Effect of ageing atmospheres on the changes in surface free energies of oxygen plasma-treated polyethylene films

The changes in the surface properties of oxygen plasma-treated polyethylene films during ageing in various atmospheres (water, dry nitrogen gas, and hexane) were studied from the viewpoint of the interaction of the surface functional groups formed on the films and the ageing media. The XPS (x-ray photoelectron spectroscopy) and the SSIMS (static secondary ion mass spectrometry) spectra indicated the formation of polar groups containing oxygen such as C=O on the film surface. The changes in the critical surface tension (_C) of the film with ageing time were largely affected by the ageing atmospheres: the _C value of the film aged in water increased, and those of the films aged in nitrogen gas and hexane decreased with an increase in ageing time. These different tendencies among the ageing media could be understood reasonably with examining the surface free energy ratios (the total energy, _S ^tot , the dispersion force component, _S ^d / _S ^tot , the polar component, _S ^p / _S ^tot , the hydrogen bonding component, _S ^h / _S ^tot ) of the films. The ageing in water of which _L is large gave the films with higher _S ^p / _S ^tot values, suggeting that the overturn and/or the orientation of the polar groups toward the water phase occurred so as to minimize the discrepancy of the surface free energy between the polymer surface and water. On the other hand, the ageing in nitrogen gas and hexane media of which _L are small gave the films with lower _S ^p / _S ^tot and _S ^h / _S ^tot values, suggesting the overturn and/or the orientation of the polar groups into the bulk polymer.     

A New Higher Order Shear Deformation Model for Static Behavior of Functionally Graded Plates

In this paper, a new displacement based high-order shear deformation theory is introduced for the static response of functionally graded plate. Unlike any other theory, the number of unknown functions involved is only four, as against five in case of other shear deformation theories. The theory presented is variationally consistent, has strong similarity with classical plate theory in many aspects, does not require shear correction factor, and gives rise to transverse shear stress variation such that the transverse shear stresses vary parabolically across the thickness satisfying shear stress free surface conditions. The mechanical properties of the plate are assumed to vary continuously in the thickness direction by a simple power-law distribution in terms of the volume fractions of the constituents. Numerical illustrations concerned flexural behavior of FG plates with Metal-Ceramic composition. Parametric studies are performed for varying ceramic volume fraction, volume fraction profiles, aspect ratios and length to thickness ratios. The validity of the present theory is investigated by comparing some of the present results with those of the classical, the first-order and the other higher-order theories. It can be concluded that the proposed theory is accurate and simple in solving the static behavior of functionally graded plates.     

Inequalities for a Simplex and an Interior Point

We establish some inequalities for the inradius, circumradius and distances between an interior point and facets of an n-simplex, and prove a recursion inequality for the radii of the circumscribed spheres of an n-simplex and its facets.     

Intramolecular Dynamics and Molecular Structure of Europium(III) Chelate Complexes with Crown Ethers as Studied by NMR Spectroscopy

Earlier the intramolecular inversion of the 18-crown-6 molecules was found in the complex ion pairs [Ln(ptfa)₂ (18-crown-6)]⁺ [Ln(ptfa)₄]⁻ (H₂O)₄ where Ln = La(1), Ce (2), Pr (3), Nd (4), and ptfa is 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione. In this work the peculiarities of the molecular structure and dynamics were studied for [Eu(ptfa)₂ (18-crown-6)]⁺ [Eu(ptfa)₄]⁻ (H₂O)₄ (5) by NMR spectroscopy techniques. Through VT-NMR spectra analysis the temperature dependence was obtained for the rate constant. The free energy ΔG^‡(320) of 18-crown-6 ring inversion activation was found to be 65 ± 5 kJ mol⁻¹ for 5 in CDCl₃. This result is comparable with the earlier data [S.P. Babailov and D.A. Mainichev: J. Inclusion Phenom. Macrocyclic Chem. 43, 187–193 (2002)] for complexes 2, 3, 4 in deuterated toluene (ΔG^‡(320)=65 ± 9, 64 ± 9, 64 ± 9 kJ mol⁻¹ respectively). It was found by relaxation NMR spectroscopy that the effective distance between Ln and protons of the crown molecule is 4.5 ± 0.2 Å. The analysis of structural parameters testifies that the crown ether and chelated anions are in the first coordination sphere of a Ln cation. Obtained geometrical parameters show that the complex cations of Eu, Ce and Pr have similar spatial structures.This revised version was published online in July 2005 with a corrected issue number.     

