Preparation and characterization of nanoporous films derived from alicyclic copolyimides having pendent poly(propyleneglycol) groups

Nanoporous films were prepared with alicyclic copolyimides (coPIs) having polypropylene glycol (PPG) side chains by way of spontaneous phase separation in the film forming process and the subsequent thermal degradation of PPG moieties. PIs having various content (6.5, 11.9, 26.3, 52.7 wt%) and different length (M_w = 1.2 × 10³ and 2.4 × 10³) of PPG side chains were examined in order to clarify the relationship between chemical structure and pore characteristics. Nanopores were formed by heating the coPI films at 200 °C for 9 h under slightly reduced pressure. The size and the number of the pores observed by SEM varied depending on the content and molecular weight of PPG moieties. In many cases, the pore size was larger than those of the reported values for related aromatic copolyimide films. The dielectric constant of the nanoporous films ranged from 2.52 to 3.38.     

A robust implicit state observer for multiple-input multiple-output uncertain systems

A new mathematical method of estimating the state for uncertain continuous-time multiple-input multiple-output minimum-phase (with respect to the relation between the disturbance and the output) dynamical systems with arbitrarily relative degrees is presented. For the systems with relative degree one, the state observer which is perfectly robust to disturbances is constructed by using only the input and output information. The estimating error of the state decays to zero exponentially. For the systems with higher relative degrees, the state observer is formulated for the first time, where the input and output information, and the a priori information of the upper and lower bounds of the disturbances are employed. In this case, the estimating error of the state can be controlled to be as small as is needed by the design parameters. The attraction of the proposed observers lies in their robustness to disturbances and insensitivity to the high-frequency noises accompanying the inputs. A design example and its simulation results are presented to illustrate the proposed algorithm.     

Effect of Vacuum Heat Treatment on Electron-Beam-Irradiation-Cured Polycarbosilane Fibers

Electron-beam-cured polycarbosilane fibers were heat-treated at 673–1773 K in a tube evacuated to 1.3 × 10⁻¹ Pa and then exposed at 1873 K in argon. The effect of vacuum heat treatment on improving the high-temperature stability of low-oxygen SiC fibers was investigated by examining gas evolution, grain growth, surface composition, tensile strength, and morphology. The fibers heat-treated at <1173 K lost strength, because of the vigorous generation of residual hydrogen. A minute amount of oxygen in the atmosphere caused the active oxidation of SiC during heat treatment at >1673 K, resulting in severe strength degradation for the as-heat-treated fibers. Vacuum heat treatment at 1573 K provided the best characteristics in low-oxygen SiC fibers.     

Thickness estimation of interface films formed on Li1−xCoO2 electrodes by hard X-ray photoelectron spectroscopy

Solid electrolyte interface (SEI) films formed on Li_1−xCoO₂ electrodes were observed with hard X-ray photoelectron spectroscopy (HX-PES). This paper particularly focuses on film thickness estimation using HX-PES with theoretical calculation. The validity of the calculation was proven by experiments using model SEI films. The native film formed on a LiCoO₂ composite electrode was estimated to be LiF with its thickness of 5 nm. Formation of Co (II) species on top of LiCoO₂ was also indicated. Storage of the electrode at 60 °C brought about considerable film growth (30-40 nm) with carbonate compounds formation. SEI film changes during charging of the LiCoO₂ electrode were also examined. The main component in the film was deduced to be LiF or a kind of fluorite, with its thickness decreased during charging. The SEI formation mechanisms are also elucidated.     

