Mechanism and dynamics of shrinking island grains in mazed bicrystal thin films of Au

This work investigates the mechanism and dynamics of grain boundary migration driven by capillary forces via in situ electron microscopy, complemented by molecular-dynamics simulations. Using thin films of Au with the mazed bicrystal geometry, the shrinkage of island grains with 90°〈1 1 0〉 tilt grain boundaries was observed by diffraction contrast and high-resolution imaging. The grains remained cylindrical throughout the shrinkage, and there was no measurable grain rotation even at very small sizes. The rate of shrinkage was found to be erratic and inconsistent with parabolic kinetics, accelerating before complete disappearance. Residual defects were found immediately after complete shrinkage, although the type and magnitude of the defects varied from grain to grain. Measurement of the grain boundary shape anisotropy showed a preference for facets on low-index planes of the crystals, including the mirror-symmetry planes of the bicrystal. These facets were also found directly on individual images extracted from high-resolution video recordings of shrinking grains at ～300 °C. The dynamics of boundary motion were found to be limited by nucleation and propagation of steps on these facets. The cylindrical geometry and size of the experimentally observed island grains allow direct comparison with molecular-dynamics simulations on the same length scale, which reproduced many of the experimentally observed features, including non-parabolic shrinkage, absence of systematic grain rotation, step-controlled migration and dislocation debris after complete grain shrinkage. Differences between model and experiment are discussed in terms of the possible role of impurities, surfaces and interfacial steps.     

Ni_3Al－Cr－Zr－B－Mg合金的高温晶界脆性

应用电镜及Ｘ线衍射技术，研究了高温下Ｎｉ_（７５）Ａｌ_（１６．６）Ｃｒ_（７．８４）Ｚｒ_（０．４５）Ｂ_（０．１）Ｍｇ_（０．０１）合金晶界失效行为。经１１８０℃保温，由于偏聚晶界区Ｍｇ含量（ａｔ．－％）达１５－１９。同时Ｚｒ含量（ａｔ，－％）明显增大可达２８－３３；并观察到局部晶界共晶熔化现象。通过１０００℃固溶及变温热循环处理，合金中晶内出现ＣｒＮ相沉淀，沿晶界有Ｃｒ２（Ｃ，Ｎ）相析出。     

A convenient one step preparation of crosslinked polystyrene mercaptomethyl resin

A highly convenient and efficient one step procedure for the synthesis of polystyrene thiol resin from Merrifield resin is described. Potassium O,O-diethyl thionophosphate is used as a thiolating reagent for the conversion of halogen (chloro) group to thiol functionality in refluxing DMF. By a simple procedure chloro methylated cross-linked polystyrene was thiolated through a nucleophilic substitution reaction. The modified beads were characterized by IR, laser Raman spectroscopy and elemental analysis. Evaluations of the functionalized beads were done by their halide scavenging and chelating efficiency. The novel feature of this method is simple and safe reaction, shorter reaction time and efficient loading of thiol functionality.     

SBA-15-supported ionic liquid compounds containing silver salts: Novel mesoporous π-complexing sorbents for separating polyunsaturated fatty acid methyl esters

Novel π-complexing sorbents were prepared by covalently immobilizing ionic liquids (ILs) onto mesoporous SBA-15 using a one-pot sol–gel process followed by coating these SBA-15-supported IL compounds with silver salts. The mesoporous π-complexing sorbents were characterized by small angle X-ray scattering (SAXS), FTIR, TEM, SEM, nitrogen adsorption desorption isotherm, NMR, and nitrogen elemental analysis. Two advantages were obtained using these novel mesoporous π-complexing sorbents versus the traditional π-complexing sorbents formed by directly anchoring silver salts onto silica gel. (1) Higher extraction capacities were found. The extraction capacity for the polyunsaturated fatty acid methyl ester (PUFAME), methyl all-cis-5,8,11,14,17-eicosapentaenoate (20:5 or EPA), was 195 mg/g sorbent using the mesoporous AgBF₄/SBA-15 · IL · PF₆ sorbent. The capacity decreased to 121 mg/g sorbent with microporous complexing sorbent AgBF₄/SiO₂ · IL · PF₆. (2) Better reusability was also achieved. The supported IL phase immobilized and retained silver salt on SBA-15 due to the interaction between the ionic liquid’s imidazolium cations and silver ions. Eight successive sorption runs with the AgBF₄/SBA-15 · IL · PF₆ sorbent showed a satisfactory reusability. The traditional π-complexing sorbent has a silver salt directly anchored on silica without the supported ionic liquid phase. Higher silver leaching into organic solution occurred from the AgBF₄/SBA-15 sorbent determined by ICP-AES. The combined percentage (wt%) of the omega-3 PUFAMEs: 20:5 and methyl all-cis-4,7,10,13,16,19-docosahexaenoate (22:6 or DHA) stripped from the AgBF₄/SBA-15 · IL · PF₆ by 1-hexene was significantly enriched from 18% in the original cod liver oil to 90.5%.     

