Proton‐conducting blend membranes of crosslinked poly(vinyl alcohol)–sulfosuccinic acid ester and poly(1‐vinyl‐1,2,4‐triazole) for high temperature fuel cells

New type of composite membranes were synthesized by crosslinking of poly(vinyl alcohol) (PVA) with sulfosuccinic acid (SSA) and intercalating poly(1‐vinyl‐1,2,4‐triazole) (PVTri) into the resulting matrix. The complexed structure of the membranes was confirmed by Fourier transform infrared (FTIR) spectroscopy. The resulting hybrid membranes were transparent, flexible, and showed good thermal stability up to ～200°C. The proton conductivities of the membranes were investigated as a function of PVTri and SSA and operating temperature. The water/methanol uptake was measured and the results showed that solvent absorption of the materials increased with increasing PVTri content in the matrix. The proton conductivity of the membranes continuously increased with increasing SO₃H content, PVTri content, and the temperature. In the anhydrous state, the maximum proton conductivity is 7.7 × 10^?5 S/cm for PVA–SSA–PVTri‐1 and for PVA–SSA–PVTri‐3 is 1.6 × 10^?5 S/cm at 150°C. After humidification (RH = 100%), PVA–SSA–PVTri‐4 showed a maximum proton conductivity of 0.0028 S/cm at 60°C. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

High residual mechanical properties at elevated temperatures of bamboo/glass reinforced‐polybenzoxazine hybrid composite

We successfully added bamboo and glass fibers into bisphenol A‐aniline based benzoxazine (BA‐a) resin by hot‐pressing method. In order to improve the interfacial adhesion between bamboo fibers and the matrix, bamboo fibers were pretreated in 6 wt% NaOH solutions for 12 h. The results showed alkali‐treatment had a positive effect on mechanical properties of the composites at both room and elevated temperatures (60°C, 110°C, 160°C, and 210°C). Due to the incorporation of glass fibers, the bamboo/glass reinforced‐polybenzoxazine hybrid composites exhibited highest strength and modulus among all samples and had high residual mechanical properties at elevated temperatures (residual mechanical properties refers to the ratio of strength and modulus of the composites at elevated temperatures to that measured at room temperature). The fractured surface morphologies of the composites were observed by scanning electron microscope. The results showed with the increase of temperature, the debonding and fiber pull‐out became apparent, and the matrix softening could be clearly observed at 210°C. In addition, thermal and thermomechanical properties of neat benzoxazine and the composites were also investigated through thermogravimetric analysis and dynamic mechanical analyzer, respectively. POLYM. ENG. SCI., 59:1818–1829, 2019. © 2019 Society of Plastics Engineers     

Galvanic deposition of silver on 80‐μm‐Cu‐fiber for gas‐phase oxidation of alcohols

Microstructured Ag‐based catalysts were developed by galvanically depositing Ag onto 80‐μm‐Cu‐fibers for the gas‐phase oxidation of alcohols. By taking advantages including large voidage, open porous structure and high heat/mass transfer, as‐made catalysts provided a nice combination of high activity/selectivity and enhanced heat transfer. The best catalyst was Ag‐10/80‐Cu‐fiber‐400 (Ag‐loading: 10 wt%; Cu‐fiber pretreated at 400 °C in air), being effective for oxidizing acyclic, benzylic and polynary alcohols. For benzyl alcohol, conversion of 94% was achieved with 99% selectivity to benzaldehyde at 300 °C using a high WHSV of 20 h^?1. Computational fluid dynamics (CFD) calculation and experimental result illustrated significant enhancement of the heat transfer. The temperature difference from reactor wall to central line was about 10–20 °C for the Ag‐10/80‐Cu‐fiber‐400, much lower than that of 100–110 °C for the Ag‐10‐Cu‐2/Al₂O₃ at equivalent conversion and selectivity. Synergistic interaction between Cu₂O and Ag was discussed, being assignable to the activity improvement. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1045–1053, 2014     

Segmented and nonsegmented polyurethanes: Polyaddition products of 4,4′‐bis(2‐hydroxyethoxy)diphenyl ether and 1,6‐hexanediisocyanate

