Synthesis of syndiotacticity‐rich high molecular weight poly(vinyl alcohol) by suspension polymerization of vinyl pivalate and saponification

Vinyl pivalate (VPi) was suspension‐polymerized to synthesize high molecular weight (HMW) poly(vinyl pivalate) (PVPi) with a high conversion above 95% for a precursor of syndiotacticity‐rich HMW poly(vinyl alcohol) (PVA). Also, the effects of the polymerization conditions on the conversion, molecular weight, and degree of branching (DB) of PVPi and PVA prepared by the saponification of PVPi were investigated. Bulk polymerization was slightly superior to suspension polymerization in increasing the molecular weight of PVA. On the other hand, the latter was absolutely superior to the former in increasing the conversion of the polymer, indicating that the suspension polymerization rate of VPi was faster than that of the bulk one. These effects could be explained by a kinetic order of a 2,2′‐azobis(2,4‐dimethylvaleronitrile) concentration calculated by the initial rate method. Suspension polymerization of VPi at 55°C by controlling various polymerization factors proved to be successful in preparing PVA of HMW [number‐average degree of polymerization (P_n): 8200–10,500], high syndiotactic diad content (58%), and very high yield (ultimate conversion of VPi into PVPi: 94–98%). In the case of the bulk polymerization of VPi at the same conditions, the maximum P_n and conversion of 10,700–11,800 and 32–43% were obtained, respectively. The DB was lower and the P_n was higher with PVA prepared from PVPi polymerized at lower initiator concentrations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 832–839, 2003     

Preparation of water‐soluble syndiotacticity‐rich high molecular weight poly(vinyl alcohol) microfibrillar fibers using copolymerization of vinyl pivalate and vinyl acetate and saponification

Water‐soluble high molecular weight (HMW) syndiotactic poly(vinyl alcohol) (s‐PVA) microfibrillar fibers were prepared by the saponification with various conditions such as amount of alkali solution, saponification temperature, and saponification concentration from copoly(vinyl pivalate (VPi)/vinyl acetate (VAc)) copolymerized using various VPi/VAc feed ratios. To produce s‐PVA microbrillar fibers having various water‐soluble temperatures for many industrial applications, the intrinsic viscosities, syndiotactic diad (S‐diad) contents, and degrees of saponification (DS)s of PVAs were finely controlled to 1.2–3.6 dL/g, 56.3–58.3%, and 91.4–98.3%, respectively. Through a series of experiments, it was found that the amount of alkali may alter the structure of the saponified polymers, primarily the DS, and the structural variation changes viscosity. That is, intrinsic viscosity was sharply decreased as the amount of alkali solution was increased. DS was increased with an increase in the amount of alkali solution. S‐diad content was increased with an increase in the VPi content. HMW s‐PVA microfibrillar fibers having S‐diad content of 56.3–58.3% prepared by the saponification of copoly(VPi/VAc) were completely soluble in water at 100°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1482–1487, 2003     

Continuous ethanol production from wood hydrolysate by chemostat and total cell retention culture

Chemostat and total cell retention cultures with internal filter system ofSaecharomyc.es cerevisiae H1-7 were carried out to produce ethanol from wood hydrolysate. Maximum ethanol productivity obtained in a chemostat with the aeration rate of 1 vvm was 3.79 g/(L·h). This was 20% higher than that in a chemostat without aeration. However, the substrate was not completely consumed at the dilution rate with the maximum productivity. The realistic productivity, which has higher than 99% conversion rate of substrate, was. 2.95 g/(L·h). The maximum productivity in the total cell retention culture was 6.65 g/(L·h) at the dilution rate of 0.19 h¹ and the residual glucose concentration was negligible.     

Temperature effect on the permeation through poly(2-hydroxyethyl methacrylate) membrane

The temperature dependence of permeability through highly syndiotactic poly(2-hydroxyethyl methacrylate) [P(HEMA)] membrane is reported for highly polar organic solutes such as ureas, methyl substituted ureas and amides, and for NaCl and Na₂SO₄. The membranes used were equilibrated in distilled water at each temperature before measurements. From the linear correlationship between the excess heat capacities, ?C_p^o(excess) in aqueous solution at infinite dilution and the permeability parameter PM^1/3, it is found that the water structure perturbing capability of the polar organic solutes is a controlling factor in the permeation mechanism at relatively low temperature, where P(HEMA) membrane has higher water content and more structured water. In addition, it is found that the poor separation for urea of cellulose acetate membrane in the reverse osmosis practice is due to the higher water structure-breaking capability of urea.     

