Measurement of the rheological properties of polymer melts with annular rheometer

An annular die has been designed having a very thin gap distance between two coaxial cylinders. The die was then used to measure wall normal stresses along the longitudinal direction of polymer melts flowing through the thin annulus. The materials investigated were high-density polyethylene, low-density polyethylene, polypropylene, and polystyrene. Also investigated were blends of polystyrene and polypropylene, and blends of polystyrene and high-density polyethylene The measurements of wall normal stresses were used to determine the rheological properties of the melts, namely, the melt viscosity from the slope of axial wall normal stress profiles and the melt elasticity from exit pressures. The interpretation of the experimental data was made possible by the fact that the narrow-gap annular die can be considered as a substitute for a thin slit die. It has been found that the results obtained in the present study are consistent with those reported earlier by the author, who at that time used both capillary and slit dies.     

Collaborative representation with reduced residual for face recognition

Collaboration representation-based classification (CRC) was proposed as an alternative approach to the sparse representation method with similar efficiency. The CRC is essentially a competition scheme for the training samples to compete with each other in representing the test sample, and the training class with the minimum representation residual from the test sample wins the competition in the classification. However, the representation error is usually calculated based on the Euclidean distance between a test sample and the weighted sum of all the same-class samples. This paper exploits alternative methods of calculating the representation error in the CRC methods to reduce the representation residual in a more optimal way, so that the sample classes compete with each other in a closer range to represent the test sample. A large number of face recognition experiments on three face image databases show that the CRC methods with optimized presentation residual achieve better performance than the original CRC, and the maximum improvement in classification accuracy is up to 12 %.     

Rheological properties of mixtures of molten polymer and fluorocarbon blowing agent. I. Mixtures of low-density polyethylene and fluorocarbon blowing agent

The viscosities of mixtures of low-density polyethylene and fluorocarbon blowing agent were determined from the measurement of wall normal stress along the longitudinal axis of a capillary die. For the study, three different grades of commercial high-pressure low-density polyethylene were used, together with the following fluorocarbon blowing agents, dichlorodifluoromethane (FC-12), dichlorotetrafluoroethane (FC-114), and blends of FC-12 and FC-114. In the experiment, blowing agent concentration and melt temperature were varied for each combination of polymer and blowing agent employed. Analysis of the experimental data has led to a correlation between the viscosity reduction factor (VRF) and the blowing agent concentration, in which VRF is defined as the ratio of the viscosity of polymer-blowing agent mixture to that of the polymer alone. It was found that the correlation obtained is independent of shear rate and temperature and dependent upon only the type of fluorocarbon blowing agent. The practical significance of the correlation is discussed. We have shown that the entrance pressure drop obtained in the absence of phase separation in the entrance region may be used as a measure of the elastic properties of mixtures of fluorocarbon blowing agent and low-density polyethylene resin.     

Synthesis and self-assembly of hyperbranched polyester peripherally modified by touluene-4-sulfonyl groups

In this paper, hyperbranched polyesters (HPs) were synthesized in the molten state from 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) and 2-ethyl-2-hydroxymethyl-1,3-propanediol (TMP) using acid catalysis. The modified hyperbranched polyesters were obtained through the chemical modification of the hyperbranched polyester cores by substituting a controlled fraction of the terminal hydroxyl groups with touluene-4-sulfonyl chloride using triethylamine (TEA) as an acceptor of HCl. The resultant polyesters were characterized by ¹H NMR, ¹³C NMR, FT-IR, UV and GPC and their self-assembly behaviors were investigated. The results revealed that self-assembled structures could be formed in selected solvents (trichloromethane/acetone or trichloromethane/n-hexane).     

Studies on the semirigid chain polyamide—poly(1,4-phenyleneterephthalamide)

In this article, the polycondensation of terephthaloyl chloride and p-phenylenediamine was systematically studied, including the liquid–crystalline state of the solution and the spinning of poly(1,4-phenyleneterephthalamide) (PPTA). High-molecular-weight PPTA with ε_inh = 5–7 was prepared and the main factors influencing the solution polycondensation of 1,4-phenylenediamine with terephthaloyl chloride were studied in detail. Experimental results showed that the water content of the reaction system, reactant concentration, and volume ratio of mix solvents have a great influence on the inherent viscosity of the poly(1,4-phenyleneterephthalamide) obtained. The highest ε_inh was obtained at 0.3M/liter reactant concentration in a mixed solvent ratio HMPA/DMAC of 4/1 (by volume), at 0.35M/liter reactant concentration in a mixed solvent of HMPA/NMP = 7/3, and at 0.5M/liter of reactant concentration in a mixed solvent of HMPA/THF = 9/1. The water content must be controlled to less than 100 ppm in the polymerization system. In the early stage of the polycondensation process, the ε_inh of the polymer obtained increased rapidly with time. The system gelled within 2 or 3 min, while the monomer conversion reached about 100%. However, the reaction of polycondensation continued after gelation and the ε_inh of the polymer increased appreciably. We have studied the viscosity behavior at 20–155°C for the anisotropic solution of PPTA in 100% sulfuric acid (ε_inh of PPTA 2.5–4.9). Experimental results showed that, at low concentrations the viscosity of isotropic solution increases with the increase of polymer concentration to reach a maxium near the critical polymer concentration, beyond which the solution changes to an anisotropic liquid–crystalline solution. The appropriate spinning region was obtained as shown in the phase diagram determined by viscosity, degree of depolarization anisotropy, and region of thermal depolymerization. Fibers of PPTA with high modulus and high tenacity were obtained by dry-jet wet spinning. The fibers obtained have a tenacity of ～22 g/denier, a modulus of ～600 g/denier, and elongation at break ～3.5%.     

