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11.
Gisele G. Santos Oscar Peitl Akio Koike Shusaku Akiba Shigeki Sawamura Mikio Nagano Yoshitaka Saijo Susumu Harako Satoshi Yoshida Edgar D. Zanotto 《Journal of the American Ceramic Society》2023,106(1):596-612
A few authors have reasonably proposed that liquid–liquid phase-separated (LLPS) glasses could show improved fracture strength, Sf, and toughness, KIc, as the second phase could provide a barrier to crack propagation via deflection, bowing, trapping, or bridging. Due to the associated tensile or compressive residual stresses, the second phase could also act as a toughening or a weakening mechanism. In this work, we investigated five glasses of the PbO–B2O3–Al2O3 system spanning across the miscibility gap: Four of them undergo LLPS—three are binodal (two B2O3-rich and one PbO-rich) and one is spinodal—and one does not show LLPS (composition outside the miscibility gap). Their compositions were designed in such a way that the amorphous particles are under compressive residual stresses in some and under tensile residual stresses in others. The following mechanical properties were determined: the Vickers hardness, ball on three balls (B3B) strength, and toughness, KIc-SEVNB (single-edge V-notch beam [SEVNB]). The microstructures and compositions were analyzed using scanning electron microscopy with energy-dispersive X-ray spectrometry. The spinodal glass showed, by far, the best mechanical properties. Its KIc-SEVNB = 1.6 ± 0.1 MPa m1/2, which embodies an increase of almost 50% over the B2O3-rich binodal composition, and 90% considering the PbO-rich binodal composition. Moreover, its fracture strength, Sf = 166 ± 7 MPa, is one of the highest ones ever reported for an LLPS glass. Fracture analyses evidenced that the spinodal composition exhibited the lowest net stress at the fracture point. Moreover, calculations indicate that the internal residual stress level is the lowest in the spinodal glass. The overall results indicate that the microstructural effect of the spinodal glass is the most significant factor for its superior mechanical properties. This work corroborates the idea that LLPS provides a feasible and stimulating solution to improve the mechanical properties of glasses. 相似文献
12.
Kazuhiro Yamamura Syuji Fujii Yoshinobu Nakamura Kazuko Fujiwara Shigeki Hikasa Yoshiaki Urahama 《应用聚合物科学杂志》2013,129(3):1008-1018
The influence of diblock copolymer addition on the tack properties of a polyacrylic triblock copolymer/tackifier system was investigated. For this purpose, poly(methyl methacrylate)‐block‐poly(n‐butyl acrylate)‐block‐poly(methyl methacrylate) triblock copolymer (MAM) and a 1/1 blend with a diblock copolymer consisting of the same components (MA) were used as base polymers, and a tackifier was added in amounts ranging from 10 to 30 wt %. The temperature dependence of tack was measured by a probe tack test. The tack of MAM/MA at room temperature was significantly higher than that of MAM, and the improvement of MAM/MA upon the addition of the tackifier was higher than that of MAM. The peeling process at the probe/adhesive interface during the probe tack test was observed using a high‐speed microscope. It was found that for MAM/MA, cavitation was caused in the entire adhesive layer, and peeling initiation was delayed by the absorption of strain energy due to deformation of the adhesive layer. In contrast, for MAM, peeling progressed linearly from the edge to the center of the probe. The greater flexibility of the soft block chain in the diblock copolymer resulted in improved interfacial adhesion. 1H pulse nuclear magnetic resonance analysis showed that the addition of the tackifier improved the cohesive strength of the adhesive. Adhesion strength is affected by two factors: the development of interfacial adhesion and cohesive strength. In the MAM/MA/tackifier system, the presence of MA and the tackifier improved the interfacial adhesion and cohesive strength, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
13.
