Synthesis and characterization of novel sulfonated poly(arylene ether ketone) copolymers with pendant carboxylic acid groups for proton exchange membranes

A series of novel side-chain-type sulfonated poly(arylene ether ketone)s with pendant carboxylic acid groups copolymers (C-SPAEKs) were synthesized by direct copolymerization of sodium 5,5'-carbonyl-bis(2-fluorobenzenesulfonate), 4,4'-difluorobenzophenone and 4,4'-bis(4-hydroxyphenyl) valeric acid (DPA). The expected structure of the sulfonated copolymers was confirmed by FT-IR and H-1 NMR. Membranes with good thermal and mechanical stability could be obtained by solvent cast process. It should be noted that the proton conductivity of these copolymers with high sulfonation degree (DS > 0.6) was higher than 0.03 S cm(-1) and increased with increasing temperature. At 80 degrees C, the conductivity of C-SPAEK-3 (DS = 0.6) and C-SPAEK-4 (DS = 0.8) reached up to 0.12 and 0.16 S cm-1, respectively, which were higher than that of Nafion 117 (0.10 S cm(-1)).

Poly(aryl ether)s containing ter- and pentafluorene pendants for efficient blue light emission

Four novel thermally stable poly(aryl ether)s, e.g., P3F, P5F, P2A3F, and P2A5K containing ter- or pentafluorene units in the side chains for efficient blue light emission have been designed and synthesized. All the polymers show the optical properties identical to the corresponding monomers and are amorphous with higher glass transition temperature (T-g) than their monomeric Counterparts. The polymer light-emitting diodes (PLEDs) were fabricated with the device structure of ITO/(PEDOT:PSS)/polymer/Ca/Al. The incorporation of diphenylamine group to oligofluorene terminals significantly reduces the hole-injection energy barrier in PLEDs. The devices based on P2A3F and P2A5F show the luminous efficiencies of 1.2 and 2.0 cd/A at a brightness of 300 cd/m(2) with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.15, 0.13) and (0.19, 0.20), respectively. All these indicate that the high-performance light-emitting polymers can be synthesized with the traditional condensation polymerization through careful design of polymer structures.

Synthesis and characterization of blue-light-emitting poly(aryl ether)s containing oligofluorenes in the main chain

A series of blue light-emitting poly(aryl ether)s (PAEs) containing ter- or pentafluorenes in the main chain have been synthesized via nucleophilic substitution polycondensation reaction. The energy levels of the polymers were tuned by introducing hole-transporting triaryamine groups in the side chains and/or incorporating electron-transporting oxadiazole segments in the main chain. The optical properties of the polymers are dominantly determined by the well-defined oligofluorene segments, and therefore all polymers show high photoluminescence quantum yield. Differential scanning calorimeter (DSC) characterizations indicate that they are vitrified polymers with high glass transition temperature (up to 156 degrees C). The polymers comprising pentafluorenes exhibit electroluminescent properties equal to or better than fully conjugated fluorene homopolymers. With the device structure of ITO/PEDOT:PSS/polymer/Ca/Al, an external quantum efficiency of 1.4% along with Commission Internationale de L'Eclairage (CIE) coordinates of (0.17, 0.09) has

Gas and water vapor transport through a series of novel poly(aryl ether sulfone) membranes

The permeation behavior of water vapor, H-2, CO2, O-2, N-2, and CH4 gases in a series of novel poly(aryl ether sulfone)s has been examined over a temperature range of 30-100 degreesC. These polymers include four alkyl-substituted cardo poly(aryl ether sulfone)s and four intermolecular interaction enhanced poly(aryl ether sulfone)s. Their water vapor and gas transport properties were compared to the unmodified cardo poly(aryl ether sulfone) (PES-C). It was found that the bulky alkyl substituents on the phenylene rings were advantageous for gas permeability, while the intermolecular hydrogen bonds and ionic bonds resulted in a considerable increase in gas permselectivity. The causes of the trend were interpreted according to free volume, interchain distance, and glass transition temperature, together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest was the observation that IMPES-L, which simultaneously bears bulky isopropyl substituent and pendant carboxylic groups, displayed 377% higher O-2 permeability and 5.3% higher O-2/N-2 permselectivity than PES-C. Furthermore, sodium salt form PES-Na+ and potassium salt form PES-K+ exhibited water vapor permeability twice as high as PES-C and H2O/N-2 selectivity in 10(5) order of magnitude.

