Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. III. Adhesive Joint Strengths of Grafted Power Feed Copolymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. Power feed copolymer had a very broad glass transition temperature compared with random copolymer, even if grafting and/or crosslinking were introduced to the system. This tendency was almost the same as the non-grafted power feed copolymer where only low molecular weight surfactant was used.

Adhesive joint strengths of power feed copolymers were evaluated compared with random copolymers. In the case of usual linear power feed copolymer, the adhesive joint strengths were not higher than those of random copolymer, which was considered to be due to the lower film strengths of the power feed copolymer. Power feed copolymer having grafting showed slightly higher adhesive joint strengths over a wide range of temperatures than random copolymer. When crosslinking was introduced to the system, power feed copolymer showed much higher adhesive joint strengths over a wide temperature range.     

New type of tin support for hydroprocessing catalyst

TiN supported molybdenum sulfide catalysts showed much higher activity for cleavage of C-C bonds than oxide supported molybdenum sulfide catalysts, indicating the possibility of a new generation of supports for hydroprocessing catalysts.     

Critical temperature for production of MAG by esterification of different FA with glycerol using <Emphasis Type="Italic">Penicillium camembertii</Emphasis> lipase

Production of MAG by a lipase-catalyzed reaction is known to be effective at low temperature. This phenomenon can be explained by assuming that synthesized MAG are excluded from the reaction system because MAG, which have low m.p., are solidified at low temperatures. Consequently, MAG are efficiently accumulated and do not serve as the precursor of DAG. If this hypothesis is correct, the critical temperature for MAG production, defined as the highest temperature at which DAG synthesis is repressed, should depend on the m.p. of the MAG. Esterification of FFA with glycerol using Candida rugosa, Rhizopus oryzae, and Penicillium camembertii lipases produced MAG efficiently at low temperatures. However, Candida lipase showed very low esterification activity at high temperatures (>20°C), and Rhizopus lipase produced not only MAG but also DAG even at low temperatures. Meanwhile, P. camembertii lipase catalyzed synthesis of MAG only from FFA and glycerol at low temperatures, although the enzyme catalyzed synthesis of DAG from MAG in addition to synthesis of MAG at high temperatures. We thus studied the effect of temperature on esterification of C₁₀−C₁₈ FFA with glycerol using Penicillium lipase as a catalyst and determined the critical temperatures for production of MAG. The critical temperature for production of each MAG showed a linear correlation with m.p. of the MAG, which supported the hypothesis. In addition, because the m.p. of MAG are estimated from that of the constituent FA, the optimal temperature for production of MAG can be predicted from the m.p. of the FFA used as a substrate.     

The structure of acetylene flames for diamond synthesis

An acetylene flame was photographed with an SIT camera through optical filters, and the signals were Abel transformed to obtain two-dimensional emission-intensity profiles. It was found that the intensive emissions of CH* and C*₂ are localized at the feather boundary, while the OH* emission is localized at the intermediate zone. The structure of the acetylene flame was made clear: it consists of a carbon-radical-rich feather and an oxygen-radical-rich intermediate zone. The carbon-radical concentrations are approximately in equilibrium near the burner exit while they decrease almost linearly via interdiffusion and reactions with the oxygen-radicals in the intermediate zone.Numerical simulations including detailed gaseous and surface reactions reproduced well previous preliminary calculations showing that CH₄ is rapidly produced in the boundary layer near the substrate followed by an increase in CH₃. This result satisfactorily explains the measured dependence of growth rate on the substrate temperature and ratio.     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.     

Bending of ionic polymer gel caused by swelling under sinusoidally varying electric fields

Deformation of poly(vinyl alcohol)–poly(sodium acrylate) composite hydrogel (PVA–PAA gel) under sinusoidally varying electric fields was studied in electrolyte solutions. The PVA–PAA gel was prepared by repeatedly freezing and thawing a mixed solution of PVA and polyacrylic acid. A cyclic bending–straightening motion of the PVA–PAA gel rods of about 1 mm in diameter have been observed in Na₂CO₃ aqueous solutions under the fields. The PVA–PAA gel had a response time of less than several hundreds milliseconds. The bending has also been observed in organic solvents containing an electrolyte when the organic solvent is electrolyzed. It was found that the motion of the gel under electric fields of less than 1 Hz occurred mainly through swelling due to the change of the osmotic pressure based upon the difference of the ion concentration. However, it has not been determined whether the motion at higher frequencies is caused by the osmotic effect. © 1993 John Wiley & Sons, Inc.     

Continuous-velocity lattice gas cellular automata for miscible binary fluid and its application to simulation of interface instability

Continuous-velocity lattice gas cellular automata (CVLGA) is extended to miscible binary fluid systems. A new parameter is introduced in order to control the diffusivity of the fluids. The correlation between the diffusivity and the new parameter proves that there exists the maximum value of the diffusivity. Quantitative verifications of the model are carried out with numerical simulations of the diffusion phenomena across a falling fluid film. The model is then applied to the simulations of Rayleigh-Taylor instability during the gravitational mixing phenomena. The qualitative tendency of the growth of the interface instability is the same as that obtained in conventional numerical methods.     

Crosslinked acrylic pressure sensitive adhesives. 3. Effect of adherend on film formation

The reaction of isocyanate in pressure sensitive adhesive (PSA) films adhered on to various adherends having different surface tensions was monitored by depth profiling using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy.In the latter stages of crosslinking reaction, unreacted isocyanate and its derivatives exist more in the bulk of the PSA than in the interfaces between PSA and adherends which are Teflon sheet and PE film having relatively lower surface tensions. In the case of using stainless steel having relatively higher surface tension as adherend, opposite segregation was observed compared to Teflon and PE.From X-ray photoelectron spectroscopy (XPS), it was revealed that N atoms exist more in surface than in bulk when stainless steel is used as adherend. We conclude that polyisocyanates migrate in the PSA film in order to minimize the magnitude of interfacial free energy between the PSA and the adherend, which leads to the change of surface tension of PSA film.     

退火对Inconel718合金氢脆特性的影响

通过实施不同的退火热处理工艺，调整合金中强化相的析出状态，制备具有不同退火状态的几组拉伸试样。对每组试样在未充氢和充氢后按相同的条件进行拉伸试验对该组试样的脆化作用。通过比较不同组试样的脆化表现通过比较未充氢试样和充氢后试样的强度和塑性，评价氢考察退火状态对Inconel 718氢脆倾向的影响。试验结果表明，随着退火程度的加强，强化相体积分数减少，氢引起的塑性损失下降，即抗氢脆性能改善。该结果说明，强化相γ″和γ′对Inconel 718合金的氢脆有促进作用。因此，根据不同工业应用要求，在符合强度要求的前提下，可以通过热处理改善零件的抗氢脆性能。     

Microstructures and magnetic properties of heatproof domain-refined grain-oriented silicon steel sheets

Microstructures and magnetic properties of heatproof domain- refined grain- oriented silicon steel sheets were studied. Local strains were introduced using two types of gear roll as well as cog tips, one 35 Μm and the other 85 Μm. After the local strains were introduced onto sheets, the distribution of hardness near the groove was measured. The nuclei of micrograins were investigated at various applied rolling loads. After stress-relief annealing, various shapes of microgranes and grooves were observed. The effect of these various shapes of grooves and micrograins on magnetic properties was clarified. The role of micrograins and grooves on domain refining is discussed.