Oishi M Nagatsugi F Sasaki S Nagasaki Y Kataoka K 《Chembiochem : a European journal of chemical biology》2005,6(4):718-725
A novel pH-sensitive and targetable antisense ODN delivery system based on multimolecular assembly into polyion complex (PIC) micelles of poly(L-lysine) (PLL) and a lactosylated poly(ethylene glycol)-antisense ODN conjugate (Lac-PEG-ODN) containing an acid-labile linkage (beta-propionate) between the PEG and ODN segments has been developed. The PIC micelles thus prepared had clustered lactose moieties on their peripheries and achieved a significant antisense effect against luciferase gene expression in HuH-7 cells (hepatoma cells), far more efficiently than that produced by the nonmicelle systems (ODN and Lac-PEG-ODN) alone, as well as by the lactose-free PIC micelle. In line with this pronounced antisense effect, the lactosylated PIC micelles showed better uptake than the lactose-free PIC micelles into HuH-7 cells; this suggested the involvement of an asialoglycoprotein (ASGP) receptor-mediated endocytosis process. Furthermore, a significant decrease in the antisense effect (27 % inhibition) was observed for a lactosylated PIC micelle without an acid-labile linkage (thiomaleimide linkage); this suggested the release of the active (free) antisense ODN molecules into the cellular interior in response to the pH decrease in the endosomal compartment is a key process in the antisense effect. Use of branched poly(ethylenimine) (B-PEI) instead of the PLL for PIC micellization led to a substantial decrease in the antisense effect, probably due to the buffer effect of the B-PEI in the endosome compartment, preventing the cleavage of the acid-labile linkage in the conjugate. The approach reported here is expected to be useful for the construction of smart intracellular delivery systems for antisense ODNs with therapeutic value. 相似文献
14.
Summary The oxidative coupling polymerization of racemic 3,3’-dihydroxy-2,2’-dimethoxy-1,1’-binaphthalene with copper(II) chloride-(-)-sparteine [(-)Sp] in methanol at room temperature was carried out and the enantiomer-selectivity during the polymerization was examined. The (R)-monomer preferentially reacted, and the purity of the unreacted monomer reached 80%ee (S) after 15 h, while that of the polymerized monomer gradually decreased from 26%ee (R) as a function of the polymerization. The ratio of the rate constants of both enantiomers, s=kR/kS, was determined to be 2.3. The model coupling reaction of the mono-benzylated (R)-monomer with CuCl2-(-)Sp showed that the R-configuration with respect to the carbon-carbon bonds between the monomer units was selectively constructed during the polymerization. 相似文献
15.
In this work, entropic expressions of UNIFAC‐FV and Entropic‐FV models were evaluated by using an extensive database of infinite dilution vapor–liquid equilibrium (VLE) data of athermal systems containing polypropylene, polyethylene, and polyisobutylene. For the infinite dilution athermal systems, performance of the Entropic‐FV model was better than that of the UNIFAC‐FV model. Then, finite concentration VLE data of non‐athermal systems that consisted of 16 polymers and 36 solvents containing a large variety of solvent–polymer systems ranging from nonpolar to polar substances were considered to optimized 46 pairs of group interaction parameters of the Entropic‐FV model. For systems containing polar solvents of three types of solvents studied, revised group interaction parameters gave significant improvements from 17.9 to 13.0% average absolute deviation (AAD) of solvent activities. For overall results, improvements were achieved from 15.1 to 12.4% AAD. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1145–1153, 2005 相似文献
16.
Md. Zaved Hossain Khan Takuya Nakanishi Shigeki Kuroiwa Yoichi Hoshi Tetsuya Osaka 《Electrochimica acta》2011,(24):8657
The effect of surface modification of indium tin oxide (ITO) electrode on its potential response to tryptophan was investigated for ITO substrates with different surface roughness. It was found that a small difference in surface roughness, between ∼1 and ∼2 nm of Ra evaluated by atomic force microscopy, affects the rest potential of ITO electrode in the electrolyte. A slight difference in In:Sn ratio at the near surface of the ITO substrates, measured by angle-resolved X-ray photoelectron spectrometry and Auger electron spectroscopy is remarkable, and considered to relate with surface roughness. Interestingly, successive modification of the ITO surface with aminopropylsilane and disuccinimidyl suberate, of which essentiality to the potential response to indole compounds we previously reported, improved the stability of the rest potential and enabled the electrodes to respond to tryptophan in case of specimens with Ra values ranging between ∼2 and ∼3 nm but not for those with Ra of ∼1 nm. It was suggested that there are optimum values of effective work function of ITO for specific potential response to tryptophan, which can be obtained by the successive modification of ITO surface. 相似文献
17.
