Covalent linking of near-infrared luminescent ternary lanthanide (Er3+, Nd3+, Yb3+) complexes on functionalized mesoporous MCM-41 and SBA-15

The near-infrared (NIR) luminescent lanthanide ions, such as Er(III), Nd(III), and Yb(III), have been paid much attention for the potential use in the optical communications or laser systems. For the first time, the NIR-luminescent Ln(dbm)(3)phen complexes have been covalently bonded to the ordered mesoporous materials MCM-41 and SBA-15 via a functionalized phen group phen-Si (phen-Si = 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline; dbm = dibenzoylmethanate; Ln = Er, Nd, Yb). The synthesis parameters X = 12 and Y = 6 h (X denotes Ln(dbM)(3)(H2O)(2)/phen-MCM-41 molar ratio or Ln(dbM)(3)(H2O)(2)/phenSBA-15 molar ratio and Y is the reaction time for the ligand exchange reaction; phen-MCM-41 and phenSBA-15 are phen-functionalized MCM-41 and SBA-15 mesoporous materials, respectively) were selected through a systematic and comparative study. The derivative materials, denoted as Ln(dbM)(3)phen-MCM-41 and Ln(dbm)(3)phen-SBA-15 (Ln = Er, Nd, Yb), were characterized by powder X-ray diffraction, nitrogen adsorption/desorption, Fourier transform infrared (FT-IR), elemental analysis, and fluorescence spectra. Upon excitation of the ligands absorption bands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide ions through the intramolecular energy transfer from the ligands to the lanthanide ions.

What has brought on the effects of number-average molecular weight on the spinodals in polymer mixtures?

On the basis of the thermodynamics of Gibbs, the spinodal for the quasibinary system was derived in the framework of the Sanchez-Lacombe lattice fluid theory. All of the spinodals were calculated based on a model polydisperse polymer mixture, where each polymer contains three different molecular weight subcomponents. According to our calculations, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights, whereas that of the z-average molecular weight is invisible. Moreover, the extreme of the spinodal decreases when the polydispersity index (eta = (M) over bar (w)/(M) over bar (n)) of the polymer increases. The effect of polydispersity on the spinodal decreases when the molecular weight gets larger and can be negligible at a certain large molecular weight. It is well-known that the influence of polydispersity on the phase equilibrium (coexisting curve, cloud point curves) is much more pronounced than on the spinodal. The effect of M, on the spinodal is discussed as it results from the infuluence of composition temperatures, molecular weight, and the latter's distribution on free volume. An approximate expression, which is in the assumptions of v* v(1)* = v(2)* and 1/r --> 0 for both of the polymers, was also derived for simplification. It can be used in high molecular weight, although it failed to make visible the effect of number-average molecular weight on the spinodal.

Effect of cross-linking of high-density polyethylene. I. On spherulitic structures

Crystallization behavior and spherulitic structure of linear high-density polyethylene (HDPE), after being irradiated in its molten state by gamma -rays, was investigated by small-angle laser scattering (SALS) and differential scanning calorimetry (DSC). Significant changes in the crystallization of HDPE during cooling in air before and after being irradiated in the melt were observed. A critical minimum average molar mass between cross-links (200 carbon-carbon bonds) for spherulite formation in such an irradiated HDPE network was obtained.

Advanced research work on radiation cross-linking of polymers in CIAC

Recent research carried out at the Chinese Institute of Applied Chemistry has contributed significantly to the understanding of the radiation chemistry of polymers. High energy radiation has been successfully used to cross-link fluoropolymers and polyimides. Here chain flexibility has been shown to play an important role, and T-type structures were found to exist in the cross-linked fluoropolymers. A modified Charlesby-Pinner equation, based upon the importance of chain flexibility, was developed to account for the sol-radiation dose relationship in systems of this type. An XPS method has been developed to measure the cross-linking yields in aromatic polymers and fluoropolymers, based upon the dose dependence of the aromatic shake-up peaks and the F/C ratios, respectively. Methods for radiation cross-linking degrading polymers in polymer blends have also been developed, as have methods for improving the radiation resistance of polymers through radiation cross-linking.

A novel electrochemical method for simultaneously measuring diffusion coefficient and ion transference number

This paper introduces a new method to estimate the diffusion coefficient and transference number of a salt or an electroactive ion in a solution with little or no supporting electrolyte. The above two parameters can be obtained from a single potential step experiment without previous knowledge of either one. It would appear that the method could also be used in the study of ion transport in a high viscosity solvent or a solid electrolyte. (C) 1998 Elsevier Science S.A.