柱前衍生-反相高效液相色谱法测定不同方法煮制的猪肉及其汤汁中的游离氨基酸

建立了反相高效液相色谱(RP-HPLC)分离检测用不同方法煮制的猪肉及其汤汁中17种游离氨基酸的方法.样品经6-氨基喹啉基-N-羟基琥珀酰亚氨基甲酸酯(AQC)柱前衍生后,采用Nova- PakTMC18色谱柱分离,以AccQ·Tag Eluent A稀释液、乙腈和超纯水为流动相,梯度洗脱,检测波长为248 nm,在4...     

基于宽度可调节的线缺陷平板型光子晶体的空气槽微腔

研究了一种空气槽光子晶体微腔,这种腔是由在平板型光子晶体上引入一条宽度可以调节的线缺陷空气槽形成的.腔模的电场被强烈局限在空气槽中,由于介电常量的不连续性,电场得到很大的提高,同时模体积被大大地降低.数值模拟与分析了微腔的能带结构和场分布,考虑到腔模的谐振频率和对称性,发现一阶偶膜同时具有较高的品质因子和较小的模体积;应用有限时域差分法,得到腔模的品质因子可以高达10⁶,模体积仅为0.02(λ/n)³.计算了一阶偶模谐振波长随空气槽宽度以及空气孔半径的变化,发现随着宽度的增加,波长越来越短.而随着空气孔半径的增加,波长近似线性地减小;当空气孔半径为170 nm时,可以获得最高的腔品质因子.     

A Practical Knoevenagel Condensation Catalyzed by PEG400 and Anhydrous K2CO3 Without Solvent

Abstract

Knoevenagel condensation of aromatic aldehydes with active methylene compounds under solvent‐free conditions to synthesize arylidene compounds in good to excellent yields using powdered anhydrous K₂CO₃ and PEG400 as catalysts has been described.     

"LIVING" FREE RADICAL SYNTHESIS OF NOVEL RODCOIL DIBLOCK COPOLYMERS WITH POLYSTYRENE AND MESOGEN-JACKETED LIQUID CRYSTAL POLYMER SEGMENTS*

The synthesis of rod-coil diblock copolymers was achieved for the firsttime by TEMPO-mediated "living" free radical polymerization of styrene and 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene(MPCS). The block architecture of the two diblockcopolymers thus prepared, MPCS-b-St(5400/2400) and MPCS-b-St(10800/8700), was con-firmed by GPC, DSC studies and the formation of multimolecular micelles.     

Initiation mechanisms in copolymerization: Reaction of t-butoxyl radicals with co-monomers ethyl vinyl ether and methyl methacrylate

The radical trapping technique employing 1,1,3,3-tetramethyl-1,3-dihydro-1H-isoindol-2-yloxyl as a scavenger has been used to investigate the reaction of t-butoxyl radicals with mixtures of ethyl vinyl ether and methyl methacrylate. The range of identified products includes those from both addition and hydrogen abstraction with both monomers, head addition with ethyl vinyl ether, and some second monomer addition products. Relative rate constants have been obtained for various pairs of constituent reactions. t-Butoxyl radicals add to ethyl vinyl ether one to two times faster than to methyl methacrylate, depending on which monomer is in excess. The ratio is less than 1 in nonolefinic solvents and as high as 6 in t-butanol. This solvent effect is thought to be due to the radicals complexing to either methyl methacrylate or t-butanol (H-bonding), thereby increasing its electrophilic character. © 1997 John Wiley & Sons, Inc.     

PAN预氧丝环化程度的定量表征

应用恒温定长方法制备聚丙烯腈(PAN)预氧丝, 并测量该预氧丝长周期多层结构的小角X射线衍射谱. 解析图谱发现, 经不同预氧化时间所得预氧丝的长周期L均为11.7 nm; 当预氧时间从20 min增加到210 min, 预氧丝中环化结构相的体积分数X0/L从7.9％增加到86.5％. 而应用广角X射线衍射法测得同批的预氧丝试样环化指数AI值则小很多. 因此, 用X0/L定量表征预氧丝环化程度更为严格准确.