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61.
Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D3). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D3 initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D3 by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D3 to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×104 to 19.4×104 and were close to the predicted values calculated from the of the TMPS prepolymer and the amount of D3 added. In the case of method 2, weight-average molecular weights ranged from 19.5×104 to 24.2×104. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers. 相似文献
62.
Yoshinobu Fujishiro Motoyuki Miyata Masanobu Awano Kunihiro Maeda 《Journal of the American Ceramic Society》2003,86(12):2063-2066
The thermal conductivity of polycrystalline Al-doped ZnO was controlled through the fabrication of nanostructured polycrystalline materials, by hot-pressing nanosized Zn1– x Al x O ( x = 0.01, 0.02) particles, which were synthesized by a coprecipitation and spray-drying method. This process resulted in an improved thermoelectric power factor because of the nanosized Zn0.99 Al0.01 O particles of the polycrystalline products. The thermal conductivity also was decreased as a result of the formation of nanocrystalline Zn0.99 Al0.01 O. 相似文献
63.
Tetsuya Tanigami Kanna Kai Koji Tanaka Shuji Matsuzawa 《Journal of Inorganic and Organometallic Polymers》2003,13(4):237-253
Poly[bis(-phenoxyethoxy)phosphazene] [PBPEP] had been shown in our previous paper to be a very useful polymer for investigating the crystallization mechanism of polymers, as the crystallization rate of PBPEP is extraordinarily small when isothermally crystallized from the melt. The crystallization of the low molecular weight oligomers of PBPEP was first studied in comparison to the high molecular weight polymers. The oligomer-rich fraction was obtained by fractionation of the as-polymerized sample, which had a broad molecular weight distribution. The fractions thus obtained were characterized by solution viscometry and size exclusion chromatography. The melting temperature and the growth rate of the spherulite from the melt were investigated by differential scanning calorimetry and optical microscopy. The growth rate was one or two orders of magnitude smaller in the oligomer-rich fraction than in the other high molecular weight fractions. A collapsed spherulite appeared in the oligomer-rich fraction at high crystallization temperatures. It is speculated that in the oligomer-rich fraction there is an excess free energy due to defects in the crystal phase. This defect is considerably larger in the oligomer-rich fraction than in the other fractions because a large quantity of short length chains is present. 相似文献
64.
Blending a crosslinked high‐density polyethylene (xHDPE) enhances melt strength and strain hardening behavior in elongational viscosity of high‐density polyethylene (HDPE) to a great degree. Gel fraction of xHDPE has a stronger effect on the strain hardening than sol fraction, although sol fraction also enhances the strain hardening to some degree. Further, the xHDPE crosslinked by peroxide in a compression mold exhibits more pronounced effect than xHDPE by radiation, which is attributed to the difference in the amount of the gel fraction. The xHDPE, which enhances the strain hardening, has sparse crosslink points in the network. Moreover, it was found from linear viscoelastic measurements, such as oscillatory modulus and relaxation modulus, that the xHDPE is characterized as a critical gel, which was also supported by the result of tensile testing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 73–78, 2002 相似文献
65.
The effect of the N-linked glycans on structural features and physicochemical functions of soybean β-conglycinin homotrimers 总被引:2,自引:0,他引:2
Nobuyuki Maruyama Mohamad Ramlan Mohamed Salleh Koji Takahashi Kazuhiro Yagasaki Hideyuki Goto Naho Hontani Shuko Nakagawa Shigeru Utsumi 《Journal of the American Oil Chemists' Society》2002,79(2):139-144
β-Conglycinin is a trimeric protein consisting of three subunits, α,α′,and β, which are N-glycosylated. The α and α′ subunits
contain extension regions in addition to core regions common to all subunits. We purified homogeneous trimers consisting of
only α, α′, or β from mutant soybean cultivars containing β-conglycinin lacking one or two subunits: α homotrimers from an
α′-lacking mutant, α′ homotrimers from an α-lacking mutant, and β homotrimers from an α-and α′-lacking mutant. Structural
features and physicochemical functions of the three homotrimers were examined and compared with those of recombinant homotrimers
having no N-linked glycans. The native homotrimers have secondary structures very similar to those of the recombinant ones.
In analogy with the recombinant homotrimers, the native ones exhibit different thermal stabilities from one another (β>α′>α),
and the native α and α′ homotrimers exhibit better solubility, emulsifying ability, and heat-induced association than the
native β homotrimer. Further, the N-linked glycans contribute to solubilities of the three subunits at low ionic strength
(μ=0.08) and to the emulsifying ability of the native β homotrimer. N-Linked glycans also prevent heat-induced associations
of the native α and α′ homotrimers but do not contribute to the secondary structure and the thermal stability of β-conglycinin. 相似文献
66.
