Blends of ethylene 1‐octene copolymer synthesized by Ziegler–Natta and metallocene catalysts. II. Rheology and morphological behaviors

The rheological and morphological behaviors of commercially available three binary blends of ethylene 1‐octene copolymer (EOC) regarding the melt index (MI), density and comonomer contents, one component made by the Ziegler–Natta and the other by the metallocene catalysts, were investigated to elucidate miscibility and phase behavior. Miscibility of the EOCs blend in a melt state was related to the value of the MI, density, and comonomer content. If the comonomer contents are similar, then the melt viscosity is weight average value, otherwise it is positively or negatively deviated. The microtomed surface prepared by two different cooling processes—one is fast cooling and the other is slow cooling—indicated that all the blends were not homogenous regardless the density, MI, and comonomer content. The Ziegler–Natta catalyzed EOCs exhibited bigger spherulitic diameter and larger ring space than those of the metallocene EOCs prepared by a cooling process. The blends consisting of similar MI showed banded spherulites with different diameter, whereas the blend consisting of different MI and density takes place of explicit phase separation and phase inversion at 1 : 1 blend composition. The melt rheology appeared to influence the mechanical and film properties in the solid state. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1950–1964, 2000     

Compatibility of poly(vinylidene fluoride) (PVDF)/polyamide 12 (PA12) blends

Poly(vinylidene fluoride) (PVDF)/polyamide 12 (PA12) blends showed new peaks in XRD profile with increasing PA12 and the crystallinity of PA12 significantly decreased with the addition of PVDF. PVDF showed three relaxation regions at about −40, 40, and 100°C, respectively, and glass transition temperature (T_g ) of PA12 increased in blends (10.8→30.14°C) and α‐relaxation of PVDF decreased from 100.26 to 86.46°C. Complex viscosities (η*) vs. composition curve showed a great positive deviation in PVDF‐rich and a small negative deviation in PA12‐rich blends. The N—H and C=O stretching band of PA12 shifted slightly toward higher wavelength, and from curve‐fitted data the area of hydrogen‐bonded C=O stretching bands of PA12 decreased with the addition of PVDF, especially in the 30/70 blend, implying the existence of interactions between the β‐hydrogen atom of PVDF and amide carbonyl group of PA12 in the blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1374–1380, 2000     

Preparation of high molecular weight poly(N‐vinylcarbazole) in high yield by low‐temperature precipitation polymerization of N‐vinylcarbazole

To produce high molecular weight poly(N‐vinylcarbazole) (PVCZ) with high conversion, N‐vinylcarbazole (VCZ) was heterogeneously polymerized in methanol at 30, 40 and 50 °C using a low temperature initiator, 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN), and the effects of polymerization temperature and concentration of initiator and solvent on the polymerization behaviour and molecular parameters of PVCZ investigated. Globally, experimental results correspond to predicted ones. Low polymerization temperature using ADMVN and a heterogeneous system using methanol proved to be successful in obtaining poly(N‐vinylcarbazole) (PVCZ) of high molecular weight and high conversion with small temperature rise during polymerization, although free radical polymerization by azoinitiator was used. The polymerization rate of VCZ in methanol at 30 °C is proportional to the 0.88th power of ADMVN concentration. The molecular weight is higher and the molecular weight distribution is narrower with PVCZ polymerized at lower temperatures. For PVCZ produced in methanol at 30 °C using an ADMVN concentration of 0.0001 mol/mol of VCZ, a weight average molecular weight of 1 750 000 g mol⁻¹ is obtained, with a polydispersity index of 1.82 © 2000 Society of Chemical Industry     

Phase transition and thermal stability of ceramics from Na-based geopolymers

Geopolymer ceramics undergo a series of thermal phase transitions, progressing from an amorphous geopolymer gel to a crystalline phase, and eventually to an amorphous glass phase as the temperature increases. However, there is a lack of mechanism understanding regarding to the crystallization process and the subsequent thermal degradation. Here, we fundamentally investigated the kinetics of nepheline formation in Na-based geopolymer systems and its thermal stability up to 1400°C. Nepheline crystallization is controlled by bulk nucleation and three-dimensional crystal growth based on the Avrami factor of 4.64, where the activation energy of nepheline formation is 350.59 kJ/mol. High thermal stability of geopolymer ceramics is achieved due to the appearance of nepheline up to 1400°C with the Si/Al ratio ranging from 1.40 to 1.94, while melting and amorphous structure are formed above a higher Si/Al ratio of 2.22. The nature of sintering for geopolymer ceramics consists of shrinkage, expansion and shrinkage corresponding to dehydroxylation, crystallization, and densification, leading to a thermal shrinkage of 21% at 1400°C.     

