Fe3O4 nanoparticles decorated smectite nanocomposite: Characterization,photocatalytic and electrocatalytic activities

Magnetite nanoparticles-decorated smectite nanocomposite was prepared by precipitation method and the obtained nanocomposite was used as both nanophotocatalyst for removal of rhodamine B from wastewater under UVA irradiation and electrocatalyst for the electrooxidation of chlorite ion on the carbon paste electrode. The raw smectite, bare magnetite and the synthesized nanocomposite catalyst were comparatively characterized by using XRD, FTIR, SEM, EDX, XPS, VSM, TG/DTG, DTA, DSC, electrophoretic mobility and BET techniques in detail. The XRD, SEM, electrophoretic mobility and VSM results indicated that the magnetite nanoparticles were uniformly distributed on the surface of smectite with a diameter of about 7 nm by electrostatic interactions and the prepared nanocomposite displayed well superparamagnetic behaviour with strong saturation magnetization at room temperature. The XPS, EDX, FTIR and thermal analysis data of synthesized nanocomposite further confirmed that the magnetite nanoparticles were successfully decorated on the smectite without formation of another ferric phase species. Furthermore, the surface area of magnetite smectite nanocomposite is higher than that of raw smectite, which is related to the magnetite nanoparticles decorated onto the smectite. The catalytic activities of all samples were comparatively investigated by using the degradation of aqueous rhodamine B solutions as a model pollutant in the heterogeneous photo-like-Fenton process which is well defined by the pseudo-first-order equation in kinetics. The resultant magnetite-smectite nanocomposite showed excellent magnetic separability and much better photocatalytic activity in a short period compared to the bare magnetite and smectite. The synergetic effect between magnetite and smectite showed high activity not only in photodegradation but also in electrocatalytic applications. Because the developed nanocomposite material exhibited enhanced catalytic activity towards to chlorite ion oxidation it was applied for the voltammetric quantification of chlorite ion in aqueous medium. After the optimization of the measurement parameters, the limit of detection and quantification of the method were calculated as 3.0 and 10.0 μM, respectively.     

Development and research for applying innovative magnetic soft mold imprinting techniques in microstructure component manufacturing

The present study employs an innovative technique, which uses PDMS soft mold, blended with magnetic powder as the transmission and imprinting methods, and integrates features from soft micromolding PMMA, an electro‐magnetically controlled, well‐proportioned, pressing technique in order to study how to create microlens arrays through a magnetic soft mold imprinting resist technique. Thus, it renders nanometer imprinting applications, and its technology, more developed and mature. The research findings revealed that, PDMS, blended with magnetic powder, can accurately recast and duplicate nanometer microstructures. Under well‐proportioned magnetic pressing, controlled by an electro‐magnetic disk, it can effectively fill and shape resist microstructures. The composite material of PDMS, with added magnetic iron powder, can effectively improve mechanical strength properties of pure PDMS soft mold, which is easily transformed for imprinting. Meanwhile, owing to the unique features of PDMS soft mold, conformal contact with the base material is possible; therefore, the effective imprinting area and the duplicated representation are significantly improved. In addition, as magnetic PDMS soft mold is easily produced and fast in recasting, the costs can be effectively reduced. In addition, due to features such as low surface free energy and a tendency not to stick to resist in imprinting, the soft mold is evenly controlled by the electro‐magnetic disk for imprinting duplication, highlighting the advantages of microstructure imprinting procedures. Copyright © 2008 John Wiley & Sons, Ltd.     

