Studies on wire coating extrusion. I. The rheology of wire coating extrusion

Wire coating extrusion was studied, both experimentally and theoretically, using a pressure-type die. For the experimental study, a wire coating apparatus of laboratory scale was constructed, consisting of a pay-off device, extruder, cross-head and pressure-type die, cooling trough, and take-up device. The materials used were low- and high-density polyethylenes and thermoplastic rubber. The following measurements were taken during the experiments: (1) the axial pressure profiles in the die, (2) melt flow rate, and (3) take-up speed. The measurements were then used to determine the effect of the rheological properties of the polymers on the performance of the wire coating operation. It was found that a reduction in axial pressure gradient and a reduction in the recoverable elastic strain of a molten polymer at the die exit can be realized as the speed of the wire is increased. For the theoretical study, using a power-law model, the equations of motion were solved numerically to predict the volumetric flow rate as functions of the pressure gradient in the die and the rheological properties of the polymer being extruded. Solution of the system equations permitted us to predict the velocity profile and shear stress distributions of a molten polymer inside a pressure-type wire coating die.     

Measurement of the rheological properties of polymer melts with slit rheometer. I. Homopolymer systems

Two slit dies have been designed, having aspect ratios of 10 and 20. Three melt pressure transducers were flush-mounted on the long side of the rectangular slot, along the longitudinal centerline of each die. The dies were then used to measure wall normal stresses along the longitudinal direction of polymer melts flowing through the thin slit. The polymeric materials investigated were high-density polyethylene, low-density polyethylene, polypropylene, and polystyrene. The measurement of wall normal stresses were used to determine the rheological properties of melts, namely, the melt viscosity from the slope of axial pressure profiles and the melt elasticity from exit pressures. The present study shows that the rheological properties determined from the slit rheometer are in good agreement with those from the capillary rheometer reported in the author's earlier papers. Therefore it may be concluded that a slit die also may be used as a means of characterizing polymeric materials by their viscous and elastic properties in the molten state.     

Dynamics of single-walled carbon nanotube (SWNT)/polyisoprene (PI) nanocomposites in electric and mechanical fields

Relaxation dynamics of single-walled carbon nanotube (SWNT)/polyisoprene (PI) nanocomposites were examined by dielectric relaxation spectroscopy (DRS) and dynamic mechanical spectroscopy (DMS) over a wide range of frequency and temperature. Both functionalized (SWNT-f) and pristine (SWNT-p) nanotubes were used and their effect on dynamics compared. Functionalized (PISF) nanocomposites were characterized by an increase in the time scale of the normal mode process as a consequence of the strong surface interactions between the polymer matrix and the nanotubes. The exact opposite is seen in pristine (PISP) nanocomposites where a decrease in the time scale of the normal mode relaxation is observed and attributed to weaker surface interactions and the effect of confinement on dynamics. The segmental process in PISF or PISP is not affected by the presence of nanotubes. The temperature dependence of the average relaxation time for normal and segmental modes is of the Vogel-Fulcher-Tammann (VFT) type. A good agreement is observed in the time scale of processes measured by DRS and DMS in PISF nanocomposites. In PISP nanocomposites, however, the time scales obtained from DRS and DMS measurements are not in consistently good agreement and an explanation is offered in terms of confinement.     

Effect of water on HDS of DBT over a dispersed Mo catalyst using in situ generated hydrogen

A novel process was developed for the bitumen emulsion upgrading, wherein emulsion breaking and upgrading occurred in the same reactor using H₂ generated in situ from the water in the emulsion via the water gas shift reaction (WGSR). In this study, dibenzothiophene (DBT) was chosen as a model compound to investigate the effect of water and in situ H₂ on hydrodesulfurization (HDS). All the experiments were performed in a 1-L autoclave reactor at temperatures between 300 and 380 °C using in situ H₂ and ex situ H₂ (externally supplied H₂) over a dispersed Mo catalyst formed from phosphomolybdic acid (PMA). At very low water content, water was found to promote the HDS reaction in the ex situ H₂ run probably because it facilitates the formation of more active dispersed MoS_x species. At higher water content, however, water inhibits every individual reaction in the reaction network in the HDS of DBT, blocking the hydrogenation pathway more than the hydrogenolysis pathway. The relative reactivity of the in situ and ex situ H₂ depends on the water content present in the reaction system. At an optimized mole ratio of H₂O:CO (1.35), higher HDS activity was observed in the in situ H₂ run compared to ex situ H₂ run, and particularly, the hydrogenation pathway was promoted in the in situ H₂ run.     