New linear polyurethanes (PUs) derived from 4,4′‐bis(2‐hydroxyethoxy)diphenyl ether (4‐HEDE) and 1,6‐hexanediisocyanate (HDI) were synthesized by either melt or solution polymerization. We found that the properties of PUs obtained are dependent mainly on the kind of organic solvent, contribution of the catalyst, and concentration of the monomers used. Good results are obtained using aprotic solvent‐N,N‐dimethylformamide, ∼ 30 wt % concentration of monomers, dibutyltin dilaurate as a catalyst, and conducting the process at 90–100°C for 4 h. This article presents basic properties of the series of PUs obtained. Thermal properties of the polymers were investigated by means of thermal gravimetric analysis and differential scanning calorimetry. Molecular weight distribution was determined by gel permeation chromatography. Shore hardness and tensile test results are also presented. The structure of the resulting products was confirmed by elemental analysis, Fourier transform infrared spectroscopy and X‐ray diffractometry. We also present the properties of copolyurethanes type 4‐HEDE/HDI/1,6‐hexanediol or 4‐HEDE/HDI/polytetramethylene oxide containing variable amounts of 1,6‐hexanediol or polytetramethylene oxide (M _n ∼ 650) synthesized in the optimal conditions established earlier for PU 4‐HEDE/HDI. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 83–91, 1999     

Synthesis,characterization, and thermal degradation of novel poly(2‐(5‐bromo benzofuran‐2‐yl)‐2‐oxoethyl methacrylate)

A novel methacrylate monomer containing benzofuran side group, 2‐(5‐bromo benzofuran‐2‐yl)‐2‐oxoethyl methacrylate (BOEMA), was synthesized from esterification reaction of 2‐bromo‐1‐(5‐bromo benzofuran‐2‐yl) ethanone with sodium methacrylate at 85°C in the presence of 1,4‐dioxane solvent. After characterization with Fourier transform infrared spectrophotometer, nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR), its homopolymerization was carried out by free radical polymerization at 60°C in the presence of benzoyl peroxide initiator and 1,4‐dioxane solvent. The glass transition temperature (T_g) of the synthesized novel polymer, poly(2‐(5‐bromo benzofuran‐2‐yl)‐2‐oxoethyl methacrylate) [poly(BOEMA)], was determined to be 137°C with differential scanning calorimetry technique. Thermal degradation kinetics of poly(BOEMA) was investigated by thermogravimetric analysis method at different heating rates with 5°C/min intervals between measurements. From dynamic measurements, the analysis of each process mechanism of Coats–Redfern and Van Krevelen methods showed that the most probable model for the decomposition process of poly(BOEMA) homopolymer agrees with the random nucleation, F₁ mechanism. The apparent decomposition activation energies of poly(BOEMA) by Kissinger's and Flynn–Wall–Ozawa methods in the studied conversion range were 188.47 and 180.13 kJ/mol, respectively. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

X‐ray Diffraction Study of the Effect of High‐Temperature Heat Treatment on the Microstructural Stability of Third‐Generation SiC Fibers

Third‐generation SiC fibers [High Nicalon S (HNS) and Tyranno SA3 (Ty–SA3)] were studied by X‐ray diffraction and transmission electron microscopy (TEM) after heat treatments in neutral atmosphere up to 1900°C. The microstructural changes in both materials were determined using a modified Hall–Williamson method introducing an anisotropy parameter taking into account the high density of planar defects. HNS fibers exhibit significant modifications in the coherent diffraction domains (CDD) size, which drastically increases from 24 to 70 nm in the range 1600°C–1900°C. TEM observations support these results. The residual microstrain values decrease from 0.0015 to 0.0005 between 1750°C and 1850°C. Similarly, the anisotropy parameter significantly decreases in the same temperature range. Concerning the Ty–SA3 fibers, no evolution in terms of CDD size and residual microstrain was observed. However, the anisotropy parameter decreases at 1800°C. TEM observations did not show noticeable grain growth. The grain size was found to be larger than the CDD and the planar defects density to decrease at high temperature. In both types of fibers, the CDD sizes are similar for the highest temperature heat treatments.     

