Application of CO2 laser heating zone drawing and zone annealing to nylon 6 fibers

Nlon 6 fibers were zone drawn and zone annealed by using a continuous wave carbon dioxide laser to develop their mechanical properties. A laser‐heating zone drawing was carried out under a applied tension of 35.4 MPa at a power density of 9.65 W · cm^?2, and then the zone‐drawn fiber was annealed. A laser‐heating zone annealing was carried out in two steps at a power density of 9.65 W · cm^?2; the first step was carried out under 423 MPa and the second under 517 MPa. The treating temperature of the fiber heated by the CO₂ laser was measured by using an infrared thermographic camera equipped with a magnifying lens. The treating temperature at the zone drawing is 138°C, and those at the first and the second zone annealing are 121 and 125°C, respectively. The second laser‐heated zone‐annealed fiber has a birefringence of 65.2 × 10^?3, a degree of crystallinity of 54%, and a storage modulus of 21 GPa at 25°C. Wide‐angle X‐ray diffraction patterns for the laser‐heated zone‐drawn and the zone‐annealed fibers show (200) reflection and (002/202) doublet due to only an α form on the equator. The laser‐heated zone‐drawn fiber has a melting endotherm peaking at 216°C and a trace of shoulder on the higher temperature side of its peak, and the laser‐heated zone‐annealed fibers have a single melting endotherm peaking at 216°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1711–1716, 2002     

Continuous emulsion polymerization of vinyl acetate. II Operation in a single Couette–Taylor vortex flow reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were conducted at 50°C in a single continuous Couette–Taylor vortex flow reactor (CCTVFR) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. The polymerization can be carried out very smoothly and stably, but the steady‐state monomer conversion attained in a CCTVFR is not as high as that in a plug flow reactor (PFR), but only slightly higher than that in a continuous stirred tank reactor (CSTR), even if the Taylor number is adjusted to an optimum value. Also, the effects of operating variables, such as the emulsifier, initiator, and monomer concentrations in the feed and the mean residence time on the kinetic behaviors were almost the same as those observed in a CSTR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2755–2762, 2002     

Ethanol production from raw starch by a recombinant yeast having saccharification and fermentation activities

In order to develop a method for converting raw starch into ethanol efficiently, direct fermentation of ozonized raw starch using a recombinant yeast was investigated. Ozonolysis was carried out as a pretreatment to convert raw starch into ethanol rapidly and efficiently, and then the effect of the ozone degradation conditions on the degree of polymerization and the amount of amylose in a raw starch was determined. Since the degree of polymerization was low and the amount of amylose was high, raw starch treated with an ozone concentration of 40 gm^?3 and an ozonation time of 30 min was the material chosen for alcohol fermentation. Though the recombinant yeast could not convert the untreated raw starch, it converted the soluble starch and the ozonized raw starch at a comparatively high yield into ethanol. About 56% of the ozonized raw starch decomposed, and the ethanol concentration obtained from the ozonized raw starch was markedly greater than that obtained from untreated raw starch. The dynamic behavior of cell growth, substrate degradation, and ethanol production was examined in a continuous culture under various dilution rates, and the optimal dilution rate, ie 0.15 h^?1, was determined for maximizing the ethanol productivity (amount of ethanol produced per unit time). © 2002 Society of Chemical Industry     

Properties of graphite prepared from boron-doped pitch as an anode for a rechargeable Li ion battery

Boron-doped graphites were derived from a naphthalene-based pitch mixed with para-xylene glycol (PXG) or dimethyl para-xylene glycol (DMPXG) as a cross-linking agent and three types of boron-containing compounds as a graphitization catalyst, and their anode performances were investigated. The structural analysis of the obtained graphites revealed that PXG functioned mainly as a two-dimensional cross-linking agent during the heat treatment process and DMPXG functioned partially as a three-dimensional. The average interlayer spacing decreased and lattice constant, a₀, and graphitizability increased with increasing the amount of boron atoms added. The result indicated that the carbon atoms were replaced by boron atoms. The anode performance was improved by the enhancement of graphitizability. The structural parameters and anode performance of boron-doped graphites did not depend on the kind of boron-containing compounds but the amount of boron atoms added in pitch and the kind of cross-linking agent.     

Heavy oil sorption and recovery by using carbon fiber felts

On fibrous carbon materials, including activated carbon fibers, sorption capacity for heavy oils, less viscous A-grade and more viscous C-grade, was determined. Sorption capacity depended strongly on their bulk density; the correlation was the same as that found previously on exfoliated graphite and carbonized fir fibers. On carbon fiber felts, excellent recycling performance was observed, though sorption capacity was not so high as on exfoliated graphite and carbonized fir fibers. By filtration under suction, about 90% of sorbed A-grade heavy oil could be recovered and no decrease in sorption capacity was detected even after eight cycles. By washing with solvents, n-hexane for A- and C-grade oils and A-grade oil for C-grade oil, almost 100% recovery with no marked reduction in sorption capacity was found for each cycle. For the felts of PAN-based carbon fibers, rather severe operations for oil recovery, centrifugation and squeezing with twisting, could be applied without pronounced decreases in sorption capacity and recovery ratio.     

