Permeability,permselectivity, and penetrant‐induced plasticization in fluorinated polyimides studied by positron lifetime measurements

The ortho‐positronium (o‐Ps) lifetime τ₃ and its intensity I₃ in various fluorinated polyimides were determined by the positron annihilation technique and were studied with the spin–lattice relaxation time T₁ and the propylene permeability, solubility, diffusivity, and permselectivity for propylene/propane in them. τ₃, I₃, and the distribution of τ₃ changed when the bulky moieties in the polyimides were changed. The polyimides, having both large τ₃ and I₃ values, exhibited a short T₁ and a high permeability with a low permselectivity. The propylene permeability and diffusivity were exponentially correlated with the product of I₃ and the average free‐volume hole size estimated from τ₃. In highly plasticized states induced by the sorption of propylene, the permeability increased with the propylene pressure in excellent agreement with the change in the free‐volume hole properties probed by o‐Ps. The large and broad distribution of the free‐volume holes and increased local chain mobility for the 2,2‐bis(3,4‐decarboxyphenyl) hexafluoropropane dianhydride‐based polyimides are thought to be important physical properties for promoting penetrant‐induced plasticization. These results suggest that o‐Ps is a powerful probe of not only the free‐volume holes but also the corresponding permeation mechanism and penetrant‐induced plasticization phenomenon. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 308–318, 2003     

Spectral Analysis of Powers of the Operator (Vf)(x)=q(x)∫0 xw(t)f(t),dt

Mathematical Notes -     

Determination of the rheological behavior of epoxy–amine thermosets by dynamic mechanical analysis: Isothermal methods versus nonisothermal methods

The reticulation process of an epoxy resin using an amine as a cure agent was studied at different temperatures and concentrations of the cure agent with dynamic mechanical thermal analysis. The study was performed under both isothermal and nonisothermal conditions, and a temperature–time–transformation diagram was obtained. The measurements from the two modes gave similar results, although the nonisothermal mode required fewer experiments. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1965–1977, 2003     

四个麦芽品质性状的杂种优势和相关分析

本文对四个主要麦芽品质性状—a一淀粉酶活力、麦芽汁粘度、麦芽汁色度和搪化力进行了杂种优势和相关分析.(1)相对优势结果表明，在84个组合次中，呈正向优势的46个，占54.76男，负向优势34个，占40.48男，无显性4个，占4.75男;(2)四个品质性状的中亲优势平均值分别为一6.117、一9.965 40.452和一。.545s a-淀粉酶活力和糖化力的超高亲优势分别为一14.578和一8.201,麦芽汁粘度和色度的超低亲优势分别为5.442和70.455.四个性状杂种优势的变异系数均很大.(3)麦芽汁色度的F，对MP的回归系数(B)和相关系数(r)均达显著水平，分别为。..43和0.50，麦芽汁粘度的相关系数达显著水平，为一。.45,其余均未达显著水平，(4)除麦芽汁色度性状外，另三个性状的中亲优势、超亲优势和特殊配合力的相关均达显著或极显著水平.(5)四个麦芽品质性状间的相关结果表明，仅有a-淀粉酶活力和麦芽汁粘度间呈极显著负相关(r=一0.56').最后，文章根据实验结果，就啤酒大麦麦芽品质改良的遗传育种及其杂种优势应用进行了初步讨论.     

光致折射效应中空间电荷场建立过程的研究

本文推导了包含自衍射及非线性吸收影响、用以描述空间电荷场建立过程的微分方程组,阐明了周期性的空间电荷场与光强干涉条纹之间的相位差在建立过程中所起的作用,并推导了描述条纹倾斜和弯曲的微分方程。通过数值计算找到了硅酸铋(BSO)晶体中能量转移的规律,讨论了材料特性对过程快慢的影响,提出了用CW激光来探讨瞬态过程快慢的可能性。     

HL—1装置SiC涂层辐照实验的表面分析

本文应用表面分析技术研究HL-1装置中SiC涂层的等离子体辐照性能。结果表明,SiC材料应用于孔栏和壁涂层有利于减少杂质和提高等离子体品质。     

A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007