Polyaniline doped with α, ω‐alkanedisulfonic acids: preparation and characterization

The use of α, ω‐alkanedisulfonic acid, HO₃S(CH₂)_nSO₃H (n = 1, 4, 6 and 12), as a dopant for polyaniline (PANi) was investigated. This series of disulfonic acids with varying chain lengths were synthesized and used in the doping of PANi. The doped polymers showed conductivity in the range 10^?2 to 10^?1 S cm^?1. Thermal studies showed that the doped polymers, depending on the chain length of α,ω‐alkanedisulfonic acid, were stable up to ca 300 °C and the thermal stability decreased with increasing dopant chain length. The thermal stability of α,ω‐alkanedisulfonic acid‐doped PANi was higher than that of alkanesulfonic acid‐doped PANi which typically degrades around 250 °C, suggesting a moderately broader processing window for α,ω‐alkanedisulfonic acid‐doped PANi for blending with other thermoplastics. Copyright © 2012 Society of Chemical Industry     

Determination of 3‐D Alumina Grain Orientation,Size, Shape,and Growth Kinetics from 2‐D Data in Nextel™ 610 Fibers

Nextel^? 610 alumina fibers were heat‐treated at 1100°C–1500°C for 1–100 h in air. Grain size distributions (GSDs) and grain orientation distributions (ODs) with respect to the fiber axis were characterized by analysis of TEM images from longitudinal fiber sections. The 2‐D GSDs and ODs were characterized as ellipses. 3‐D GSDs and ODs were calculated by fitting distributions of oriented oblate ellipsoids to 2‐D GSDs and ODs formed by ellipsoid–section‐plane intersections. The standard deviations (SDs) of log‐normal GSDs consistently increased with grain size, which is not diagnostic of normal grain growth. The grain aspect ratio (α) and the tendency of the short grain axis to orient perpendicular to the fiber axis also increased with grain size, resulting in more textured fibers at larger grain sizes. Average 3‐D grain sizes were larger than 2‐D sizes for GSDs with small SDs, but smaller for GSDs with large SDs because of under sampling of small grains. 3‐D grain growth kinetics had the same 815 kJ/mol activation energy as that found by 2‐D analysis, but the grain growth exponent m of 6.0 was larger and the pre‐exponential factor much smaller. Expressions for 3‐D log‐normal GSDs as a function of heat treatment temperature and time were determined. α‐distributions and ODs were determined as a function of grain size. Methods for determining 3‐D GSDs are discussed.     

A copolymer of poly[2,2′‐(m‐phenylene)‐5,5′‐ bibenzimidazole] and poly(2,5‐benzimidazole) for high‐temperature proton‐conducting membranes

A novel copolymer of polybenzimidazoles was prepared by copolymerization of 3,3′‐diaminobenzidine tetrahydrochloride, 3,4‐diaminobenzoic acid and isophthalic acid in polyphosphoric acid at 200 °C. The polymerization could be performed within 90–110 min with the assistance of microwave irradiation. The solubility of the copolymer obtained in N,N‐dimethylacetamide (DMAc) was improved compared with those of poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] and poly(2,5‐benzimidazole). Thus copolymer membranes could be readily prepared by dissolving the copolymer powders in DMAc with refluxing under ambient pressure. The decomposition temperature of the copolymer was about 520 °C in air according to thermogravimetric analysis data. The proton conductivity and mechanical strength of the phosphoric acid‐doped copolymer membranes were investigated at elevated temperatures. A conductivity of 0.09 S cm^?1 at 180 °C and a tensile stress at break of 5.9 MPa at 120 °C were achieved for the acid‐doped copolymer membranes by doping acids in a 75 wt% H₃PO₄ solution. Copyright © 2010 Society of Chemical Industry     

