Isothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone) (PEEKK)

Isothermal melt and cold crystallization kinetics of PEEKK have been investigated by differential scanning calorimetry in two temperature regions. During the primary crystallization process, the relative crystallinity develops with a time dependence described by the Avrami equation, with exponent n = 2 for both melt and cold crystallization. The activation energies are -544.5 and 466.7 kJ/mol for crystallization from the melt and amorphous glassy state, respectively. The equilibrium melting point T-m(o) is estimated to be 371 degrees C by using the Hoffman-Weeks approach. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma=10 erg/cm(2) and sigma(e) = 60 erg/cm(2), respectively. The work of chain folding q is determined as 3.98 kcal/mol. These observed crystallization kinetic characteristics of PEEKK are compared with those of PEEK. (C) 1997 Elsevier Science Ltd.

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.

Poly(vinyl methyl ether) poly(methyl methacrylate) blends using diblock copolymer of styrene and methyl methacrylate as compatibilizer

Blends of poly(vinyl methyl ether) (PVME) and poly(methyl methacrylate) (PMMA) compatibilized by poly(styrene-block-methyl methacrylate) (P(S-b-MMA)) ale studied by FT-IR, DSC, excimer fluorescence spectrometry, and scanning electron microscopy (SEM). In FT-IR measurement the ratio of absorption intensity at 1107 cm(-1) to that at 1085 cm(-1) (I-1107/I-1085) reaches a minimum at about 10wt% block copolymer content. DSC results show that the glass transition temperature of PVME in the blends has a maximum at 10 wt% copolymer content. In plots of the ratio of excimer-to-monomer fluorescence emission intensities (I-E/I-M) VS block copolymer content, I-E/I-M increases rapidly above 10%. Ail these phenomena show that PS block chains penetrate into PVME: domains on addition of block copolymer. Above 10% copolymer content, block copolymer chains tend to form micelles in bulk phase.

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.

Effect of crystal-disrupting chlorohydroquinone on the first-order transitions of poly(aryl ether ketone)s containing biphenyl units

The novel poly(aryl ether ketone)s were synthesized by nucleophilic substitution reactions of 4,4'-difluorobenzophenone with 4,4'-biphenyldiol and chlorohydroquinone. As expected, the copolymers have lower melting transitions than the biphenyldiol-based homopoly(aryl ether ketone) because of the copolymerization effect of the crystal-disrupting monomer chlorohydroquinone. Copolymers containing 50 and 70% biphenyldiol show two first-order transitions which are associated with the crystal-to-liquid crystal transition and the liquid crystal-to-isotropic transition.

Studies on poly(ether ether ketone ketone) poly(ether biphenyl ether ketone ketone) copolymers and blends

We synthesized a series of polymers: poly(ether ether ketone ketone)(PEEKK), poly(ether biphenyl ether ketone ketone) (PEBEKK) and their copolymer by polycondensation, We also prepared a series of PEEKK-PEBEKK blends, By using DSC method, we found that T-g of the copolymers and the blends rose with the increasing of biphenyl contents in the polymers, T-c of the copolymers and the blends is higher than the corresponding homopolymer. From the results, we think that PEEKK-PEBEKK copolymer and blends are miscible and the copolymer is random.

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.

Liquid crystalline polymer as a processing agent in blends of poly(ether-ketone)/LCP70

Blends of a liquid crystalline thermotropic copolyester (LCP70) and an amorphous phenolphthalein based poly(ether-ketone)(PEK-C) with two viscosities were prepared by melt blending. The blends' morphology, rheological and mechanical properties were investigated by DSC, SEM, mechanical and rheological tests. It was observed that the optimum composition of the PEK-C/LCP70 blend was 10 wt% LCP for both mechanical and rheological properties. When the LCP content was less than 10%, the LCP phase existed as finely dispersed fibrous domains with a diameter of about 1 mu m in the matrix, and both tensile and flexural properties were improved. In contrast, when the LCP content reached 20% or more, the LCP domains coalesced to ellipsoidal particles with a diameter of about 5 mu m, and the mechanical properties decreased as a result. It is demonstrated that pure PEK-C with a high viscosity which was difficult to process by melt extrusion, could be extruded conveniently when 10% LCP70 was incorporated. It is emphasized that LCP not only can be used as a reinforcing phase but also an effective processing agent for engineering thermoplastics, especially for those with high viscosity and narrow processing window. (C) 1997 Elsevier Science Ltd.

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.

Reinforced effect of wollastonite on phenolphthalein poly(ether ketone)

The mechanical properties of wollastonite-filled phenolphthalein poly(ether ketone) (PEK-C) composites have been studied at room temperature and 200 degrees C. The dispersion of wollastonite particles in PEK-C matrix were investigated by means of scanning electron microscope. The modulus and strength of the composites increased with filler content. The reinforced effect of wollastonite on PEK-C is more marked at elevated temperature. The glass transition temperature of the composites is higher than that of PEK-C and is independent of filler content. The restriction effect of tiller particles on the molecular mobility of the polymer matrix should be attributed to the reinforcement. (C) 1997 John Wiley & Sons, Inc.