Numerical simulation of thermal and mass transport during Czochralski crystal growth of sapphire

The thermal and flow transport in an inductively heated Czochralski crystal growth furnace during a crystal growth process is investigated numerically. The temperature and flow fields inside the furnace, coupled with the heat generation in the iridium crucible induced by the electromagnetic field generated by the RF coil, are computed. The results indicate that for an RF coil fixed in position during the growth process, although the maximum value of the magnetic, temperature and velocity fields decrease, the convexity of the crystal‐melt interface increases for longer crystal growth lengths. The convexity of the crystal‐melt interface and the power consumption can be reduced by adjusting the relative position between the crucible and the induction coil during growth. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Proton transportation in an organic–inorganic hybrid polymer electrolyte based on a polysiloxane/poly(allylamine) network

A new class of proton‐conducting polymer was developed via the sol–gel process from amino‐containing organic–inorganic hybrids by the treatment of poly(allylamine) with 3‐glycidoxypropyltrimethoxysilane doped with ortho‐phosphoric acid. The polymer matrix contains many hydrophilic sites and consists of a double‐crosslinked framework of polysiloxane and amine/epoxide. Differential scanning calorimetry results suggest that hydrogen bonding or electrostatic forces are present between H₃PO₄ and the amine nitrogen, resulting in an increase in the glass‐transition temperature of the poly(allylamine) chain with an increasing P/N ratio. The ³¹P magic‐angle spinning NMR spectra indicate that three types of phosphate species are involved in the proton conduction, and the motional freedom of H₃PO₄ is increased with increasing P/N ratios. The conductivity above 80 °C does not drop off but increases instead. Under a dry atmosphere, a high conductivity of 10^?3 S/cm at temperatures up to 130 °C has been achieved. The maximum activation energy obtained at P/N = 0.5 suggests that a transition of proton‐conducting behavior exits between Grotthus‐ and vehicle‐type mechanisms. The dependence of conductivity on relative humidity (RH) above 50% is smaller for H₃PO₄‐doped membranes compared with H₃PO₄‐free ones. These hybrid polymers have characteristics of low water content (23 wt %) and high conductivity (10^?2 S/cm at 95% RH), making them promising candidates as electrolytes for fuel cells. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3359–3367, 2005     

Influence of organoclay dispersed state of poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate)/organoclay nanocomposites on their characteristics

This work prepared poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate) (PETG)/organoclay nanocomposites via a melt intercalation process and investigated the influences of organoclay aspect ratio and organoclay content on the dispersed state, mechanical, thermal, gas barrier, and heat recovery properties of PETG/organoclay nanocomposites. X‐ray diffraction (XRD) and transmission electron microscopic analyses showed that the organoclay dispersed in the polymer matrix with intercalation in the nanometer scale range. Differential scanning calorimetry (DSC) analysis demonstrated that all of the obtained nanocomposites were amorphous, indicating that the addition of organoclay did not affect the amorphous nature of PETG. The gas barrier properties of the nanocomposites improved with organoclay content and the properties were also affected by the organoclay aspect ratio. Water vapor and oxygen transmission rates (OTRs) of PETG/organoclay nanocomposites containing 3 phr Cloisite 15A, and 3 phr modified polymer grade Na‐montmorillonites (MPGN) were the lowest among the samples tested, and were 41.7 and 44.3%, respectively, of those of neat PETG. Similar organoclay content‐ and aspect ratio‐related effects were observed in the mechanical and heat recovery properties of the tested nanocomposites. Copyright © 2010 John Wiley & Sons, Ltd.     

Electrostatic Charge Measurement and Charge Neutralization of Fine Aerosol Particles during the Generation Process

An aerosol charge analyzer has been constructed to measure the charge distribution of NaCl particles generated in the laboratory. A radioactive electrostatic charge neutralizer utilizing Po‐210 was used to neutralize the electrostatic charge of the particles. The atomization technique was used to generate NaCl particles with diameters of 0.2 to 0.8 μm, while the evaporation and condensation method was adopted to generate particles of 0.01 to 0.2 μm in diameter. The experimental data demonstrates that the absolute average particle charge depends on the particle diameter, and is higher than that calculated by the Boltzmann charge equilibrium for particles within the range of 0.2 to 0.8 μm. The charge increases with decreasing NaCl concentration. When these particles are neutralized using the Po‐210 neutralizer, it is found that the electrostatic charge reaches the Boltzmann charge equilibrium. For 0.01 to 0.2 μm NaCl particles generated using the evaporation and condensation method, test results show that the absolute average particle charge is higher than that calculated by the Boltzmann charge equilibrium for particles larger than 0.03 to 0.05 μm in diameter, while it is lower than that predicted by the Fuchs theory [1], for particles smaller than 0.03 to 0.05 μm. However, after charge neutralization, particles with diameter above 0.05 μm reach the Boltzmann charge equilibrium condition, and the charges for particles with diameters of 0.010 to 0.05 μm, agree well with Fuchs' theory.     

