Magnetic field assisting DC electrodeposition: general methods for high-performance Ni nanowire array fabrication

One-dimensional magnetic nanowires are generally thought to show fine axial magnetism for their special high aspect ratio of the shape. However, the magnetic nanowire arrays fabricated by DC electrodeposition in template pores always show a low squareness in parallel to the nanowire direction. We developed two general and simple methods to improve the squareness of the as-fabricated Ni nanowire arrays parallel to the nanowire direction. The nanowires are found to be polycrystalline. The magnetism of the nanowire is also analyzed based on the microstructure.     

Stability of microfabricated high aspect ratio structures in poly(dimethylsiloxane)

The stability of structures microfabricated in soft elastomeric polymers is an important concern in most applications that use these structures. Although relevant for several applications, the collapse to the ground of high aspect ratio structures (ground collapse) is still poorly understood. The stability of soft microfabricated high aspect ratio structures versus ground collapse was experimentally assessed, and a new model of ground collapse involving adhesion was developed. Sets of posts with diameters from 0.36 to 2.29 microm were fabricated in poly(dimethylsiloxane) and tested in air or immersed in water and ethanol to change the work of adhesion. The critical aspect ratio (the highest length-to-width ratio for which a post is not at risk of collapsing) was determined as a function of the diameter. The critical aspect ratio in air ranged from 2 to 4 and increased with the diameter. Work of adhesion was found to be determinant for and inversely correlated to stability. These results highlight the role played by adhesion and offer the possibility of improving stability by reducing the work of adhesion. The ground collapse model developed accounted for the main features of structure stability. The results indicate that ground collapse can be a limiting factor in the design of soft polymer structures.     

The role of oxidative etching in the synthesis of ultrathin single-crystalline Au nanowires

The fabrication of ultrathin single-crystal Au nanowires with high aspect ratio and that are stable in air is challenging. Recently, a simple wet-chemical approach using oleylamine has been reported for the synthesis of Au nanowires with micrometer length and 2 nm in diameter. Despite efforts to understand the mechanism of the reaction, an ultimate question about the role of oxygen (O(2)) during the synthesis remained unclear. Here we report that the synthesis of ultrathin Au nanowires employing oleylamine is strongly affected by the amount of O(2) absorbed in the reaction solution. Saturating the solution with O(2) leads to both a high-yield production of nanowires and an increase in their length. Nanowires with diameters of about 2 nm and lengths of 8 μm, which corresponds to an aspect ratio of approximately 4000, were produced. The role of oxygen is attributed to the enhanced oxidation of twin defects on Au nanoparticles formed in the first stage of the reaction. Understanding the role of oxidative etching is crucial to significantly increasing the yield and the length of ultrathin Au nanowires.     

Polymer ferroelectret based on polypropylene foam: piezoelectric properties prediction using dynamic mechanical analysis

Thin polypropylene (PP) foam films were produced by continuous extrusion using supercritical nitrogen (N₂) and then charged via corona discharge. The samples were characterized by dynamic mechanical analysis as a simple method to predict the piezoelectric properties of the cellular PP obtained. The results were then related to morphological analysis based on scanning electron microscopy and mechanical properties in tension. The results showed that the presence of a nucleating agent (CaCO₃) substantially improved the morphology (in terms of cell size and cell density) of the produced foam. Also, an optimization of the extrusion (screw design, temperature profile, blowing agent, and nucleating agent content) and post‐extrusion (calendering temperature and speed) conditions led to the development of a stretched eye‐like cellular structure with uniform cell size distribution. This morphology produced higher storage and loss moduli in the machine (longitudinal) direction than for the transverse direction, as well as higher piezoelectric properties. The morphological and mechanical results showed that higher cell aspect ratio led to lower Young's modulus, which is suitable to achieve higher piezoelectric properties. Finally, the best quasi‐static piezoelectric d₃₃ coefficient was 550 pC/N for a cellular PP ferroelectret having a uniform eye‐like cellular structure using N₂ as the ionizing gas inside the cells, while the highest value was only 250 pC/N when air was used. Hence, the value of d₃₃ can be improved by more than 100% just by replacing air with N₂ as the ionizing gas. Copyright © 2016 John Wiley & Sons, Ltd.     