Blistering in carbon‐fiber‐filled fluorinated polyimide

A blistering study was performed on a fluorinated polyimide resin and its carbon‐fiber composite in an effort to determine the blister‐formation temperature and the influence of blisters on composite performance. The fluorinated resin and carbon‐fiber composite exhibit higher glass‐transition (435–455°C) and decomposition temperatures (above 520°C) than similar polyimide resins and their carbon‐fiber composites currently used. Two techniques were used to determine moisture‐induced blister formation. A transverse extensometer with quartz lamps as a heating source measured thickness expansion, as did a thermomechanical analyzer as a function of temperature. Both methods successfully measured the onset of blister formation with varying amounts of absorbed moisture (up to 3 wt%) in the samples. The polyimide resin exhibited blister temperatures ranging from 225 to 362°C, with 1.7–3.0 wt% absorbed moisture, and the polyimide composite had blister temperatures from 246 to 294°C with 0.5–1.5 wt% moisture. The blistering effects of the polyimide composites were found to have little correlation with modulus. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Residual solvent and its diffusion in acrylic fibers

A survey showed that some commercial acrylic fiber products contain small quantities of residual solvent (dimethylacetamide). No diffusion of solvent from these products could be detected on laundering, dry cleaning, or exposure to synthetic perspiration. Acrylic carpets containing residual solvent were enclosed in sealed boxes to simulate a closed room. Air in the boxes was monitored for solvent content over a 14-day period at 24°C (75°F) and 38°C (100°F) at both low and high humidity conditions. In all cases the solvent content of the air was below the detection limit of the best analytical procedure available (below 0.1 ppm). Diffusion rates of sol vent from 15-denier carpel fiber into nitrogen were measured over the temperature range of 25–100°C. There was no detectable diffusion below 60°C measured over a 24-h period. Mass diffusivities ranged from 2.5 × 10^?19 cm²/s at 60°C to 6.4 × 10^?14 cm²/s at 100°C. Under the conditions of expected use, the rate of diffusion of residual solvent from acrylic fibers is very low. Based on the low concentrations of residual solvent and its very low diffusion rate, there is an extremely low probability of any exposure to solvent from the residual solvent present in commercial acrylic fiber products.     

High‐resolution thermogravimetry of poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The thermal degradation and kinetics of poly(2,6‐dimethylphenylene oxide) (PPO) were studied by high‐resolution thermogravimetry. The thermogravimetry measurements were conducted at an initial heating rate of 50°C min⁻¹, resolution 4.0, and sensitivity 1.0 in both nitrogen and air from room temperature to 900°C. A two‐step degradation process was clearly revealed in air at the temperatures of 430°C and 521°C. The thermal degradation temperatures and kinetic parameters of the PPO appear to be higher in air than in nitrogen, indicative of a higher thermostability in air. The temperature, activation energy, order, and frequency factor of the thermal degradation of the PPO in nitrogen are 419°C, 100–120 kJ mol⁻¹, 0.5, and 13–17 min⁻¹, respectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1887–1892, 1999     

Spinning and drawing properties of ultrahigh‐molecular‐weight polyethylene fibers prepared at varying concentrations and temperatures

The concentrations and temperatures of ultrahigh‐molecular‐weight polyethylene (UHMWPE) gel solutions exhibited a significant influence on their rheological and spinning properties. The shear viscosities of UHMWPE solutions increased consistently with increasing concentrations at a constant temperature above 80°C. Tremendously high shear viscosities of UHMWPE gel solutions were found as the temperatures reached 120–140°C, at which their shear viscosity values approached the maximum. The spinnable solutions are those gel solutions with optimum shear viscosities and relatively good homogeneity in nature. Moreover, the gel solution concentrations and spinning temperatures exhibited a significant influence on the drawability and microstructure of the as‐spun fibers. At each spinning temperature, the achievable draw ratios obtained for as‐spun fibers prepared near the optimum concentration are significantly higher than those of as‐spun fibers prepared at other concentrations. The critical draw ratio of the as‐spun fiber prepared at the optimum concentration approached a maximum value, as the spinning temperature reached the optimum value of 150°C. Further investigations indicated that the best orientation of the precursors of shish‐kebab‐like entities, birefringence, crystallinity, thermal and tensile properties were always accompanied with the as‐spun fiber prepared at the optimum concentration and temperature. Similar to those found for the as‐spun fibers, the birefringence and tensile properties of the draw fibers prepared at the optimum condition were always higher than those of drawn fibers prepared at other conditions but stretched to the same draw ratio. Possible mechanisms accounting for these interesting phenomena are proposed.     

