Crystallization behavior of poly(ether ether ketone ketone)

The melting behavior of semicrystalline poly(ether ether ketone ketone) (PEEKK) has been studied by differential scanning calorimetry (DSC). When PEEKK is annealed from the amorphous state, it usually shows two melting peaks. The upper melting peaks arise first, and the lower melting peaks are developed later. The upper melting peaks shown in the DSC thermogram are the combination (addition) of three parts: initial crystal formed before scanning; reorganization; and melting-recrystallization of lower melting peaks in the DSC scanning period. In the study of isothermal crystallization kinetics, the Avrami equation was used to analyze the primary process of the isothermal crystallization; the Avrami constant, n, is about 2 for PEEKK from the melt and 1.5 for PEEKK from the glass state. According to the Lauritzen-Hoffman equation, the kinetic parameter of PEEKK from the melt is 851.5 K; the crystallization kinetic parameter of PEEKK is higher than that of PEEK, and suggests the crystallizability of PEEKK is less than that of PEEK. The study of crystallization on PEEKK under nonisothermal conditions is also reported for cooling rates from 2.5 degrees C/min to 40 degrees C/min, and the nonisothermal condition was studied by Mandelkern analysis. The results show the nonisothermal crystallization is different from the isothermal crystallization. (C) 1996 John Wiley & Sons, Inc.

Studies on the fusion heat of poly(ether ether ketone ketone)-poly(ether biphenyl ether ketone ketone) copolymers

On the basis of DSC measurements, the Delta H-f(0) values of the fusion heat for PEEKK-PEBEKK copolymers with various biphenyl contents were obtained by using thermodynamics statistical theory proposed by Flory and graphical method of the specific volume-fusion heat. The results reveal that Delta H-f(0) values determined by these two methods for PEEKK-PEBEKK copolymers with various biphenyl content are nearly the same, and that Delta H-f(0) values are closely dependent on biphenyl content. Delta H-f(0) value is minimum at n(B)=0.35.

Effect of heat treatment on the parameters of crystal structure and degree of crystallinity of poly(aryl-ether-ether-ketone)

The variations of unit cell parameters and crystallite size of nine PEEK samples treated at various temperatures have been studied by using Wide-Angle X-ray Diffraction (WAXD), The results indicate a decrease in unit cell parameter a,b and c but an increase in crystallite size L(hkl) With the increase beat treatment temperature. Based on X-ray scattering intensity theory and using the graphic multipeak resolution method, the formula of degree of crystallinity (W-c,W-X) for PEEK is derived. The results calculated are compatible with the density measurement and calorimetry.

In situ external reflection FTIR spectroelectrochemical investigation of poly(o-phenylenediamine) film coated on a platinum electrode

The electrochemically deposited poly(o-phenylenediamine) film on a Pt electrode has been investigated utilizing in situ external reflection FTIR spectroelectrochemistry technique. The prepared ladder polymer film is found to be partially ring-opened. The dopant ClO4- is evidenced to orient in such a way that more than one oxygen atom attach to the charge sites of the polymer. This suggests that positive charges of oxidized polymer are partially delocalized over the whole chains. The proton movement observed during the oxidation reaction is associated with the solvated MeCN molecule. It is proposed that the proton diffusion, dissolvation and protonation of the film may be essential to the electrochemical reduction reaction of the film. Copyright (C) 1996 Elsevier Science Ltd.

Polyepichlorohydrin polyurethane/poly(methyl methacrylate) interpenetrating polymer networks

Polyurethane (PU) based on polyepichlorohydrin/poly(methyl methacrylate) (PECH/PMMA) interpenetrating polymer networks (IPNs) was synthesized by a simultaneous method. The effects of composition, hydroxyl group number of PECH, NCO/OH ratio and crosslinking agent content in IPNs were investigated in detail. Some other glycols, such as poly(ethylene glycol), poly(propylene glycol) and hydroxyl-terminated polybutadiene, were also used to obtain PU/PMMA IPNs. The interpenetrating and fracture behaviors of the IPNs are explained briefly.

Morphological studies on a novel poly(aryl ether ketone)

The morphology of a novel poly(aryl ether ketone) [PEDEKmK] was investigated via polarizing optical microscopy (POM), TEM, DSC, SAXS and electron diffraction (ED). A distinct change in lamellar thickness, orientation, and spherulitic morphology was observed due to crystal melting and recrystallization. However, the crystal packing mode is found to be identical before and after the recrystallization process.

