复注及多孔注浆理论研究

针对柱面注浆方式，研究了有关渗透注浆的单孔复注及不同方式布孔时多孔注浆的相互影响等问题，推导出一些有价值的岩体注浆理论公式，可用于指导现场注浆工程的设计与施工．     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

超稳Y沸石制备技术对沸石铝分布的影响 Ⅱ.均匀铝分布的超稳Y沸石的制备

对水热处理后得到的USY沸石作进一步的酸处理以及采用改进的氟硅酸盐溶液骨架富硅工艺,分别得到了经XPS剖面分析证实为铝分布均匀的超稳Y沸石HAY-Ⅰ和HAY-Ⅱ。IR分析表明,在酸处理过程中从USY沸石中去掉的那部分非骨架铝类与3690cm~(-1)处羟基有关,仍残留在HAY-Ⅰ沸石中的那部分非骨架铝类与3670cm~(-1)和3600cm~(-1)处羟基有关。XRD和化学分析表明HAY-Ⅰ沸石仍含有约50％的非骨架铝类,而HAY-Ⅱ沸石则基本上不含非骨架铝类,HAY-Ⅱ沸石还显示更高的结晶保留度。DTA分析表明,HAY-Ⅰ和HAY-Ⅱ两种沸石的热稳定性均高于USY沸石。     

Copolymerization of N‐vinylcaprolactam and glycidyl methacrylate: Reactivity ratio and composition control

Free‐radical copolymerizations of N‐vinylcaprolactam (VCL) and glycidyl methacrylate (GMA) were investigated to synthesize temperature‐responsive reactive copolymers with minimized compositional heterogeneity. The average copolymer composition was determined by Fourier transform infrared and nuclear magnetic resonance techniques. The reactivity ratios for VCL and GMA were found to be 0.0365 ± 0.0009 and 6.44 ± 0.36 by the Fineman–Ross method and 0.039 ± 0.006 and 6.75 ± 0.29 by the Kelen–Tudos method, respectively. When prepared by batch polymerization, VCL–GMA copolymers had a highly heterogeneous composition and fractions of different solubilities in water. The use of a gradual feeding technique, which included the sequential addition of more reactive GMA monomer into the reaction, yielded copolymers with much more homogeneous composition. The produced copolymers with 0.9 and 0.11 fractional GMA contents preserved their temperature‐responsive properties and precipitated from aqueous solutions when the temperature exceeded 31 °C. The GMA units in the VCL–GMA copolymers were capable of reacting with amino end‐functionalized poly(ethylene oxide) at room temperature to produce poly(N‐vinylcaprolactam)–poly(ethylene oxide) graft copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 183–191, 2006     

Investigation of sulfonated poly(ether ether ketone sulfone)/heteropolyacid composite membranes for high temperature fuel cell applications

The sulfonated poly(ether ether ketone sulfone) (SPEEKS)/heteropolyacid (HPA) composite membranes with different HPA content in SPEEKS copolymers matrix with different degree of sulfonation (DS) were investigated for high temperature proton exchange membrane fuel cells. Composite membranes were characterized by Fourier transfer infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR band shifts suggested that the sulfonic acid groups on the copolymer backbone strongly interact with HPA particles. SEM pictures showed that the HPA particles were uniformly distributed throughout the SPEEKS membranes matrix and particle sizes decreased with the increment of copolymers' DS. The holes were not found in SPEEKS‐4/HPA30 (consisting of 70% SPEEKS copolymers with DS = 0.8 and 30% HPA) composite membrane after composite membranes were treated with boiling water for 24 h. Thermal stabilities of the composite membranes were better than those of pure sulfonated copolymers membranes. Although the composite membranes possessed lower water uptake, it exhibited higher proton conductivity for SPEEKS‐4/HPA30 especially at high temperature (above 100 °C). Its proton conductivity linearly increased from 0.068 S/cm at 25 °C to 0.095 S/cm at 120 °C, which was higher than 0.06 S/cm of Nafion 117. In contrast, proton conductivity of pure SPEEKS‐4 membrane only increased from 0.062 S/cm at 25 °C to 0.078 S/cm at 80 °C. At 120 °C, proton conductivity decreased to poor 0.073 S/cm. The result indicated that composite membranes exhibited high proton conductivity at high temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1967–1978, 2006     

Interval parameter perturbation method for evaluating the bounds on natural frequencies of structures with interval parameters

For structural parameters with uncertainties, interval mathematics can, in the case where the probabilistic distribution density of uncertain variables is unavailable, deal with the influence of uncertainties in structural parameters on the response of structures. In order to evaluate the region containing natural frequencies of structures with interval parameters, the interval parameter perturbation method is presented in this paper. The advantage of the present method is its computational efficiency in evaluating the region containing natural frequencies. A numerical example is used to illustrate the efficiency of the method proposed. The project is supported by National Youth Natural Science Foundation of China and National Outstanding Youth Science Foundation of China.     

Theoretical study of the surface energy and electronic structure of pyrite FeS2 (100) using a total-energy pseudopotential method, CASTEP

The geometric and electronic structures of FeS(2) (100) surface have been studied by a quantum-mechanical calculation using a total-energy pseudopotential code, CASTEP. The (100) surface is very stable and does not give any significant geometric relaxation. The electronic structure of FeS(2) (100) surface is characterized by the appearance of new native surface states in the bulk band gap, which correspond to antibonding mixed Fea-Ssp(3) states. These surface states play an important role as mediators of electron transfer on both anodic and cathodic sites in the incipient oxidation of pyrite. Moreover, the (100) surface has small band gaps and shows some metallic character. It is predicted that the rate of cathodic reductive reaction of O(2) in the incipient oxidation of pyrite is much faster than previously considered. The transport of electrons from the anodic sites to the cathodic sites on the (100) surface is faster and hole injection of anodic sites is not the rate-determining step. So we can deduce that the rate-determining step of incipient oxidation for pyrite consists of both electron transfer of pyrite/aqueous O(2) interface and the splitting of H(2)O.