Beugung am Kegel elliptischen Querschnitts und die Sommerfeldsche Lösung des Halbebenenproblems

Übersicht In dieser Arbeit wird die Beugung am Kegel elliptischen Querschnitts behandelt. Wir leiten zwei Greensche Funktionen ab, die der Dirichlet- bzw. der Neumann-Bedingung auf dem Kegel genügen und die Ausstrahlungsbedingung erfüllen. Das Randwertproblem wird zurückgeführt auf die Lösung eines zweiparametrigen Eigenwertproblems mit zwei gekoppelten Laméschen Differentialgleichungen. Wir analysieren insbesondere die Beugung einer ebenen Welle an der sektorförmigen Fläche. Im Grenzfall eines Sektoröffnungswinkels von 180° gehen die Reihenentwicklungen unter Zuhilfenahme eines speziellen Gegenbauerschen Additionstheorems und einer erzeugenden Funktion für Besselfunktionen mit ganzzahligem und halbzahligem Index über in die Sommerfeldsche Lösung des Halbebenenproblems.

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Diffraction by an elliptic cone and Sommerfeld's half-plane solution

Contents In this article we examine the diffraction by an elliptic cone. We derive two Green's functions satisfying the Dirichlet-resp. Neumann-condition on the boundary of the cone. The boundary value problem is reduced to a two-parametric eigenvalue problem with two coupled Lamé equations. We analyse the diffraction of a plane wave by a plane angular sector. In the limiting case of a sector angle of 180° the series expansions pass — using a special form of Gegenbauer's addition theorem and the generating function for Bessel functions with integral and half-integral indices — into Sommerfeld's half-plane solution.

     

Towards monitoring electrostatics in gas–solid fluidized beds

The electrostatic charge distribution in a lab‐scale 2‐D fluidized bed of 900 µm glass beads was determined using arrays of induction probes, and the influence of relative humidity and superficial gas velocity was examined. The bubble presence, relative humidity, and superficial gas velocity were found to influence charge separation. Bipolar charging was observed; the net charge build‐up was found to be negligible. Moreover, the system was monitored by applying the attractor comparison method to the electrostatic charge signals from an induction probe. It was concluded that this approach can indeed be used to monitor changes in the electrostatic behaviour.     

Study on microhardness,dynamic mechanical,and tribological properties of PEEK/Al2O3 composites

The wear and friction properties of poly (ether‐ether‐ketone) (PEEK) reinforced with 0–33 vol % (60 wt %) micron size Al₂O₃ composites were evaluated at a sliding speed of 1.0 m/s and nominal pressure from 0.5 to 1.25 MPa under dry sliding conditions using a pin‐on‐disk wear tester. The wear resistance of the pure PEEK is 10‐fold higher than that of mild steel under the similar test condition. It is improved to 18‐fold as compared with mild steel at 3.5 vol % Al₂O₃ content. The improvement in wear properties may be attributed to the thin, tenacious, and coherent transfer film formed between the steel countersurface and composite pin. However, the wear resistance of PEEK containing above 3.5 vol % Al₂O₃ was deteriorated, despite their higher hardness and stiffness as compared with that of composites containing lower Al₂O₃ content. This is attributed to the formation of thick and noncoherent transfer film, which does not prevent the wear of the composites from hard asperities of countersurface. Moreover, hard Al₂O₃ particles present in transfer film act as third body wear mechanism. The coefficient of friction of the composites is higher than that of pure PEEK. SEM and optical microscopy have shown that wear of pure PEEK occurs by the mechanism of adhesion mainly whereas of PEEK composites by microploughing and abrasion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Sila-haloperidol, a silicon analogue of the dopamine (D2) receptor antagonist haloperidol: synthesis, pharmacological properties, and metabolic fate

