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 effect of sputter etching on the surface characteristics of dyed aramid fabrics

Three kinds of aramid fabrics, Technora (modified p-aramid), Conex (m-aramid) and Kevlar (p-aramid), were subjected to sputter etching and argon low-temperature plasma treatments after dyeing in black with disperse dyes. The depth of shade increased considerably on Technora and Kevlar with the sputter etching treatment, but not on Conex fabrics. Argon low-temperature plasma treatment had virtually no effect on the depth of shade on the aramid fabrics.     

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.     

Graft polymerization of some vinyl monomers onto acrylic rubber. II. Mechanical properties of graft polymers

Some mechanical properties of styrene and acrylonitrile copolymers grafted onto acrylic rubber are investigated. The impact strength of graft polymers depended upon the nature and the concentration of the catalyst, the composition and the intrinsic viscosity of the rubber, and the acrylonitrile content in the rigid matrix. The most desirable result was obtained when benzoyl peroxide as the catalyst, n-butyl acrylate–acrylonitrile copolymer of 7–10% acrylonitrile content, and about 0–5% acrylonitrile in the rigid matrix were used. Dynamic mechanical tests show the increase in efficiency of rubber modification by the grafted chains. The better weathering resistance of these graft polymers, as compared with commercial ABS plastics, was confirmed.     

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.     

Quantitative determination of corrosion products and adsorbed water on copper in humid air containing SO2 by IR-RAS measurements

The time dependency of the amounts of corrosion products and co-existing adsorbed water on copper in humid air containing SO₂ was estimated from a series of in situ time-resolved IR-RAS spectra on the basis of the relations between the band intensities and the mass changes of the corrosion products, which were determined by simultaneous measurement of IR-RAS and QCM. The amounts of both corrosion products increased slowly at the initial stage and later increased rapidly. Although the relative humidity was kept constant, the amount of adsorbed water increased nearly the same behavior as that of corrosion products in the stage of relatively small amounts of corrosion products and later increased rapidly when the amounts of corrosion products increased. In humid air without SO₂, sulfite gradually decomposed and some of it changed into sulfate.     

Penetration treatment of plasma-sprayed ZrO2 coating by liquid Mn alloys

The penetration phenomena of liquid manganese (Mn) alloy into porous ZrO₂ (8 vvt % Y₂O₃) coating plasma sprayed on SS400 steel substrate was studied by heating in a vacuum atmosphere. The improvement in mechanical properties of the coating by heat treatment with liquid Mn alloys was examined. Liquid Mn alloys, such as Mn-Cu, Mn-Sn, and Mn-In, rapidly penetrated the coating and formed a chemical bond between the coating and the substrate. The densification of the ZrO₂ coating occurred when ZrO₂ particles were sintered with liquid Mn alloys that penetrated the porous coating. The dense coating was free of porosity, and its hardness increased after heat treatment with Mn alloys, compared with assprayed ZrO₂ coating. Moreover, the fracture toughness of the coating reached the same levels as those of sintered yttria-stabilized PSZ.     

激光退火对Inconel 718微观组织和硬度的影响

研究激光退火对Inconel718时效合金的显微组织和硬度的影响.一台2.5kW的CO2激光机被用来照射试样的表面.在激光能作用下,试样表面层被加热后空冷.通过控制激光工艺参数,在表面不发生熔化的前提下,能够使一定厚度表面层内的硬度降低到标准退火合金的水平,而不影响试样内部母材的硬度.显微组织观察显示表面层的基体强化相(γ″和γ‘)在激光照射过程中被固溶,而其它二次相没有变化.γ″和γ‘的固溶被确定是表面层硬度下降的原因.在其它试验条件不变时,确立了退火层生成时由激光散焦距离和扫描速度描述的工艺参数范围.     

Scattering mechanism and reduction of insertion losses in a laminated polarization splitter

We experimentally found the unexpected phenomena of scattering in laminated polarization splitters (LPS's) composed of a-Si:H-SiO(2) multilayer and studied its mechanism. The scattering phenomena strongly depend on the incident angle and polarization of the incident light. To reduce the scattering loss in LPS's, a multilayer with flat layer boundaries is fabricated with rf bias sputtering. As a result, the insertion loss of the LPS is reduced to ~ 1 × 10(-3) dB/ μm, which is acceptable for practical uses.     

Theoretical analysis of the spatial phase-matching loci for second-harmonic generation and multiwave-mixing interactions

We report a theoretical analysis on spatial noncolinear phase matching of multiwave mixing and its application to a second-harmonic-generation (SHG) experiment. From the numeric calculations, the noncolinear phase-matching properties in general situations were determined. The theory gives the applicability for all noncolinear phase matching. Fine coincidences between theoretical calculations and observed spatial loci on noncollinear phase-matching SHG were confirmed. Relations that allow the calculation of the noncollinear phase-matching angle for any case of SHG are established. As an example, the noncolinear phase-matched SHG pattern on a screen is calculated numerically in the case of SHG of 1064 nm from a Nd:YAG laser under the phase-matched condition for two organic nonlinear crystals: 1-(2-thienyl)-3-(4-methyphenyl) propene-1 (TC-28), which is biaxial, and (2-furyl) methacrylic anhydride (FMA), which is uniaxial. Experimental results compared quite favorably with the theoretical analysis. Noncolinear phase matching may be of great practical interest in optical multiwave-mixing processes, such as optical parametric oscillation and optical parametric amplification. This technique also can be used for the measurement of crystal optical constants.