Anisotropy in optical transmittance and molecular chain orientation of silver- dispersed uniaxially drawn polyimide films

The anisotropy in optical transmittance in the visible and near-infrared region observed for uniaxially drawn and silver-dispersed polyimide (PI) films was investigated. The films were prepared in a one-step operation that consists of thermal curing and simultaneous uniaxial drawing of poly(amic acid) (PAA) films dissolving 5.7 ∼ 20 mol% of silver nitrate. The PAA was converted to PI by heating, and the PI chains were orientated along the drawing direction during curing. Silver nanoparticles were precipitated in the films when they were cured in air and under nitrogen. In particular, silver nanoparticles aggregated along drawing direction and spheroidal nanoparticles (size of longer axis: 10–25 nm, aspect ratio: ca. 1.5) were observed in the films cured in air, and distinct anisotropy in optical transmittance was observed. The maximum optical anisotropy was obtained with a specific holding time at the final curing temperature (320 °C). In addition, the anisotropy can be controlled by polymer chain orientation when films are cured with the optimal holding time. In optimized preparing conditions, anisotropies in transmittance larger than 500 : 1 were obtained at the wavelengths between 700 and 900 nm, and its optical properties were retained after annealing at 150 °C for 1 hr. The PI films thus obtained can be used as thermally stable thin-film polarizers. Copyright © 2003 John Wiley & Sons, Ltd.     

Rheological Properties and Orientational Distributions of Dilute Ferromagnetic Spherocylinder Particle Dispersions

We have investigated the rheological properties and the orientational distributions of particles of a dilute colloidal dispersion, which is composed of ferromagnetic spherocylinder particles, subject to a simple shear flow. The governing equation of an orientational distribution function has been derived from the balance of the torques acting on a particle in an applied magnetic field. After a spherical harmonic expansion, an approximate solution to the governing equation has been found by Galerkin's method. The results obtained are summarized as follows. The orientational distribution function has a sharper peak for a stronger magnetic field, and the position of the peak changes from the flow direction to the magnetic field direction as the magnetic field comes to govern the shear flow. Since the orientation of the particle is highly restricted in the field direction as the magnetic field becomes strong, the viscosity increases significantly. The particles with a larger aspect ratio lead to the larger increment in the viscosity, since they induce a larger resistance in a flow field. Copyright 2001 Academic Press.     

Biofouling potentials of microporous polysulfone membranes containing a sulfonated polyether-ethersulfone/polyethersulfone block copolymer: correlation of membrane surface properties with bacterial attachment

Multivariate methods were used to identify relationships between bacterial attachment (biofouling potential), water transport, and the surface properties of nine modified polysulfone (MPS) membranes comprising blends of polysulfone (PS) with a sulfonated polyether-ethersulfone/polyethersulfone block copolymer. The topology of the microporous MPS membranes, including surface roughness, surface height, pore size and pore geometry were determined by atomic force microscopy (AFM) and digital image analysis. Other measurements included relative surface hydrophobicity by captive bubble contact angle, surface charge (i.e., degree of sulfonation) by uranyl cation binding, wt% solids, porosity, membrane thickness, water flux, and the affinity of membranes for a hydrophilic Flavobacterium and hydrophobic Mycobacterium species. The mycobacteria attached best to the MPS membranes, but the attachment of both organisms was inversely correlated with the mean aspect ratio of pores, suggesting that irregular or elliptic pores discouraged attachment. Multivariate regression analyses identified the pore mean aspect ratio, mean surface height, PS content, and the n-methylpyrrolidone+propionic acid (NMP–PA) solvent concentration as influential factors in Mycobacterium attachment, whereas membrane thickness, surface roughness, pore mean aspect ratio, porosity, and the mean pore area/image area ratio influenced Flavobacterium attachment. Cluster analyses revealed that Mycobacterium attachment was associated with hydrophobic determinants of the MPS membranes, including PS content, wt% solids, and air bubble contact angle. In contrast, Flavobacterium attachment was primarily associated with membrane thickness and charge (i.e., uranyl cation binding or degree of sulfonation). Membrane flux was inversely correlated with surface hydrophobicity and PS content, but (in contrast to cell attachment) positively correlated with most pore geometry parameters including the mean aspect ratio, suggesting that pore geometry can be optimized to minimize cell attachment and maximize water transport. Other variables influencing water flux included the NMP–PA solvent concentration and membrane roughness. The results should facilitate the design of novel microporous PS membranes having reduced biofouling potentials and greater water fluxes.     