表面印迹纳米磁性壳聚糖的制备及对Cu(Ⅱ)的吸附研究

将壳聚糖与自制的纳米四氧化三铁反应,加入一定量的铜盐使其与壳聚糖络合,再用环氧氯丙烷交联,用酸洗脱铜离子,得到表面印迹的纳米磁性壳聚糖.考察了阴离子、交联剂浓度对铜印迹效果的影响.用振动磁力仪及透射电镜对样品的性质进行表征.研究了表面印迹的纳米磁性壳聚糖对Cu2 的吸附性能.研究结果显示,用硝酸铜印迹制备的表面印迹纳米磁性壳聚糖吸附剂平均粒径为25nm,饱和磁化强度为98.56emu/g,壳聚糖含量为18.7%.吸附剂吸附容量大,吸附速度快.在Cu2 初始浓度为3.91mmol/L,pH为5时,15min即达到吸附平衡,以壳聚糖计Cu2 的饱和吸附量为4.07mmol/g,比纯壳聚糖粉高2倍.在含Zn2 或Cd2 、Pb2 的二元体系溶液中,离子印迹吸附剂对Cu2 具有明显的选择吸附性,而未印迹的纯壳聚糖粉几乎没有选择性.吸附剂易回收,重复使用性好,重复使用4次后,吸附量约保留最初饱和吸附量的98%.     

Swollen poly(dimethylsiloxane) (PDMS) as a template for inorganic morphologies

We report a series of silica, titania, and zirconia microstructures synthesized within swollen poly(dimethylsiloxane) (PDMS). Voids created by solvent-swelling the polymer are used to template the product. The inorganic morphologies range from spheres to networks, depending upon the nature of the polymer, its degree of swelling, and the synthetic conditions. Organic solvents as well as pure metal alkoxide liquids have been used to swell the polymer. Once the alkoxide precursor is inside the swollen polymer, water is introduced to bring about hydrolysis and condensation polymerization. The product is a textured metal oxide within a PDMS matrix. Scanning electron microscopy (SEM), optical microscopy, nuclear magnetic resonance (NMR), and powder X-ray diffraction (PXRD) were used to characterize the products. Microstructures formed in this manner have potential use as an inexpensive route to catalysts, fillers, capsules, or membranes for separations.     

Preparation and electrochemical properties of core-shell Si/SiO nanocomposite as anode material for lithium ion batteries

The Si/SiO nanocomposite was synthesized by a sol–gel method in combination with a following heat-treatment process. It was analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV) and capacity measurement as anode material for lithium ion battery. Si nanoparticles were coated with SiO and a core-shell structured nanocomposite was formed. The core-shell Si/SiO nanocomposite displays better reversibility of lithium insertion/extraction and higher coulomb efficiency than virginal Si nanoparticles. The SiO shell envelops the Si nanoparticles to suppress the aggregation of the nanoparticles during cycling. As a result, the core-shell Si/SiO nanocomposite exhibits better capacity retention than virginal Si nanoparticles, indicating that this is a promising approach to improve the electrochemical performance of nano anode materials for lithium ion battery.     

Preparation,Micro-Patterning and Electrical Characterization of Functionalized Carbon-Nanotube Polydimethylsiloxane Nanocomposite Polymer

Summary : We present the preparation, improved micro-patterning, and electrical property characterization of COOH- functionalized mutli-walled carbon nanotube (MWCNT) and polydimethylsiloxane (PDMS) conductive nanocomposite polymers that can be employed for lab on a chip applications. The nanocomposites are prepared by mixing functionalized MWCNTs into an uncured PDMS matrix and employing high frequency ultrasonics (∼ 42-50 kHz) using a horn tip probe. The prepared nanocomposites are micromolded using soft lithography techniques down to a feature size of 25 µm against a micropatterned SU-8 polymer master. An array of peg like microstructures have been fabricated with a radii of 25 µm and height of 100 µm, that are embedded on a non-conductive PDMS substrate using novel and improved fabrication techniques. The percolation threshold of the prepared nanocomposite is achieved at 1.5 weight percentage (wt.%) of COOH- functionalized MWCNT in the PDMS matrix. Resistivity levels at 2 wt.% of functionalized MWCNTs are 62 Ω-cm or better, which is an improvement over our previously reported nanocomposite resistivity value of 100 Ω-cm at 2 wt.% of nonfunctionalized MWCNT's in a PDMS matrix. The nanocomposites also have fairly uniform dispersion and no agglomeration of COOH- functionalized MWCNT as shown by SEM analysis. Furthermore, the nanocomposites show a negative temperature coefficient of resistivity (NTCR), making them ideal candidates for micropatternable temperature microsensors for lab on a chip systems.     

