Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

Phase-Only Encryption and Single Path Decryption System Using Phase-Encoded Exclusive-OR Rules in Fourier Domain

A phase-only encryption scheme using phase-encoded exclusive-OR (XOR) rules in a Fourier plane and a single path decryption system are presented. To generate phase-only encrypted data, a zero-padded original image, multiplied by a random phase image, is Fourier transformed and its real-valued data is encrypted with key data by using phase-encoded XOR rules. Since the original information is encrypted on the Fourier plane, the proposed encryption is more tolerant to loss of key information by scratching or cutting than previous XOR encryption in a space domain. A decryption is simply performed based on 2-f setup with spatial filter by Fourier transform for multiplication phase-only encrypted data with phase-only key data. Due to single path architecture without a reference wave, the proposed system is resistant to mechanical vibrations and fluctuation. Numerical simulations have confirmed the validity of the proposed encryption scheme and simple decryption architecture.     

In‐line monitoring of UV photopolymerization with a quartz crystal resonator

An in‐line monitoring device using a quartz crystal resonator for thin film polymerization was proposed, and its performance has been evaluated by implementing in the UV polymerization of 2‐hydroxyethyl methacrylate with a photoinitiator of 1‐chloroanthraquinone. Because the variation of resonant resistance of the resonator is proportional to the square root of viscosity change that is closely related to the polymerization degree, the resistance can be used as a measure of the polymerization degree. The resistance measurements were compared with the outcome of instrumental analyses of polymerization degree using an FTIR spectrometer and a gel permeation chromatograph. The experimental results showed that the resistance measurements were consistent with the experimental outcome of the instrumental analyses, and this indicates the effectiveness of the proposed device. Owing to the simplicity and availability of the resonator system, its wide utilization in the monitoring of a variety of film polymerization processes, including photoresistor application, is expected. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2428–2439, 2006     

Effect of the pore surface modification of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes

We have investigated the effect of the surface state and surface treatment of the pores of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes. Shirasu porous glass (SPG) was used as the inorganic substrate, and methyl acrylate was used as the grafting monomer. The grafting rate increased as the density of silanol on the SPG substrate increased. This result suggests that radicals are generated mainly at the silanol groups on the pore surface by plasma irradiation. The SPG substrates were treated with silane coupling agents used to control the mass of organic material bonded to the pore surface. The thickness of the grafted layer became thinner as the mass of organic material bonded to the pore surface of SPG increased. This decrease in the thickness of the grafted layer could be explained by the decrease in the penetration depth of vacuum ultraviolet rays contained in plasma having a wavelength of less than 160 nm that generated radicals in the pores of the substrate. The thickness of the grafted layer inside the SPG substrates could be controlled through the control of the mass of organic material bonded to the pore surface of the SPG substrate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 846–856, 2006     

Local chemical distribution and electronic structure of Ge1−xTx DMS single crystals (T=Cr,Mn, Fe)

The spatial concentration distribution and local electronic structure of ferromagnetic Ge_1−xT_x (T=Cr, Mn, Fe) DMS single crystals have been investigated by using scanning photoelectron microscopy (SPEM), X-ray absorption spectroscopy (XAS), and photoemission spectroscopy (PES). It is found that doped T ions in Ge_1−xT_x crystals are chemically phase-separated, suggesting that the observed ferromagnetism arises from the phase-separated T-rich phases in Ge_1−xT_x.     

Partial molal heat capacities of aqueous tetraalkylammonium bromides as functions of temperature

Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate for aqueous Bu₄NBr over a similar temperature range. These data, along with similar data for Me₄NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions.     

Determination of vibrational level spacings of van der waals molecules from the Lennard-Jones potential

An approximate expression for the eigenvalues for van der Waals molecules by use of the Lennard-Jones (12-6) potential in the WKB approximation is presented. The expression is applied to the rare gas molecules. Ar₂, Kr₂, and Xe₂ by fitting the potential function to the observed potential parameters. Calculated results of vibrational energy spacings for these molecules agree well with the experiment and other calculations which are based on numerical integration of the Schrödinger equation. For Xe₂, the energy spacing expression is used to determine the thermodynamic functions of the van der Waals bond.     

Idealized collision model for reactive scattering: Energy dependence of the cross section for CH3I + K → CH3 + Kl

The energy and temperature dependence of the reaction cross section for CH₃I + K → CH₃ + KI have been calculated using the reaction probability obtained from the idealized model of collinear, impulsive interaction between the atoms K and I and between the group CH₃ and I. Calculated values of the cross section agree very closely with the postmaximum data by Gersh and Berastein.