Haloperidol (1 a), a dopamine (D(2)) receptor antagonist, is in clinical use as an antipsychotic agent. Carbon/silicon exchange (sila-substitution) at the 4-position of the piperidine ring of 1 a (R(3)COH --> R(3)SiOH) leads to sila-haloperidol (1 b). Sila-haloperidol was synthesized in a new multistep synthesis, starting from tetramethoxysilane and taking advantage of the properties of the 2,4,6-trimethoxyphenyl unit as a unique protecting group for silicon. The pharmacological profiles of the C/Si analogues 1 a and 1 b were studied in competitive receptor binding assays at D(1)-D(5), sigma(1), and sigma(2) receptors. Sila-haloperidol (1 b) exhibits significantly different receptor subtype selectivities from haloperidol (1 a) at both receptor families. The C/Si analogues 1 a and 1 b were also studied for 1) their physicochemical properties (log D, pK(a), solubility in HBSS buffer (pH 7.4)), 2) their permeability in a human Caco-2 model, 3) their pharmacokinetic profiles in human and rat liver microsomes, and 4) their inhibition of the five major cytochrome P450 isoforms. In addition, the major in vitro metabolites of sila-haloperidol (1 b) in human liver microsomes were identified using mass-spectrometric techniques. Due to the special chemical properties of silicon, the metabolic fates of the C/Si analogues 1 a and 1 b are totally different.     

Low temperature production of glass ceramics in the anorthite–diopside system via sintering and crystallization of glass powder compacts

The production of glass ceramics (GCs) with theoretical anorthite–diopside (An–Di) weight ratios of 60/40, 50/50 and 45/55 via sintering and crystallization of glass powder compacts was investigated at different temperatures between 800 and 950 °C. The investigated compositions are located in the cross-section of the ternary fluorapatite–An–Di system close to An–Di binary joint, with constant fluorapatite content of 4.8 wt.%. Two different groups of glass powders, with mean particle size of 2 and 10 μm, were used. The experimental results showed that sintering is almost complete at 800 °C, preceding crystallization, which takes place via surface crystallization mechanism. The properties values of the produced GCs, which are the best for the composition close to An–Di eutectic line, are discussed with respect to the evolution of crystalline phases and the microstructure over increasing firing temperature. Under the technology perspective, the investigated processing route is significantly superior in comparison to the attempts reported in earlier studies.     

Sintering of clay-chamotte ceramic composites for refractory bricks

Clay-chamotte composites were realized for manufacturing refractory bricks. We used two kaolinitic refractory clays mined in Cameroon and two calcined clays (chamottes) with a large grain size (0.1–4 mm). Clay-chamotte composites containing various quantities of chamotte (0–50 wt%) were shaped and sintered at 1200–1350 °C. The structural characteristics of composites indicated the presence of quartz from the initial clay, cristobalite and mullite. SEM observations revealed very heterogeneous microstructures where porosity is weakly distributed and large pores are entrapped at the vicinity of large chamotte and quartz grains. In general, the global porosity increases with the chamotte content. A specific interpretation of the matrix role on the global sintering behaviour reveals that only a part of the matrix acts effectively. Since the most part of the global porosity is within the matrix, it is distributed in matrix zones, which participate effectively to sintering and in inert matrix zones where larger pores occur. The global mechanical strength is controlled by the matrix behaviour, but the high porosity of this phase is unfavourable to high strength values. Besides, the occurrence of larges pores and local cracks at large grain interfaces from thermal stresses are critical flaws, which reduce the mechanical strength.