Using electroless deposition for the preparation of micron sized polymer/metal core/shell particles and hollow metal spheres

Uniform and stable core-shell microspheres composed of a poly(methyl methacrylate) (PMMA) core and a thin metallic shell of nickel-phosphorus, cobalt-phosphorus, or mixed metal alloys (CoNiP, NiFeP, CoFeP) were prepared by dispersion polymerization of methyl methacrylate followed by electroless plating. The presence of the metallic shell around the particles was confirmed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and photoelectron spectroscopy. Transmission electron microscopy images of the cross-section of individual particles show that the thickness of the metal/alloy can be precisely tuned by adjusting the immersion time of the microspheres in the electroless bath. Depending on the deposited metallic material, various magnetic properties, from paramagnetic to ferromagnetic, are achieved. Finally, uniform hollow metallic spheres composed of nickel, cobalt, or nickel-cobalt alloy are obtained by dissolving the polymer core.     

The role of the solvation shell decomposition of alkali metal ions in their selective complexation by resorcinarene and its cavitand

2-Methylresorcinarene and its methylene-bridged cavitand derivative as host compounds were investigated in selective complexation of alkali metal ions as guests in methanol media by photoluminescence measurements. These host molecules possess either flexible (2-methylresorcinarene) or rigid (cavitand) molecular skeleton. The Benesi–Hildebrand method and the van't Hoff theory have been applied to determine the stability constants and the thermodynamic parameters, respectively. Considerable interactions between 2-methylresorcinarene and Li⁺ or Na⁺ ions have been observed while the rigid cavitand derivative can interact only with K⁺ or Cs⁺ ions. Neither the complexes of 2-methylresorcinarene with K⁺ or Cs⁺ nor those of the cavitand derivative with Li⁺ or Na⁺ ions are stable at room temperature in methanol media. Quantum-chemical investigations justified that only solvated Li⁺ and Na⁺ ions can form stable complexes with 2-methylresorcinarene while unsolvated K⁺ and Cs⁺ ions form stable complexes with the methylene-bridged cavitand. These results highlight that the stability of the guest solvation shell and its size could play a key role in the selectivity behaviour of host molecules.     

CEPA calculations on open-shell molecules. V. The vibration frequencies of SF and SCl

Ab initio calculations for the ² ground states of SF and SCl have been performed on Hartree-Fock level and with inclusion of valence shell correlation effects by means of the CI and CEPA approaches. The calculated properties are: Equilibrium distances, vibration frequencies, and dipole moment curves in the vicinity of the respective equilibrium geometries. Our best estimates for the 0 1 infrared absorption frequencies _o for SF and SCl are 786 cm^–1 and 520 cm^–1, respectively, both with an uncertainty of about 10 cm^–1. This confirms a recent experimental value obtained by Willner for SF (791 cm^–1), but indicates that for SCl both experimental values reported previously in the literature (617 cm^–1 and 574 cm^–1) are wrong. The S—F and S—Cl bonds in SF and SCl are very similar to the ones in SF₂ and SCl₂, being essentially single p-bonds in either case. In the analogous oxygen-halogen molecules the situation is different, the O—F and O—Cl bonds in the diatomic radicals OF and OCl have partial double bond character and are much stronger than those in OF₂ and OCl₂ or in HOF and HOCl.     

Synthesis and properties of organo-fly ash/polyaniline with core/shell structure based on emulsion polymerization

Organo-fly ash(OFA) was prepared with pretreated fly ash(FA) and hexadecyltrimethyl ammonium bromide (HDTMAB),and the composites composed of OFA and polyaniline were obtained by emulsion polymerization at different OFA weight ratios(2.0 wt%,5.0 wt%,10.0 wt%,15.0 wt%and 20.0 wt%) in the presence of dodecylbenzenesulfonic acid as dopant and emulsifier.A polymerization procedure was supposed.The electrical conductivities of the composites were tested by the four-probe technique.The chemical structure and crystallinity of the composites were confirmed by FT-IR and X-ray diffraction,respectively.Morphologies of FA,OFA and the composites were observed by SEM.The element analysis was performed by energy dispersive spectrometry.The thermal stability of the composites was analyzed by TGA.The results showed that the electrical conductivity of the composites decreased with increasing the feed weight ratio of OFA,and the lowest value was 0.62 S/cm.HDTMAB and PAn were just adsorbed on the surface of FA and OFA,respectively according to the physical adsorption without destroying the crystalline structure of FA or OFA.The surface became smoother after organification of FA by using HDTMAB,and its content on FA surfaces was about 26.9 wt%.The core/shell structure of the composite was observed by SEM analysis.The composites showed a higher thermal stability than pure PAn by introduction of OFA into this polymerization system,the heat stability of PAn was increased by decreasing 31.8 wt%of weight loss after introducing 20 wt%of OFA.     