Nanoparticle enabled thermal control of ions in liquid crystals

Typically, ionic species in thermotropic liquid crystals are nearly fully ionised. Therefore, the concentration of mobile ions practically does not depend on the temperature. Interestingly, the same liquid crystals doped with nanoparticles exhibit totally different behaviour. The concentration of mobile ions become temperature dependent. This paper reports the effects of the temperature on the concentration of ions in liquid crystal nanocolloids. Liquid crystals doped with both 100% pure and contaminated nanoparticles are considered. Regardless the ionic purity of nanodopants, the concentration of mobile ions in liquid crystal nanocolloids increases towards the saturation as their temperature goes up. The magnitude of this saturation level equals the initial concentration of ions in liquid crystals doped with 100% pure nanoparticles. The temperature induced release of ions by contaminated nanoparticles in liquid crystals increases the above-mentioned saturation level. While the dispersion of 100% pure nanoparticles in liquid crystals leads to the temperature-dependent purification only, the use of contaminated nanoparticles results in the temperature-driven switching between the purification and contamination regimes enabling thermal control of ions.     

Modeling diffusion mass transport in multiphase polymer systems for gas barrier applications: A review

Polymer nanocomposites offer a great interest as gas barrier materials because of their much‐enhanced properties arising from the nanoparticles shape, size, and spatial arrangement within the matrix. However, optimization and further development of such materials requires fundamental understanding of the influence of the nanocomposite structure on permeating gas diffusion. This step can be greatly facilitated through modeling/simulation strategies able to establish relationships between the material microstructure and the achieved enhancement of barrier properties. This review first presents the analytical models developed to estimate the effective diffusivity in polymer nanocomposites. The predictions of the models are analyzed with respect to experimental data reported in the literature and their ability to describe accurately the nanocomposite transport properties when the microstructure complexity increases is discussed. Then, modeling approaches based on numerical simulation techniques (e.g., the finite element method) that allow simulating the diffusion processes and assessing the effect of filler shape, orientation, dispersion, and spatial arrangement are reviewed and discussed. Finally, the importance of 3D simulation strategies for the understanding and prediction of transport properties in the most complex nanocomposite microstructures is addressed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 621–638     

Preparation of PDMS-ormosil and its application in miniemulsion polymerization

With the assistance of ultrasound, octamethylcyclotetrasiloxane (D4) and slight silane coupling agent γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560) were sufficiently mixed with silica sol, and the in situ ring-opening polymerization of D4 on the surface of silica nanoparticles, catalyzed by dodecylbenzene sulfonic acid (DBSA), was enhanced as well. Thus, polydimethylsiloxane (PDMS)-modified silica (PDMS-ormosil) mixture was obtained. A slight addition of silane coupling agent γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560) could significantly enhance the modified efficiency. The PDMS-ormosil mixtures were directly dispersed in the mixed monomer methyl methacrylate and butyl methacrylate. Then, miniemulsion polymerizations of acrylate monomers containing PDMS-ormosils were carried out, with free PDMS as hydrophobe and neutralized DBSA as emulsifier, both preexisted in the PDMS-ormosil mixture. Thus, the troubles of separation, purification, and redispersion in the traditional techniques can be omitted. Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscope, scanning electron microscope, and water contact angle tests were utilized to demonstrate that nanocomposite particles with a core–shell structure were synthesized; when the silica content was 3 wt% of the monomers, the average particle size was 97 nm, and the generated PDMS improved the hydrophobicity of the nanocomposite latex.     

Synthesis of silver nanoparticles using dl-alanine for ESR dosimetry applications

The potential use of alanine for the production of nanoparticles is presented here for the first time. Silver nanoparticles were synthesized using a simple green method, namely the thermal treatment of silver nitrate aqueous solutions with dl-alanine. The latter compound was employed both as a reducing and a capping agent. Particles with average size equal to 7.5 nm, face-centered cubic crystalline structure, narrow size distribution, and spherical shape were obtained. Interaction between the silver ions present on the surface of the nanoparticles and the amine group of the dl-alanine molecule seems to be responsible for reduction of the silver ions and for the stability of the colloid. The bio-hybrid nano-composite was used as an ESR dosimeter. The amount of silver nanoparticles in the nanocomposite was not sufficient to cause considerable loss of tissue equivalency. Moreover, the samples containing nanoparticles presented increased sensitivity and reduced energetic dependence as compared with pure dl-alanine, contributing to the construction of small-sized dosimeters.     