Maghnite‐H+ as a cationic catalyst in the synthesis of poly(1,3‐dioxolane) and α,ω‐methacryloyloxy‐poly(1,3‐dioxolane)

The polymerization of 1,3‐dioxolane catalyzed by Maghnite‐H^+; (Mag‐H⁺), a montmorillonite sheet silicate clay exchanged with protons, was investigated. The cationic ring‐opening polymerization of 1,3‐dioxolane was initiated by Mag‐H⁺ at different temperatures (20, 30, 50, and 70°C) in bulk and in a solvent (dichloromethane). The effects of the amount of Mag‐H⁺ and the temperature were studied. The polymerization rate and the average molecular weights increased with an increase in the temperature and the proportion of the catalyst. These results indicated the cationic nature of the polymerization and suggested that the polymerization was initiated by proton addition to the monomer from Mag‐H⁺. Moreover, we used a simple method, in one step in bulk and in solution at room temperature (20°C), to prepare a telechelic bismacromonomer: α,ω‐bisunsaturated poly(1,3‐dioxolane). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 78–82, 2006     

Radiation effect on the thermal conductivity and diffusivity of ramie fibers in a range of low temperatures by γ rays

To understand the influence on the thermal conductivity by the length of the molecular chain in the polymer fiber, the thermal conductivity and thermal diffusivity of ramie fibers and those irradiated by γ rays, which induced molecular chain scission of cellulose, were investigated in a range of low temperatures. The degrees of polymerization, crystallinities, and orientation angles of ramie fibers and those irradiated by γ rays (γ‐ray treatment) were measured by the solution viscosity method, solid‐state NMR, and X‐ray diffraction. Only the degree of polymerization decreased with the γ‐ray treatment, and the crystallinities and orientation angles were almost independent of the γ‐ray treatment. The thermal conductivities of the ramie fibers with and without γ‐ray treatments decreased with decreasing temperature. The thermal diffusivities of the ramie fibers and those irradiated by γ rays were almost constant from 250 to 100 K, increased slightly with the temperature decreasing from 100 to 50 K, and increased rapidly with the temperature decreasing below 50 K. The thermal conductivity and thermal diffusivity of the ramie fibers decreased with the γ‐ray treatment. The mean free path of the phonon in the ramie fibers was reduced by the γ‐ray treatment. This decrease of the thermal diffusivity and thermal conductivity was explained by the reduction of the mean free path of the phonon by molecular chain scission with γ rays. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 5007–5018, 2006     

Thermal conductivity of pristine and brominated highly graphitized pitch based carbon fibers

The thermal conductivity of brominated and pristine Union Carbide P-100 graphite fibers in the 30–160°C temperature range was determined by measuring the thermal conductivities of graphite fiber epoxy composite samples and then excluding the epoxy contribution. A comparative thermal conductivity instrument was used to measure the thermal conductivity of the samples containing fibers. Results showed that the thermal conductivity values were 225–370 W/m-k and 215–340 W/m-K for pristine and brominated fibers respectively. Furthermore, the thermal conductivity ratio of brominated to pristine P-100 fibers was 0.89, 0.91 and 0.92 at 55–80°C, 108 and 130°C respectively. Such a decrease in thermal conductivity results almost entirely from the 10% increase in the fiber cross-sectional area due to bromination. This result suggested that bromination effects on P-100 fiber structure is small and that some structural changes (presumably the sharp-angled domain wall becomes less sharp) occurred in the 80–108°C temperature range.     

