Polymerization of methyl methacrylate by tri-n-butylborane in the presence of amino acid esters

The polymerization of methyl methacrylate by tri-n-butylborane in the presence of amino acid esters was investigated. The binary systems of tri-n-butylborane and amino esters were found to be more effective for initiating the polymerization than tri-n-butylborane alone. Co-catalytic effects of amino acid esters were in the order: tyrosinate > glutamate > aspartate ? phenyl alaninate > serinate > glycinate. The rate of polymerization in a mixture of dimethylsulphoxide and toluene was proportional to the square root of the concentration of the initiator system, to the monomer concentration, and to the concentration of dimethylsulphoxide in the solvent. The overall energy of activation was estimated to be 4.6 kcal/mol for the tri-n-butylborane/methyl tyrosinate system. Copolymerization curves gave a typical free-radical character.     

Characterization and application of polypropylene films modified with stimuli‐sensitive copolymers with an Ar‐plasma postpolymerization technique

Surface‐modified polypropylene (PP) films with thermally and photochemically sensitive copolymers consisting of N‐(2‐hydroxypropyl)methacrylamide (HPMA) and 4‐(4‐methoxyphenylazo)phenyl methacrylate (MPAP), poly(HPMA‐co‐MPAP)‐g‐PP (abbreviated g‐PP) film, were prepared by graft copolymerization with an Ar‐plasma postpolymerization technique. The surfaces of the g‐PP films were characterized by means of X‐ray photoelectron spectroscopy; the percentage grafting of poly(HPMA‐co‐MPAP) with a number‐average molecular weight of 3.28 × 10⁴ was 7.12%, and the molar ratio of HPMA–MPAH in the copolymer was 0.75:0.25. The stimuli‐sensitive adsorption of albumin and polystyrene microspheres on the g‐PP film was also measured. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 143–148, 2003     

Effects of amino acid replacements around the reactive site of chicken ovomucoid domain 3 on the inhibitory activity toward chymotrypsin and trypsin

We have previously shown that replacing the P1-site residue(Ala) of chicken ovomucoid domain 3 (OMCHI3) with a Met or Lysresults in the acquisition of inhibitory activity toward chymotrypsinor trypsin, respectively. However, the inhibitory activitiesthus induced are not strong. In the present study, we introducedadditional amino acid replacements around the reactive siteto try to make the P1-site mutants more effective inhibitorsof chymotrypsin or trypsin. The amino acid replacement AspTyrat the P2' site of OMCHI3(P1Met) resulted in conversion to a35000-fold more effective inhibitor of chymotrypsin with aninhibitor constant (K_i) of 1.17x10^–11 M. The K_i valueof OMCHI3(P1Met, P2'Ala) indicated that the effect on the interactionwith chymotrypsin of removing a negative charge from the P2'site was greater than that of introducing an aromatic ring.Similarly, enhanced inhibition of trypsin was observed whenthe AspTyr replacement was introduced into the P2' site of OMCHI3(P1Lys).Two additional replacements, AspAla at the P4 site and ArgAlaat the P3' site, made the mutant a more effective inhibitorof trypsin with a K_i value of 1.44x10^–9 M. By contrast,ArgAla replacement at the P3' site of OMCHI3(P1Met, P2'Tyr)resulted in a greatly reduced inhibition of chymotrypsin, andAspAla replacement at the P4 site produced only a small changewhen compared with a natural variant of OMCHI3. These resultsclearly indicate that not only the P1-site residue but alsothe characteristics, particularly the electrostatic properties,of the amino acid residues around the reactive site of the proteaseinhibitor determine the strength of its interactions with proteases.Furthermore, amino acids with different characteristics arerequired around the reactive site for strong inhibition of chymotrypsinand trypsin.     

Prooxidant effects of inorganic chromium compounds in the autoxidation of methyl linoleate

The prooxidant property of inorganic chromium compounds was determined in methyl linoleate free from natural antioxidants and metals. Prooxidant properties of inorganic chromium compounds appeared in order of sodium chromate > chromium (VI)-oxide > chromium chloride > potassium chromate > chromium (III)-oxide > potassium dichomate. In comparison with the control, additions of chromium compounds induced different amounts of autoxidation products derived from methyl linoleate, such as small amounts of hydroperoxides and conjugated dienes and large amounts of hydroxy groups,α,β,γ,δ-unsaturated carbonyls, isolatedtrans double bonds, polymers, and free radicals. From these analytical data, the catalysis of chromium compounds in the autoxidation of methyl linoleate seemed to be based on their abilities of abstracting a hydrogen from methyl linoleate and decomposing hydroperoxides derived from the autoxidation of methyl linoleate.     

OXIDATION OF SULFUR DIOXIDE IN DIFFERENT TYPES OF THREE PHASE REACTORS

Five different types of three-phase reactors are compared with each other by using oxidation of sulfur dioxide on activated carbon. The kinetic measurements were carried out by changing concentrations of sulfur dioxide from 0.04 to 0.17% (volume) and those of oxygen from 2 to 21%. The reaction rate was 0.2 order with respect to sulfur dioxide and 0.5 order with respect to oxygen. The catalytic effectiveness factor and intraparticle diffusivity were evaluated by changing particle sizes of activated carbon from 0.03 to 1.6 mm. Resistances of gas-liquid, liquid-solid mass transfer and intraparticle diffusion were estimated for individual reactors. The optimum reactor was dependent on operating conditions such as gas flow rates, rotating speeds and particle sizes.     

