Effect of temperature on polymer migration II: Concentration equation

Polymer migration is a generally well-known phenomenon in a flow field, and it has been verified that the sources of such phenomena are nonhomogeneity of the flow, concentration effects and hydrodynamic interactions between the polymer molecules. In addition, temperature effects were found to be another source of polymer migration. The Langevin equation for a polymer molecule was first derived from single chain dynamics using a kinetic theory for the bead-spring elastic harmonic dumbbell model, as described in part I (reference [1]). In this paper the diffusion equation and concentration profile of the polymer molecules induced by a temperature gradient are obtained from the Fokker-Planck equation. A new differential operator is also introduced to calculate the concentration profile. From the concentration equation obtained in the general flow geometry, we find that in dilute polymer solution there are significant effects on the polymer migration not only due to the nonhomogeneity of the flow field but also due to temperature gradients.     

Blends of chlorinated isotactic polypropylene with poly(ethylene-co-vinyl acetate) I. Effect of component polymers composition on the blend miscibility

Chlorinated isotactic polypropylenes (CPP) having various chlorine contents were blended with poly(ethylene-co-vinyl acetate)s (EVA) having various vinyl acetate (VA) contents. The blends were made by casting films from dilute THF solutions and miscibility of the blends was identified by single glass transition temperature, which was confirmed by DSC and dynamic mechanical measurements. Based on the miscibility data from a large number of CPP/EVA combinations, a miscibility map was depicted where CO equivalent weight (CO-EQW) of EVA was plotted against chlorine equivalent weight (Cl-EQW) of CPP. Though an attractive interaction between CPP and EVA could be detected in all the miscible and immiscible blend pairs, miscibility of the CPP/EVA blends could solely be observed in a relatively narrow range of Cl-EQW ca. 65–100 and CO-EQW ca. 170–230.     

Analysis of deformation processes in glassy polycarbonate using internal friction measurements during a tensile test

Internal friction has been measured by torsion at 1 Hz during tensile tests performed on glassy polycarbonate at room-temperature. Steady-state flow and transient effects have been studied during continuous tensile tests and strain-rate changes. During steady-state, internal friction and flow-stress vary in a similar way with strain-rate. But during transients, internal friction varies continuously while flow-stress passes through a maximum (or a minimum). These results are interpreted assuming that non-elastic deformation of glassy polymers requires some microscopic discontinuous processes such as motion of defects. Two parameters are considered: the velocity v and the density ρ of mobile defects. Assuming that the former is directly related to the flow stress, it has been shown that internal friction is related to the density of mobile defects ρ. This feature is used to interpret the different stages of a tensile test curve. Activation volumes for both velocity and density of mobile defects are calculated from experimental data.     

Thermal conductivity of high polymers—the influence of molecular weight

Some earlier observations on the influence of molecular weight, plasticizer, and irradiation on the thermal conductivity of polymers is reviewed. Also some new data on polystyrene and some new calculations based on the theory of Hansen and Ho are presented. These data show almost a two fold increase in the thermal conductivity of polystyrene as the molecular weight goes from 900 to 100,000. Data on the moleculer weight effect on thermal conductivity appear to be consistent with the theoretical calculations.     

Interaction of CETP inhibitory peptide and lipoprotein substrates in cholesteryl ester transfer assay: relationship between association properties and inhibitory activities

In a previous study, CETP inhibitory peptide (3 kDa) was isolated from hog plasma. The peptide, synthesized chemically according to the amino acid sequence of the 3-kDa peptide (designated P₂₈), showed CETP inhibitory activity both in vitro and in vivo [Cho et al. (1998) Biochim. Biophys. Acta 1391, 133–144]. We report herein further unique features of P₂₈ when it was associated with the cholesteryl ester (CE)-donor and-acceptor lipoproteins. Lipoprotein substrates with P₂₈ present in both HDL (as a CE-donor) and LDL (as a CE-acceptor) served as poor substrates, with CE-transfer activity decreased up to 60% compared to normal substrates without P₂₈. P₂₈ was found to be located in HDL fractions of hog plasma and showed the same electromobility as that visualized by PAGE on 7% polyacrylamide gel under nondenaturing conditions. Addition of apolipoprotein A-1 (apoA-1) or apoB antibody to a normal CE-transfer mixture did not alter CE-transfer activity. However, addition of apoA-1 or −B antibody to a CETP-inhibition mixture decreased the inhibitory activity of P₂₈ by ca. 20%. Western blot analysis revealed that P₂₈ was associated only with human and hog HDL among several lipoproteins purified from human, hog, and rabbit. CFTP-inhibition assays with various lipoprotein substrates revealed that P₂₈ exhibited substrate-specific inhibitory activity. The inhibitory activity of P₂₈ was highly dependent on the type of lipoprotein substrate (whether CE-donor or-acceptor); P₂₈ inhibited CE transfer from HDL to LDL, but it did not inhibit CE transfer from HDL to HDL.     