Effects of the oxidation temperature on the structure and properties of polyacrylonitrile‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate, oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of the oxidation temperature of the PAN hollow fiber precursor on the microstructure, specific surface, pore size distribution, and adsorption properties of PAN‐based activated carbon hollow fiber (PAN‐ACHF) were studied. When PAN hollow fibers were oxidized at 270°C, because of drastic oxidation, chain scission occurred, and the number of pores within and on the surface of the resultant PAN‐ACHF increased, but the pores were just in the thinner region of the skin of PAN‐ACHF. The surface area of PAN‐ACHF reached a maximum when the oxidation temperature was 270°C. The adsorption ratios to creatinine were all higher than 90% at all oxidation temperatures, and the adsorption ratio to VB₁₂ reached a maximum (97%) at 230°C. The dominant pore sizes of the mesopores in PAN‐ACHF ranged from 2 to 5 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 203–207, 2005     

Joining of SiC Fiber‐Bonded Ceramics using Silver,Copper, Nickel,Palladium, and Silicon‐Based Alloy Interlayers

SiC fiber‐bonded ceramics, SA‐Tyrannohex^®, (SA‐THX) with perpendicular and parallel fiber orientations were brazed using Ag‐, Ni‐ and Pd‐base brazes, and four Si–X (X: Ti, Cr, Y, Ta) eutectics. Outcomes were variable, ranging from bonded joints through partially bonded to un‐bonded joints. Prominent Ti‐ and Si‐rich interfaces developed with Cusil‐ABA, Ticusil, and Copper‐ABA and Ni‐ and Si‐rich layers with MBF‐20. Stress rupture tests at 650 and 750°C on Cusil‐ABA‐bonded joints revealed a temperature‐dependent behavior for the perpendicular joints but not for the parallel joints with failure occurring at brazed interface. Higher‐use temperatures can be targeted with eutectic Si–Ti and Si–Cr alloys.     

Microwave pre‐oxidation for polyacrylonitrile precursor coated with nano‐carbon black

A surface coating was successfully applied through dipping the polyacrylonitrile (PAN) precursor fibers in a carbon black (CB) bath containing a hydrolyzed binder. The coated fibers were pre‐oxidized over the microwave furnace at temperatures ranging from 100°C to 170°C for different heating times. The changes in chemical structure were studied by Fourier transfer infrared spectroscopy combined with elemental analyzer. X‐ray diffraction was employed to study the crystalline structure and its related parameters. Differential scanning calorimeter and thermogravimetry were used for thermal analysis. In addition, the fiber morphology and the mechanical properties were also evaluated. Scanning electron microscopy results confirmed the presence of CB on the surface of PAN precursor. The analysis in the chemical structure showed an apparent response of coated PAN fibers to the microwave heating, since the microwave field induced the cyclization and crosslinking reactions. The crystallinity and the crystallite height decreased. Furthermore, the tensile strength and elongation of pre‐oxidized fibers decreased with the increase of heating time. The measured oxygen content revealed that the pre‐oxidized fibers can withstand the high temperatures on the following stage (carbonization). POLYM. ENG. SCI., 59:457–464, 2019. © 2018 Society of Plastics Engineers     

Solvothermal Conversion of Nanofiber to Nanorod‐Like Mesoporous γ‐Al2O3 Powders,and Study Their Adsorption Efficiency for Congo Red

Mesoporous γ‐Al₂O₃ powders with nanofiber and nanorod‐like structures were synthesized using boehmite sols in the presence of triblock copolymer, P123 in ethanol by solvothermal process at different temparatures (100°C–165°C) followed by calcination at 400°C–1000°C. The powders were characterized by low‐ and wide‐angle X‐ray diffraction (XRD), N₂ adsorption–desorption, and transmission electron microscopy (TEM). The adsorption efficiency of the powders with Congo red (CR) was studied by UV–vis spectroscopy. The γ‐Al₂O₃ phase became stable up to 1000°C. The nanorods obtained at 165°C had narrower pore size distribution (PSD) than nanofibers synthesized at 100°C, the former showed higher CR adsorption efficiency. The stepwise growth mechanism of nanofibers to nanorods conversion with increase in solvothermal temperatures was illustrated.