Diffusioosmotic flow in rectangular microchannels

The diffusioosmosis of an electrolyte solution inside a uniformly charged rectangular channel at steady locally developed conditions is the subject of this study. Utilizing a finite element based numerical procedure, we try to estimate the errors incurred by modeling the actual rectangular geometry of typical microchannels as a slit. We demonstrate that the flow pattern and direction are generally dependent upon the width‐to‐height ratio of the channel. Such a finding, besides showing the ineffectiveness of the slit geometry in representing a rectangular channel of small aspect ratio, informs us of another mechanism of controlling the diffusioosmotic flow. Inspections of the mean velocity reveal that, although it drastically grows by increasing the aspect ratio at smaller values of this parameter, no significant change is observed when the aspect ratio is 5 or higher. The same trend is observed when EDL is shrunk and is considered as a basis for the introduction of a slip‐like velocity, similar to the concept of the Helmholtz–Smoluchowski electroosmotic velocity, which will be of high practical importance when dealing with a micronsized channel. Because of its significance, an expression is presented for this slip velocity utilizing the curve fitting of the results, assuming a typical Peclet number.     

Dynamic shape and wall correction factors of cylindrical particles falling vertically in a Newtonian liquid

Results of numerical calculations of dynamic shape and wall correction factors for the flow of a Newtonian fluid over a vertically oriented cylindrical particle in a cylindrical tube are reported. Mathematical model of the flow was solved using the finite element method by means of the COMSOL Multiphysics software. Dependences of the shape factor on the cylinder aspect ratio and of the wall correction factor, F _W , on the ratio of the cylindrical particle diameter to the tube diameter, and on the aspect ratio were obtained. Numerical dependences were approximated by simple relationships suitable for dynamic shape and wall correction factors prediction.     

Transport coefficients and orientational distributions of rodlike particles with magnetic moment normal to the particle axis under circumstances of a simple shear flow

We have investigated the influences of the magnetic field strength, shear rate, and random forces on transport coefficients such as viscosity and diffusion coefficient, and also on the orientational distributions of rodlike particles of a dilute colloidal dispersion. This dispersion is composed of ferromagnetic spheroidal particles with a magnetic moment normal to the particle axis. In the present analysis, these spheroidal particles are assumed to conduct the rotational Brownian motion in a simple shear flow as well as an external magnetic field. The basic equation of the orientational distribution function has been derived from the balance of the torques and solved numerically. The results obtained here are summarized as follows. For a very strong magnetic field, the rodlike particle is significantly restricted in the field direction, so that the particle points to a direction normal to the flow direction (and also to the magnetic field direction). However, the present particle does not exhibit a strong directional characteristic, which is one of the typical properties for the previous particle with a magnetic moment parallel to the particle axis. That is, the particle can rotate around the axis of the magnetic moment, although the magnetic moment nearly points to the field direction. The viscosity significantly increases with the field strength, as in the previous particle model. The particle of a larger aspect ratio leads to the larger increase in the viscosity, since such elongated particles induce larger resistance in a flow field. The diffusion coefficient under circumstances of an applied magnetic field is in reasonable agreement between theoretical and experimental results.     

Hydrothermal synthesis of ZnO nanorods in the diameter regime of 50 nm

We report a novel wet-chemical approach at 180 degrees C for the synthesis of monodispersed ZnO nanorods with high single-crystallinity. The method has successfully brought the ZnO nanorod diameter from a reported 150 nm down to the 50 nm regime in this work. The aspect ratio of the synthesized nanorods achieved is exceptionally high (in the range of 30-40). This simple low-cost approach should promise us a future large-scale synthesis of ZnO nanostructures for many important applications in nanotechnology in a controlled manner.     

