Predicting the electrospinnability of polymer solutions with electromechanical simulation

The number of polymers successfully electrospun is increasing, and methods are needed predict the electrospinnability of polymers. With such methods, researchers should consider the polymer solution parameters and perform measurements in conditions that mimic the electrospinning process. A novel test method based on the electromechanical simulation of the fiber formation was developed. We formed fibers by mechanically dragging a conductive ball from the solution at an applied voltage and measuring the electrical current. The changes in the time of the electrical current (the ball current) reflect the fiber‐formation process, which depended on certain polymer solution properties (e.g., viscosity, surface tension, liquid flow) and on the influence of charges on the fiber surface. The data obtained with the proposed method was compared with experimental data from electrospinning trials with the spinneret and bubble electrospinning. The results demonstrate that the ball‐current method made it possible to predict the polymer solution behavior in the electrospinning process. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41091.     

Poly(vinylidene fluoride) membrane with piezoelectric β‐form prepared by immersion precipitation from mixed solvents containing an ionic liquid

Poly(vinylidene fluoride) (PVDF) membranes with exclusive β‐form have been directly obtained by immersion precipitation from the mixed solvents containing an ionic liquid (IL). In contrast, without the IL only the α‐form is generated. The ion–dipole interactions between the IL and PVDF chains should account for the formation of the β‐form with TTTT conformation. In addition, the presence of the IL accelerates the crystallization and gelation of PVDF, responsible for the particulate morphology and high water flux in the membranes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40505.     

Analyses of structurally modified quasi‐solid‐state electrolytes using electrochemical impedance spectroscopy for dye‐sensitized solar cells

Electrochemical properties of structurally modified quasi‐solid‐state electrolytes were examined using porous substrates (PSs). The PS was prepared into two categories by a phase inversion method with a brominated poly(phenylene oxide) (BPPO): the sponge and finger types. Effects of the humidification and cosolvent compositions on the morphology of the PS were analyzed by scanning electron microscopy. In all cases of the PSs, a higher V_OC was observed of about 0.1 V than that of a liquid electrolyte owing to a suppressed back electron charge transfer. In addition, the PS prepared by the polymer solution of 1 : 4 : 1 (BPPO : N‐methyl‐2‐pyrrolidone : butyl alcohol) with the humidification process showed better photovoltaic properties in terms of the current density and conversion efficiency owing to the appropriate combinations of pore size, tortuosity, and interconnectivity. Effects of the pore structures were intensively examined using electrochemical impedance spectroscopy. The impedance results revealed that large pores at the surface layers are advantageous for a lower R_S and R_TiO2. Meanwhile, the straight inner structure is beneficial for the facile I^?/I₃^? diffusion, thus lowering R_Pt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39739.     

How Different Characterization Techniques Elucidate the Nature of the Gold Species in a Polycrystalline Au/TiO2 Catalyst

TiO₂‐supported gold species were prepared via the deposition‐precipitation route, with conservation of the initial speciation by freeze‐drying. The structural and electronic properties of the Au species were investigated by X‐ray absorption spectroscopy, electron microscopy, and IR spectroscopy of adsorbed CO in four states. Exclusively Au^III was deposited on the TiO₂ surface in patches ranging from isolated Au ions to three‐dimensional clusters. This paper illustrates in detail the unique contributions of all characterization techniques to this structural model.     

Controllable reinforcement of stiffness and toughness of polypropylene via thermally induced self‐assembly of β‐nucleating agent

An easy approach was reported to achieve the simultaneous reinforcement and toughening of polypropylene (PP) via thermally induced self‐assembly of β‐nucleating agent (TMB‐5). The results showed that the processing temperatures dictated the solubility and self‐assembly of TMB‐5 in the polymer melts to determine the subsequent morphology development of PP. At low processing temperature, TMB‐5 did not dissolve into the polymer melt but remained original shape to induce PP to crystallize into spherulites so that it only promoted the formation of β‐form crystals to enhance the toughness of the samples. At high processing temperature, TMB‐5 gradually dissolved into the polymer melts. On cooling, the dissolved nucleating agent self‐assembled into high aspect ratio fibrils through intermolecular hydrogen‐bonding interactions. Due to a favorable matching between PP and TMB‐5, PP preferred to nucleate and grow orthogonally to the fibril axis and into oriented hybrid shish‐kebab morphology with rich β‐form crystals. Compared with isotropic spherulites, the anisotropic structure exhibited excellent properties of the β‐form crystal and shish‐kebab morphology to simultaneously improve the strength and toughness of TMB‐5‐modified PP samples. With the increasing processing temperature, more dissolved TMB‐5 was involved in the self‐assembly procedure to generate longer fibrils and induce more lamellae to grow on the surface. As a consequence, the anisotropy of the PP samples increased further, bringing out more improvements of the tensile strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40605.     

Characterization and performance of dodecyl amine functionalized graphene oxide and dodecyl amine functionalized graphene/high‐density polyethylene nanocomposites: A comparative study

Dodecyl amine (DA) functionalized graphene oxide(DA‐GO) and dodecyl amine functionalized reduced graphene oxide (DA‐RGO) were produced by using amidation reaction and chemical reduction, then two kinds of well dispersed DA‐GO/high‐density polyethylene (HDPE) and DA‐RGO/HDPE nanocomposites were prepared by solution mixing method and hot‐pressing process. Thermogravimetric, X‐ray photoelectron spectroscopy, Fourier transforms infrared spectroscopy, X‐ray diffractions, and Raman spectroscopy analyses showed that DA was successfully grafted onto the graphene oxide surface by uncleophilic substitution and the amidation reaction, which increased the intragallery spacing of graphite oxide, resulting in the uniform dispersion of DA‐GO and DA‐RGO in the nonpolar xylene solvent. Morphological analysis of nanocomposites showed that both DA‐GO and DA‐RGO were homogeneously dispersed in HDPE matrix and formed strong interfacial interaction. Although the crystallinity, dynamic mechanical, gas barrier, and thermal stability properties of HDPE were significantly improved by addition of small amount of DA‐GO or DA‐RGO, the performance comparison of DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites indicated that the reduction of DA‐GO was not necessary because the interfacial adhesion and aspect ratio of graphene sheets had hardly changed after reduction, which resulting in almost the same properties between DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39803.     

