Hydrogen cycling induced diffraction peak broadening in C14 and C15 Laves phases

The diffraction peak broadening induced by hydrogen absorption-desorption cycling has been analyzed in four different Laves phase compounds with the C14 and C15 structures. The broadening is due to strain most probably originating from dislocations generated at the interface between the α and β hydride phases in connection with the cell volume difference between the two phases. It has been shown that it is strongly compound dependent. In the case of the C14 structure, the broadening is large and isotropic, and the latter can be related to the isotropy of the elastic constants of the metallic phase. The broadening is less for the compounds with the C15 structure, which can be related to a possibly softer lattice. Better ageing properties after long-term cycling are predicted for this crystal structure.     

激光诱导等离子体中的电子密度和电子温度的测量

脉冲激光诱发等离子体的谱诊断技术用来对其电子密度和电子温度的测量结果与理论计算进行了比较，同时讨论了运用这个方法的物理条件．     

The effect of electroosmotic and hydrodynamic flow profile superposition on band broadening in capillary electrophoresis

The effect of the superposition of electroosmotic flow and pressureinduced hydrodynamic counterflow on efficiency has been investigated for different capillary electrophoretic systems. Results are shown for 50 and 75 μm internal diameter capillaries at several voltage and counterpressure levels. Hydrodynamic counterflows were successfully applied in electrokinetic chromatography in order to delay the entry of a UV-active pseudostationary phase, tetraphenyl porphyrintetrasulfonate, into the detection zone allowing the separation of neutral nitroaromatics. The separations are based on the weak charge-transfer interactions between the porphyrin and the analytes.     

Two‐dimensional chromatography as a tool for studying band broadening in size‐exclusion chromatography

Comprehensive 2‐D size‐exclusion chromatography (SEC×SEC) has been realized. SEC×SEC is not a useful technique for characterizing complex polymers. However, it is potentially an elegant tool to study band‐broadening phenomena. If narrow fractions can be collected from the first dimension, the band broadening in the second dimension is only due to chromatographic dispersion. This would allow a clear distinction to be made between chromatographic band broadening (column and extra‐column) and SEC selectivity (band broadening due to sample polydispersity). In comparison with MALDI‐MS, SEC×SEC allows the study of polymers across a much broader molar‐mass range.     

Leray–Hopf solutions to a viscoelastoplastic fluid model with nonsmooth stress–strain relation

We consider a fluid model including viscoelastic and viscoplastic effects. The state is given by the fluid velocity and an internal stress tensor that is transported along the flow with the Zaremba–Jaumann derivative. Moreover, the stress tensor obeys a nonlinear and nonsmooth dissipation law as well as stress diffusion. We prove the existence of global-in-time weak solutions satisfying an energy inequality under general Dirichlet conditions for the velocity field and Neumann conditions for the stress tensor.     

Time-resolved fluorescence relaxation of 3-methyllumiflavin in polar solution

We have studied the fluorescent properties of a well-defined model flavin compound (3-methyllumiflavin) in a relatively polar solvent like propylene glycol or ethanol. Inhomogeneous spectral broadening effects were directly time-resolved by detection at the extreme blue and red edges of the fluorescence band of 3-methyllumiflavin using excitation in the main absorption band. At the high-energy side of the emission band a rapid decay component (tens of picoseconds) was resolved indicative for the disappearance of the initially prepared, nonequilibrium state with a characteristic dipolar relaxation time. At the low-energy side the rise of a solvent relaxed fluorescent species could be time-resolved. The wavelength-dependent effects on the dipolar relaxation were abolished when excitation was at the low-energy side of the absorption band. The experimental decays of the flavin solvate at different energies of fluorescence and excitation are presented as they represent an easy diagnosis for energy dependent solvation dynamics. Wavelength dependent rotation of 3-methyllumiflavin, examined by fluorescence anisotropy decay, turned out to be absent for 3-methyllumiflavin in propylene glycol between 263 and 293 K, probably because of the small change in dipole moment upon flavin excitation.     

聚合物微晶尺寸和晶格畸变

聚合物微晶尺寸和晶格畸变是对聚合物材料性能有着重要影响的结构参数。本文介绍了应用Ｘ射线衍射方法测定聚合物微晶尺寸和结构畸变的几种方法：近似函数、次晶模型法、方差法、矩法。     

Estimation of the instrumental band broadening contribution to the column elution profiles in open tubular capillary liquid chromatography

In comparison with conventionally packed HPLC columns, from a theoretical point of view, open capillary liquid chromatography (OTLC) systems offer a number of advantages like high plate numbers and short analysis times. On the other hand, drastic changes have to be made to the instrumentation. In particular, the contribution to band broadening by the chromatographic equipment must be considerably reduced. In the present study an OTLC system was developed and evaluated, which yields satisfactory results for 26 μm i. d. columns. The determination of the contribution of the chromatographic equipment to the total band broadening is discussed.     

On the statistical independence of various column contributions to band broadening. Part 1: Second moment contributions from statistically independent,longitudinal diffusion in both phases

The total length-based second moment contribution from longitudinal sample diffusion in both phases on a column, σD , is derived by adding individual partial differential contributions to a partial differential equation accounting for the longitudinal diffusion processes only. Although each diffusion-dispersed sample part is equilibrated between two phases, the resulting σ,D (= 2D _mt _m + 2D _st _s) can be interpreted as the sum of two independent contributions in accordance with the variance addition rule. (D _m and D _s are the mean diffusion coefficients and t _mand t _s the mean residence times of the sample in the mobile and stationary phases, respectively.) The same σD expression is derived from the random walk model of Giddings by treating the diffusional process in each phase as statistically independent of the other processes. Under these conditions the broadening contribution from longitudinal diffusion in the mobile phase is shown to be independent of the velocity profile.     

A molecular theory of inhomogeneous broadening,including the correlation between different transitions,in liquids and glasses

Summary We present a molecular theory of the energy distributions for the internal quantum states of a solute in a liquid or glassy solvent. We show that the energy distributions for different states are correlated in a way that depends on the solute-solvent interactions. We show how the theory can be modified easily to describe the transition-energy distributions for different pairs of states, which are of course related to inhomogeneously broadened absorption spectra. We also show that the distributions for different transitions are correlated, and describe how this correlation is measured by nonresonant fluorescence- and phosphorescence-line-narrowing and hole-burning experiments. The theory provides a microscopic framework within which to interpret different phenomenological models. For the case of a Lennard-Jones solute in a Lennard-Jones liquid solvent, we compare our theory to Monte Carlo simulation.