Ichiro Fujii Shin Ariizumi Shintaro Ueno Chikako Moriyoshi Yoshihiro Kuroiwa Satoshi Wada 《Ceramics International》2018,44(9):10657-10662
We fabricated xBaTiO3 (BT)/(1-x)[BaTiO3-Bi(Mg1/2Ti1/2)O3-BiFeO3] (BT-BMT-BF)?+?0.1?wt%MnCO3 composites by spark plasma sintering and investigated the effect of BT content x, BT powder size, and BT-BMT-BF composition on piezoelectric properties. For xBT/(1-x)(0.3BT-0.1BMT-0.6BF) +?0.1?wt%MnCO3 (x?=?0–0.75) composites with a 0.5-µm BT powder, the dielectric constant was increased with x, and the relative density was decreased at x?=?0.67 and 0.75, creating optimum BT content of x?=?0.50 with a piezoelectric constant d33 of 107?pC/N. When a larger 1.5-µm BT powder was utilized for the composite with x?=?0.50, the d33 value increased to 150?pC/N due to the grain size effect of the BT grains. To compensate for a compositional change from the optimum 0.3BT-0.1BMT-0.6BF due to partial diffusion between the BT and 0.3BT-0.1BMT-0.6BF grains, a 0.5BT/0.5(0.275BT-0.1BMT-0.625BF)?+?0.1?wt%MnCO3 composite with the 1.5-µm BT powder was fabricated. We obtained an increased d33 value of 166?pC/N. These results provided a useful composite design to enhance the piezoelectric properties. 相似文献
18.
Takashi Tatsumi Shigeki Kunitomi Jun Yoshiwara Atsushi Muramatsu Hiro-o Tominaga 《Catalysis Letters》1989,3(3):223-226
In the reaction of CO-H2-NH3 on Mo/SiO2 catalysts, HCN is formed and is considered to be the principal intermediate for the formation of CH3CN. At low temperature methylamine is also formed. 相似文献
19.
Kazuo Fujiura Yasutake Ohishi Shigeki Sakaguchi Yukio Terunuma 《Journal of the American Ceramic Society》1989,72(8):1368-1372
A technique for synthesizing ultra-high-purity ZrF4 using chemical vapor deposition in a ZrBr4 –HF system is developed and a purification mechanism is clarified. The Fe concentration in ZrF4 is evaluated at less than 10 ppb based on analysis of the transmission loss spectrum of a fiber prepared using synthesized ZrF4 . Purification is achieved mainly in a sublimation process of ZrBr4 , and purification efficiency is determined by sublimation temperature and activity of impurities in ZrBr4 . The concentration of transition-metal impurities in ZrF4 , synthesized by chemical vapor deposition in the ZrBr4 –HF system, is expected to be less than 1 ppb. 相似文献
20.
Mitaku Shigeki; Hirokawa Takatsugu 《Protein engineering, design & selection : PEDS》1999,12(11):953-957
The average hydrophobicity of a polypeptide segment is consideredto be the most important factor in the formation of transmembranehelices, and the partitioning of the most hydrophobic (MH) segmentinto the alternative nonpolar environment, a membrane or hydrophobiccore of a globular protein may determine the type of proteinproduced. In order to elucidate the importance of the MH segmentin determining which of the two types of protein results froma given amino acid sequence, we statistically studied the characteristicsof MH helices, longer than 19 residues in length, in 97 membraneproteins whose three-dimensional structure or topology is known,as well as 397 soluble proteins selected from the Protein DataBank. The average hydrophobicity of MH helices in membrane proteinshad a characteristic relationship with the length of the protein.All MH helices in membrane proteins that were longer than 500residues had a hydrophobicity greater than 1.75 (Kyte and Doolittlescale), while the MH helices in membrane proteins smaller than100 residues could be as hydrophilic as 0.1. The possibilityof developing a method to discriminate membrane proteins fromsoluble ones, based on the effect of size on the type of proteinproduced, is discussed. 相似文献