Effects of molecular weight and interaction parameter on the glass transition temperature of polystyrene mixtures and its blends with polystyrene/poly(2,6-dimethyl-p-phenylene oxide)

The glass transition temperature (T-g) of mixtures of polystyrene (PS) with different molecular weight and of blends of poly(2,6-dimethyl-p-phenylene oxide) (PPO) and polystyrene with different molecular weight (DMWPS) was studied by a DSC method. For the whole range of composition, the curves of T-g vs composition obtained by experiment were compared with predictions from the Fox, Gordon-Taylor, Couchman and Lu-Weiss, equations. It was found that the experimental results were not in agreement with those from the Fox, Gordon-TayIor and Couchman equations for the binary mixtures of DMWPS, where the interaction parameter chi was approximately zero. However, for the blends PPO/DMWPS (chi < 0), with an increase of molecular weight of PS, it was shown that the experimental results fitted well with those obtained from the Couchman, Gordon-Taylor and Fox equations, respectively. Furthermore, the Gordon-Taylor equation was nearly identical to the Lu-Weiss equation when \chi\ was not very large. Further, the dependence of the change of heat capacity associated with the glass transition (Delta C-p) on the molecular weight of PS was investigated and an empirical equation was presented. (C) 1997 Elsevier Science Ltd.

Miscibility and crystallization of poly(beta-hydroxybutyrate) and poly(p-vinylphenol) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB) and poly(p-vinylphenol) (PVPh) blends were studied by differential scanning calorimetry and optical microscopy (OM). The blends exhibit a single composition-dependent glass transition temperature, characteristic of miscible systems, A depression of the equilibrium melting temperature of PHB is observed. The interaction parameter values obtained from analysis of the melting point depression are of large negative values, which suggests that PHB and PVPh blends are thermodynamically miscible in the melt. Isothermal crystallization kinetics in the miscible blend system PHB/PVPh was examined by OM. The presence of the amorphous PVPh component results in a reduction in the rate of spherulite growth of PHB. The spherulite growth rate is analyzed using the Lauritzen-Hoffman model, The isothermally crystallized blends of PHB/PVPh were examined by wide-angle X-ray diffraction and smell-angle X-ray scattering (SAXS). The long period obtained from SAXS increases with the increase in PVPh component, which implies that the amorphous PVPh is squeezed into the interlamallar region of PHB.

Miscibility of linear low density polyethylene (LLDPE)-graft-poly(methyl methacrylate) with poly(vinylidene fluoride) (PVF2) and its application as compatibilizer LLDPE/PVF2 blends

Differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) were used to study the miscibility of blends of a graft copolymer of poly(methyl methacrylate) on linear low density polyethylene (LLDPE-g-PMMA, G-3) with poly(vinylidene fluoride)(b) (PVF2) and the compatibilization of blends of LLDPE/PVF2. The specific interaction between PMMA side chains and PVF2 in G-3/PVF2 binary blends is weaker than that between the homopolymers PMMA and PVF2. There are two states of PVF2 in the melt of a G-3/PVF2 (60/40, w/w) blend, one as pure PVF2 and the other interacting with PMMA side chains. The miscibility between PMMA side chains and PVF2 affects the crystallization of PVF2. LLDPE-g-PMMA was demonstrated to be a good compatibilizer in LLDPE/PVF2 blends, improving the interfacial adhesion and dispersion in the latter. Diffusion of PMMA side chains into PVF2 in the interfacial region reduces the crystallization rate and lowers the melting point (T-m) and the crystallization temperature (T-c) of PVF2 in the blends.