Ordered honeycomb-structured gold nanoparticle films with changeable pore morphology: from circle to ellipse

Two-dimensionally ordered honeycomb structures have been prepared on dodecanethiol-capped gold nanoparticle films by blowing moist air across the surface of the nanoparticle solution. The pore morphology can be altered from circle to ellipse with tunable aspect ratios by carefully controlling the direction and velocity of airflow. The formation mechanisms of different surface morphologies have been discussed in terms of the surface and interfacial tension.     

Diffusion in heterogeneous media containing impermeable domains arranged in parallel arrays of variable orientation

Effective diffusivity through heterogeneous media containing impermeable and geometrically anisotropic domains depends on the domain orientation relative to the diffusion direction. A particular class of heterogeneous membranes in which domain orientation can be controlled in situ, side-chain liquid-crystalline polymers (SCLCPs), are being investigated as responsive, or variable permeability membranes for use in a variety of applications including controlled release drug delivery. This paper describes a geometric model for predicting the effective diffusivity through this type of membranes as a function of domain orientation, volume fraction, and aspect ratio. Estimates of effective diffusivity were also generated using random walk simulations. Results from the two methods agree well with each other. Predicted effective diffusivities in systems with domains aligned either orthogonal or parallel to the diffusion direction are compared to results from available literature models. Model predictions are compared to experimentally obtained transport properties through SCLCPs in which liquid-crystalline domain orientation is modulated by externally applied electric field.     

Orientation effects and rheology of short glass fiber-reinforced thermoplastics

The rheology of polyolefines, polyamide 6, and polystyrene-acrylonitrile filled with glass fibers of different concentrations and aspect ratios have been investigated in simple shear flow, capillary rheometry, and uniaxial elongation. A comparison is made with unfilled and glass bead-filled melts. Fiber orientation was investigated by X-ray microradiography.Steady-state viscosities are obtained on fibers aligned parallel to the direction of flow. Entrance pressure losses, the shape of the viscosity function, and the appearance of a yield stress are depending on the fiber aspect ratio. The temperature dependence of the viscosity function is not significantly different from that of the unfilled melt.Transient shear stresses were measured on samples of different initial orientations of the fibers. The change of fiber orientation during shear flow gives rise to a pronounced overshoot of shear stress and normal stress difference. Elastic strains in shear are increased by the fibers but elastic elongational strains are reduced. Mechanisms are proposed to explain the experimental observations.Dedicated to Dr. D. Heinze on the occasion of his 60th birthday.     

Flushing time and storage effects on the accuracy and precision of carbon and oxygen isotope ratios of sample using the Gasbench II technique

Continuous-flow isotope ratio mass spectrometry interfaced with a Gasbench II is used for automated and faster analyses of delta(13)C and delta(18)O in water, carbonate, and air samples that are accurate and highly precise. Prior to online chemistry and measurement using the Gasbench technique, rubber septa-capped glass vials are routinely flushed to remove air. Due to the small amounts of sample gas required for isotope analyses using current techniques, care should be taken to properly flush these vials to avoid contamination of sample gas with air. Our results indicate that isotopic composition of sample CO(2) gas remains constant when 10 mL vials are flushed (rate of 100 mL/min) for > or =600 s, whereas for vials flushed <600 s, the isotopic composition becomes substantially lighter with decreasing time of flushing, which affects the accuracy of analyses. This largely depends on the isotopic composition (and volume) of air that still remains after flushing. This effect is more pronounced on delta(18)O than on delta(13)C of sample CO(2) gas because there is very little carbon in the air. After 24 h storage in vials with punctured septa, both delta(13)C and delta(18)O of CO(2) become isotopically heavier compared with first day analyses, suggesting time-dependent changes in isotopic composition. The magnitude of shift depends on the concentration and the isotopic composition of CO(2) in laboratory air as well as on fractionation due to outflow of sample gas or inflow of air via punctured septa. Contamination of sample gas with air can be observed as a secondary peak on chromatograms that precedes sample peaks, and the intensity of these peaks depends on the amount of air. Such peaks are always present with short flushing times. For accuracy and better precision, irrespective of the magnitude of the secondary peaks, the analyses should be discarded if these appear in the chromatograms.     