Enzyme attached on polymeric micelles as a nanoscale reactor

Similar to what lipase does, a surface-active enzyme was developed by attaching peroxidase on combshaped polymaleic anhydride-alt-1-tetradecene (PMA-TD) in a microemulsion system composed of n-butyl acetate and buffer solution, and its catalytic characteristics of polyphenol synthesis were investigated in an aqueous solution. The modified peroxidase with PMA-TD tended to form self-assembled aggregates like micelles in the aqueous solution and could be concentrated at solvent/water interfaces without unfolding of the enzyme. The efficiency of conversion of 2,4-dichlorophenol to phenolic oligomers was approximately 2-fold improved with the modified peroxidase compared to native peroxidase. The K _m and V _max values for the modified peroxidase were 1.5-fold lower and 2-fold higher, respectively. The hydrodynamic diameter of the micelle on the modified peroxidase increased with the reaction time, indicating that phenolic products were accumulated in the hydrophobic interior of micelles. In addition, the molecular weight (MW) of phenolic polymers was much larger in the system with the modified peroxidase. These observations implied that the modified peroxidase with hydrophobic side chains formed micellar structures by solubilization of phenolic products and further polymerization reaction could occur in the hydrophobic interior of the micelles.     

Equilibrium of one-pot polymerization of polyimide

One-pot polymerization of polyimide from 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA) and 4,4′-oxydianiline (ODA) was examined. The equilibrium in the polyimide with water was examined in detail in p-chlorophenol solution during the polymerization. The equilibrium constant was expressed by log K = 1.50 + 1433 (1/T). The polymerization reaction is exothermic. The molecular weight increased with decrease of temperature. © 1996 John Wiley & Sons, Inc.     

Preparation of high-modulus poly(ethylene terephthalate) fibers by vibrating hot drawing

A novel drawing method, vibrating hot drawing, was successfully applied to poly(ethylene terephthalate) fiber, which has a normal molecular weight (IV = 0.7 dL/g) and was prepared by melt spinning. The process was divided into three steps, with differing conditions in drawing temperature, applied tension, vibrating frequency, and amplitude. The drawing temperature and vibration frequency were decided by considering the α_a dispersion of the polymer. In spite of a low draw ratio (7.7) and a low crystallinity (0.55), the birefringence and dynamic storage modulus at room temperature of the 3rd-step fiber reached 0.260 and 36 GPa, respectively. The modulus remains at a high level at elevated temperatures, for example, 29 GPa at 100°C and 17 GPa at 200°C. Further, it was found from temperature and intensity of the α_a dispersion peak that the movements of amorphous chains are strongly inhibited. © 1996 John Wiley & Sons, Inc.     

Properties of copolyimides prepared from different tetracarboxylic dianhydrides and diamines

Various copolymides were prepared from two acid dianhydrides (BPDA, 3,3′,4,4′-biphenyl tetracarboxylic dianhydride; PMDA, pyromelitic dianhydride) and two diamines (PPD, p-phenylene diamine; ODA, 4,4′-oxydianiline). The thermal and mechanical properties of these polyimides were examined in detail. By appropriately selecting the ratios of the acid dianhydride component and the diamine component, polyimide films having desirable mechanical and thermal characteristics can be obtained. Further, it was proved that there is a correlation between the properties and the compositions of the copolyimides and that the properties could be estimated from the compositions by the use of multiple regression analysis. © 1996 John Wiley & Sons, Inc.     

Nucleotide sequences of alcohol acetyltransferase genes from lager brewing yeast,Saccharomyces carlsbergensis

The nucleotide sequences of alcohol acetyltransferase genes isolated from lager brewing yeast, Saccharomyces carlsbergensis have been determined. S. carlsbergensis has one ATF1 gene and another homologous gene, the Lg-ATF1 gene. There was a high degree of homology between the amino acid sequences deduced for the ATF1 protein and the Lg-ATF1 protein (75·7%), but the N-terminal region has a relatively low degree of homology. Southern analysis and contour-clamped homogeneous electric field analysis of Saccharomyces strains suggest that the ATF1 gene is located on chromosome XV in S. cerevisiae and that the Lg-ATF1 gene might originate from the ‘non-S. cerevisiae’ genome of S. carlsbergensis, which is similar to that of S. bayanus and S. pastorianus. The nucleotide sequence data reported in this paper will appear in the DDBJ, EMBL and GenBank data banks with the Accession Numbers D63449 (ATF1) and D63450 (Lg-ATF1).