Effect of agglomeration of triacylglycerols on the stabilization of a model cream

This study has been carried out on solidification of a model cream using palm oil as a sole fat source. It was found that the addition of 1‐palmitoylglycerol to palm oil promoted the solidification of the model cream while the addition of 1‐oleoylglycerol had no such effect. Solid fat content of palm oil in the cream with 1‐palmitoylglycerol was found to be lower than those of palm oil and palm oil with 1‐oleoylglycerol after cooling from 60 to 5 °C. Crystallization behaviors of bulk palm oil and mixture of 1, 3‐dipalmitoyl‐ 2‐oleoyl‐glycerol (POP) and 1‐palmitoyl‐2, 3‐dioleoyl‐glycerol (POO) were then studied in the presence of monoacylglycerols. Formation of granular crystals was observed for palm oil and POP/POO mixture in the presence of 1‐palmitoylglycerol. HPLC of the granular crystals revealed that agglomeration of higher melting point triacylglycerols (TAGs) around 1‐palmitolyglycerol took place, which promoted the formation of granular crystals. It was suggested that the agglomeration of higher melting point TAGs around 1‐palmitoylglycerol which was preferentially adsorbed at the oil‐water interface of oil droplets in the model cream led to destabilization of oil‐in‐water emulsion and the solidification of the model cream. At the same time, it was suggested that the fatty acid moiety of emulsifiers played an important role in the agglomeration of TAGs and stabilization of o/w emulsions.     

Design and synthesis of zero–zero-birefringence polymers in a quaternary copolymerization system

We designed and synthesized quaternary copolymers of methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate (TFEMA), benzyl methacrylate (BzMA), and 3,3,5-trimethylcyclohexyl methacrylate (TMCHMA) and we investigated their birefringence, thermal properties, and other optical properties. When the copolymer composition was MMA/TFEMA/BzMA/TMCHMA = 50:38:8:4, 40:30:7:23, or 30:21:7:42 (wt%), a zero–zero-birefringence polymer that exhibited neither orientational nor photoelastic birefringence was obtained. We demonstrated that such zero–zero-birefringence polymers with a variety of compositions could be successfully prepared in the quaternary system by using the same compensation method as applied in ternary random copolymerization. We also demonstrated that the glass-transition temperature (T_g) and refractive index (n_D) of these copolymers could be controlled with high accuracy while retaining their zero–zero-birefringence property. We can therefore predict the type of birefringence, the T_g, and the n_D of a particular copolymer before polymerization. Zero–zero-birefringence polymers with the most appropriate characteristics can then be synthesized selectively by quaternary copolymerization.     

Continuous emulsion polymerization of styrene in a single Couette–Taylor vortex flow reactor

The effect of the geometrical and operational parameters on the mixing characteristics of a Couette–Taylor vortex flow reactor (CTVFR) were investigated and were correlated with the same parameters by using the tank‐in‐series model. Continuous emulsion polymerization of styrene was conducted at 50°C in a CTVFR to clarify the effects on kinetic behavior and reactor performance of operational parameters such as rotational speed of inner cylinder (Taylor number), reactor mean residence time, and emulsifier and initiator concentrations in the feed streams. It was found that steady‐state monomer conversion and particle number could be freely varied only by varying the Taylor number. In order to explain the observed kinetic behavior of this polymerization system, a mathematical model was developed by combining the empirical correlation of the mixing characteristics of a CTVFR and a previously proposed kinetic model for the continuous emulsion polymerization of styrene in continuous stirred tank reactors connected in series (CSTRs). On the basis of these experimental results, it was concluded that a CTVFR is suitable for the first reactor (prereactor) of a continuous emulsion polymerization reactor system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1931–1942, 2001     

Counter‐ion‐specific helix formation of poly(γ‐methyl L‐glutamate) derivatives containing sulfonate group in aqueous alcohols

Charged polypeptides containing sulfonate groups were prepared by transesterification of poly(γ‐methyl L ‐glutamate) with isethionic acid. The coil–helix transition of the sulfonated polypeptides was investigated in aqueous alcohols. Marked counter‐ion specificity was observed for helix formation: Li⁺ < Na⁺ < Cs⁺ ≦ Rb⁺ ≦ K⁺; this was different to that for poly(L ‐glutamate) (PLG): Cs⁺ ? K⁺ < Li⁺ < Na⁺. Specific helix stabilization by counter‐ion mixing, which has been found for the PLG system, was not observed for the sulfonated polypeptides. The counter‐ion‐ and solvent‐specific helix formation is discussed and compared with that in PLG. © 2001 Society of Chemical Industry     

Mechanisms of orientational and photoelastic birefringence generation of methacrylates for the design of zero–zero‐birefringence polymers

The intrinsic birefringence Δn⁰ and photoelastic coefficient C of poly(methyl methacrylate), poly(2,2,2‐trifluroethyl methacrylate), poly(phenyl methacrylate), and poly(2,2,3,3,3‐pentafluorophenyl methacrylate) were determined. We categorized these methacrylate polymers into four birefringence‐types, even though their molecular structures differed only by the substituents on the side chains. Based on the results of Δn⁰ and C, novel polymers that exhibit neither orientational nor photoelastic birefringence, i.e., zero–zero‐birefringence polymers, were designed and synthesized by quaternary copolymerization system. Furthermore, we confirmed that the mechanisms of orientational birefringence and photoelastic birefringence generation were different in these methacrylate polymers. The conformation of the repeat unit of the polymers was nearly constant during the generation of orientational birefringence. In contrast, the conformation of the repeat unit of the polymers changed during the generation of photoelastic birefringence in the glassy state. These findings demonstrated the reasonability of evaluating orientational and photoelastic birefringence separately, as well as the adequacy of the classification of polymers into four birefringence‐types. Given these results and the fact that zero–zero‐birefringence polymers could be prepared successfully by four‐birefringence type monomers, we demonstrated the reasonability of the method for designing the zero–zero‐birefringence polymers. POLYM. ENG. SCI., 55:1330–1338, 2015. © 2015 Society of Plastics Engineers