Antitumor activity of synthetic alkylphospholipids with or without PAF activity

1-O-Octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (ET-18-OMe) has been reported to possess definite antitumor activity in vivo. Twenty-two alkyl lysophospholipid analogs were chemically synthesized, and their antitumor activity against mouse experimental tumors (Sarcoma 180, MM46, P388) was examined. Among them, 1-O-octadecyl-2-O-acetoacetyl-rac-glycerol-3-phosphocholine was found to show antitumor activity similar to ET-18-OMe with less acute toxicity. Intravenous injection of the ET-18-OMe withsn-3 configuration retarded the subcutaneous growth of Sarcoma 180 cells effectively, while the growth inhibition by thesn-1 isomer was much less effective. This stereospecificity was similar to that observed in their activities as platelet-activating factor (PAF) agonists. The acetoacetyl compound, another PAF agonist, showed similar stereospecific antitumor action in vivo. These findings suggest that some alkyl lysophospholipids may activate host cells to a cytostatic stage against tumor cells in vivo through binding to a PAF receptor. Our preliminary results indicated that the responsible cells under these conditions might be primarily immature macrophages present in the bone marrow. No appreciable or even adverse stereospecificity was observed in the different sets of experiments where the activity of ET-18-OMe against MM46 tumor cells in vivo or the direct cytotoxicity against human promyelocytic leukemia HL-60 cells in vitro was examined. Under, some conditions, the antitumor activity of ET-18-OMe in vivo may be revealed through direct cytotoxicity and/or modulation of the host defense system by “nonspecific” mechanisms. Some alkylphospholipids without PAF activity may also show antitumor activity through similar, “nonspecific” mechanisms.     

A generalized method for correcting instrument spreading in gel permeation chromatography

A general method of chromatogram correction for skewed instrument spreading in gel permeation chromatography is presented. The correction method is so general that there is no restriction on the shape of the spreading function. It admits nonsymmetric, non-Gaussian as well as nonconvolution type. Aspects of solution techniques are discussed and an illustrative example is given to elucidate the method.     

Studies on multilayer film coextrusion III. The rheology of blown film coextrusion

Multilayer blown film coextrusion was studied, both experimentally and theoretically. For the experimental study, an annular die with a feed-port system was designed and multilayer blown films were produced by rotating the inner mandrel with a one horsepower variable-speed drive at speeds from nearly 2 to 6 rpm, and by inflating the tubular molten film with air. The die has 16 feed slots and melt pressure transducers are mounted along the axial direction of the outer wall of the annular flow channel. The transducers were used to determine the pressure gradient in the annular flow channel, which then permitted determination of the reduction in pressure drop when different combinations of two polymer systems were coextruded. Polymers used for b own film coextrusion were: (1) low-density polyethylene with ethylene-vinyl acetate; (2) low-density polyethylene with high-density polyethylene; (3) low-density polyethylene with polypropylene; (4) high-density polyethylene with ethylene-vinyl acetate. For the theoretical study, stratified helical flow was analyzed using a power-law non-Newtonian model. A computational procedure was developed to predict the number of layers, layer thickness, and the volumetric flow rate as functions of certain processing variables (namely, the pressure drop in the die, and the angular speed of rotation of the inner mandrel of the die) and the rheological parameters of the individual polymers concerned. Comparison was made of the theoretical prediction of volumetric flow rate with experimental ones. Some representative results are presented of the theoretically predicted axial and angular velocity distributions, shear stress profiles, and shear rate profiles.     

宽温耐硫变换催化剂制备工艺研究

利用催化剂活性评价、催化剂活性组分含量测定、Ｘ—光衍射等手段，研究了共浸法制备宽温耐硫变换催化剂制备工艺过程中载体氧化铝的吸水率、浸渍条件、煅烧温度等对催化剂性能的影响。