PACK/UNPACK on Coarse-Grained Distributed Memory Parallel Machines

PACK/UNPACK are Fortran 90/HPF array construction functions that derive new arrays from existing arrays. We present algorithms for performing these operations on coarse-grained parallel machines. Our algorithms are relatively architecture independent and can be applied to arrays of arbitrary dimensions with arbitrary distribution along every dimension. Experimental results are presented on the CM-5.     

Crystallization kinetics of poly(ethylene terephthalate) with thermotropic liquid crystalline polymer blends

The isothermal and dynamic crystallization behaviors of polyethylene terephthalate (PET) blended with three types of liquid crystal polymers, i.e., PHB60–PET40, HBA73–HNA27, [(PHB60–PET40)–(HBA73–HNA27) 50 : 50], have been studied using differential scanning calorimetry (DSC). The kinetics were calculated using the slope of the crystallization versus time plot, the time for 50% reduced crystallinity, the time to attain maximum rate of crystallization, and the Avrami equation. All the liquid crystalline polymer reinforcements with 10 wt % added accelerated the rate of crystallization of PET; however, the order of the acceleration effect among the liquid crystalline polymers could not be defined from the isothermal crystallization kinetics. The order of the effect for liquid crystalline polymer on the crystallization of PET is as follows: (PHB60–PET40)–(HBA73–HNA27) (50 : 50); HBA73–HNA27; PHB60–PET40: This order forms the dynamic scan of the DSC measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1383–1392, 1998     

Miscibility and processibility in linear low density polyethylene and ethylene-propylene-butene-1 terpolymer binary blends

Blends of linear low density polyethylene (ethylene-octene-1 copolymer) and ethylene-propylene-butene-1 terpolymer (ter-PP) mixed in a twin-screw extruder have been characterized by using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis, scanning electron microscopy (SEM), rheometric mechanical spectrometry, a capillary rheometer, and a universal test machine. Melting and crystallization behaviors by DSC and the α, β, and γ dynamic mechanical relaxations proposed that the blend is immiscible in the amorphous and crystalline phases by observing the characteristic peaks arised solely from those of the constituents. The lack of interfacial interaction between the components was suggested by the SEM study. A strong negative deviation of melt viscosity from the additive rule and the Cole-Cole plot confirmed the immiscibility in melt state. Incorporation of ter-PP induced a reduction in melt viscosity, shear stress, and final load. Flexural modulus and yield stress were linearly increased with ter-PP content, while the tensile strength and elongation at break were more or less changed. Although this blend system is immiscible in the solid and melt states, addition of less than 20 wt % ter-PP in the blend is viable for engineering applications with the advantages of improved processibility and mechanical properties. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1265–1274, 1997     

Viscosity reduction of polymeric liquid by dissolved carbon dioxide

The viscosities of polydimethylsiloxane (PDMS)/CO₂ solutions were measured over the range of pressures of 1–3 MPa and at the ambient temperature. The viscosities were measured by using a specially designed falling ball viscometer (FBV). The Stokes equation was used to determine the viscosities and the Stokes force expressing the viscous drag of the sphere was corrected for the effect of the lateral cylindrical wall. The Kelley-Bueche (KB) free-volume treatment of the viscosities of polymeric solutions was modified to account for the gas solvent and applied to interpret our data on PDMS/CO₂ systems. It was shown that the theoretical equation, based on the assumption of the additivity of free volumes of the components, was capable of predicting with remarkable accuracy the concentration and pressure dependence of the viscosities of the investigated polymeric solutions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 459–466, 1997