Micropatterning of proteins on the surface of three-dimensional poly(ethylene glycol) hydrogel microstructures

This paper describes micropatterning of proteins on the surface of three-dimensional hydrogel microstructures. Poly(ethylene glycol) (PEG)-based hydrogel microstructures were fabricated on a glass substrate using a poly(dimethylsiloxane) (PDMS) replica as a molding insert and photolithography. The lateral dimension and height of the hydrogel microstructures were easily controlled by the feature size of the photomask and depth of the PDMS replica, respectively. Bovine serum albumin (BSA), a model protein, was covalently immobilized to the surface of the hydrogel microstructure via a 5-azidonitrobenzoyloxy N-hydroxysuccinimide bifunctional linker at a surface density of 1.48 mg cm⁻². The immobilization of BSA on the PEG hydrogel surface was demonstrated with XPS by confirming the formation of a new nitrogen peak, and the selective immobilization of fluorescent-labeled BSA on the outer region of the three-dimensional hydrogel micropattern was demonstrated by fluorescence. A hydrogel microstructure could immobilize two different enzymes separately, and sequential bienzymatic reaction was demonstrated by reacting glucose and Amplex Red with a hydrogel microstructure where glucose oxidase was immobilized on the surface and peroxidase was encapsulated. Activity of immobilized glucose oxidase was 16.5 U mg⁻¹, and different glucose concentration ranged from 0.1 to 20 mM could be successfully detected.     

Magnetic Nitrogen-Doped Porous Carbon Nanocomposite for Pb(II) Adsorption from Aqueous Solution

We report in the present study the in situ formation of magnetic nanoparticles (Fe₃O₄ or Fe) within porous N-doped carbon (Fe₃O₄/N@C) via simple impregnation, polymerization, and calcination sequentially. The synthesized nanocomposite structural properties were investigated using different techniques showing its good construction. The formed nanocomposite showed a saturation magnetization (M_s) of 23.0 emu g⁻¹ due to the implanted magnetic nanoparticles and high surface area from the porous N-doped carbon. The nanocomposite was formed as graphite-type layers. The well-synthesized nanocomposite showed a high adsorption affinity toward Pb²⁺ toxic ions. The nanosorbent showed a maximum adsorption capacity of 250.0 mg/g toward the Pb²⁺ metallic ions at pH of 5.5, initial Pb²⁺ concentration of 180.0 mg/L, and room temperature. Due to its superparamagnetic characteristics, an external magnet was used for the fast separation of the nanocomposite. This enabled the study of the nanocomposite reusability toward Pb²⁺ ions, showing good chemical stability even after six cycles. Subsequently, Fe₃O₄/N@C nanocomposite was shown to have excellent efficiency for the removal of toxic Pb²⁺ ions from water.     

碳纳米管@SiO_2@Ag纳米复合材料的制备及其表面增强拉曼效应

本文以SiO2为中间层,在多壁碳纳米管(MWCNTs)表面负载Ag纳米粒子,制备出CNTs@SiO2@Ag纳米复合材料,并采用TEM、XRD、UV-Vis、XPS等对纳米复合材料的结构、形貌和成分进行了表征,同时对该纳米复合材料的表面增强拉曼散射(Surface-enhanced Raman scattering,SERS)效应进行了研究。结果显示,Ag纳米颗粒有效提高了CNTs的SERS活性,纳米复合材料的拉曼峰强度是单纯CNTs拉曼峰强的近5倍。进一步研究了吸附罗丹明6G生物染料分子的SERS光谱,结果表明R6G分子的拉曼信号的质量与强度得到显著提高。因此,所制备的CNTs@SiO2@Ag纳米复合材料有望作为SERS的活性基底,应用于生物无损检测领域。     