A theoretical investigation on the potential energy surface of CN2H rotation of the encapsulated 1-bicyclo[2.2.1]heptyldiazirine

The potential energy surface (PES) of CN₂H rotation of the encapsulated 1-bicyclo[2.2.1]heptyldiazirine (BHD) inside a molecular container: Cram’s hemicarcerand (CH) was explored using two different DFT involved ONIOM methods: B3LYP/6-31G^**//ONIOM(B3LYP/6-31G^*: AM1) and B971/6-31G^**//ONIOM(B971/6-31G^*: AM1). The free-state PES of CN₂H rotation was also calculated, respectively by B3LYP/6-31G^**//B3LYP/6-31G^* and B971/6-31G^**//B971/6-31G^* methods for comparison. The findings in this study have shown that the PES profiles differ from each other notably in the two states. In the encapsulated state the rotation barrier corresponding to the free-state conversion with the largest rotation barrier increases by about 2 kcal/mol, which has exceeded the largest rotation barrier in the free-state. The conformational preference behavior towards certain BHD isomers, which might be in better conformational compatibility with the container, has been demonstrated.     

The effect of shell side hydrodynamics on the performance of axial flow hollow fibre modules

Fluid flow and mass transfer experiments have been performed on axial flow hollow fibre modules of varying packing density (32 to 76%). Shell-side pressure drop was found to be proportional to (flowrate)ⁿ, where n varied from about 1.1 at high packing density to 1.5 at low packing density, for shellside Reynolds numbers < 350. Assuming an Ergun-type pressure drop relationship it was found that for packing densities < about 50% the inertial (turbulent) losses exceeded the viscous (laminar) losses. Inspection of cross-sections taken from the middle of modules revealed non-uniform fibre packing with regions of high and low packing density. The cross-sections also change along the length of the module. It is inferred that, in addition to axial flow along fibres, there is also a degree of stream splitting which provides transverse flow across fibres as fluid continuously seeks preferential paths through regions of lower packing density. The presence of transverse flow would explain the higher than expected velocity exponent. Mass transfer experiments involving the removal of oxygen from water flowing through the shell to a sweep gas in the fibre lumens produced higher than expected shell-side mass transfer coefficients. The results are correlated within ± 15% by Sh = (0.53 − 0.58φ)Re^0.53Sc^0.33. The exponent on Re is consistent with entry region conditions, caused by repeated stream splitting and transverse flow. Compared with mass transfer predicted for axial flow through a uniformly packed shell the experimental results are up to 2× higher, with the most significant enhancement at the lower packing densities. The implication of this work is that module design requires a more sophisticated approach than the traditional assumption of laminar flow through parallel axial ducts.     

Effect of the Shell Crosslinking Level andCore/Shell Ratio on the Morphology of LatexParticles in the Preparation of Hollow Latexes简

Three-layer core/shell latex particles with various shell crosslinking level and shell thickness were prepared by multistep emulsion polymerization, and the hollow latex particles with different morphologies were then obtained after alkali post-treatment. Influences of divinyl benzene(DVB) content and the core/shell mass ratio on emulsion polymerization and particle morphology were investigated. Results showed that with the increase of DVB content, the percentage of total amount of ―COOH on the particle surface and free in aqueous phase(PSFa) decreased, and the morphology of the post-treated particles underwent evolution from cracked, intact hollow to deficient swelling structure. Decreasing the core/shell mass ratio could not only make more carboxyl groups encapsulated by the shell, but also increase the shell resistance to the swelling of the core. The uniform hollow latex particles with intact morphology were obtained when the DVB content was 3.54 wt% and the core/shell mass ratio was 1/6.     