The miscibility of homopolymer random copolymer blends .1. Poly(styrene-co-acrylonitrile) poly(ethyl methacrylate) and poly(styrene-co-acrylonitrile) poly(methyl methacrylate) blends

The miscibility of blends of poly(styrene-co-acrylonitrile) (SAN) with poly(methyl methacrylate) (PMMA) or poly(ethyl methacrylate) (PEMA) has been investigated by means of NMR and DSC techniques. It is found that there are intermolecular interactions between the phenyl groups in SAN and carbonyl groups in PMMA or PEMA, and the strength of this intermolecular interaction strongly depends on the properties of ester side groups in PEMA or PMMA, composition of the blends and a certain composition of the copolymer. It is this specific interaction instead of the intramolecular repulsion force within the copolymer that plays a key role for the miscibility of SAN/PMMA and SAN/PEMA blends.

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.

MISCIBILITY STUDIES OF POLY(ETHYLENE OXIDE)-POLY(VINYL ACETATE) BLENDS BY VISCOMETRY METHODS

The intrinsic viscosities of poly(ethylene oxide)-poly(vinyl acetate) blends (PEO-PVA) have been measured in chloroform as a function of molecular weights of blend components and compositions. The interaction parameters Delta b obtained from the modified Krigbaum and Wall theory and the differences between the intrinsic viscosities of polymer mixtures and the weight-average intrinsic viscosities of the two blend components were both used to characterize the extent of miscibility of the blend mixtures. (C) 1995 John Wiley and Sons, Inc.

MOLECULAR-STATE OF GRAFT-COPOLYMERS IN THE INTERFACIAL AREA OF POLYOLEFIN AND POLAR POLYMER

In order to characterize the interface in polymer blends, a new method is suggested, in which the interface is exposed by selectively dissolving in solvent. By means of X-ray photoelectron spectrometry, we studied the molecular state in the interfacial ar

FRACTIONATED CRYSTALLIZATION IN POLYOLEFINS-NYLON-6 BLENDS

The crystallization behavior of polyolefins-nylon 6 polymer blends was studied by differential scanning calorimetry (DSC) measurements. In these blends, the crystallization of the minor component often starts with distinctly deeper supercooling than that

PC/ABS BLENDS:COMPATIBILIZATION AND MECHANICAL-BEHAVIOR

PC/ABS(M) blends, encompassing the whole composition range between pure PC and ABS(M), were prepared by melt-mixing in a Brabender-like apparatus. Thermal, mechanical and impact tests were performed on compression moulded specimens. Inward Tg shifts were

STATISTICAL THERMODYNAMICS OF POLYDISPERSE POLYMER MIXTURES

A statistical thermodynamics theory of polydisperse polymer blends based on a lattice model description of a fluid is formulated. Characterization of a binary polydisperse polymer mixture requires a knowledge of the pure polymer system and the interaction energy. It is assumed that the intrinsic and interactive properties of polymer (for example, T*, P*, rho*, and epsilon(ij)*) are independent of molecular size. Thermodynamic properties of ternary and higher order mixtures are completely defined in terms of the pure fluid polymer parameters and the binary interaction energies. Thermodynamic stability criteria for the phase transitions of a binary mixture are shown. The binodal and spinodal of general binary systems and of special binary systems are discussed.

INFLUENCE OF ESTER GROUP-SIZE IN PMAS ON BETA-PHASE CRYSTALLIZATION OF PVF2 IN HIGHLY ORIENTED FILMS OF PVF2/PMAS BLENDS

Influence of ester group size in polymethacrylates (PMAs) , including PMMA, PEMA and PBMA, on beta phase crystallization of poly(vinylidene fluoride) (PVF2) in highly oriented films of PVF2/PMAs=80/20 blends has been investigated by FTIR and TEM. The melt-drawn films of pure PVF2 consist of highly oriented lamellae, in which the alpha phase is predominant. Adding a given amount of PMAs (20 wt%) into PVF2 results in formation of fibrillar crystals and increase of relative amount of the beta phase. The influence extent is in order of PMMA > PEMA > PBMA, regarding the ester group size in the PMAs.