Studies on droplet size distributions during coalescence in immiscible polymer blends filled with silica nanoparticles

The effect of silica nanoparticles on the morphology of （10/90 wt%） PDMS/PBD blends during the shear induced coalescence of droplets of the minor phase at low shear rate was investigated systematically in situ by using an optical shear technique. Two blending procedures were used： silica nanoparticles were introduced to the blends by pre-blending silica particles first in PDMS dispersed phase （procedure 1） or in PBD matrix phase （procedure 2）. Bimodal or unimodal droplet size distributions were observed for the filled blends during coalescence, which depend not so much on the surface characteristics of silica but mainly on blending procedure. For pure （10/90 wt%） PDMS/PBD blend, the droplet size distribution exhibits bimodality during the early coalescence. When silica nanoparticles （hydrophobic and hydrophilic） were added to the blends with procedure l, bimodal droplet size distributions disappear and unimodal droplet size distributions can be maintained during coalescence; the shape of the different peaks is invariably Gaussian. Simultaneously, coalescence of the PDMS droplets was suppressed efficiently by the silica nanoparticles. It was proposed that with this blending procedure the nanoparticles should be mainly kinetically trapped at the interface or in the PDMS dispersed phase, which provides an efficient steric barrier against coalescence of the PDMS dispersed phase. However, bimodal droplet size distributions in the early stage of coalescence still occur when incorporating silica nanoparticles into the blends with procedure 2, and then coalescence of the PDMS droplets cannot be suppressed efficiently by the silica nanoparticles. It was proposed that with this blending protocol the nanoparticles should be mainly located in the PBD matrix phase, which leads to an inefficient steric barrier against coalescence of the PDMS dispersed phase; thus the morphology evolution in these filled blends is similar to that in pure blend and bimodal droplet size distributions can be observed during the early coalescence. These results imply that exploiting non-equilibrium processes by varying preparation protocol may provide an elegant route to regulate the temporal morphology of the filled blends during coalescence.     

Nanocomposites of genipin-crosslinked chitosan/silver nanoparticles--structural reinforcement and antimicrobial properties

This study investigates the feasibility of a novel nanocomposite (GC/Ag) of a genipin-crosslinked chitosan (GC) film in which was embedded various amounts of Ag nanoparticles for wound-dressing applications. In situ UV-vis results revealed that adding chitosan solution did not affect the characteristics of Ag nanoparticles. The water uptake ratios and surface hydrophilicity of the GC/Ag nanocomposite were better and the degradation rates slightly lower than those of the pure GC film. The presence of Ag nanoparticles enhanced L929 cell attachment and growth. Its function as an anti-microbial agent in a GC/Ag nanocomposite was assessed for Ag contents of over 100 ppm. In conclusion, silver ions had dual functions--structural reinforcement and provision of antimicrobial properties to a biocompatible polymer.     

Evolution of microstructure and crack pattern in NiO thin films under 200 MeV Au ion irradiation

NiO thin films grown on Si (100) substrate by electron beam evaporation method and sintered at 700 °C were irradiated with 200 MeV Au¹⁵⁺ ions. The fcc structure of the sintered films was retained up to the highest fluence (1×10¹³ ions cm^?2) of irradiation. However the microstructure of the pristine film underwent a considerable modification with increasing ion fluence. 200 MeV Au ion irradiation led to compressive stress generation in NiO medium. The diameter of the stressed region created by 200 MeV Au ions along the ion path was estimated from the variation of stress with ion fluence and found to be ～11.6 nm. The film surface started cracking when irradiated at and above the fluence of 3×10¹² ions cm^?2. Ratio of the fractal dimension of the cracked surface obtained at 200 MeV and 120 MeV (Mallick et al., 2010a) Au ions was compared with the ratio of the radii of ion tracks calculated based on Coulomb explosion and thermal spike models. This comparison indicated applicability of thermal spike model for crack formation.     

