Orientation in uniaxially drawn polystyrene plasticized by CO2 sorption

Uniaxial drawing experiments of the polystyrene films plasticized by a sorption of compressed CO₂ gas at pressures up to about 18 MPa were carried out with strain rates ε of 0.0290 and 0.0079 s^?1. The drawing was performed successfully with draw ratio λ up to 4 at the temperatures of 308.15, 318.15, 328.15, and 338.15 K. The Hermans orientation function f of the drawn samples was determined from the dichroic ratio measured by an infrared spectrophotmeter. While f value increases with increasing ε or λ, it decreases with increasing CO₂ pressure or temperature. © 1995 John Wiley & Sons, Inc.     

Interaction of cation-exchange membrane with polycation I. Poly(N-methyl-4-vinylpyridinium chloride)

We elucidated the effect of the molecular weight of poly(N-methyl-4-vinylpyridinium chloride) (PMVP) on its adsorbed or ion-exchanged amount on the cation-exchange membrane and the preferntial permselectivity of the membrane for sodium ion to calcium ion. The amount of the adsorbed or ion-exchanged PMVP increases with time and then attains to a definite value at a definite concentration. Also, the ultimate value increases with increasing the concentration of PMVP. When the molecular weight of PMVP is 3090, the ratio of the pyridinium groups of PMVP ion-exchanged with the sulfonic acid groups on the membrane surface to the total pyridinium groups of the cohered PMVP is in the range of 70–80%. The relative transport number of calcium ions to sodium ions(P_Na^Ca) decreases with increasing the amount of adsorbed or ion-exchanged PMVP and the numbe rof non-ion-exchanged pyridinium groups of PMVP and the number of non-ion-exchanged pyridinium groups of PMVP on the membrane surface. The smaller the molecular weight of PMVP, the more the adsorbed or ion-exchanged amount and the more preferable the permselectivity for sodium ion.     

Ni-Mo alloying of nickel surface by alternating pulsed electrolysis using molybdenum(VI) baths

Electrochemical Ni-Mo alloying of the surface of a nickel substrate was investigated using alternating pulsed electrolysis in an aqueous solution containing only molybdate ions (MoO₄²⁻) as a metal ion component. In this electrochemical process, the nickel substrate was slightly dissolved during the anodic pulses, providing nickel ions into the solution in the vicinity of the substrate, while Ni and Mo were both electrodeposited on the substrate surface during the subsequent cathodic pulses. Through the optimization of anodic and cathodic conditions independently based on a set of direct-current electrolysis data, amorphous Ni-Mo alloy layers were found to be formed at the surface of the nickel substrate by the alternating pulsed electrolysis using the MoO₄²⁻ solution of pH 3.0-5.0. The conditions for Ni-Mo alloy formation were discussed in terms of the dissolving regime of ionic species in the electrolytes determined by an equilibrium calculation.     

Studies on syntheses and permeabilities of special polymer membranes

Summary The permeabilities of various cellulose ester membranes and cellulose membranes were investigated using pure water and aqueous solution of glycerol as feed. In all membranes, the permeation rate for aqueous solution of glycerol was greater than for pure water. The permeation rates of cellulose ester membranes increased with an increase in number of carbon atoms of the substituent group in cellulose ester.     

Reaction of sodium perborate with a chlorinated cyclic hindered amine (TMP-Cl): I. Quantitative evaluation of active oxygen species in fabric bleaching

The reaction of N-chloro-4-hydroxy-2,2,6,6-tetramethylpiperidine (TMP-Cl) with sodium perborate (PB) was investigated with special reference to the generation of singlet oxygen and the possible application to a new oxidative bleaching process. Generation of the singlet oxygen (¹O₂), the hydroxyl radical (HO·) and superoxide anion radical (O₂·⁻) in the PB/TMP-Cl mixed solution was confirmed by the trapping reagent method. From the results of another experiment, in which the bleaching abilities of each active oxygen species were confirmed, the main active oxygen species contributing to the bleaching of purpurogallin, the skeleton of black tea pigment, in the PB/TMP-Cl system was concluded to be¹O₂.     

