Generation of highly stable amidate anion in anionic polymerization of 3‐(triethylsilyl)propyl isocyanate

To study living anionic polymerization, 3‐(triethylsilyl)propyl isocyanate (TEtSPI) monomer was synthesized by hydrosilylation of allylamine with triethylsilane and treatment of the resulting amine with triphosgene. The polymerization of TEtSPI was performed with sodium naphthalenide (Na‐Naph) as an initiator and in the absence and presence of sodium tetraphenylborate (NaBPh₄) as an additive in tetrahydrofuran (THF) at ?78 and at ?98 °C. A highly stabilized amidate anion for living polymerization of isocyanates was generated for the first time with the combined effect of the bulky substituent and the shielding action of the additive NaBPh₄, extending the living character at least up to 120 min at ?98 °C. Even the anion could exist at ?78 °C for 10 min. A block copolymer, poly(n‐hexyl isocyanate)‐b‐poly[(3‐triethylsilyl)propyl isocyanate]‐b‐poly(n‐hexyl isocyanate), was synthesized with quantitative yields and controlled molecular weights via living anionic polymerization in THF at ?78 °C for TEtSPI and ?98 °C for n‐hexyl isocyanate, respectively, with Na‐Naph with three times of NaBPh₄ as a common ion salt. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 933–940, 2004     

Intramolecular energy transferable (2,2‐diphenylvinyl)phenyl substituted poly(p‐phenylenevinylene) derivative with efficient photoluminescence and electroluminescence

A poly(p‐phenylenevinylene) (PPV) derivative containing a bulky (2,2‐diphenylvinyl)phenyl group in the side chain, EHDVP‐PPV, was synthesized by Gilch route. The reduced tolane‐bisbenzyl (TBB) defects, as well as the structure of the polymer, was confirmed by various spectroscopic methods. The intramolecular energy transfer from the (2,2‐diphenylvinyl)phenyl side group to the PPV backbone was studied by UV‐vis and photoluminescence (PL) of the obtained polymer and model compound. The polymer film showed maximum absorption and emission peaks at 454 and 546 nm, respectively, and high PL efficiency of 57%. A yellow electroluminescence (λ_max = 548 nm) was obtained with intensities of 6479 cd/m² when the light‐emitting diodes of ITO/PEDOT/EHDVP‐PPV/LiF/Al were fabricated. The maximum power efficiency of the devices was 0.729 lm/W with a turn‐on voltage of 3.6 V. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5636–5646, 2004     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Analytic Feynman integrals of transforms of variation of cylinder type functions over Wiener paths in abstract Wiener space

In this paper, we evaluate various analytic Feynman integrals of first variation, conditional first variation, Fourier-Feynman transform and conditional Fourier-Feynman transform of cylinder type functions defined over Wiener paths in abstract Wiener space. We also derive the analytic Feynman integral of the conditional Fourier-Feynman transform for the product of the cylinder type functions which define the functions in a Banach algebra introduced by Yoo, with n linear factors.     

Superfield form of discrete gauge states in ĉ = 1 2d supergravity

A general formula for the discrete states (NeveuSchwarz sector) in N = 1 2D super-Liouville theory is written down in the world-sheet supersymmetric form. We then derive a set of gauge states at the discrete momenta. These discrete gauge states are shown to carry the ω_∞ charges and serve as the symmetry parameters in the old covariant quantization of the theory.     

Photoswitching of holographic polymer-dispersed liquid crystals doped with chiral dopant

Chiral dopants were added to the formulation of holographic polymer-dispersed liquid crystals and the effects studied in terms of grating formation dynamics, morphology, diffraction efficiency, contrast ratio and electro-optical properties of the films. A gradual increase of real-time diffraction efficiency, decrease of droplet size and increase of diffraction efficiency of the composite film were obtained with the addition and increasing content of chiral dopant, due to the increased viscosity of the liquid crystal (LC) doped with the chiral dopant leading to decreased droplet coalescence. The contrast ratio decreased with increasing content of chiral dopant due to the difficult orientation of LC molecules caused by the formation of a helical structure. Addition of a small amount of the chiral dopant increased the driving voltage slightly, whereas the decay time is decreased significantly as a result of the high twisting of the helical structure.     

Phase transformation of Ni-B, Ni-P diffusion barrier deposited electrolessly on Cu interconnect

In this paper, we report that the phase transformation of Ni-B, Ni-P diffusion barriers deposited electrolessly on Cu, for the reason that the Ni-P layer is a more effective diffusion barrier than the Ni-B layer. The Ni₃B crystallized was decomposed to Ni and B₂O₃ above 400 °C and the Ni₃P crystallized was decomposed to Ni and P₂O₅ above 600 °C respectively in Ar atmosphere. Also, the Ni₃B was decomposed to Ni and free B above 400 °C and the Ni₃P was decomposed to Ni and free P above 600 °C respectively in H₂ atmosphere. The decomposed Ni formed a solid solution with Cu. The Cu diffusion occurred above 400 °C for Ni-B layer and above 600 °C for Ni-P layer, respectively. Because the decomposition temperature of Ni-P layer is about 200 °C higher than that of Ni-B layer, the Ni-P layer is a more effective barrier for Cu than the Ni-B layer.     

Temperature effect on deposition rate of silicon nitride films

Temperature effects on deposition rate of silicon nitride films were characterized by building a neural network prediction model. The silicon nitride films were deposited by using a plasma enhanced chemical vapor deposition system and process parameter effects were systematically characterized by 2⁶⁻¹ fractional factorial experiment. The process parameters involved include a radio frequency power, pressure, temperature, SiH₄, N₂, and NH₃ flow rates. The prediction performance of generalized regression neural network was drastically improved by optimizing multi-valued training factors using a genetic algorithm. Several 3D plots were generated to investigate parameter effects at various temperatures. Predicted variations were experimentally validated. The temperature effect on the deposition rate was a complex function of parameters but N₂ flow rate. Larger decreases in the deposition rate with the temperature were only noticed at lower SiH₄ (or higher NH₃) flow rates. Typical effects of SiH₄ or NH₃ flow rate were only observed at higher or lower temperatures. A comparison with the refractive index model facilitated a selective choice of either SiH₄ or NH₃ for process optimization.