Lipase-catalyzed alcoholysis of triglycerides for short-chain monoglyceride production

Lipase from Pseudomonas fluorescens efficiently catalyzed the alcoholysis of various TG in dry alcohols. For TG with short-chain FA, more MG were accumulated. The yields of MG were affected by the alcohols used. The maximum yields of MG were as follows: 85% for monoacetin in n-butanol, 96% for monobutyrin in ethanol or n-butanol, 50% for monocaprylin in n-butanol, 48% for monolaurin in isopropanol, and 45% for monopalmitin in isopropanol. The MG produced were judged to be 2-MG by TLC analysis. The presence of organic cosolvent affected the reaction rate of the lipase-catalyzed alcoholysis of TG. For the alcoholysis of various TG in ethanol and cosolvent (1∶1, vol/vol), the rates had the following orders: (i) for tributyrin, hexane > toluene > acetone > ethyl acetate > chloroform > acetonitrile > pyridine; (ii) for tricaprylin, hexane > acetone > toluene > acetonitrile > ethyl acetate > pyridine > chloroform; and (iii) for trialurin, hexane > acetonitrile=acetone > ethyl acetate > pyridine=chloroform > toluene.     

Identification of organochlorines and organobromines in coals

Four Chinese bituminous coals were extracted with CS₂, n-hexane, benzene, methanol, acetone, tetrahydrofuran (THF) and THF/methanol (1: 3 vol/vol) mixed solvent sequentially. The resulting 28 extracts were analyzed with GC/MS. Six organochlorines (OCs) and two organobromines (OBs) were identified in eight extracts from the coals. Our experiments provide, for the first time, the information on the molecular structure of OCs and OBs in coals.     

Model for drying during fluidized-bed combustion of wet low-rank coals

An unsteady state heat conduction model with a convective boundary condition is proposed for the drying of low-rank, high-porosity coals, such as lignites, during fluidized-bed combustion. The drying front is assumed to be the receding surface of a wet core. The solution technique for this moving boundary problem is based on the heat balance integral approach with immobilization of the moving boundary by a change in space variable. The governing cubic equation describing the drying curve in dimensionless form may be solved easily by the Newton—Raphson method. The model predictions are compared with experimental data for Mississippi lignite with excellent agreement. A correlation for estimation of total drying time is proposed. The temperature profiles obtained may be used for the study of the coupled drying and devolatilization in fluidized-bed combustors. The profiles could also be of importance in the study of formation of fissures/cracks in lignites subjected to intense heating conditions encountered during fluidized-bed combustion.     

The study on the conductivity of styrene-maleic anhydride copolymer electrolytes based on poly(ethylene glycol)400 and LiClO4

Polyelectrolytes, in this study were synthesized from styrene-maleic anhydride (SMA) copolymer, poly(ethylene glycol)400 (PEG400), and lithium perchlorate (LiClO₄). Fourier transform infrared spectroscopy (FTIR), and magic angle spinning (MAS) solid-state NMR were used to monitor the interaction between Li⁺ ions and polymer. The results of FTIR and MAS solid-state NMR indicate the Li⁺ ions are preferentially coordinated to the ether oxygen of PEG. The T_g of the PEG segments in polyelectrolyte increases with LiClO₄ concentration, as determined by differential scanning calorimetry (DSC), indicating that solubility of the Li⁺ ions in the host polymer increases with the PEG content. Impedance spectroscopy (IS) shows that the bulk conductivity of polyelectrolytes and the conductivity behavior obeys the Vogel-Tamman-Fulcher (VTF) equation.     

Odors in traps: Does most recent occupant influence capture rates for house mice?

Responses of house mice (Mus domesticus) to odors in live traps were studied in a series of eight 0.1-ha outdoor field enclosures. It was assumed that the most recent mouse capture would provide the predominant odor in a trap for at least one week. Three different populations were tested, one in 1989 and two in 1992, involving over 800 different mice. Similar response patterns were recorded from all three groups. Two types of questions were tested: (1) Were there any biases contingent upon what had been previously caught? (2) Were there consistent responses of mice of particular age, sex, or reproductive classes to trap odors? Traps soiled by juvenile females caught adult females significantly less often than expected, but there were no consistent relationships in terms of the effects of specific residual odors on the subsequent capture at a particular trap. For various age, sex, and reproductive classes, (1) adult males preferred odors from juvenile and estrous females and avoided odors of other males significantly more than expected, (2) juvenile females selected traps with odors of other juvenile females and avoided all other types of female odors significantly more than expected, (3) nonestrous females exhibited a significant preference for adult male odor, and (4) estrous females selected traps containing odors from adult males but avoided those that had previously contained either nonestrous or pregnant/lactating females significantly more than expected. These findings have potential implications with regard to both the methods used for trapping small rodents and the social biology of house mice.     

Radiation flux distribution over solar images formed on the focal plane by a paraboloidal reflector with tracking errors

The radiation flux distribution of off-centered solar images formed by a sun-tracking paraboloidal reflector is theoretically analyzed for several tracking error angles using Jose’s sunshape equation and assuming a specularly reflecting surface without taking meteorological conditions into consideration. The results are printed out by computer in the form of shade density maps to bring out a clear contrast to the low and high flux areas of a full image.