Rotational Motion of a Solute Molecule in a Highly Viscous Liquid Studied byC NMR: 1,3-Dibromoadamantane in Polymeric Chlorotrifluoroethene

The viscosity-dependent retarding effect of a polymeric solvent on the rotation of small solute molecules is investigated by¹³C NMR relaxation measurements. It is found that the relaxation data of 1,3-dibromoadamantane in highly viscous polymeric chlorotrifluoroethene can be explained neither by isotropic nor by realistic anisotropic tumbling in a single environment. The experimental data are rationalized in terms of fast exchange between at least two environments with correlation times differing by up to two orders of magnitude. The study shows that a uniform retardation of molecular tumbling by a polymeric solvent, desirable for shifting the NMR observation window in studies of intramolecular mobility, is not always feasible.     

Dimensionally and thermally stable polymer,containing disordered graphitic structure and adamantane

In an attempt to develop a low‐k interlayer dielectric, adamantane‐diphenyldiethynyl moiety containing oligomer is prepared. Oligomerization of 1,3,5,7‐tetrakis[3/4‐ethynylphenyl]adamantane ( 4 ) is accomplished by a Glaser–Hay oxidative coupling with 1,3,5‐triethynylbenzene and phenylacetylene end‐capping agent. The CHCl₃ soluble oligomer is then thermally treated by step‐curing at 200, 300, 380, and 450 °C for 30 min at each temperature under nitrogen flow to render a shiny void‐free black polymer. TGA analysis indicates that the polymer is stable under nitrogen up to 500 °C with a marginal decomposition up to 800 °C. Solid‐state ¹³C NMR, Raman scattering, and FTIR are used to characterize the structure of the polymer. The polymer consists of amorphous carbon networks with the adamantane moieties and nanosized graphitic regions (clusters), which are generated from the thermal crosslinking of the diphenyldiethynyl units. It shows a remarkably low linear coefficient of thermal expansion (～25 ppm/°C), presumably due to the presence of the disordered graphitic structure. Its high density (～1.21 g/cm³), refractive index (～1.80 at 632 nm), and Young's modulus (～17.0 GPa) are also consistent with the interpretation. This study reveals important details about the effect of microscopic structure on the macroscopic properties of the highly crosslinked polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6909–6925, 2006     

Ce3+对Er3+/Yb3+共掺氟磷酸盐玻璃光谱性质的影响

研究了能量接受离子Ce³⁺对Er³⁺上转换发光强度以及Er³⁺在1.5μm附近波段发光性能参数的影响，并从能量匹配及能级结构角度出发对Er³⁺/Ce³⁺间的能量转移机制进行了分析.分析认为，⁴I_11/2能级的Er³⁺通过无辐射能量转移把能量传递给²F_5/2能级的Ce³⁺关键词： 氟磷酸盐玻璃 光谱性质 光纤放大器 3+和Ce³⁺')" href="#">Er³⁺和Ce³⁺     

Interactions between kinetic and radiative processes inside moving absorbing fluids

The aim of this paper is to present several features of the couplings occurring between radiative transfer and the kinetics of a moving dielectric. After determining how the velocity field affects the apparent thermo-optical properties of matter, the energy transport problem is investigated in instationary regime and the general form of transient radiative transfer equation inside a moving medium is built. Then, the model is applied to the particular case of turbulent flows: a system of two equations for mean and fluctuating radiative energies is presented, and the resolution of this system is finally carried out.     

Unconventional antiferromagnetic correlations of the doped Haldane gapsystem Y 2 BaNi 1 - x Zn x O 5

We make a new proposal to describe the very low temperature susceptibility of the doped Haldane gap compound Y₂BaNi_1-xZn_xO₅. We propose a new mean field model relevant for this compound. The ground state of this mean field model is unconventional because antiferromagnetism coexists with random dimers. We present new susceptibility experiments at very low temperature. We obtain a Curie-Weiss susceptibility χ( T ) ∼ C /(Θ + T ) as expected for antiferromagnetic correlations but we do not obtain a direct signature of antiferromagnetic long range order. We explain how to obtain the “impurity” susceptibility ( T ) by subtracting the Haldane gap contribution to the total susceptibility. In the temperature range [1 K, 300 K] the experimental data are well fitted by T ( T ) = C _imp 1 + T _imp / T . In the temperature range [100 mK, 1 K] the experimental data are well fitted by T ( T ) = A ln( T / T _c ), where T _c increases with x. This fit suggests the existence of a finite Néel temperature which is however too small to be probed directly in our experiments. We also obtain a maximum in the temperature dependence of the ac-susceptibility ( T ) which suggests the existence of antiferromagnetic correlations at very low temperature. Received 17 July 2001     