The Transition State of Free Radical SH2′ Reaction of Allyl Chloride with Organomercurial Study by Inverse Secondary α‐Deuterium Kinetic Isotope Effect

The concerted mechanism of free radical S_H2′ reaction of 2‐substituted allyl chloride was suggested again by inverse secondary α‐deuterium isotope effect. The transition state of free radical S_H2′ reaction of allyl chlorides seems to be symmetrical and is not as early as that of a free radical addition reaction.     

Single‐Electron Transfer between CuX2 and Thiols Determined by Extended X‐Ray Absorption Fine Structure Analysis: Application in Markovnikov‐Type Hydrothiolation of Styrenes

Transition‐metal mediated C?S bond formation using thiol compounds has been widely used in recent years. However, there has been less focus on the interaction between the metal and thiol compounds. In this work, we have successfully evidenced the single‐electron transfer between CuX₂ and thiophenol utilizing EXAFS. The fitting EXAFS results reveal that two halide anions are coordinated with the Cu^I center, whereas no sulfur atom is observed in the first coordination sphere. This Cu^I ate complex serves as the key intermediate for the proton transfer in the application of Markovnikov‐type hydrothiolation reactions.     

Effect of post treatment on the photorefractive properties of Ru‐doped lithium niobate

The effect of post treatment on the photorefractive properties of Ru‐doped lithium niobate was studied. The absorption spectra examination of Ru‐doped LiNbO₃ crystals with different post treatments showed that the absorption coefficient at 530 nm increased after the reduced treatment was employed and the absorption edge of the reduced crystal shifted towards the infrared band. On the contrary, the trend reversed after the oxidized treatment was employed. In addition, the photorefractive properties were investigated with the two‐beam coupling method conducted via a 532 nm solid state laser. It was found that the oxidized Ru:LiNbO₃ had smaller exponential gain coefficient and diffraction efficiency because the charges in the shallow level were exchanged to the deep level. On the other hand, the reduced Ru:LiNbO₃ crystals had larger exponential gain coefficient and diffraction efficiency due to the increase of the Ru³⁺ which existed in the shallow level. The response times of both oxidized and reduced Ru:LiNbO₃ were longer than those of the as‐grown ones. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Solid polymer electrolytes. VI. Microstructure of organic–inorganic hybrid networks composed of 3‐glycidoxypropyltrimethoxysilane and LiClO4 and affected by different synthetic routes

Hybrid organic–inorganic materials derived from 3‐glycidoxypropyltrimethoxylsilane were prepared via two different synthetic routes: (1) the HCl‐catalyzed sol–gel approach of silane followed by the lithium perchlorate (LiClO₄)/HCl‐catalyzed opening of epoxide and (2) the simultaneous gelation of tin/LiClO₄‐catalyzed silane/epoxide groups. LiClO₄ catalyzed the epoxide polymerization, and its effects on the structures of these hybrid materials were studied by NMR. The structure of the inorganic side was probed by solid‐state ²⁹Si NMR spectroscopy, and the characterizations of the organic side and the chemical processes involved in the different synthetic routes were performed with solid‐state cross‐polarity/magic‐angle‐spinning ¹³C NMR. The different synthetic routes significantly affected the polymerization behaviors of the organic and inorganic sides in the presence of LiClO₄. A larger amount of LiClO₄ promoted the opening of epoxide and led to the formation of longer poly(ethylene oxide) chains via the HCl‐catalyzed sol–gel approach, whereas in the case of the tin‐catalyzed approach, the faster polymerization of the inorganic side hindered the growth of the organic network. The addition of LiClO₄ was proven to be without crystalline salt present in the hybrid networks by wide‐angle X‐ray powder diffraction. Also, the interactions between the ions and hybrid host, examined with Fourier transform infrared and ⁷Li proton‐decoupled magic‐angle‐spinning NMR, further demonstrated that extensive ion aggregation existed in these hybrid materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 151–161, 2004