Tension-tension fatigue failure behaviour of poly(phenylene ether ketone) (PEK-C)

Tension-tension fatigue tests were conducted on unnotched injection moulded poly(phenylene ether ketone) (PEK-C) specimens with two stress ratios, R. The fatigue behaviour of this material is described. The S-N curves (S = alternating stress, N = number of cycles to failure) for different R values have the same general shape, but the curve for bigger R is shifted to long cycles. A fatigue lifetime inversion is observed from constructed S-N curves. Examinations of failure surfaces and analyses of the fatigue data reveal that the fatigue failure mechanism of the material studied is crack growth dominated. But the manner of the fatigue crack initiation and propagation depends on the maximum cyclic stress applied. At higher stresses, the fatigue crack originates at the corner of the specimen and propagates inward; at lower stresses, the fatigue crack nucleates at an internal flaw of the specimen and propagates outward. The fatigue lifetime inversion corresponds to the transition of crack initiation and propagation from one mode to the other. Copyright (C) 1996 Elsevier Science Ltd.

Ionic conductivity of polymer gel electrolytes based on poly(polyethylene glycol dimethacrylate)

Gel electrolytes have been prepared by thermal polymerization of poly(polyethylene glycol dimethacrylate) (P(PEGD)) in the presence of propylene carbonate (PC) and alkali metal salts, such as LiClO4, LICF(3)SO(3) and LiBF4. The conductivity was studied by means of impedance spectroscopy, and it is found that the temperature dependence of conductivities follow a Arrhenius relationship when the molar percentage of PC is higher than 75% or LiClO4 concentration is lower than 0.9 mol/l. However, when LiCF3SO3 or LiBF4 is used instead of LiClO4 as the salt, the situation is different. For LICF(3)SO(3), the Arrhenius relationship almost holds true for all the salt concentrations studied; while for LiBF4, the Arrhenius equation hardly fits for any salt concentration. The dependence of activation energy on salt concentration is also examined, both for LiClO4 and LiCF3SO3, the values of E(a) tend to reach a minimum value with increasing salt concentration. Copyright (C) 1996 Elsevier Science Ltd.

The solution properties of phenolphthalein poly(arylether sulfone) .1. The solubility behavior and determination of M-II equations

A series of narrow molecular weight distribution fractions of phenolphthalein polyarylether sulfone(PES-C) had been prepared, The <(M) over bar (w)> of these fractions were determined by conventional light scattering method. The [eta] and the Huggins slope constant k' in DMF, CHCl3 and 1,2-dichloroethane were also determined. The Huggins constants are greater than 0.5 in all of these solvents showing a special solubility behavior. The Mark-Houwink equations of PES-C in these solvents at 25 degrees C are [eta] = 2.79 x 10(-2) <(M) over bar (0.615)(w)> (DMF); [eta] = 3.96 x 10(-2) <(M) over bar (0.58)(w)> (CHCl3); [eta] = 7.40 x 10(-2) <(M) over bar (0.52)(w)> (CH2ClCH2Cl).

Dynamic light-scattering characterization of the molecular weight distribution of a broadly distributed phenolphthalein poly(aryl ether ketone)

Using a recently developed laser light-scattering (LLS) procedure, we accomplished the characterization of a broadly distributed unfractionated phenolphthalein poly(aryl ether ketone) (PEK-C) in CHCl3 at 25 degrees C. The laplace inversion of precisely measured intensity-intensity time correlation function from dynamic LLS leads us first to an estimate of the characteristic line-width distribution G(Gamma) and then to the translational diffusion coefficient distribution G(D). By using a previously established calibration of D (cm(2)/s) = 2.37 X 10(-4)M(-0.57), were able to convert G(D) into a differential weight distribution f(w)(M). The weight-average molecular weight M(w) calculated from f(w)(M) agrees well with that directly measured in static LLS. Our results indicate that both the calibration and LLS procedure used in this study are ready to be applied as a routine method for the characterization of the molecular weight distribution of PEK-C. (C) 1996 John Wiley & Sons, Inc.

Miscibility and crystallization behaviour of poly(ether ether ketone)/polyimide blends

The miscibility and crystallization behaviour of the blends of poly(ether ether ketone) (PEEK) with two thermoplastic polyimides (PI), PEI-E and YS-30, prepared by solution blending were studied by the use of small-angle X-ray scattering (SAXS), differential scanning calorimetry (d.s.c.) and polarizing microscopy techniques. The results obtained show that PEEK/YS-30 is miscible, while PEEK/PEI-E is partially miscible only in the composition range with PEI-E content up to 20 wt%. The crystallization behaviour of PEEK in PEEK/PI blends depends on the crystallization condition of the blend sample as well as the chemical structure and the content of the PI added. Our SAXS results indicate that the segregation of PI molecular chains during crystallization of PEEK chains in the blends is interfibrillar for PEEK/PEI-E blends, but interlamellar for PEEK/YS-30 blends. The compatibility and the crystallization behaviour are discussed in terms of charge transfer interaction between PI and PI molecules and between PI and PEEK molecules.