Generally, sorption isotherms for gases like CO2 in glassy polymers are concave to the pressure axis, whereas in the rubbery state these isotherms are linear for gases or sometimes convex to the pressure axis for more condensable vapors. Examples of CO2 isotherms are reported here that show at low pressure the curvature characteristic of glasses and then become linear at higher pressures. This is observed when the glass transition temperature Tg is not much greater than the observation temperature T, and plasticization of the polymer by sorbed CO2 causes Tg to become equal to T within the range of pressures employed in the isotherm measurement. For the sorption of vapors in glassy polymers, this can lead to sigmoidal isotherms, as discussed using an illustration from the literature. 相似文献
67.
Natural graphite particles with high crystallinity sieved to obtain a particle size range of under 63 μm were ground with a ball mill, under various well-controlled grinding atmospheres such as N2, O2, He, H2, and vacuum. The ratio, Xdif50/Xst50, i.e. between the 50 wt.% Stokes diameter and the 50 wt.% laser diffraction diameter, of the ground particles, was used as an index of the flakiness of the particles. The specific resistance of films composed of the ground graphite particles was systematically measured. The rate of reduction in the size of the particles by grinding was slow under an O2-rich atmosphere such as 100% O2 and dry air. On the other hand, it was relatively fast in vacuum, or under an N2 or He atmosphere, and a gas mixture of 99% N2 and 1% O2. The rate of size reduction by grinding under a H2 atmosphere was intermediate. In our experimental conditions, the flakiness of the ground particles increased with the decrease in the particles’ sizes. The electrical conductivity of the ground particles, however, tended to decrease with the decrease in their sizes. Under the condition that the Stokes diameter of the ground particles remains constant, the electrical conductivity of films made from the ground particles increases with the increase in the flakiness of the particles. It was finally determined from our systematic grinding experiments that small flaky particles, which had a size, Xst of ∼1 μm, with a high electrical conductivity can be produced by grinding in a gas mixture of 99% N2 and 1% O2. In this case, the flaky shape of the ground particles was visually confirmed by scanning electron microscopy. 相似文献
68.
A new emulsion-type paint was prepared by utilizing a nano-composite emulsion (NCE), which contained nano-size particles (ca. 60 nm in diameter) consisting of silica (inorganic core, ca. 30 nm in diameter) and polyacrylate (organic shell), and evaluated as wall paint. By applying NCE for the wall paint, about 35 wt.% of the organic content in the paint could be reduced in comparison with the commodity emulsion-type paint, which is highly effective to save the petroleum resources. The basic properties of the white NCE paint film on gloss, surface hardness, adhesion, and solvent resistance were evaluated and compared with those of acrylic emulsion-type paints as well as those of silica-containing paints which were prepared simply by blending the acrylic emulsion with silica sol. The NCE paint was especially excellent in solvent resistance. Then the practical tests were performed to evaluate its appropriateness as wall paint, which clarified the excellent antipollution property and the high flame resistance of the NCE paint. 相似文献
69.
Koji Makino 《Electrochimica acta》2005,51(5):961-965
The electrodes prepared by a sputtering method were evaluated as the cathodes for direct methanol fuel cells (DMFCs). Pt loading below 0.25 mg cm−2 achieved higher mass activities than that of 0.5 mg cm−2 prepared by the paste method, which was general conventional method. However, an increase in Pt loading reduced the catalyst activity for the oxygen reduction reaction (ORR). This result may suggest an increase in only electrochemically inactive Pt. Pt utilization efficiency can be found about ten times higher at Pt loading of 0.04 mg cm−2. Moreover, addition of Nafion to sputter-deposited Pt cathodes is found possible to improve the catalyst activity for the ORR, but the excess Nafion over the optimum condition reduces the active sites. 相似文献
70.
Koji Matsui Kenji Tanaka Takanori Yamakawa Masato Uehara Naoya Enomoto Junichi Hojo 《Journal of the American Ceramic Society》2007,90(2):443-447
The shrinkage behavior of fine zirconia powders containing 2.9 and 7.8 mol% Y2 O3 was investigated to clarify the effect of Y2 O3 concentration on the initial sintering stage. The shrinkage of powder compact was measured under both conditions of constant rates of heating (CRH) and constant temperatures. CRH measurements revealed that when the Y2 O3 concentration of fine zirconia powder increased, the starting temperature of shrinkage shifted to a high temperature. Isothermal shrinkage measurements revealed that the increase in Y2 O3 concentration causes the shrinkage rate to decrease. The values of activation energy ( Q ) and frequency-factor term (β0 ) of diffusion at initial sintering were estimated by applying the sintering-rate equation to the isothermal shrinkage data. When the Y2 O3 concentration increases, both Q and β0 of diffusion increase. It is, therefore, concluded that the increase in Y2 O3 concentration of fine zirconia powder decreases the shrinkage rate because of increasing Q of diffusion at the initial stage of sintering. 相似文献