Wide‐angle X‐ray diffraction and differential scanning calorimetry study of the crystallization of poly(ethylene naphthalate), poly(butylene naphthalate), and their copolymers

The crystallization behavior of a series of poly(ethylene‐co‐butylene naphthalate) (PEBN) random copolymers was studied. Wide‐angle X‐ray diffraction (WAXD) patterns showed that the crystallization of these copolymers could occur over the entire range of compositions. This resulted in the formation of poly(ethylene naphthalate) or poly(butylene naphthalate) crystals, depending on the composition of the copolymers. Sharp diffraction peaks were observed, except for 50/50 PEBN. Eutectic behavior was also observed. This showed isodimorphic cocrystallization of the PEBN copolymers. The variation of the enthalpy of fusion of the copolymers with the composition was estimated. The isothermal and nonisothermal crystallization kinetics were studied. The crystallization rates were found to decrease as the comonomer unit content increased. The tensile properties were also measured and were found to decrease as the butylene naphthalate content of the copolymers increased. For initially amorphous specimens, orientation was proved by WAXD patterns after drawing, but no crystalline reflections were observed. However, the fast crystallization of drawn specimens occurred when they were heated above the glass‐transition temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 843–860, 2004     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 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     

Photodegradation of a herbicide derivative, 2,4-dichlorophenoxy acetic acid in aqueous suspensions of titanium dioxide

The photocatalytic degradation of a herbicide derivative, 2,4-dichlorophenoxy acetic acid (2,4-D, 1), has been investigated in aqueous suspensions of titanium dioxide. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic analysis and decrease in Total Organic Carbon (TOC) content as a function of irradiation time in the presence of UV light source. The degradation kinetics was investigated under a variety of conditions, such as different types of TiO₂, pH, catalyst and substrate concentrations. Higher photonic efficiencies were observed with Degussa P25 as compared with other photocatalysts. The degradation products were analysed by GC-MS and probable pathways for the formation of different products were proposed.     

类钙钛矿化合物Ca(Mn2 Cu1)Mn4 O12的磁性与磁电阻效应

利用固相反应法制备了名义成分为Ca(Mn2 Cu1 )Mn4 O1 2 的类钙钛矿锰氧化物 .x射线衍射表明 ,为了获得较为致密的样品和减小杂相含量 ,可以采用高温烧结再在 10 73K长时间空气中退火的制备方法 .样品在低温下同时存在铁磁相和反铁磁相 ,由于反铁磁相的存在导致样品在 4 5K时的磁化强度显著降低 ,并在 8T的高磁场下仍未达到饱和 .样品呈半导体导电性质 ,在 85K和 6T磁场下磁电阻比的最大值可达 - 4 6 % .     

Cr3+：MgAl2O4晶体EPR参量及其电子精细光谱的研究

考虑了SS(Spin-Spin)作用和SOO(Spin-Other-Orbit)作用，采用完全对角化方法，结合自旋Hamiltonian理论，研究了Cr³⁺∶MgAl₂O₄晶体EPR参量及其吸收光谱，理论与实验符合甚好. 在此基础上，进一步研究了⁴A₂(3d³)离子EPR参量的微观起源. 研究表明，EPR参量起源于四种微观机制：(1) SO(Spin-Orbit) 耦合机制；(2) SS耦合机制；(3)SOO耦合机制；(4) SO～SS～SOO总联合作用机制. 在这些机制中，SO机制是最主要的.     

高压增氧T′相R_2CuO_(4+δ)(R=Nd～Tm)低温磁性研究

T′相R2CuO4稀土铜氧化合物由于尺度效应而产生弱铁磁性行为已经被人们关注,报导了通过高温高氧压(6GPa,1000℃)合成稀土T′相R2CuO4(R=Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er和Tm)化合物的结构和磁学性能。磁化率曲线显示,在低温下所有的高压增氧R2CuO4样品都出现新的低温弱铁磁性反常行为,转变温度在28K附近。新的低温弱铁磁性行为是由于CuO2面上微量氧空穴的掺入,使处于反铁磁有序CuO2面形成局域化的铁磁性团簇造成。实验证明新发现的低温弱铁磁性行为与尺度效应产生弱铁磁性行为属于完全不同的物理机制。结果还预示T′相R2CuO4稀土铜氧化合物很难通过空穴掺杂而实现超导。     

闪烁光纤在γ射线辐照下部分特性的蒙特卡罗模拟

 闪烁光纤在射线成像方面的应用越来越广泛。为了进一步了解闪烁光纤在射线辐照下的基本特性，基于蒙特卡罗方法，利用计算机模拟分析了γ射线在闪烁光纤中的好事例率与光纤长度及射线能量的关系，能量沉积效率与光纤长度及射线能量的关系。此项工作对于闪烁光纤阵列在射线成像，剂量场测量等方面的研究很有价值。     

Syntheses, Characterization and Crystal Structures of Two-dimensional 4,4''-Bipyridyl Lead Halides,PbI2 (4,4'' -bpy) and PbBr2 (4,4'' -bpy)

Two-dimensional 4,4-bipyridyllead halides, PbI2 (4,4'-bpy) (1) and PbBr2 (4,4'-bpy) (2), were synthesized. The structures were determined by means of X-ray single crystal diffraction.The structure shows a distorted octahedral configuration with six-coordinated central lead atoms. In crystals 1 and 2, the molecules are packed in a two-dimensional network structure through bridging halide atoms and 4,4'-bipyridine ligands between the adjacent lead atoms.     

Synthesis under Micromave Irradition and Crystal Structure of 4''-Acetylbenzo-15 -crown-5thiosemicarbazone

The title compound is a bifunctional receptors including a thiourea group and a crown ether ring. Due to many possible potentials as a new class of reagents for membrane transports,ion-selective electrodes as well as reaction catalysts, the design and synthesis of bifunctional receptors for simultaneous binding of cations and anions is of ongoning interest in srprarnolecular chemistry1-5. In bifunctional receptors, the binding sites for anions and cations are covalently linked so as to exhibit allosteric or cooperative complexation where the binding affinity for anions(cations)is modified as a result of the cation(anion) complexation.Literature[6] reported that the ability of the thiourea group to bind anions is significantly enhanced when Na+ is bound to the crown moiety. To date, however only a few receptors of this class have been reported.6-8In this paper, we report an improved procedure under microwave irradiation that gives higher yields of title compound and needs fewer reaction times than traditional method.The structure of this compound was determined by IR ,element analysis and X-ray analysis.Scheme 1 The reaction equationThe crystal belongs to triclinic crystal system, P-1 space group, a=0.9547(0)nm, b=1.3637(3)nm,c=1.6029(3)nm, α =75.33(3) , β =83.62(3) , γ =70.99(3) ,Z=4,Dc=1.335g/cm3,F(000)=816,R1= 0.0557 ,wR2=0.1281. It is assembled into a three-dimensionalsupramolecule by intermolecular hydrogen bonds.