Effect of postcasting heat‐treatment on the structure and properties of semicrystalline phase‐inversion poly(vinylidene fluoride) membranes

Microporous PVDF membranes were prepared by immersion‐precipitation in 1‐octanol of casting dopes dissolved at different temperatures, with dissolution temperature affecting strongly the membrane microstructure. The effect of postcoagulation thermal annealing, which is an additional thermal parameter, on membrane microstructure and properties is probed herein. Membranes obtained were annealed at temperatures up to 160 °C, which is close to the melting point of PVDF polymer. Annealing leads to a substantial modification of the nano‐scale fine structure of the membranes, while the overall‐microporous structure is preserved. At elevated annealing temperatures, nano‐grains, fibrils, and stick‐like crystalline entities gradually eclipse, while globules develop more robust connections based on wide bands of crystal elements. Probing by X‐ray diffraction and dynamic scanning calorimetry shows that crystallinity increases when annealing temperature and time are increased. As regards mechanical properties, the tensile strength of the membranes can be enhanced substantially, up to about 10 times, upon appropriate high temperature prolonged annealing. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1880–1893, 2009     

An investigation of nanoscale tribological characteristics under different interaction forces

The present study employs a Finite Element Method (FEM) atomic approach to investigate the nanoscale mechanisms of sliding friction. The current investigation chooses diamond-like carbon as the hard material, and copper as the soft material. The atomic configurations following sliding under non-interactive, attractive, and repulsive interaction forces are observed for soft-to-soft, hard-to-soft, and hard-to-hard sliding systems. The relationships between the normal force, the friction force, and the sliding distance are discussed. The current simulation results exhibit a similar trend with the findings of previous studies using molecular dynamics approach.     

Application of Analytic Continuations to Avoided Crossings

The two-root (i,j,k) generalized Padé approximation (GPA) and three-root (i,j,k,l) GPA as well as the two-root continued fraction approximation (CFA) and the three-root CFA are applied to the model of a three-state avoided crossing. These two procedures for analytic continuation are compared. The results indicate that both methods provide good continuation into the complex plane and can be applied to locate the complex branch point. When the same input data are chosen, the GPA works slightly better than the CFA. According to our analysis, the two-root procedure can be applied to locate the branch point around each region of avoided crossing in the problem of a multi-state avoided crossing. The accuracy of the result is found to be associated the location of complex branch point.     

Ferroelectric liquid crystalline polymers based on mesogens with halogen-containing terminal groups

A new series of halogen-containing side chain ferroelectric liquid crystal polymers was synthesized. Mesophases were characterized by differential scanning calorimetry, polarizing optical microscopy, X-ray diffraction and molecular simulation. The behaviour of the liquid crystalline phase was investigated with variation of chiral centres, spacer units and grafted ratios. It was found that the thermal stability and temperature range of the chiral smectic C phase decreased with increasing length of the oligo-oxyethylene spacer, and decreasing mesogenic group content. The bulky substituent attached to the chiral centre reduces molecular packing in smectic liquid crystal phases, which disturbs the orientation of the side chain liquid crystal polymer. Furthermore, the influence of molecular structure on electrooptical properties of FLCPs has been studied by broad band dielectric spectroscopy (from 0.1 to 1 ×10 6 Hz).     

Multicompartment polymer nanostructures with ratiometric dual-emission pH-sensitivity

Pyrazine-labeled multicompartment nanostructures are shown to exhibit enhanced pH-responsive blue-shifted fluorescence emission intensities compared to their simpler core-shell spherical analogs. An amphiphilic linear triblock terpolymer of ethylene oxide, N-acryloxysuccinimide, and styrene, PEO(45)-b-PNAS(105)-b-PS(45), which lacks significant incompatibility for the hydrophobic block segments and undergoes gradual hydrolysis of the NAS units, underwent supramolecular assembly in mixtures of organic solvent and water to afford multicompartment micelles (MCMs) with a narrow size distribution. The assembly process was followed over time and found to evolve from individual polymer nanodroplets containing internally phase segregated domains, of increasing definition, and ultimately to dissociate into discrete micelles. Upon covalent cross-linking of the MCMs with pH-insensitive pyrazine-based diamino cross-linkers, pH-responsive, photonic multicompartment nanostructures (MCNs) were produced. These MCNs exhibited significant enhancement of overall structural stability, in comparison with the MCMs, and internal structural tunability through the cross-linking chemistry. Meanwhile, the complex compartmentalized morphology exerted unique pH-responsive fluorescence dual-emission properties, indicating promise in ratiometric pH-sensing applications.     