Silk‐inspired polyurethane containing glyalaglyala tetrapeptide. III. morphological,thermal, and mechanical features of electrosprayed and electrospun deposition

Morphological, thermal, and mechanical features of electrosprayed and electrospun deposition of the silk‐inspired polyurethane (PU) containing GlycineAlanineGlycineAlanine (GlyAlaGlyAla, the featured peptide sequence of silkworm silk fibroin) tetrapeptide, which was synthesized by the traditional liquid‐phase peptide synthesis method and the classical two‐step polymerization method using Boc‐protected amino acids and diisocyanates as starting materials, were characterized. The results show that the synthesized silk‐inspired PU dissolved in tetrahydrofuran (THF) can be easily electrosprayed or electrospun into the film form, although its molecular weight ranging from 13,000 to 15,000 is quite low. Elastomeric fibrous membranes with surface morphologies of “droplets,” “bead‐on‐string,” and “nonwoven fibers” have been obtained by electrospraying and electrospinning the silk‐inspired PU/THF solution of varying concentrations. The thermograms confirm high thermostability of the silk‐inspired PU between 350 and 400°C due to the polar peptide linkages. The tanδ peak of dynamic mechanical analysis curve corresponding to its glass transition temperatures is detected at ?34.3°C. Its elongation at break is about 140–150%, and the breaking tensile strength ranges from 22 to 27 MPa, which is consistent with the data of other PUs containing l ‐alanine residue. Information provided by this study can be used to better understand the correlation between the natural and man‐made silk polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40245.     

Preparation and characterization of carboxymethyl starch under ultrasound‐microwave synergistic interaction

Using native cassava starch as raw materials, carboxymethyl starch (CMS) was prepared by ethanol solvent method under the ultrasound‐microwave synergistic interaction. And the structure of CMS was characterized employing Fourier transform infrared (FTIR) spectrometer, scanning electron microscopy (SEM), X‐ray diffraction (XRD) and thermogravimetric analyzer. Typically, the optimal synthesis conditions for the preparation process confirmed by orthogonal experiment L₁₈ (6¹ × 3⁶) were shown as follows: the ultrasonic treatment temperature was fixed to 35°C and two steps alkalization was employed; the ultrasonic time was 40 min before alkalizing and the ultrasonic power was 220 W; the amount of sodium hydroxide was 8.8 g, the microwave alkalization time was 2 min; the amount of monochloroacetic acid was 11.34 g; the amount of 95% (v/v) ethanol was 70 mL; the microwave etherification time was 3 min. The degree of substitution of prepared CMS was 1.089 ± 0.041, which was increased 30.4% compared with the prepared sample without ultrasound‐microwave synergistic treatment. FTIR results showed that the strong ? COO? characteristic absorption peaks of the stretching vibration were observed at 1613 and 1421 cm^?1, which proved that the carboxymethylation of cassava starch was occurred. SEM results suggested that there were many cracks and dents on CMS granules; and, XRD results indicated that the carboxymethylation of starch occurred both in amorphous region and crystalline region, the noticeable damage of crystalline region by carboxymethylation was observed. Thermogravimetric analysis (TG) and derivative TG showed that thermal stability of CMS changed better compared with native starch. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40906.     

Bio‐oil from whole‐tree feedstock in resol‐type phenolic resins

Renewable chemicals are of growing importance in terms of opportunities for environmental concerns over fossil‐based chemicals. Lignocellulosic biomass can be converted into energy and chemicals via thermal and biological processes. Among all the transformation processes available, fast pyrolysis is the only one to produce a high yield of a liquid‐phase product called bio‐oil or pyrolysis oil. Bio‐oil is considered to be a promising substitute for phenol in phenol formaldehyde (PF) resin synthesis. In this work, bio‐based phenolic resins have been formulated, partially substituting phenol by bio‐oils from two Canadian whole‐tree species. The new resins are produced by replacing 25, 50, and 75% of phenol with bio‐oil for each species (three bioresins per species). The aim of this study is to synthesize renewable resins with competitive price and satisfactory quality. The results obtained have shown that substitution degree up to 50% provided reactivity and performance equal or superior to the pure PF resin. They also present a good storage stability, improved shear strength, and thermal stability comparable to the pure PF. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40014.     

Terpolymers as precursors for CuO nanoparticles synthesis

This work describes the synthesis of terpolymers of aniline, diphenylamine, and o‐anthranilic acid (PANIDPAA) by 1 : 1 : 1 molar ratio of the respective monomers doped by different concentration of copper ions via in situ chemical terpolymerization. The results are justified by measuring spectral characteristics namely, UV‐vis absorption spectra, FTIR, and TGA. Calcining these PANIDPAA terpolymers doped by copper at temperatures in the range of 700°C led to the formation of CuO nanoparticles in the nanoscale by thermal decomposition in air directly. The stages of decompositions and the calcination temperature of the precursors have been determined from thermal analysis data sheet. The obtained CuO nanoparticles have been characterized by X‐ray diffraction and transmission electron microscope (TEM). TEM showed a particle size less than 40 nm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41150.