New studies on the apparent allyl rotation in scorpion-like palladium complexes. The influence of non-directly bonded groups. X-ray molecular structures of [Pd(η-2-Me-C3H4)L]TfO, L=bpzmArOMe and bpz*mCy

New cationic 2-Me-allylpalladium complexes were prepared with the N,N-donor chelate ligands bis(pyrazol-1-yl)(R)methane (R=anisol-2-yl, bpzmArOMe; 2-hydroxyphenyl, bpzmArOH) and bis(3,5-dimethylpyrazol-1-yl)(R)methane (R=anisol-2-yl, bpz*mArOMe; cyclohexyl, bpz*mCy and ferrocenyl, bpz*mFc). The bpz′mR ligands adopt a rigid boat conformation after coordination to the Pd center and the R group is in the axial position of the metallacycle. The new complexes exhibit two isomeric forms in solution that differ in the relative orientation of the 2-Me-allyl group with respect to the bpz′mRPd fragment. The fluxional behavior of the new complexes, mainly in the context of the isomerization process, has been analyzed. Conclusions concerning the influence on this isomerization of the R group and the pyrazole substituents in positions 3 and 5 are discussed. The isomerization process was found to be affected by the presence of coordinating anions (Cl⁻) or by a change in the complex concentration. The molecular structures of the complexes [Pd(η³-2-Me-C₃H₄)(bpzmArOMe)]TfO and [Pd(η³-2-Me-C₃H₄)(bpz*mCy)]TfO have been determined by X-ray diffraction studies.     

The effects of cross-linking and anodic surface roughening on quinone polymer/carbon electrodes

A polymer in which anthraquinone-2-carbonyl groups were bound to polyethyleneimine was coated onto a glassy carbon electrode. Electrodes of this kind were studied using cyclic voltammetry and pH 7 aqueous solutions. At pH <10 only those quinone units in contact with the carbon surface are electroactive. It was shown that anodic surface roughening increased the limited number of electroactive groups in the polymer film and gave more stable activity and narrower voltammetric peaks. Above pH 10 redox propagation through the layer is more rapid but the anionic product desorbs. This desorption was inhibited by cathodically cross-linking a layer of mixed polymers on a polyethyleneimine backboned polymer containing fluorenone units as well as anthraquinone units.     

Confinement effects on the electronic structure of M‐shell atoms: A study with explicitly correlated wave functions

The ground and some excited states of Na and Mg atoms confined at the center of a spherical box with impenetrable walls are studied. Variational wave functions including dynamic correlations and configuration mixing have been obtained. Level crossings induced by confinement have been analyzed in terms of the energy of the occupied orbitals of the M shell and the weight of the different configurations. Confinement effects on the correlation energy have been studied. The parameterized optimized effective potential and the variational Monte Carlo methods have been employed. A cut off‐factor has been included to account for the hard wall confinement.     

Anchored Ni-dimethylglyoxime complex on Fe3O4@SiO2 core/shell nanoparticles for the clean catalytical synthesis of dicoumarols

Ni-Dimethylglyoxime complex immobilized on functionalized Fe₃O₄ was synthesized by a post-grafting way and utilized as a novel, thermally stable, recoverable, and efficient for green synthesis of dicoumarols through reaction of 4-hydroxycoumarin with various aldehydes in excellent yields and higher rate. Fe₃O₄@SiO₂-silylcyclopropyl-dimethylglyoxime-Ni superparamagnetic nanoparticles (MNP_s) were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, vibrating sample magnetometer, and Brunauer–Emmett–Teller technique. This nanocatalyst could be conveniently recovered via the use of an external magnetic field and reused for subsequent reactions for at least 7 times without any remarkable change and decrease in catalytic activity.     

