Bromine addition and successive amine substitution of mesoporous ethylenesilica: Reaction, characterizations and arsenate adsorption

Bromination and subsequent ethylenediamine substitution of the CC double bond in mesoporous ethylenesilica were carried out to explore the characteristics of this periodic mesoporous organosilica. The structures of the products (BrPMO and EDA–BrPMO, respectively) were analysed by IR, Br K-edge EXAFS and NMR spectroscopies, as well as X-ray diffraction and nitrogen adsorption. We showed (1) that the formulae of the two products that formed were [CHBrSiO_1.5]_0.45[CHSiO_1.5]_0.55 and [NH₂CH₂CH₂NHCHSiO_1.5]_0.05 [CHBrSiO_1.5]_0.40[CHSiO_1.5]_0.55, respectively, (2) that the addition of Br₂ at room temperature occurred on the CC double bonds with disturbing the framework structure, (3) that IR absorption band of CC bonds that reacted with Br₂ is significantly different from that of inactive CC bond, (4) that the length of the C–Br bond was considerably longer than in conventional alkyl bromides, and (5) that a large proportion of the ν(C–Br) band remained at the same position in the IR absorption spectrum after the ethylenediamine (EDA) substitution, while a new ν(C–Br) absorption also appeared. The mechanisms of these reactions are discussed at both the micro and mesoscopic levels.

Arsenate adsorption on EDA–BrPMO, in which the EDA is directly bound to the “surface” of the mesopores, was compared with adsorption on EDA–Pr–PMO, which was prepared by the direct synthesis of 3-chloropropyl-functionalized mesoporous ethanesilica followed by the substitution of Cl with EDA. The strength of the adsorption, as measured with the distribution coefficient, was greater for the former adsorbent than the latter. The origin of this difference was attributed to the distance between amino group and the surface.     

Some properties of mullite powders prepared by chemical vapour deposition

The sinterability of mullite (3Al₂O₃·2SiO₂) powder prepared by chemical vapour deposition was examined to improve the conditions for fabricating dense mullite ceramics. The starting powder contained not only mullite, but also a small amount of -Al₂O₃ (Al-Si spinel) and amorphous material. Although the compressed powder was fired at a temperature between 1550 and 1700 °C for 1, 3 and 5 h, the relative densities of the sintered compacts were limited to 90%: (i) due to the creation of pores/microcracks during the solid state reaction (1100–1350 °C), and (ii) due to restriction on the rearrangement of grains because the amount of liquid phase (1550–1700 °C) was insufficient. Calcination of the starting powder was effective for preparation of easily sinterable powder with homogeneous composition. When the compact formed by compressing the calcined powder at 1400 °C for 1 h was fired at 1650 °C for 3 h, the relative density was raised up to 97.2%; moreover, mullite was the only phase detected from the sintered compact. The sintered compact was composed of polyhedral grains with sizes of 1–2 m and elongated grains with long axes of 6 m.     

Probabilistic calibration of discrete element simulations using the sequential quasi-Monte Carlo filter

The calibration of discrete element method (DEM) simulations is typically accomplished in a trial-and-error manner. It generally lacks objectivity and is filled with uncertainties. To deal with these issues, the sequential quasi-Monte Carlo (SQMC) filter is employed as a novel approach to calibrating the DEM models of granular materials. Within the sequential Bayesian framework, the posterior probability density functions (PDFs) of micromechanical parameters, conditioned to the experimentally obtained stress–strain behavior of granular soils, are approximated by independent model trajectories. In this work, two different contact laws are employed in DEM simulations and a granular soil specimen is modeled as polydisperse packing using various numbers of spherical grains. Knowing the evolution of physical states of the material, the proposed probabilistic calibration method can recursively update the posterior PDFs in a five-dimensional parameter space based on the Bayes’ rule. Both the identified parameters and posterior PDFs are analyzed to understand the effect of grain configuration and loading conditions. Numerical predictions using parameter sets with the highest posterior probabilities agree well with the experimental results. The advantage of the SQMC filter lies in the estimation of posterior PDFs, from which the robustness of the selected contact laws, the uncertainties of the micromechanical parameters and their interactions are all analyzed. The micro–macro correlations, which are byproducts of the probabilistic calibration, are extracted to provide insights into the multiscale mechanics of dense granular materials.     

The evaluation of speckle contrast with variable speckle generator

Abstract— While laser projection has many advantages, there is a problem with speckle patterns generated as a result of interference of the laser beam and results in bad effects to observers. In 2010, a variable speckle generator, which produces an angular shift of incident light to the screen and generates variable speckle patterns, was suggested. In this study, the performance of a variable speckle generator by using a volume phase holographic beam shaper and scanning mirror was investigated in detail by evaluating both the objective and subjective speckle contrast. The morphology of the speckle pattern was also investigated when the variable speckle generator was activated. With a scanning VPH beam shaper, the objective speckle was effectively reduced because each point of the VPH beam shaper generated different speckle patterns and coherency among each pattern disappeared by using the scan process. On the other hand, subjective speckle was also dramatically reduced by changing the incident angle on the screen, which resulted in generating variable subjective speckle. It was also shown that the speckle reduction rate by using a variable speckle generator did not depend on the coherent length of a laser by evaluating the normalized speckle contrast against the angular shift on the screen.     