Application of Contactless Impedance Detection to Determination of Substances in Gaseous Phase

A simple cell, consisting of two insulated wire electrodes placed in a PTFE tube through which the test gaseous phase flows, has been applied to capacitively coupled contactless conductometric detection (C⁴D) and determination of water vapour in the air, to examine the possibilities of the use of C⁴D for analyses of gaseous samples. It has been found that the measurement is sufficiently sensitive and reliable for determinations of common concentrations of water in the air. The dynamic characteristics and the signal stability demonstrate that the cell will be suitable for long‐term continuous monitoring of the air humidity. Qualitative tests indicate that vapours of organic solvents can also be monitored. To the authors knowledge, this is the first attempt to use C⁴D in gas analyses.     

银纳米棒光学性质的离散偶极近似计算

The optical properties of metal nanoparticles are quite different from those of the bulk materials mainly due to the collective oscillations of their conduction electrons known as the surface plasmon resonance（SPR）,which is strongly dependent on the particle shape and size,and the dielectric properties of the local environment where the nanoparticles are embedded in. Based on the discrete dipole approximation（DDA）method,we studied the optical properties of silver nanorods with different aspect ratios in some special dielectric environment including air,water,acetone,methylene chloride and pyridine. The DDA simulation of the ultraviolet-visible（UV-Vis）extinction spectra of silver nanorods with varying aspect ratios shows the plasmons absorption splits into two bands corresponding to the oscillation of the free electrons along and perpendicular to the long axis of the rods. The transverse mode shows almost a fixed resonance at about 350 nm while the resonance of the longitudinal mode is red-shifted and strongly depends on the aspect ratio of the nanorods. An empirical formula was given to predict the peak position of the longitudinal palsmon band of the silver nanorods with different aspect ratios in the air. The calculation result also shows the maximum of the longitudinal plasmon band of a silver nanorod with a fixed aspect ratio depends on the medium dielectric constant in a linear way. The TEM image and corresponding UV-Vis extinction spectrum of silver nanosphere and nanorods synthesized by our lab are in good agreement with the DDA simulation results.     

Study of the fracture behavior of flexible polypropylene foams using the Essential Work of Fracture (EWF)

Two types of commercial low density polypropylene based flexible foams produced by extrusion foaming were characterized in terms of their fracture behaviour using the concept of the Essential Work of Fracture (EWF), focusing on the influence of the foam’s relative density and cellular structure on the values of the fracture parameters. With that in mind, correction procedures based on the expansion ratio of the foams and their cellular structure were proposed, with the objective of taking the complexity of these materials into account in the obtained fracture parameters. Significant differences were found between the fracture parameters of the two foams related to differences in their cellular structure, particularly cell size, cell aspect ratio and preferential cell orientation. Generally speaking, the specific fracture elastic contribution in the two considered extrusion directions increased with increase of the cell aspect ratio, especially in the case of the foams with a marked cell orientation in the direction of the extrusion flow. In any case, the fracture parameters for all foams were considerably lower in the direction perpendicular to the extrusion flow, hence demonstrating the highly anisotropic fracture behaviour of these foams due to the anisotropic cellular structure induced during foaming.     

微波辐射法合成SAPO-5分子筛中硅铝比对产物结晶度和甲苯吸附性能的影响

采用硅溶胶作硅源, 用微波辐射法在酸性条件下(pH=4.5-5.0)合成了SAPO-5分子筛, 利用X射线衍射(XRD), 傅立叶变换红外光谱(FT-IR), 扫描电镜(SEM)和Brunauer-Emmett-Teller (BET)比表面积分析对样品的结晶度、形貌和比表面等进行表征, 考察了晶化原料硅铝比对分子筛结晶度和晶体颗粒长径比(c/a)的影响, 测定了分子筛对甲苯的吸附性能. 结果显示, 采用微波辐射法合成的SAPO-5分子筛, 在硅铝摩尔比为0.50附近生成产物的结晶度最好, 晶体颗粒的长径比最小(约为1.0). 尽管不同硅铝比条件下得到的样品比表面测定结果变化不大, 但对甲苯的吸附实验显示, 在硅铝比为0.50时样品的吸附速率和饱和吸附量均达到了最大值. 这与表征所得的结晶度和长径比的变化一致, 即结晶度好,长径比小的SAPO-5分子筛具有更好的甲苯吸附性能.