The effect of chiral dopant on the rewriting speed of optically driving liquid crystal display

ABSTRACT

Mixing liquid crystal with chiral dopant for increasing the response speed of optical driving liquid crystal display was investigated in this paper. It is demonstrated that by adding chiral dopant, rewriting time could be decreased from 30 s to 20 s with good repeatability. Without adding other steps in the process of making cells, this improvement is due to the stronger elastic energymaking LC molecules twist more easily.     

The effects of the potential and polarization time on the performance of ionic polymer metal composite actuators: a control of forward and reverse displacements

This paper focuses on the dependence of various waveforms of the potential on the displacement of Nafion‐platinum based IPMC actuators at 40 and 90% relative humidity (RH). In comparison with simpler square waveforms, a waveform that is being composed by inclusion of a rest potential of 0 V has given a longer displacement. This benefit was effective at lower humidity conditions. By a polarization, the actuators show three major displacement processes of maximum forward displacement, steady forward displacement, and maximum reverse displacement. Here, the dependence of the potential and polarization time on these displacements has been carefully examined. An increase in the forward displacement by the potential does not strongly affect a slower reverse relaxation. To give a suitable relaxation period before a polarity switching of the potential seems effective to release the internal stress of the actuator. An elevated drive potential has decreased in the bending speed apparently. Finally, it has been noted that the ‘recovery’ of the maximum displacement is possible if a suitable waveform is applied to the actuator. This recovery effect is more remarkable at higher dive potential. Copyright © 2007 John Wiley & Sons, Ltd.     

Phase morphology and mechanical properties of the electrospun polyoxymethylene/polyurethane blend fiber mats

Polyoxymethylene/thermoplastic polyurethane (POM/TPU) blends containing 10–30 wt % of TPU were electrospun using hexafluoroisopropanol as the solvent. The average fiber diameter increases with the increase in TPU content from 0.68 μm for neat POM fibers to 0.92 μm for POM/TPU 7:3 blend fibers due to the increase in solution viscosity. Core/sheath structure with the major component POM as the core and the minor component TPU as the sheath was observed by transmission electron microscopy and further confirmed by surface N contents of the blend fiber mats. The crystalline melting point and the degree of crystallinity of POM have no obvious change by coelectrospinning with TPU due to lack of interaction between POM and TPU as revealed by Fourier transform infrared spectroscopy. Tensile tests showed that the unusual high ductility of POM fiber mat could be further increased by coelectrospinning with 10 or 20 wt % TPU without significantly decreasing the stiffness and strength. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1853–1859, 2009     

Derivation of shell effects and magic numbers in metal clusters by the application of Strutinsky's method to the Clemenger–Nilsson and q‐deformed 3‐D harmonic oscillator models

Strutinsky's standard averaging method is applied to metal clusters described by two different potentials—Clemenger–Nilsson (CN) and q‐deformed 3‐D (Q3D) harmonic oscillator (HO). In addition, a new approximate fitting formula—of the liquid drop model type—is derived for the smooth part of the energy. The results obtained for the oscillating part of the energy (shell correction term) with the two cluster potentials through the two averaging methods are compared and discussed. It is found that with both CN and Q3D HO potentials the standard and approximate methods give similar results for clusters with a large number of particles, whereas for smaller clusters significant differences appear. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Synthesis of polymer particles possessing radical initiating sites on the surface by emulsion copolymerization and construction of core–shell structures by a photoinduced atom transfer radical polymerization approach

The crosslinked polystyrene particles possessing photofunctional N,N‐diethyldithiocarbamate groups on their surface were prepared by free‐radical emulsion copolymerization of a mixture of styrene, divinylbenzene and 4‐vinylbenzyl N,N‐diethyldithiocarbamate with redox system as an initiator under UV irradiation. In this copolymerization, the inimer 4‐vinylbenzyl N,N‐diethyldithiocarbamate acted the formation of hyperbranched structures by living radical photopolymerization. The particle sizes (number‐average particle diameter = 214–523 nm) were controlled by varying the feed amount of surfactant and size distributions were relatively narrow. Subsequently, core–shell particles were synthesized by photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by photofunctional polystyrene particles as a macroinitiator. Such core–shell particles were stabilized sterically by grafted chains in organic solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1771–1777, 2007