Relation between crystal structure and lattice oxygen content of sintered reaction-bonded silicon nitride

When reaction-bonded silicon nitride containing MgO/Y₂O₃ additives is sintered at three different temperatures to form sintered reaction-bonded silicon nitride (SRBSN), the thermal conductivity increases with sintering temperature. The β-Si₃N₄ (silicon nitride) crystals of SRBSN ceramics were synthesized and characterized to investigate the relation between the crystal structure and the lattice oxygen content. The hot-gas extraction measurement result and the crystal structure obtained using Rietveld analysis suggested that the unit cell size of the β-Si₃N₄ crystal increases with the decrease in the lattice oxygen content. This result is reasonable considering that the lattice oxygen with the smaller covalent radius substitutes nitrogen with the larger one in the β-Si₃N₄ crystals. The lattice oxygen content decreased with increasing sintering temperature which also correlated with increase in thermal conductivity. Moreover, it is noteworthy from the viewpoint that it may be possible to apply the lattice constant analysis for the nondestructive and simple measurement of the lattice oxygen content that deteriorates the thermal conductivity of the β-Si₃N₄ ceramics.     

Negative ion etching of Al−Si−Cu by employing a magnetic filter in halogen plasmas

Al etching was studied employing negative ions generated in downstream Cl₂ plasma. The Al etch rate by the alternate irradiation of positive and negative ions was two times higher than that by usual positive ions. In order to etch the Al film practically on an insulator covered electrode coupled with RF power, reduction of the negative self bias voltage (Vdc) was examined using a magnetic filter which traps electrons. The reason for the high etching reactivity is that the dominant negative ions F in SF₆ and Cl⁻ in Cl₂ plasmas are atomically very similar to the radicals. Addition of SF₆ and H₂ to a Cl₂/BCl₃ mixture reduced Vdc significantly. However, fluorine and hydrogen atoms inhibited Al etching in spite of sufficient ion energy.     

Evolution of patinas on copper exposed in a suburban area

Copper plates were exposed under sheltered outdoor conditions for up to one year, starting in September 2001 in Musashino City, Tokyo, a suburban area. Following various periods of exposure, the patinas on the plates were characterized to investigate their evolution by using X-ray fluorescence analysis, X-ray diffraction, field emission scanning electron microscopy, and glow discharge optical emission spectroscopy. The difference in the roles of sulfur and chlorine in the early stages of copper patination were identified by analyzing the depth profiles of these two elements. Sulfur was found on top of the patina as cupric sulfates such as posnjakite (Cu₄SO₄(OH)₆ · H₂O) or brochantite (Cu₄SO₄(OH)₆). Brochantite appeared only after 12 months of exposure. In contrast, chlorine was found on the surface after only one month of exposure. It gradually penetrated the patina as the exposure period lengthened, forming copper chloride complexes. Chloride ions accumulated at the patina/copper interface, forming nantokite (CuCl), which promoted corrosion.     

Differences between corrosion products formed on copper exposed in Tokyo in summer and winter

We analyzed the copper corrosion products that formed during a month in summer and a month in winter at three sites in Tokyo using several analytical techniques. The X-ray diffraction patterns revealed that cuprite Cu₂O and posnjakite Cu₄SO₄(OH)₆·H₂O formed on copper exposed in summer. By contrast, only cuprite was found in winter exposed copper. The X-ray fluorescence results indicated that the amounts of sulfur and chlorine on the copper plates exposed in summer were much greater than those in winter. This could be explained by the change in particulate sulfate and sea salt concentrations. Depth profiling analysis by Auger electron spectroscopy revealed that the oxide layer formed in summer was thicker than that in winter. This difference in oxide layer thickness could have been due to the differences in temperature, relative humidity, and the amount of sulfur and chlorine on the copper plate.     

Microstructure Control of Thermally Sprayed Co-Based Self-Fluxing Alloy Coatings by Diffusion Treatment

This article describes microstructure control aimed for wear-resistance improvement of Co-based (Co-Cr-W-B-Si) self-fluxing alloy coating by diffusion treatment. The diffusion treatments of thermally sprayed Co-based self-fluxing alloy coating on steel substrate were carried out at 1370-1450 K for 600-6000 s under an Ar gas atmosphere. Microstructural variations of the coating and the interface between the substrate and the coating were investigated in detail. A proper diffusion treatment precipitates two kinds of fine compounds in Co-based matrix. X-ray diffractometer (XRD) and electron probe microanalyzer (EPMA) analysis revealed these precipitates to be a chromium boride dissolving cobalt and a tungsten boride containing cobalt and chromium. The size of each precipitate became larger with increasing treatment temperature and time. A coating with the proper size borides showed a superior wear-resistance. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.