Seaweed Chlorophyll on the Light‐electron Efficiency of DSSC

Four different seaweed extracts were employed as the dyes of dye sensitized solar cells (DSSCs) to investigate the light‐electron efficiency. The sensitizers, extracted from Nannochloropsis spp., Tetraselmis spp., Gracilaria spp., and Ulvales spp., showed their light‐electronic transfer ability in different light intensities. Among them, Ulvales output a higher light‐voltage, about 0.4 V. The output voltage increased when light intensity increased. Gracilaria extract produced a higher output voltage at 35 Lux, but its output voltage decreased over 500 Lux. The sensitizers extracted from these seaweeds had monochromatic incident photon‐to‐electron conversion efficiencies (IPCE) between 23‐61% in 220‐260 nm wavelengths. Among them, Ulvales output higher IPCE than Tetraselmis and Nannochloropsis. SEM analysis of DSSC surfaces revealed that the efficiency of seaweed DSSCs was governed by chlorophyll size. The chlorophyll particle size of Ulvales spp. was the largest. The chlorophyll particle size of Gracilaria spp. was the smallest and yielded the lowest IPCE.     

Immobilized Fullerene C60‐Enzyme‐Based Electrochemical Glucose Sensor

A mixed‐valence cluster of cobalt(II) hexacyanoferrate and fullerene C60‐enzyme‐based electrochemical glucose sensor was developed. A water insoluble fullerene C60‐glucose oxidase (C60‐GOD) was prepared and applied as an immobilized enzyme on a glassy carbon electrode with cobalt(II) hexacyanoferrate for analysis of glucose. The glucose in 0.1 M KCl/phosphate buffer solution at pH = 6 was measured with an applied electrode potential at 0.0 mV (vs Ag/AgCl reference electrode). The C60‐GOD‐based electrochemical glucose sensor exhibited efficient electro‐catalytic activity toward the liberated hydrogen peroxide and allowed cathodic detection of glucose. The C60‐GOD electrochemical glucose sensor also showed quite good selectivity to glucose with no interference from easily oxidizable biospecies, e.g. uric acid, ascorbic acid, cysteine, tyrosine, acetaminophen and galactose. The current of H₂O₂ reduced by cobalt(II) hexacyanoferrate was found to be proportional to the concentration of glucose in aqueous solutions. The immobilized C60‐GOD enzyme‐based glucose sensor exhibited a good linear response up to 8 mM glucose with a sensitivity of 5.60 × 10² nA/mM and a quite short response time of 5 sec. The C60‐GOD‐based glucose sensor also showed a good sensitivity with a detection limit of 1.6 × 10^‐6 M and a high reproducibility with a relative standard deviation (RSD) of 4.26%. Effects of pH and temperature on the responses of the immobilized C60‐GOD/cobalt(II) hexacyanoferrate‐based electrochemical glucose sensor were also studied and discussed.     

Damage evolution in an expanding/contracting hollow sphere at large strains

A generalization of one of the classical problems of plasticity theory, expansion/contraction of a hollow sphere, is proposed assuming that the conventional constitutive equations for rigid plastic, hardening material are supplemented with an arbitrary ductile damage evolution law. No restriction is imposed on the hardening law in the analytic part of the solution. The initial/boundary value problem is reduced to two equations in characteristic coordinates. A numerical scheme to solve these equations is proposed. An illustrative example is given.     

Contactless molding of arrayed chalcogenide glass lenses

The moldable chalcogenide glass material has been developed recently. This study developed a new process to produce an arrayed chalcogenide glass lenses by a contactless molding process, which is considered to have a great potential for the mass production of arrayed glass lenses with low cost, ease of manufacture and free of surface defects. The stainless steel plate with arrayed through holes was employed as the molds. The selenium based chalcogenide glass plate was put on the mold and nitrogen gas was introduced into the closed chamber to allow gas pressure up to 4 kg/cm². IR heating allows the chalcogenide glass plate to approach the soft point, and forces glass flows into the arrayed through holes to form the arrayed glass lenses by viscoelastic deformation. A higher forming temperature, pressure and longer time duration tend to produce the arrayed lenses with a higher peak height and a smaller radius of curvature. The arrayed chalcogenide glass lenses with a peak height of 430 μm can be obtained at a forming temperature of 305 °C, a gas pressure of 1 kg/cm² and a time duration of 110 s. The contactless gas assisted molding system can avoid contact induced glass sticking and gas bubble problems. The surface qualities of molded lenses are much better than that of lenses molded by the traditional contact molding process.