Synthesis of a new aryl ether ketone polymer

The synthesis of a new aryl ether ketone polymer with an advantageous ratio of glass transition temperature to melting temperature is reported.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone). V: Estimation of temperature distribution during cure process

A numerical method to estimate temperature distribution during the cure of epoxy-terminated poly(phenylene ether ketone) (E-PEK)-based composite is suggested. The effect of the temperature distribution on the selection of cure cycle is evaluated using a suggested alternation criterion. The effect of varying heating rate and thickness on the temperature distribution, viscosity distribution and distribution of the extent of cure reaction are discussed based on the combination of the here-established temperature distribution model and the previously established curing kinetics model and chemorheological model. It is found that, for a thin composite (<=10mm) and low heating rate (<=2.5K/min), the effect of temperature distribution on cure cycle and on the processing window for pressure application can be neglected. Low heating rate is of benefit to reduce the temperature gradient. The processing window for pressure application becomes narrower with increasing thicknesses of composite sheets. The validity of the temperature distribution model and the modified processing window is evaluated through the characterization of mechanical and physical properties of E-PEK-based composite fabricated according to different temperature distribution conditions.

Studies on fracture morphology of short carbon fiber reinforced poly(phenylene ether ketone)(SCF/PEK-C) composites

The shear fracture morphology of SCF/PEK-C composite with carbon fibers treated for different times was studied carefully by SEM. The result shows that the adhesion between fiber and matrix was improved and fractured model also changed from interface fracture to brittle fracture with increasing treatment time of carbon fiber. The fracture mechanism was discussed preliminary.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .3. Determination of the time of pressure application

The curing temperature, pressure, and curing time have significant influence on finished thermosetting composite products. The time of pressure application is one of the most important processing parameters in the manufacture of a thermosetting composite. The determination of the time of pressure application relies on analysis of the viscosity variation of the polymer, associated with curing temperature and curing time. To determine it, the influence of the time of pressure application on the physical properties of epoxy-terminated poly(phenylene ether ketone) (E-PEK)-based continuous carbon fiber composite was studied. It was found that a stepwise temperature cure cycle is more suitable for manufacture of this composite. There are two viscosity valleys, in the case of the E-PEK system, associated with temperature during a stepwise cure cycle. The analysis on the effects of reinforcement fraction and defect content on the composite sheet quality indicates that the width-adjustable second viscosity valley provides a suitable pressing window. The viscosity, ranging from 400 to 1200 Pa . s at the second viscosity valley, is the optimal viscosity range for applying pressure to ensure appropriate resin flow during curing process, which enables one to get a finished composite with optimal fiber volume fraction and low void content. (C) 1997 John Wiley & Sons, Inc.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .4. Cure cycle simulation

Epoxy-terminated poly(phenylene ether ketone) (E-PEK) developed in this Institute is a candidate matrix resin for polymer composites as structural materials. Cure cycles for this reaction system were simulated according to the previously established processing model. It is found that for the E-PEK system, the curing process is best completed by a stepwise cure cycle comprising two isothermal processes at different temperatures, T-1 and T-2. The cure cycles over a wide range of processing parameters simulated, based on the established processing model, indicate that the processing window is width-adjustable. Analysis of the mechanical properties of the composite sheets showed that the simulated cure cycles are acceptable and reliable. (C) 1997 John Wiley & Sons, Inc.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .1. DSC characterization of curing reaction

