile process to prepare copper oxide thin films as solar selective absorbers

Copper oxide thin films as solar selective absorbers were conveniently prepared by one-step chemical conversion method. X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis-NIR spectra and Fourier transform infrared (FTIR) spectra were employed to characterize the composition, structure and optical properties of thin films. The results indicated that the composition, structure and optical properties of thin films were greatly influenced by reaction temperature, time and concentration of NaOH. When reaction temperature was fixed at 40 °C, the as-prepared films consist of pure cubic Cu₂O. The surface morphology of thin films was changed from square-like structure (reaction time ≤ 25 min) to porous belt-like structure (reaction time ≥ 30 min) with the elongation of reaction time. While for thin films prepared at 60 °C and 80 °C, single Cu₂O was observed after 5 min reaction. When reaction time is longer than 5 min, CuO appears and the content of CuO is increasing with the elongation of reaction time. With the increase of reaction temperature, the belt-like structure was easily formed for 60 °C/10 min and 80 °C/5 min. Decreasing concentration of NaOH also could result in the formation of CuO and porous belt-like structure. Simultaneously, the film thickness is increasing with the increase of reaction time, temperature and concentration. Films containing CuO with belt-like structure exhibited high absorptance (>0.9), and the emissivity of films increased with elongation of reaction time. Combination of the composition, structure and optical properties, it can be deduced that the porous belt-like structure like as a light trap can greatly enhance absorbance (α), while the composition, thickness and roughness of thin films can greatly influence the emissivity (?). The highest photo-thermal conversion efficiency was up to 0.86 (α/? = 0.94/0.08) for thin films prepared at 80 °C/5 min, which proved that the CuO_x thin films can be served as high performance solar selective absorbers.     

Synthesis,crystal structure,spectroscopic characterization and optical properties of bis(4-acetylanilinium) tetrachlorocobalt (II)

The chemical preparation, crystal structure, spectroscopic investigations and optical features are given for a novel organic–inorganic hybrid material [C₈H₁₀NO]₂CoCl₄.The compound is crystallized in the orthorhombic space group Cmca, with the following unit cell parameters: a=19.461(2) Å, b=15.523(2) Å, c=13.7436(15) Å, and Z=8. The atomic arrangement shows an alternation of organic and inorganic layers along the b-axis. The cohesion between these entities is performed by N–H…Cl and N–H…O hydrogen bonds and π–π stacking interactions.Infrared and Raman spectra at room temperature are recorded in the 4000−400 and 4000−0 cm⁻¹ frequency regions, respectively and analyzed on the basis of literature data. This study confirms the presence of the organic cation [C₈H₁₀NO]⁺ and of the [CoCl₄]²⁻ anion. UV–vis spectroscopy results showed the indirect transition with band gap energy 2.98 eV.     

Micro-thermal analysis of polyester coatings

The application and suitability of micro-thermal analysis to detect changes in the chemical and physical properties of coating due to ageing and especially photo-degradation is demonstrated using a model polyester coating based on neopentyl glycol isophthalic acid. The changes in chemical structure like chain scission and cross-linking are manifested by a shift of the LTA detectable T_g and by a change of the slope of the part of the LTA graph responsible for the penetration of the hot sensor into the material after passing the glass transition temperature. As such LTA is a valuable tool to have a quick look into coating surfaces and especially their ageing. The photo-degradation of polyester in air leads to the formation of a cross-linked network at a surface layer of about 3-4 μm coupled with an increase in hardness and of the glass transition temperature by ∼90 K, the effect is less drastic for a photo-degradation in a nitrogen environment. Moreover, the presence of a non-equilibrium dense surface layer with a higher T_g formed during the drying of the coating formulation and the film solidification can be shown.     

Absorbing properties and structural design of microwave absorbers based on W-type La-doped ferrite and carbon fiber composites

Sol–gel method was used to prepare W-type BaCo₂Fe₁₆O₂₇ hexaferrite and La-doped Ba_0.7La_0.3Co₂Fe₁₆O₂₇ hexaferrite. Electromagnetic parameters of the ferrites and short carbon fiber composites were measured, and reflectivity was calculated according to transmission-line theory in the range 12.4–18 GHz. The results show that reflection loss of the doped ferrite composite is higher as compared to the no doped ferrite composite. Based on the above calculation, double-layer absorbers containing La-doped ferrite and carbon fiber composites were designed, and reflectivity of the double-layer absorbers made of different thickness and composition was calculated. Finally, a kind of structural absorber having excellent absorbing properties was achieved, and the bandwidth of the reflection loss less than −10 dB can reach 5.2 GHz in the range of 12.4–18 GHz.     

