Multicomponent diffusion in phase-separating polymer blends with different frictional interactions: a mean-friction model

We present a compact formula for describing the mean frictional forces acting on a molecule in multicomponent systems. The friction-based diffusion theory of Zielinski and Hanley was extended to newly include the friction-average molar velocity as a reference frame. The results showed that the previous diffusion theories are unified by the friction-average concept by properly choosing the average velocity. The present model based on the diffusivity-related molar average velocity provides better predictions for the diffusive flux in a ternary miscible liquid compared to the other existing theories. The application of the model in phase-separating ternary systems revealed that the introduction of a highly diffusive third component into demixing polymer blends promotes a particular enhancement of the spinodal decomposition due to the difference in the frictional interactions between polymers.     

Melt-mixing by novel pitched-tip kneading disks in a co-rotating twin-screw extruder

Melt-mixing in twin-screw extruders is a key process in the development of polymer composites. Quantifying the mixing performance of kneading elements based on their internal physical processes is a challenging problem. We discuss melt-mixing by novel kneading elements called “pitched-tip kneading disk (ptKD)”. The disk-stagger angle and tip angle are the main geometric parameters of the ptKDs. We investigated four typical arrangements of the ptKDs, which are forward and backward disk-staggers combined with forward and backward tips. Numerical simulations under a certain feed rate and screw revolution speed were performed, and the mixing process was investigated using Lagrangian statistics. It was found that the four types had different mixing characteristics, and their mixing processes were explained by the coupling effect of drag flow with the disk staggering and pitched-tip and pressure flows, which are controlled by operational conditions. The use of a pitched-tip effectively controls the balance of the pressurization and mixing ability.     

Structure and properties of poly(vinyl alcohol)/κ‐carrageenan blends

Blends of a commercial atactic poly(vinyl alcohol) (a‐PVA) derived from vinyl acetate and κ‐carrageenan were prepared by mixing the aqueous solutions of both samples. Blend films prepared by casting were transparent. In the DSC curves of the blend films, the endothermic peaks shifted to lower temperature with an increase of the content of κ‐carrageenan. The Young's modulus and the strength at break increased with an increase of the content of a‐PVA. As the standing temperature of the blend solutions decreased, the gelation region increased also at high content of carrageenan. In the amorphous regions of blend films, a‐PVA and κ‐carrageenan were miscible. © 2001 Society of Chemical Industry     

High tensile strength fiber of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] processed by two‐step drawing with intermediate annealing

High tensile strength fibers of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] [P(3HB‐co‐3HH)], a type of microbial polyesters, were processed by one‐step and two‐step cold‐drawn method with intermediate annealing. Thermal degradation behaviors were characterized by differential scanning calorimeter and gel permeation chromatography measurements. Thermal analyses were revealed that molecular weights decreased drastically within melting time at a few minute. One‐step cold‐drawn fiber with drawing ratio of 10 showed tensile strength of 281 MPa, while tensile strength of as‐spun fiber was 78 MPa. When two‐step drawing was applied for P(3HB‐co‐3HH) fibers, the tensile strength was led to 420 MPa. Furthermore, the optimization of intermediate annealing condition leads to enhance the tensile strength at 552 MPa of P(3HB‐co‐3HH) fiber. Wide‐angel X‐ray diffraction measurements of these fibers suggest that the fibers with high tensile strength include much amount of the planer‐zigzag conformation (β‐form) as molecular conformation together with 2₁ helix conformation (α‐form). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41258.     