An analytical solution for geotextile-wrapped soil based on insights from DEM analysis

This paper presents a novel analytical solution for geotextile-wrapped soil based on a comprehensive numerical analysis conducted using the discrete element method (DEM). By examining the soil–geotextile interface friction, principal stress distribution, and stress–strain relations of the constituent soil and geotextile in the DEM analysis, a complete picture of the mechanical characterization of geotextile-wrapped soil under uniaxial compression is first provided. With these new insights, key assumptions are verified and developed for the proposed analytical solution. In the DEM analysis, a near-failure state line that predicts stress ratios relative to the maximums at failure with respect to deviatoric strain is uniquely identified; dilation rates are found to be related to stress ratios via a single linear correlation regardless of the tensile stiffness of the geotextile. From these new findings, the assumptions on the stress-state evolution and the stress–dilatancy relation are developed accordingly, and the wrapped granular soil can therefore be modeled as a Mohr–Coulomb elastoplastic solid with evolving stress ratio and dilation rate. The development of the proposed analytical model also demonstrates an innovative approach to take advantage of multiscale insights for the analytical modeling of complex geomaterials. The analytical model is validated with the DEM simulation results of geotextile-wrapped soil under uniaxial compression, considering a wide range of geotextile tensile stiffnesses. To further examine the predictive capacity of the analytical model, the stress–strain response under triaxial compression conditions is solved analytically, taking both different confining pressures and geotextile tensile stiffnesses into account. Good agreement is obtained between the analytical and DEM solutions, which suggests that the key assumptions developed in the uniaxial compression conditions also remain valid for triaxial compression conditions.     

Influence of LiBO2 addition on the microstructure and lithium-ion conductivity of Li1+xAlxTi2−x(PO4)3(x = 0.3) ceramic electrolyte

Concerning the safety problems of conventional Li-ion batteries with liquid electrolytes, it is crucial to develop reliable solid-state electrolytes with high ionic conductivity. Li_1+xAl_xTi_2?x(PO₄)₃ (LATP, x = 0.3) is regarded as one of the most promising solid electrolytes due to its high ionic conductivity and excellent chemical stability to humidity.Herein, a new strategy is proposed for improving the sintering behavior and enhancing the ionic conductivity of LATP by using LiBO₂ as the sintering aid via liquid phase sintering. The as-prepared sample LATP with homogeneous microstructure and high relative density of 97.1% was successfully synthesized, yielding high total ionic conductivity of 3.5 × 10^?4 S cm^?1 and low activation energy of 0.39 eV at room temperature. It was found that the addition of LiBO₂ could effectively enhance the densification and increase the ionic conductivity of LATP electrolyte, proving an effective way to synthesis LATP ceramics by a simple and reliable route.     

Advanced synthesis for monodisperse polymer nanoparticles in aqueous media with sub-millimolar surfactants

Highly monodisperse polystyrene nanoparticles with mean diameters of less than 100 nm are synthesized via aqueous emulsion polymerization using an amphoteric initiator (VA-057) in the presence of sub-millimolar concentrations of anionic surfactant. Since the net charge on the initiator is almost zero at neutral pH, the resultant latex particle size is mainly determined by surfactant adsorption. Polymerizations were performed in the presence of a range of anionic surfactants with differing critical micelle concentrations (CMC) by varying the concentrations of surfactant, initiator and monomer, and also the ionic strength. Sodium dodecyl benzene sulfonate (SDBS), sodium hexadecyl sulfate (SHS), and sodium octadecyl sulfate (SOS) have relatively low CMCs and so enable formation of highly monodisperse nanoparticles at relatively low (sub-millimolar) surfactant concentrations, C_S (i.e. below the CMC in each case). Empirically, it was found that the particle number, N_p, and coefficient of variation of the particle size, C_V, were strongly dependent on the C_S/CMC ratio: N_p increased almost in proportion with the square of this ratio, while the C_V exhibited a minimum at approximately C_S/CMC = 0.20. Higher ionic strength reduced the particle size, which is consistent with the above relationship because the addition of salt lowers the CMCs of ionic surfactants. Polymer latex particles produced using such formulations form highly regular, close-packed colloidal arrays.     

Numerical simulation of critical current performance in Nb3Sn strand subjected to periodic bending deformation

In the ITER Engineering Design Activity (EDA), four NB₃Sn model coils were developed and successfully tested. However, it was revealed that the critical current of the conductor degraded with the increase of electromagnetic force. One of the explanations of this phenomenon is a strand bending caused by enormous electromagnetic force. The authors therefore developed a simulation code using the distributed circuit model to investigate dependency of the critical current performance on the periodic bending deformation. The simulation results were in good agreement with the experiments. The dependence of the critical current on the periodic transverse load, temperature, periodic load pitch, thickness of Ta barrier which prevents Cu stabilizer from being contaminated by Sn, twist pitch of the strand, and RRR of the bronze matrix was investigated using the developed code. The results showed that the critical current degraded less with decreasing the pitch of the transverse load and increasing the Ta barrier thickness. It suggests that the shorter cabling pitch and the larger bending stiffness prevent the critical current degradation. © 2010 Wiley Periodicals, Inc. Electr Eng Jpn, 171(3): 7–15, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20923