The curing reaction process of epoxy-terminated poly(phenylene ether ketone) (E-PEK) with 4,4'-diaminodiphenyl sulfone (DDS) and hexahydrophthalic acid anhydride (Nadic) as curing agents was investigated using isothermal differential scanning calorimetry (IDSC) and nonisothermal differential scanning calorimetry (DDSC) techniques. It was found that the curing reactions of E-PEK/DDS and E-PEK/Nadic are nth-order reactions but not autoaccelerating. The experimental results revealed that the curing reaction kinetics parameters measured from IDSC and DDSC are not equivalent. This means that, in the curing reaction kinetics model for our E-PEK system, both isothermal and nonisothermal reaction kinetics parameters are needed to describe isothermal and nonisothermal curing processes, The isothermal and nonisothermal curing processes were successfully simulated using this model. A new extrapolation method was suggested. On the basis of this method the maximum extent of the curing reaction (A(ult)) that is able to reach a certain temperature can be predicted. The A(ult) for the E-PEK system estimated by the new method agrees well with the results obtained from another procedure reported in the literature. (C) 1997 John Wiley & Sons, Inc.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .2. Chemorheological modeling

Chemorheology and corresponding models for an epoxy-terminated poly(phenylene ether ketone) (E-PEK) and 4,4'-diaminodiphenyl sulfone (DDS) system were investigated using a differential scanning calorimeter (DSC) and a cone-and-plate rheometer. For this system, the reported four-parameter chemorheological model and modified WLF chemorheological model can only be used in an isothermal or nonisothermal process, respectively. In order to predict the resin viscosity variation during a stepwise temperature cure cycle actually used, a new model based on the combination of the four-parameter model and the modified WLF model was developed. The combined model can predict the resin viscosity variation during a stepwise temperature cure cycle more accurately than the above two models. In order to simplify the establishment of this model, a new five-parameter chemorheological model was then developed. The parameters in this five-parameter model can be determined through very few rheology and DSC experiments. This model is practicable to describe the resin viscosity variation for isothermal, nonisothermal, or stepwise temperature cure cycles accurately. The five-parameter chemorheological model has also successfully been used in the E-PEK systems with two other curing agents, i.e., the diamine curing agent with the addition of a boron trifluride monoethylamine (BF3-MEA) accelerator and an anhydride curing agent (hexahydrophthalic acid anhydride). (C) 1997 John Wiley & Sons, Inc.

Flexural fatigue behavior of injection-molded composites based on poly(phenylene ether ketone)

Flexural fatigue tests were conducted on injection-molded short fiber composites, carbon fiber/poly(phenylene ether ketone) (PEK-C) and glass fiber/PEK-C (with addition of polyphenylene sulfide for improving adhesion between matrix and fibers), using four-point bending at stress ratio of 0.1. The fatigue behavior of these materials was presented. By comparing the S-N curves and analyzing the fracture surfaces of the two materials, the similarity and difference of the failure mechanisms in the two materials were discussed. It is shown that the flexural fatigue failure of the studied materials is governed by their respective tensile properties. The matrix yielding is main failure mechanism at high stress, while at lower stress the fatigue properties appear fiber and interface dominated. (C) 1997 John Wiley & Sons, Inc.

Residual properties of an injection-molded poly(phenylene ether ketone) carbon composite during flexural fatigue

The present work investigates the effects of cyclic fatigue loading on the residual properties of an injection-molded composite, carbon-fiber-reinforced poly(phenylene ether ketone) (CF/PEK-C), and damage development in this material under fatigue lending. Test specimens, which had been conditioned to various preselected fatigue damage stages, were measured for their residual properties. The results indicated that cyclic fatigue loading alters the constitutive behavior of the injection-molded composite, especially in the non-linear portion of the stress/strain curve. The residual strength decreases with increase in the number of fatigue cycles as a consequence of the accumulation of fatigue damage, which is dominated by the growth of microcracks. While the residual modulus increases slightly with cyclic fatigue loading, this is probably due to the oriented hardening resulting from creep deformation which is induced during cyclic loading. (C) 1997 Elsevier Science Limited.