The onset of Taylor-Görtler vortices in impulsively decelerating swirl flow

The onset of hydrodynamical instability induced by impulsive spin-down to rest in a cylinder containing a Newtonian fluid is analyzed by using propagation theory. It is well-known that the primary transient swirl flow is laminar, but with initial high velocities secondary motion sets in at a certain time. The dimensionless critical time Τ_c to mark the onset of instability is presented here as a function of the Reynolds number Re. Available experimental data indicate that for large Re deviation of the velocity profiles from their momentum diffusion occurs starting from a certain time Τ≈4Τ_c. This means that secondary motion is detected at this characteristic time. It seems evident that during Τ_c⪯Τ⪯4Τ_c, secondary motion is relatively very weak and the primary diffusive momentum transfer is dominant.     

Effects of rosemary extracts and major constituents on lipid oxidation and soybean lipoxygenase activity

Rosemary (Rosemarinus officinalis L.) leaves were extracted with three different solvents, namely hexane, acetone and methanol. A reverse-phase high-performance liquid chromatography system in combination with a mass detector was used to quantitate the content of carnosol, carnosic acid and ursolic acid in the rosemary extracts. All rosemary extracts showed strong inhibitory effects on lipid oxidation and soybean lipoxygenase activity.     

Transient behaviour of encapsulated enzyme reactor systems

Mathematical models are developed for the transient behaviour of encapsulated enzyme reactor systems such as the continuous stirred tank reactor (CSTR) and the packed bed tubular reactor. The rate processes taking place in the encapsulated enzyme bed are approximated by using a combined rate control model of enzyme reaction and membrane diffusion. The change in transient substrate concentration is obtained by using the developed rate expression in the material balance over the substrate as a function of time for the CSTR and as a function of time and position for the packed bed tubular reactor. The effects of various parameters such as the enzymic reaction rate constant, Michaelis constant, diffusional resistance of membranes, and Peclet number on the substrate concentration distribution, which varies with respect to operating time, are investigated. This study affords insight into the transient operating characteristics of the encapsulated enzyme reactor system. The results should be useful in understanding the start-up performance of the reactor systems and to control such reactor systems at desired operating conditions.     

High Temperature Oxidation of Steels in Air and CO2–O2 Atmosphere

Three kinds of hot rolled steel slabs, viz. high strength steel, bake hardened steel and low carbon steel, were oxidized isothermally between 1100 and 1250 °C for up to 2 hr in 1 atm of air and an 85%N₂–10%CO₂–5%O₂ gas mixture. The steels were oxidized in a similar fashion in both the atmospheres. The oxidation process followed an initial linear rate law, which then gradually transformed to a nearly parabolic rate law. Thick, porous and nonadherent scales formed rapidly, due to the high oxidation temperature. The scales formed consisted of Fe₂O₃,(Fe₂O₃+Fe₃O₄), (Fe₃O₄+Fe₂O₃ +FeO) and (FeO+Fe₃O₄) from the outer surface. The presence of supersaturated oxygen beneath the scale resulted in grain boundary oxidation and the formation of internal oxide precipitates.     

Intermetallic phase formation in directionally solidified Al−Si−Fe alloy

The present study has been undertaken to better understand the solidification behavior of Al−Si−Fe alloys containing 7wt.% Si and 0.9wt.% Fe, with particular regard to the formation of phase during controlled solidification and influence of growth rates on intermetallic phase selection. The alloys studied were Al-7Si-0.9Fe alloys, which were produced by a modified Bridgman solidification arrangement. These alloys were solidified unidirectionally with different growth rates (1–30mm/min). The solidified microstructure of these alloys consists of the growth of primary aluminum and multiple second phase reactions.