Comparison of the protection effectiveness of acrylic polyurethane coatings containing bark extracts on three heat-treated North American wood species: Surface degradation

High temperature heat-treatment of wood is a very valuable technique which improves many properties (biological durability, dimensional stability, thermal insulating characteristics) of natural wood. Also, it changes the natural color of wood to a very attractive dark brown color. Unfortunately, this color is not stable if left unprotected in external environment and turns to gray or white depending on the wood species. To overcome this problem, acrylic polyurethane coatings are applied on heat-treated wood to delay surface degradations (color change, loss of gloss, and chemical modifications) during aging. The acrylic polyurethane coatings which have high resistance against aging are further modified by adding bark extracts and/or lignin stabilizer to enhance their effectiveness in preventing the wood aging behavior. The aging characteristic of this coating is compared with acrylic polyurethane combined with commercially available organic UV stabilizers. In this study, their performance on three heat-treated North American wood species (jack pine, quaking aspen and white birch) are compared under accelerated aging conditions. Both the color change data and visual assessment indicate improvement in protective characteristic of acrylic polyurethane when bark extracts and lignin stabilizer are used in place of commercially available UV stabilizer. The results showed that although acrylic polyurethane with bark extracts and lignin stabilizer was more efficient compared to acrylic polyurethane with organic UV stabilizers in protecting heat-treated jack pine, it failed to protect heat-treated aspen and birch effectively after 672 h of accelerated aging. This degradation was not due to the coating adhesion loss or coating degradation during accelerated aging; rather, it was due to the significant degradation of heat-treated aspen and birch surface beneath this coating. The XPS results revealed formation of carbonyl photoproducts after aging on the coated surfaces and chain scission of CN of urethane linkages.     

Study on the feasibility of double stack high reflector coating at 355 nm

The feasibility of the idea of double stack HR coating was discussed in this paper both in theory and experiment. The theoretical simulation was made by employing optical coating design software. The analysis results showed that the design of double stack HR coating was feasible, which made the HR coating have ascendancy not only at reflectance but also at laser damage resistance. Then, the LaF₃/MgF₂ HR coating, the HfO₂/SiO₂ HR coating and the double stack HR coating were prepared for comparison, respectively. Transmittance spectra, surface morphologies and damage morphologies of these coatings were measured. Measurement of laser-induced damage threshold (LIDT) of S polarized light of the samples was performed at 355 nm, 45° incidence. The measurement results showed that the LIDT value of the LaF₃/MgF₂ HR coating with 30 layers was very high, but the reflectance was low. When the layer number was increased up to 36, lots of cracks appeared on the surface of the LaF₃/MgF₂ HR coating, with the LIDT badly declining. It was thought that the residual stress resulted in the cracks and the decline of the LIDT. The spectra measurement showed the double stack HR coatings could provide higher reflectance and wider reflection band than LaF₃/MgF₂ HR coating with less layer pairs. Any crack was also not found on the surface of the double stack coatings. Meanwhile, the double stack HR coatings possessed greater laser damage resistances than the HfO₂/SiO₂ HR coating. The damage morphologies showed that the damage of the double stack coating was even milder than that of the HfO₂/SiO₂ coating. Therefore, the double stack design was effective to gain high reflectance and great UV laser radiation resistance simultaneously.     

Optical absorbers based on strong interference in ultra‐thin films

Optical absorbers find uses in a wide array of applications across the electromagnetic spectrum, including photovoltaic and photochemical cells, photodetectors, optical filters, stealth technology, and thermal light sources. Recent efforts have sought to reduce the footprint of optical absorbers, conventionally based on graded structures or Fabry‐Perot‐type cavities, by using emerging concepts in plasmonics, metamaterials, and metasurfaces. Unfortunately, these new absorber designs require patterning on subwavelength length scales, and are therefore impractical for many large‐scale optical and optoelectronic devices. In this article, we summarize recent progress in the development of optical absorbers based on lossy films with thicknesses significantly smaller than the incident optical wavelength. These structures have a small footprint and require no nanoscale patterning. We outline the theoretical foundation of these absorbers based on “ultra‐thin‐film interference”, including the concepts of loss‐induced phase shifts and critical coupling, and then review several applications, including ultra‐thin color coatings, decorative photovoltaics, high‐efficiency photochemical cells, and infrared scene generators.

     

Completely random nanoporous Cu4O3–CuO–C composite thin films for potential application as multiple channel photonic band gap based filter in the telecommunication wavelengths

In 2003, Babin et al. theoretically predicted (J. Appl. Phys. 94:4244, 2003) that fabrication of organic–inorganic hybrid materials would probably be required to implement structures with multiple photonic band gaps. In tune with their prediction, we report synthesis of such an inorganic–organic nanocomposite, comprising Cu₄O₃–CuO–C thin films that experimentally exhibit the highest (of any known material) number (as many as eleven) of photonic band gaps in the near infrared. On contrary to the report by Wang et al. (Appl. Phys. Lett. 84:1629, 2004) that photonic crystals with multiple stop gaps require highly correlated structural arrangement such as multilayers of variable thicknesses, we demonstrate experimental realization of multiple stop gaps in completely randomized structures comprising inorganic oxide nanocrystals (Cu₄O₃ and CuO) randomly embedded in a randomly porous carbonaceous matrix. We report one step synthesis of such nanostructured films through the metalorganic chemical vapor deposition technique using a single source metalorganic precursor, Cu₄(deaH)(dea)(oAc)₅???(CH₃)₂CO. The films displaying multiple (4/9/11) photonic band gaps with equal transmission losses in the infrared are promising materials to find applications as multiple channel photonic band gap based filter for WDM technology.