Synthesis of proton conductive membranes based on inorganic–organic hybrid structure bound with phosphonic acid

Proton conductive inorganic–organic hybrid membranes were synthesized from styrene derivatives of alkoxysilane and ethyl 2-[3-(dihydroxyphosphonyl)-2-oxopropyl] acrylate (EPA) through copolymerization followed by sol–gel reaction. Self-standing, homogeneous and transparent hybrid membranes with chemically bound phosphonic acid groups were synthesized. FT-IR analysis exhibited the hybrid membranes included phosphonic acid groups. ¹³C and ²⁹Si NMR studies indicated that alkoxysilyl functionalized styrene derivatives were not only copolymerized with EPA but also condensed yielding Si–O–Si linkages by sol–gel reaction. TG–DTA analysis revealed that these membranes were thermally stable up to 200 °C in dry O₂. The proton conductivities of the hybrid membranes increased with phosphonic acid content and temperature. The P/Si ratio of the membrane was dependent on the number of alkoxy group in the starting alkoxysilane. The hybrid membrane from (dimethylmethoxysilylmethyl)styrene (DMMSMS(M))/EPA = 1/6 revealed proton conductivities of 6.3 × 10⁻³ and 2.4 × 10⁻⁴ S cm⁻¹ at 68.0% relative humidity and 18.8% relative humidity, respectively, at 140 °C.     

Study on dominant mechanism of high-cycle fatigue life in 6061-T6 aluminum alloy through microanalyses of microstructurally small cracks

The mechanism controlling the fatigue life of a precipitation-hardened Al–Mg–Si alloy (6061-T6) at a high-cycle fatigue (HCF) regime of over 10⁷ cycles was investigated in detail. It was found that over 90% of the total fatigue life was occupied by the growth process of a microstructurally small crack at relatively low stress amplitude. The small crack was often found to be arrested and halted for a long period (more than 10⁶ cycles) before it began to grow again, which resulted in a significantly slow growth process. The small crack was then analyzed not only by the conventional fractography but also by the cross-sectional observation of the crack tip region using a focused ion beam and transmission electron microscopy. These observations, supplemented also by a grain orientation analysis using electron backscattered diffraction, explicitly revealed the following points: (i) the small crack growth observed on the specimen surface is primarily related to facet-type cracking that occurs exclusively at the specimen surface; (ii) the growth direction of the small crack has strong anisotropy (i.e. surface-induced growth); (iii) the facet-type cracking is related to the formation of persistent fine slip bands that accompany no structural change of the matrix. On the basis of these results, the micromechanism of small crack growth and its relation to the concept of fatigue limit at the HCF regime is discussed in detail.     

Luminescence properties of La1−χTmχTa7O19

The luminescence properties of Tm³⁺ in La_1−χTm_χTa₇O₁₉ solid solutions were examined systematically. The substitution of Tm³⁺ for La³⁺ was carried out by a decomposition reaction of nitrates involving the corresponding constituents at 1200 °C in air. X-Ray diffraction patterns of the solid solutions indicated that the crystal structure consisted of a network of (La_1−χ³⁺Tm_χ^staggered|3+, Ta⁵⁺)—O²⁻ polyhedra interstratified with a double layer of Ta⁵⁺—O²⁻ polyhedra. According to the excitation and emission spectra, the most intense emission was found near 460 nm and quenched above χ=0.14 in La_1−χTm_χTa₇O₁₉. Also, lifetime results verified that the emission could be assigned not to the transition ¹G₄ å ³H₆, but to the transition ¹D₂ å³H₄. Upon cathode ray excitation some emissions of Tm³⁺ were superimposed by a broad emission due to the clusters of Ta⁵⁺—O²⁻ polyhedra. As a result, a low dimensional arrangement of Tm³⁺ was much more preferable for getting intense emission because it reduced the energy migration between Tm³⁺ ions.     

N-Alkylation of amines by photocatalytic reaction in a microreaction system

A photocatalytic microreaction system was developed and photocatalytic N-alkylation process of benzylamine, aniline, and piperidine was examined. The reaction proceeded quite rapidly in the microreactors with immobilized Pt-free TiO₂ as well as Pt-loaded TiO₂, while it has been reported that the N-alkylation did not occur by the irradiation of Pt-free TiO₂ in conventional batch reactors. It was revealed that by using the unique features of the continuous-flow microreactor, for instance spatial illumination homogeneity and precise control of flow and irradiation conditions, one can control the selectivity of N-alkylation and N,N-dialkylation processes. These results suggest the possibilities of a photocatalytic microreaction system on organic synthetic reactions.     