Fundamental foaming mechanisms governing the volume expansion of extruded polypropylene foams

This article describes the fundamental foaming mechanisms that governed the volume expansion behavior of extruded polypropylene (PP) foams. A careful analysis of extended experimental results indicated that the final volume expansion ratio of the extruded PP foams blown with butane was governed by either the loss of the blowing agent or the crystallization of the polymer matrix. A charge coupling device (CCD) camera was installed at the die exit to carefully monitor the shape of the extruded PP foams. The CCD images were analyzed to illustrate both mechanisms, gas loss and crystallization, during foaming at various temperatures, and the maximum expansion ratio was achieved when the governing mechanism was changed from one to the other. In general, the gas loss mode was dominant at high temperatures and the crystallization mode was dominant at low temperatures. When the gas loss mode was dominant, the volume expansion ratio increased with decreasing temperature because of the reduced amount of gas lost. By contrast, when the crystallization mode was dominant, the expansion ratio increased with increasing temperature because of the delayed solidification of the polymer. The processing window variation with the butane concentration, the change in the temperature ranges for the two governing modes, and the sensitivity of melt temperature variations to the volume expansion ratio are discussed in detail on the basis of the obtained experimental results for both branched and linear PP materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2661–2668, 2004     

Effect of low-cycle fatigue on the hot ductility of plain carbon steel

In a continuous casting steelmaking operation, the surface of a slab is under a condition that can be characterized as high-temperature, low-cycle fatigue in which the tensile and compressive stress is repeatedly developed. For this reason, for the evaluation of the hot ductility of a slab, considering the fatigue deformation is more feasible before a tensile or compressive test. In this study, the effects of low-cycle fatigue on the hot ductility of steels with a carbon content of 0.06–0.8 wt.% are investigated at various temperatures. For a carbon content of 0.06%, there were no significant differences between the RA values from a simple tensile test and those from a tensile test after fatigue deformation. The tendency of ductility deterioration with fatigue deformation is evident in 0.1 %C steel, and is due to the deformation-induced ferrite film that forms around the prior austenite grain. Conversely, high carbon steel containing 0.8 %C did not show a recovery of hot ductility in a low temperature region, and the specimen on which the tensile was measured after fatigue showed a higher hot ductility in the low temperature region, which is thought to result from the pearlite refinement effects. As the results obtained in this work showed noticeable differences in the hot ductility of carbon steel through the test conditions, it is suggested that for more accurate data, fatigue deformation be adopted in which the temperature range in an unbending operation is determined in the steelmaking factory.     

LTCC‐based monolithic system‐in‐package (SiP) module for millimeter‐wave applications

A miniature LTCC system‐in‐package (SiP) module has been presented for millimeter‐wave applications. A typical heterodyne 61 GHz transmitter (Tx) has been designed and fabricated in a type of the SiP module as small as 36 × 12 × 0.9 mm³. Five active chips including a mixer, driver amplifier, power amplifier, and two frequency multipliers were mounted on the single LTCC package substrate, in which all passive circuits such as a stripline (SL) BPF, 2 × 2 array patch antenna, surface‐mount technology (SMT) pads, and intermediate frequency (IF) feeding lines have been monolithically embedded by using vertical and planar transitions. The embedded SL BPF shows the center frequency of 60.8 GHz, BW of 4.1%, and insertion loss of 3.74 dB. The gain and 3‐dB beam width of the fabricated 2 × 2 array patch antenna are 7 dBi and 36 degrees, respectively. The assembled LTCC 61 GHz Tx SiP module achieves an output power of 10.2 dBm and an up‐conversion gain of 7.3 dB. Because of the integrated BPF, an isolation level between a local oscillation (LO) and RF signal is below 26.4 dBc and the spurious level is suppressed by lower than 22.4 dBc. By using a 61 GHz receiver (Rx) consisting of off‐the‐shelf modules, wireless communication test was demonstrated by comparing measured IF spectrums at the Tx and Rx part.     

Inertial effects on cylindrical particle migration in linear shear flow near a wall

Micro-/nanoparticle-based systems are regarded as one of the possible candidates due to the engineerability and multifunctionality to maximize the accumulation of the nano-/microparticle-based drug delivery system on the target. Recent advances in nanotechnology enable the fabrication of diverse particle shapes from simple spherical particles to more complex shapes. The particle dynamics in blood flow and endocytosis characteristics of non-spherical particles change as the non-sphericity effect increases. We used a numerical approach to investigate the particle dynamics in linear shear flow near a wall. We examined the dynamics of slender cylindrical particles with aspect ratio γ = 5.0 in terms of particle trajectory, velocity, and force variation for different Stokes numbers over time. We identified the rotating inertia of particle near a wall as the source of inertial migration toward the wall. The drift velocity of slender cylindrical particles is comparable to that of discoidal particles. We discuss the possibilities and limitations of using slender cylindrical particles as a drug delivery system.     

Formation stabilization and resizing based on the control of inter‐agent distances

We propose a control strategy that could steer the group of mobile agents in the plane to achieve a specified formation. The control law could be implemented in a fully decentralized manner so that each agent moves on their own local reference frame. Under the acyclic minimally persistent graph topology, each agent measures the relative displacements of neighboring agents and then adjusts the distances between them to achieve the desired formation. As well as achieving a fixed formation, we could resize the formation only by changing the leader edge, which connects the leader with the first‐follower in acyclic minimally persistent graph, without changing the structures of the control law. Copyright © 2014 John Wiley & Sons, Ltd.