碳纳米管@SiO2@Ag纳米复合材料的制备及其表面增强拉曼效应

本文以SiO₂为中间层,在多壁碳纳米管(MWCNTs)表面负载Ag纳米粒子,制备出CNTs@SiO₂@Ag纳米复合材料,并采用TEM、XRD、UV-Vis、XPS等对纳米复合材料的结构、形貌和成分进行了表征,同时对该纳米复合材料的表面增强拉曼散射(Surface-enhancedRamanscattering,SERS)效应进行了研究。结果显示,Ag纳米颗粒有效提高了CNTs的SERS活性,纳米复合材料的拉曼峰强度是单纯CNTs拉曼峰强的近5倍。进一步研究了吸附罗丹明6G生物染料分子的SERS光谱,结果表明R6G分子的拉曼信号的质量与强度得到显著提高。因此,所制备的CNTs@SiO₂@Ag纳米复合材料有望作为SERS的活性基底,应用于生物无损检测领域。     

Regular arrays of triangular‐microstructure formed on silicon (111) surface via ultrafast laser irradiation in KOH solution

The regular micrometer‐scale triangular arrays were formed using ultrafast femtosecond laser irradiation on (111) surface of silicon wafer immersed in KOH solution (0.1 g/ml). At low laser fluence, the resulting surface is covered by triangular pits microstructures, whereas at high laser fluence, the structures are transformed to multilayer‐triangular stacks‐microstructures. The number of triangular stacks layer increased as the laser fluence increased. The formation of triangle microstructure arrays depends on both silicon surface crystallographic orientation and the concentration of KOH solution. Either for lower KOH solution concentration (0.02 g/ml) or other silicon crystallographic orientation, triangle arrays cannot be obtained. We attribute the formation of triangular microstructure arrays to the laser‐assisted chemical etching process. Copyright © 2013 John Wiley & Sons, Ltd.     

Graphene Nanosheets as a Platform for the 2D Ordering of Metal Oxide Nanoparticles: Mesoporous 2D Aggregate of Anatase TiO2 Nanoparticles with Improved Electrode Performance

Graphene nanosheets are successfully applied as an effective platform for the 2D ordering of metal oxide nanoparticles. Mesoporous 2D aggregates of anatase TiO₂ nanoparticles are synthesized by the heat treatment of the uniformly hybridized nanocomposite of layered titanate–reduced graphene oxide (RGO) at elevated temperatures. The precursor layered titanate–RGO nanocomposite is prepared by self‐assembly of anionic RGO nanosheets and cationic TiO₂ nanosols. The calcination of the as‐prepared layered titanate–RGO nanocomposite at 500 °C induces a structural and morphological change of layered titanate nanoplates into anatase TiO₂ nanoparticles without significant modification of the RGO nanosheet. Increasing the heating temperature to 600 °C gives rise to elimination of the RGO component, leading to the formation of sheetlike porous aggregates of RGO‐free TiO₂ nanoparticles. The nanocomposites calcined at 500–700 °C display promising functionality as negative electrodes for lithium ion batteries. Among the present calcined derivatives, the 2D sheet‐shaped aggregate of TiO₂ nanoparticles obtained from calcination at 600 °C delivers the greatest specific discharge capacity with good capacity retention for all current density conditions applied. Such superior electrode performance of the nanocomposite calcined at 600 °C is attributable both to the improved stability of the crystal structure and crystal morphology of titania and to the enhancement of Li⁺ ion transport through the enlargement of mesopores. The present findings clearly demonstrate the usefulness of RGO nanosheets as a platform for 2D‐ordered superstructures of metal oxide nanoparticles with improved electrode performance.     

SiO2纳米粒子对受限流场下聚异丁烯/聚二甲基硅氧烷共混物相形态的影响

利用显微-光学剪切联用系统构造受限剪切环境,探讨了少量不同表面性质的SiO2纳米粒子的加入对聚异丁烯(PIB)/聚二甲基硅氧烷(PDMS)不相容共混体系分散相形态演变过程的影响.研究结果表明,少量疏水性SiO2纳米粒子的加入可抑制分散相液滴的凝聚,从而抑制珍珠链状及纤维状等超级相形态的形成,使共混物表现为近似本体流体的...