Synthesis and catalytic properties of sulfonic acid-functionalized monodispersed mesoporous silica spheres

A new type of sulfonic acid-functionalized monodispersed mesoporous silica spheres (MMSS) were synthesized directly by co-condensation and subsequent oxidation. By changing the methanol ratio, sulfonic acid-functionalized MMSS with different particle diameters (390–830 nm) and the same mesopore sizes were successfully synthesized. TEM observations revealed that the mesopores were aligned radially from the center towards the outside of the spheres, even in the sulfonic acid-functionalized MMSS. The catalytic activities of the sulfonic acid-functionalized MMSS were studied in condensation reactions between 2-methylfuran and acetone, and it was found that their catalytic activities are highly dependent on the particle diameters. In addition, the catalytic activity of MMSS was much higher than that of other forms of mesoporous silica due to its radially-aligned mesopores.     

Temperature dependences of piezoelectric properties of vanadium substituted SrBi2Nb2O9 ceramics with grain orientation

The temperature dependence of the piezoelectric properties of vanadium substituted strontium bismuth niobate, SrBi₂Nb_1.95V_0.05O₉ (SBNV) ceramics, were investigated in various vibration modes. The effects of grain orientation in SBNV ceramics on the piezoelectric properties were also studied by the hot-forging (HF) method. The anisotropy of the piezoelectric properties of each vibration mode was confirmed by observing the grain orientation. In particular, HF-SBNV ceramics of the (33) and (15) modes showed excellent piezoelectric properties with relatively high mechanical quality factors, Q_m (2200, 4600), and high electrical quality factors, Q_{e max} (66.0, 21.6), respectively. In addition, HF-SBNV ceramics showed low temperature coefficients of resonance frequency TC-f_r (−16.5, −27.0). HF-SBNV ceramics are considered to be superior candidates for the lead-free piezoelectric application of ceramic resonators.     

Enhancement of melt elasticity for poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) by addition of weak gel

Rheological properties in a molten state are studied extensively for poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate), PHB‐HV, with a small amount of crosslinked poly(epichlorohydrin), PECH, having low density of crosslink points. It is found that adding 2 wt % of xPECH greatly enhances the melt elasticity of PHB‐HV, one of the serious defects of microbial PHB, whereas it has no effect on the shear viscosity. As a result, viscoelastic nature, and thus processability, of PHB‐HV can be controlled by blending the crosslinked PECH. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of friction stir processing on microstructure of laser clad cobalt-based alloy

(The microstructural refinement of cobalt-based alloy (Stellite No. 6) by laser cladding and friction stir processing (FSP) was studied. A nanometer-sized microstructure consisting of fine carbide (particle size: 100–200 nm) and a grain (grain size: 150–250 nm) was successfully fabricated by the FSP on the laser clad cobalt-based alloy. The nanostructured cobalt-based alloy (Stellite No. 6) had an extremely high hardness of about 750 HV.     

共析珠光体钢在冷轧过程中的组织变化

用SEM、TEM及XRD等方法研究了共析钢中珠光体经40％-90％的冷轧变形后所产生的显微组织变化．接渗碳体形态特点,变形珠光体组织可分为以下3种类型：(1)不规则弯曲片层型,即变形后的渗碳体与轧制面呈大角度偏离且不规则弯曲的珠光体．(2)带有剪切带的粗大片层型,即被渗碳体剪切带分开且变形轻微的珠光体．(3)精细片层型,即与轧制方向平行排列、片间距细小且渗碳体严重变形的珠光体．精细片层区域的比例随着轧制压下率的提高而增大．此外,重度冷轧变形还引起渗碳体严重塑性变形和部分溶解．     

Ultrathin protective films of two-dimensional polymers on passivated iron against corrosion in 0.1 M NaCl

Prevention of iron corrosion in an aerated 0.1 M NaCl solution was investigated by polarization and mass-loss measurements of a passivated iron electrode covered with ultrathin and ordered films of two-dimensional polymers. The films were prepared on the passivated electrode by modification of a 16-hydroxyhexadecanoate ion self-assembled monolayer with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and alkyltriethoxysilane C_nH_{2n + 1}Si(OC₂H₅)₃ (n = 8 or 18). Because crevice corrosion occurred at the initial stage of immersion in the solution preferentially, the edge of electrode covered with the polymer film was coated with epoxy resin. The open-circuit potentials of the covered electrodes in the solution were maintained high, more than −0.2 V/SCE for several hours, indicating that no breakdown of the passive film occurred on the surface. The protective efficiencies of the films were extremely high, more than 99.9% unless the passive film was broken down. The efficiencies after immersion for 24 h almost agreed with those obtained by mass-loss measurements. X-ray photoelectron spectroscopy and electron-probe microanalysis of the passivated surface covered with the polymer film after immersion in the solution for 4 h revealed that pit initiation on the passive film was suppressed by coverage with the polymer film completely.