Orbital-selective Mott-insulator transition in Ca 2 - x Sr x RuO 4

The electronic structures of the metallic and insulating phases of the alloy series Ca_2-xSr_xRuO₄ ( 0 ? x ? 2) are calculated using LDA, LDA+U and Dynamical Mean-Field Approximation methods. In the end members the groundstate respectively is an orbitally non-degenerate antiferromagnetic insulator (x = 0) and a good metal (x = 2). For x > 0.5 the observed Curie-Weiss paramagnetic metallic state which possesses a local moment with the unexpected spin S = 1/2, is explained by the coexistence of localized and itinerant Ru-4d-orbitals. For 0.2 < x < 0.5 we propose a state with partial orbital and spin ordering. An effective model for the localized orbital and spin degrees of freedom is discussed. The metal-insulator transition at x = 0.2 is attributed to a switch in the orbital occupation associated with a structural change of the crystal. Received 27 July 2001     

Effects of pH and citric acid contents on characteristics of ester-derived BaFe12O19 powder

The single domain size of BaFe₁₂O₁₉ powder with crystallite sizes less than 200 nm was produced using a citric acid precursor method. Fe³⁺ and Ba²⁺, in a molar ratio of 12, were chelated by COOH⁻ in an aqueous solution. After ethylene glycol additions, esterification, dehydration, and calcination led to the formation of ester-derived BaFe₁₂O₁₉ powder. High pH and/or high citric acid contents in the starting solution are required to complete chelate metallic ions in the solution and to form pure barium ferrite powder at 1073 K. Pure single magnetic domain BaFe₁₂O₁₉ particles of M(30 kOe)≈54 emu/g, M_r≈28 emu/g, and H_c≈3.7 kOe were produced using [citric acid]/[metallic ions]=1.5 and pH7.     

Traces of functions with a dominating mixed derivative in ℝ<Superscript>3</Superscript>

We investigate traces of functions, belonging to a class of functions with dominating mixed smoothness in ℝ³, with respect to planes in oblique position. In comparison with the classical theory for isotropic spaces a few new phenomenona occur. We shall present two different approaches. One is based on the use of the Fourier transform and restricted to p = 2. The other one is applicable in the general case of Besov-Lizorkin-Triebel spaces and based on atomic decompositions.     

Crosslinked epoxy materials exhibiting thermal remendablility and removability from multifunctional maleimide and furan compounds

Crosslinked polymeric materials, which exhibit thermal remendability and removability through Diels–Alder (DA) and retro‐DA reactions, were obtained from using multifunctional maleimide and furan compounds as monomers. The synthesized monomers possess low melting points and good solubility in organo solvents to show excellent processing properties. The performance of DA and retro‐DA reactions were demonstrated with DSC and FTIR measurements. High performance of thermal remendablility and removability of the crosslinked materials were observed with SEM and solvent tests. These materials were applicable in advanced encapsulants and structural materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 905–913, 2006     

Highly soluble and optically transparent poly (ether imide)s based on 2,6‐ or 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and aromatic bis(ether amine)s bearing trifluoromethyl groups

Two series of novel fluorinated poly(ether imide)s (coded IIIA and IIIB ) were prepared from 2,6‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride, respectively, with various trifluoromethyl‐substituted aromatic bis(ether amine)s by a standard two‐step process with thermal or chemical imidization of the poly(amic acid) precursors. These fluorinated poly(ether imide)s showed good solubility in many organic solvents and could be solution‐cast into transparent, flexible, and tough films. These films were nearly colorless, with an ultraviolet–visible absorption edge of 364–386 nm. They also showed good thermal stability with glass‐transition temperatures of 221–298 °C, 10% weight loss temperatures in excess of 489 °C, and char yields at 800 °C in nitrogen greater than 50%. The 2,7‐substituted IIIB series also showed better solubility and higher transparency than the isomeric 2,6‐substituted IIIA series. In comparison with nonfluorinated poly (ether imide)s, the fluorinated IIIA and IIIB series showed better solubility, higher transparency, and lower dielectric constants and water absorption. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5909–5922, 2006