Numerical simulations of annular extrudate swell of polymer melts

Numerical viscoelastic simulations were carried out using a K-BKZ type of separable integral constitutive equation. Both reversible and irreversible models were tried for several types of damping functions to calculate the annular extrudate behavior of high-density polyethylene (HDPE). There are two aims in this study; first, to clarify the properties of these dumping functions, and second, to investigate the influence of rheological characteristics on annular extrudate swell. In these numerical simulations, relaxation spectrum and shear viscosity were fixed, and the other characteristics were varied. The reversional response of the damping function mainly has an effect on the magnitude of the area swell even if the die is straight. The irreversible model expresses the experimental results of annular extrudate swell better than the reversible model. The accurate fitting of N1 by the damping model is important for predicting it. The magnitude of N1 predicted from the Wagner exponential model is lower than that of the PSM model, and the area swell shows the same tendency as N1. A modified PSM model that allows the N1 curve to shift can fit the magnitude of area swell. The relationship between the diameter and thickness of the extrudate depends on N2/N1, and it was estimated by simple linear elasticity of solids. The time dependent viscosity varies with the type of damping function, and it influences the time-dependent swell.     

Characterization of a Novel Thermostable Dye-Linked l-Lactate Dehydrogenase Complex and Its Application in Electrochemical Detection

Flavoenzyme dye-linked l-lactate dehydrogenase (Dye-LDH) is primarily involved in energy generation through electron transfer and exhibits potential utility in electrochemical devices. In this study, a gene encoding a Dye-LDH homolog was identified in a hyperthermophilic archaeon, Sulfurisphaera tokodaii. This gene was part of an operon that consisted of four genes that were tandemly arranged in the Sf. tokodaii genome in the following order: stk_16540, stk_16550 (dye-ldh homolog), stk_16560, and stk_16570. This gene cluster was expressed in an archaeal host, Sulfolobus acidocaldarius, and the produced enzyme was purified to homogeneity and characterized. The purified recombinant enzyme exhibited Dye-LDH activity and consisted of two different subunits (products of stk_16540 (α) and stk_16550 (β)), forming a heterohexameric structure (α3β3) with a molecular mass of approximately 253 kDa. Dye-LDH also exhibited excellent stability, retaining full activity upon incubation at 70 °C for 10 min and up to 80% activity after 30 min at 50 °C and pH 6.5–8.0. A quasi-direct electron transfer (DET)-type Dye-LDH was successfully developed by modification of the recombinant enzyme with an artificial redox mediator, phenazine ethosulfate, through amine groups on the enzyme’s surface. This study is the first report describing the development of a quasi-DET-type enzyme by using thermostable Dye-LDH.     

A neck‐in model in extrusion lamination process

In this study, the experiment of the extrusion lamination process using high‐pressure process low‐density polyethylene (LDPE) was performed. The nonisothermal viscoelastic simulation of the extrusion lamination experiment was also carried out. The simulation results were in good agreement with the experimental data within wide range of take up velocity and air gap length. We developed the theoretical model based on force balance and deformation type of a film to predict the neck‐in behavior in the extrusion lamination or cast film process. It was suggested from the neck‐in model that the neck‐in correlates with the ratio of planar to uniaxial elongational viscosity. It was confirmed that the neck‐in model could predict the film edge shape and neck‐in properly for conventional LDPE. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Formation and emission of volatile polonium compound by microbial activity and polonium methylation with methylcobalamin

We observed biologically mediated emission of Po from culture solution inoculated sea sediment extract and incubated under natural light/dark cycle condition or dark condition the emitted Po compound would be lipophilic because of effective collection in organic solvent. Sterilization of the culture medium with antibiotics or CuSO4 completely suppressed growth of microorganisms and resulted in no emission of Po, indicating biological activity of microorganisms is responsible for formation and emission of volatile Po compound. Po emission also occurred when seawater was used as a culture medium. Our finding indicates a possibility of biotic source for atmospheric Po in the environment, which has been believed to be originated from abiotic sources. We compared emission behavior of Po and S in the culture experiments, the elements belong to XVI group in the Periodical Table, and consider that their emission mechanisms involved would be different though the emission of both elements is supported by biological activity of microorganisms. One of the chemical forms of S emitted was confirmed to be dimethyl sulfide (DMS) but that of Po is not known. Methylation experiments of Po with methylcobalamin demonstrated a formation and emission of volatile Po compound. The methylation of Po with methylcobalamin might be related to the observed Po emission in the culture experiments.