Laser light-scattering study of novel thermoplastics .2. Phenolphthalein poly(ether sulfone) (PES-C)

Five narrowly distributed fractions of phenolphthalein poly(ether sulfone) (PES-C) were studied in CHCl3 by both static and dynamic laser light scattering (LLS) at 25 degrees C. The dynamic LLS showed that the PES-C samples contain some large polymer clusters as in previously studied phenolphthalein poly(ether ketone)(PEK-C). These large clusters can be removed by a 0.1-mu m filter. Our results showed that [R(g)(2)](1/2)(z) = (3.35 +/- 0.13) x 10(-2) M(w)((0.52 +/- 0.03)) and [D] = (2.26 +/- 0.02) x 10(-4)M(w)-((0.54) +/- 0.03)) with [R(g)(2)](1/2)(z), M(w) and [D] being the z-average radius of gyration, the weight-average molecular weight, and the z-average translational diffusion coefficient, respectively. A combination of static and dynamic LLS results enabled us to determine D = (2.45 +/- 0.04) x 10(-4)M-((0.55 +/- 0.05)), where D and M correspond to monodisperse species. Using this scaling relationship, we have successfully converted the translational diffusion coefficient distribution into the molecular weight distribution for each of the five PES-C fractional The weight-average molecular weights obtained from dynamic light scattering have a good agreement with that obtained from static laser light-scattering measurements.

Local chain motions in a dilute solution of phenolphthalein poly(ether sulfone)

C-13 and H-1 relaxation times were measured as a function of temperature in two magnetic fields for dilute solutions of phenolphthalein poly(ether sulfone) (PES-C) in deuterated chloroform. The spin-lattice relaxation times were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (J. S. model). The phenyl group rotation is treated as a stochastic diffusion by the J. S. model. The restricted butterfly motion of the phenyl group attached to the cardo ring in PES-C is mentioned but is not discussed in detail in this work. Correlation times for the segmental motion are in the picosecond range which indicates the high flexibility of PES-C chains. The correlation time for the phenyl group internal rotation is similar to that of the segmental motion. The temperature dependence of these motions is weak. The apparent activation energy of the motions considered is less than 10 kJ/mol. The simulating results for PES are also reasonable considering the differences in structure compared with PES-C. The correlation times and the apparent activation energy obtained using the J. S. model for the main chain motion of PES-C are the same as those obtained using the damped orientational diffusion model and the conformational jump model.

Miscibility and phase behavior in blends containing random copolymers of poly(ether ether ketone) and phenolphthalein poly(ether ether ketone)

The miscibility and phase behavior of polysulfone (PSF) and poly(hydroxyether of bisphenol A) (phenoxy) with a series of copoly(ether ether ketone) (COPEEK), a random copolymer of poly(ether ether ketone) (PEEK), and phenolphthalein poly(ether ether ketone) (PEK-C) was studied using differential scanning calorimetry. A COPEEK copolymer containing 6 mol % ether ether ketone (EEK) repeat units is miscible with PSF, whereas copolymers containing 12 mol % EEK and more are not. COPEEK copolymers containing 6 and 12 mol % EEK are completely miscible with phenoxy, but those containing 24 mol % EEK and more are immiscible with phenoxy. Moreover, a copolymer containing 17 mol % EEK is partially miscible with phenoxy; the blends show two transitions in the midcomposition region and single transitions at either extreme. Two T(g)s were observed for the 50/50 blend of phenoxy with the copolymer containing 17 mol % EEK, whereas a single composition-dependent T-g appeared for all the other compositions. An FTIR study revealed that there exist hydrogen-bonding interactions between phenoxy and the copolymers. The strengths of the hydrogen-bonding interactions in the blends of the COPEEK copolymers containing 6 and 12 mol % EEK are the same as that in the phenoxy/PEK-C blend. However, for the blends of copolymers containing 17, 24, and 28 mol % EEK, the hydrogen-bonding interactions become increasingly unfavorable and the self-association of the hydroxyl groups of phenoxy is preferable as the content of EEK units in the copolymer increases. The observed miscibility was interpreted qualitatively in terms of the mean-field approach. (C) 1996 John Wiley & Sons, Inc.