Synthesis and Magneto-mechanical Properties of Ce-TZP/La M-Type Hexaferrite Composite

An in situ composite composed of ceria-stabilized tetragonal zirconia polycrystals (Ce-TZP) and La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ was synthesized from a powder mixture of Ce-TZP, La(Fe_0.9Al_0.1)O₃, Fe₂O₃, Al₂O₃, and CoO. The dense Ce-TZP dispersed with platelike La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ crystals as a second phase were formed after sintering from 1250° to 1350°C. The saturation magnetization of the in situ composite Ce-TZP/La{Co_0.5Fe_0.5(Fe_0.9Al_0.1)₁₁}O₁₉ was proportional to the mass fraction of the hexaferrite second phase in Ce-TZP. The coercivity of the composite with a 20 mass% of second phase decreased from 9.14 to 2.52 kOe (from 728 to 201 kA/m) after the pulverization of the composite. The susceptibility (χ) increased by 15%–25% under uniaxial stress on the composite. The change of the susceptibility (Δχ/χ) value increased with decreasing the mass fraction of the second phase in the composite. The Δχ was found to increase linearly with applied stress and abruptly change on cracking, which is expected for the application in fracture sensing of the composite.     

Autoxidation of ethyl eicosapentaenoate and docosahexaenoate

The extent of oxidation of ethyl esters of eicosapentaenoic (EPA) and docosahexaenoic acids (DHA) was compared quantitatively with that of ethyl linoleate (Lo) and ethyl linolenate (Ln) by oxygen uptake and formation of conjugated diene, hydroperoxide and secondary oxidation products. EPA and DHA esters were oxidized rapidly even at 5 C in the dark after an induction period of 3–4 days, while the induction periods of Ln and Lo esters were 20 days and more than 60 days, respectively. Oxygen uptake of EPA and DHA esters after the induction period was 5.2 and 8.5 times faster than that of ethyl Ln, respectively. Hydroperoxides of EPA and DHA esters are much less stable than those of ethyl Lo. The peroxide value is not necessarily a good indication of oxidation in these polyenoic acids because a considerable amount of secondary products is formed at the early stage of oxidation. Polymers were found to be major secondary products in these polyenoic esters.     

Adaptive interpolation scheme for NURBS curves with the integration of machining dynamics

This paper develops a comprehensive interpolation scheme for non-uniform rational B-spline (NURBS) curves, which does not only simultaneously meet the requirements of both constant feedrate and chord accuracy, but also real-time integrates machining dynamics in the interpolation stage. Although the existing work in this regard has realized the importance to simultaneously consider chord error and machining dynamics, none has really incorporated these in one complete interpolation scheme. In this paper, machining dynamics is considered for three aspects: sharp corners or feedrate sensitive corners on the curves, components with high frequencies or frequencies matching machine natural ones and high jerks. A look-ahead module was developed for detecting and adaptively adjusting the feedrate at the sharp corners. By Fast Fourier Transform (FFT) analysis with a moving window in the interpolation stage identified were some special frequency components such as those containing high frequencies or with frequencies matching machine natural ones. Then, the notch filtering or time spacing method was used to eliminate these components. To more completely reduce feedrate and acceleration fluctuations, the jerk-limited algorithm was also developed. Finally, the interpolated feedrate was further smoothened with B-spline fitting method and the NURBS curves were re-interpolated with the smoothened feedrate. During the interpolation, the chord error was repeatedly checked and confined in the prescribed tolerance. Two NURBS curves were used as examples to test the feasibility of the developed interpolation scheme.     

A manufacturing XML schema definition and its application to a data management system on the shop floor

Digitization for sharing knowledge on the shop floor in the machinery industry has been given much attention recently. To help engineers use digitization practically and efficiently, this paper proposes a method based on manufacturing case data that has a direct relation to manufacturing operations. The data are represented in XML schema, as it can be easily applied to Web-based systems on the shop floor. The definitions were made for eight manufacturing methods including machining and welding. The derived definitions consist of four divisions of metadata, work-piece, process and evaluation. Three divisions except for the “process” division are common to the manufacturing methods. The average number of elements for a manufacturing method is about 200. The represented schema is also used to convey knowledge such as operation standards and manufacturing troubleshooting on the shop floor. Using the definitions, a data management system is developed. It is a Web-based Q&A system, in which the engineers specify the manufacturing case data mainly by selecting from the candidates. Then, the system fills in the blank portions and/or shows messages to help complete the case data. The proposed method is evaluated through practical scenarios of arc welding and machining.     

Quantitative structural analysis of twin boundary in alpha-Zn7Sb2O12 using HAADF STEM method

The structure and composition of the 1/4{110} twin boundary in alpha-Zn7Sb2O12 have been determined by using quantitative high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) analysis. The noise in the experimental HAADF STEM images is reduced by using the maximum entropy method and average processing, and the parameters used in dynamical simulations are experimentally determined. From the analysis, it has been found that octahedral sites in the twin boundary slightly shift parallel to the [110] direction, and a reduction of the Sb concentration at the octahedral sites on the plane adjacent to the twin boundary was detected. The reduction was measured from three regions in the same twin boundary, and the Sb concentrations were 4 +/- 3, 8 +/- 3 and 19 +/-2 at% from 33 at%.