Effect of the silanization conditions on chromatographic behavior of an open-tubular capillary column coated with a modified silica-gel thin layer.

The performance of an open-tubular capillary column coated with a modified silica-gel thin layer was investigated, particularly concerning the effect of the silanization process on it. Although the increase in the octadecyltriethoxysilane (ODTES) concentration in the silanization process could enhance the retention factor of naphthalene, its theoretical plate number was significantly reduced (ODTES, 5 to 50%; k, 0.2 to 4.3; N, 79600 to 2600 m(-1)). Namely, the increase in the retention factor was accompanied by a decrease in the theoretical plate number. A similar phenomenon was also observed when octadecyldimethylchlorosilane (ODCS) was used as the silanization regent. However, increases in both the retention factor and the theoretical plate number could be achieved (sample, naphthalene; k, 0.05 to 0.09; N, 149000 to 220000 m(-1)) by a NaOH treatment to the fabricated thin porous silica-gel layer before silanization with ODCS. The electrochromatographic separation of proteins and peptides by using the NaOH-treated column could obtain more peaks than electrophoretic separation.     

Structure and properties of the δ‐form and mesophase of syndiotactic polystyrene membranes prepared from different organic solvents

Syndiotactic polystyrene (sPS) membranes were prepared with different organic solvent systems and compared to get the information about the δ‐form complexing behavior of sPS. Further, the guest molecules included in the clathrate δ form of sPS are removed by stepwise extraction method. The conformational changes during the TTGG helical formation of sPS/organic solvent systems have been identified by FTIR spectroscopy, and it was concluded that the TTGG helices were constructed in regular sequences, which depends on the nature of the respective solvents. The TTGG content in the mesophase is found to be increased by removing the guest molecules. The structural changes of sPS/organic solvent systems have been characterized by WAXD analysis. Moreover, the different clathrate structures were found and showed the different crystalline reflections in the WAXD profiles, which are significantly changed with the kind of guest solvent included in sPS. The content of solvents in the clathrated sPS and the desorption temperatures were determined by thermal analysis. The resulted mesophase of sPS membrane contains the nanoporous molecular cavities that depend on the size of the guest molecule. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1873–1880, 2005     

Influence of the surface treatment of graphitized carbon fibers on the curing of an amine-catalyzed epoxy-anhydride system

The surface of graphitized carbon fibers is oxidatively treated by nitric acid. Fourier transform infrared attenuated total reflection spectroscopy has been utilized to monitor the influence of the surface species on the curing of an epoxy system. A curve-fitting program is used to deconvolve the overlapped infrared bands. The integrated intensities of the ester, anhydride, epoxy, and carboxylic acid, plotted against the curing time, clearly show the dependence of the crosslinking process on the concentration of the surface species. The surface groups themselves act as a catalyst: there exists an optimal concentration below which an activation of the curing process occurs. Above that concentration, a retardation of the curing process has been detected.     

Analysis of anisotropy in dielectric absorption due to defects in the polyoxymethylene crystal

The dielectric absorption due to terminal polar groups localized in defect regions of polyoxymethylene crystals shows an anisotropy relative to an applied field. An attempt to interpret this anisotropy has been made by applying the barrier theory of Hoffman. The potential energy map for the rotation of the terminal polar group calculated from conformational analysis gives two minima. The angle between the dipole moment of the terminal OH and the fiber axis calculated in terms of the two conformations corresponding to the potential energy minima is in good agreement with results from infrared dichroism. This agreement is considered as evidence that the conformational analysis is reliable for estimating the potential energy minima required in the calculation according to the barrier theory. The barrier height obtained by the conformational analysis and the anisotropy calculated from the components of the dipole moments for the terminal polar group in terms of the barrier theory are in qualitative agreement with the experimental data.     

Effects of a static electric field upon dielectric properties of poly(vinylidene fluoride) and poly(vinyl fluoride)

Dielectric measurements on poly(vinylidene fluoride) at higher temperatures result in anomalously large values of ε′ and ε″ at lower frequencies. When a static field is applied, a drastic decrease of ε′ and ε″ occurs. The effects of a static field can be summarized as follows: (1) the field effect upon ε′and ε″ is more significant at lower frequencies; (2) with increasing field strength, the rate of decrease of ε′and ε″ with time becomes greater and the ultimate values are smaller; (3) when the field is removed, ε′and ε″ recover but the ultimate recovery is incomplete; (4) the field effect depends strongly on temperature. Such behavior seems to be attributable to the displacement of ionic impurities and to their electrolysis. These results provided a method to remove the contribution of ionic impurities to ε′and ε″ and to measure the relaxation process due only to dipoles of a polymer. The application of this method revealed the dielectric high temperature absorption which had been masked by the ionic conduction in poly(vinyl fluoride).     

Observation of transition from a reactive-medium instability to an inverse Landau damping in a beam-plasma system

The wave excited by a coaxial probe in a beam-plasma system usually propagates as two waves which are independent of each other, i.e., a damped Trivelpiece mode of the plasma and a growing space charge wave of the beam (referred to a reactive-medium instability). While, when the beam velocity is equal to or slightly larger than the phase velocity of the plasma wave, the inverse Landau damping of the wave is observed, instead of the damped Trivelpiece mode.     

Dielectric relaxation in concentrated solutions of poly(γ-benzyl-L-glutamate)

Measurements of dielectric constant and loss, broad-line nuclear magnetic resonance, and differential thermal analysis of concentrated solutions of poly(γ-benzyl-L -glutamate) (PBLG) were carried out to determine the effects of intermolecular interactions on the mobility of the side group and the solvent (dichloromethane or dioxane). Only one dielectric loss peak due to the cooperative motion of the side group and the solvent was found. The activation energy of this relaxation process varied from 3 to 47 kcal/mole with increasing concentration of PBLG from 20 to 100% by weight accompanied with steep increases at about 40 and 80%. This result is explained as due to entanglement of neighboring side groups. In NMR, narrowing of the line was observed near the temperature where the dielectric loss was observed. The glass transition was also observed by differential thermal analysis. From these results it was concluded that the relaxation observed in PBLG solution and in pure PBLG have the nature of primary or α relaxations.