MISCIBILITY AND PHASE-BEHAVIOR IN BLENDS OF POLY(HYDROXYETHER OF BISPHENOL-A) WITH POLY(ETHYLENE OXIDE-CO-PROPYLENE OXIDE)

The miscibility of poly(hydroxyether of bisphenol A) (phenoxy) with a series of poly(ethylene oxide-co-propylene oxide) (EPO) has been studied. It was found that the critical copolymer composition for achieving miscibility with phenoxy around 60-degrees-C is about 22 mol % ethylene oxide (EO). Some blends undergo phase separation at elevated temperatures, but there is no maximum in the miscibility window. The mean-field approach has been used to describe this homopolymer/copolymer system. From the miscibility maps and the melting-point depression of the crystallizable component in the blends, the binary interaction energy densities, B(ij), have been calculated for all three pairs. The miscibility of phenoxy with EPO is considered to be caused mainly by the intermolecular hydrogen-bonding interactions between the hydroxyl groups of phenoxy and the ether oxygens of the EO units in the copolymers, while the intramolecular repulsion between EO and propylene oxide units in the copolymers contributes relatively little to the miscibility.

CRITERION OF POLYMER POLYMER MISCIBILITY DETERMINED BY VISCOMETRY

The criteria of polymer-polymer miscibility determined by viscometry are reviewed, and a new criterion is proposed based on the classical Huggins equation and the Huggins coefficient K(m) in the blends. It was found that, in a ternary (polymer-A)-(polymer-B)-solvent system, [GRAPHICS] In the absence of strong specific interaction forces between molecules that would encourage aggregation and at sufficiently low concentration, the above equation can be written thus: [GRAPHICS] This equation can be used to determine the miscibility of polymer blends, when: alpha greater-than-or-equal-to 0 miscible, alpha < 0 immiscible. It is found that the new criterion is reasonable and suitable to predict polymer-polymer miscibility by the viscometry method.

CHARACTERIZATION OF BLENDS OF POLYPROPYLENE WITH A SEMIRIGID LIQUID-CRYSTAL COPOLYESTER

Blends with a liquid-crystal polymers (LCP) as one component show, in general, very interesting properties. Reduction of shear visocity and improvement of mechanical properties are very remarkable. High melting temperatures and high costs of the LCP limit the use of these blends. A new class of thermotropic LCPs with flexible spaces, with relatively low melting temperatures, can overcome the first problem. In this work, rheological and mechanical properties of blends of polypropylene with low contents of this LCP are presented. Torque during extrusion and viscosity decrease with LCP content. Elastic modulus is remarkably increased when the LCP phase is oriented.

BLENDS OF PHENOLPHTHALEIN POLY(ETHER ETHER KETONE) WITH PHENOXY AND EPOXY-RESIN

The properties of miscible phenolphthalein poly(ether ether ketone)/phenoxy (PEK-C/phenoxy) blends have been measured by dynamic mechanical analysis and tensile testing. The blends were found to have single glass transition temperatures (T(g)) that vary continuously with composition. The tensile moduli exhibit positive deviations from simple additivity. Marked positive deviations were also observed for tensile strength. The tensile strengths of the 90/10 and 75/25 PEK-C/phenoxy blends are higher than those of both the pure components. Embrittlement, or transition from the brittle to the ductile mode of failure, occurs in the composition range of 50-25 wt% PEK-C. These observations suggest that mixing on the segmental level has occurred and that there is enough interaction between the components to decrease its internal mobility significantly. PEK-C was also found to be miscible with the epoxy monomer, diglycidyl ether of bisphenol A (DGEBA), as shown by the existence of a single glass transition temperature (T(g)) within the whole composition range. Miscibility between PEK-C and DGEBA could be considered to be due mainly to entropy. However, PEK-C was judged to be immiscible with the diaminodiphenylmethane-curved epoxy resin (DDM-cured ER). It was observed that the PEK-C/ER blends have two T(g), which remain invariant with composition and are almost the same as those of the pure components, respectively. Scanning electron microscopy showed that the PEK-C/ER blends have a two-phase structure. The different miscibility with PEK-C between DGEBA and the DDM-cured ER is considered to be due to the dramatic change in the chemical and physical nature of ER after curing.