Study on the beta relaxation mechanism of thermosetting polyimide thermoplastic polyimide blends

The thermosetting polyimide PMR-I5 and its blends with thermoplastic polyimides have been studied by dynamic mechanical analysis. The results obtained indicate that the level of beta relaxations in PMR-15 are increased with an increase in cross-linking density. This phenomenon is interpreted as a change of chemical structure during the cross-linking process. Addition of thermoplastic polyimide makes the magnitude of beta relaxations increase when PMR-15 is the major component. This might be due to the strong intermolecular charge-transfer interaction between PI and PI or PMR-15 and PMR-15 molecular chains being partly replaced by the weak intermolecular interaction between PI and PMR-15 in PMR-15/PI blends, resulting in some phenylene rings or imide groups in PIs and PMR-15 chains being able to participate in beta relaxation. However, this increment in beta relaxation magnitude can be reduced by heat treatment of the sample, as a result of phase separation. Hence, it is concluded that the beta relaxation magnitude is determined by the number of groups which can participate in relaxation per unit length, i.e. the magnitude of beta relaxation increases with decreasing interaction between the molecular chains. Copyright (C) 1996 Elsevier Science Ltd

RADIATION CROSS-LINKING OF POLYTETRAFLUOROETHYLENE

Polytetrafluoroethylene (PTFE) is considered to be a typical radiation degradative polymer. In this work the polymer was crosslinked by means of radiation at 335 +/- 5-degrees-C under vacuum. Crosslinked PTFE showed a great improvement in high temperature

EFFECTS OF STRUCTURE MULTIPLICITY ON MECHANISM OF RADIATION CROSS-LINKING OF POLYMERS

In an attempt to explore the effects of structural multiplicity of polymers on the mechanism of radiation crosslinking, the adaptability of the Charlesby-Pinner's equation and its various modified versions are examined. It is recognized that both chemical

EFFECT OF HYDROPHOBIC OXIDES ON RADIATION CROSS-LINKING OF LOW-DENSITY POLYETHYLENE

Effect of hydrophobic oxide, containing =Si-CH=CH2 groups, on the radiation crosslinking of low density polyethylene (LDPE) has been studied. It was found that mechanical stability of irradiated LDPE containing improved SiO2 is higher than that of samples containing unimproved SiO2.

MECHANISM OF RADIATION CROSS-LINKING OF POLYMERS AND ITS RELATIONSHIP WITH STRUCTURAL MULTIPLICITY

In an attempt to explore the effect of structural multiplicity of polymers on the mechanism of radiation crosslinking, the adaptability of the Charlesby-Pinner's equation and its various modified versions are examined. It is recognized that both chemical and morphological multiplicity of polymer structure results in the multiplicity of crosslinking mechanism, and that any single equation can only be applicable to a certain step of the whole radiation process.

STUDIES ON RADIATION-INDUCED CROSS-LINKING OF POLYISOBUTYLENE

Polyisobutylene can be crosslinked under irradiation as to be expected by either introducing radiation sensitive groups into its macromolecules or blending with a proper radiation crosslinkable polymer.

STUDIES ON RADIATION CROSS-LINKING OF FLUOROPOLYMERS

The research work on radiation modification of a series of fluoropolymers were performed . The radiation crosslinked fluoropolymers obtain a great improvement in high temperature resistance, high temperature mechanical properties and radiation stability.

RADIATION CROSS-LINKING OF CHLORINATED POLYISOBUTYLENE

The effects of radiation on chlorinated polyisobutylene were studied. It was found that polyisobutylene, which is generally considered to be a typical radiation-degradative polymer, could be crosslinked by gamma-ray irradiation after chlorine had been introduced into its macromolecules. Carbon-chlorine bonds act both as radiation-sensitive groups and reaction species in the radiation process of chlorinated polyisobutylene.

THE EFFECT OF RADIATION-INDUCED CROSS-LINKING ON THE RELAXATION OF TAUT TIE MOLECULES DURING ANNEALING OF DRAWN LDPE

Shrinkage, retractive stress, and infrared dichroism of the drawn low-density polyethylene (LDPE) as-drawn and irradiated by Co-60-ray have been measured under different annealing conditions. The shrinkage and the disorientation of the irradiated sample was undergone more rapidly than that of unirradiated one as the temperature was continuously increased, surpassing a certain value, and a higher degree of shrinkage and disorientation was achieved finally for the irradiated sample when the samples were annealed with free ends. For the samples heated isothermally with fixed ends, the retractive stress went through a maximum and then attenuated to a limited value, and the degree of such a stress attenuation for the unirradiated sample was much more than that for the irradiated sample. These results show that the taut tie molecules (TTMs) in drawn PE can relax by the pulling of chain segments out of crystal blocks that they anchored in at elevated temperatures higher than the a transition and also by the displacing of microfibrils if the samples were annealed with free ends. The cross-links produced by irradiation prohibit the former process. It was further observed that the dependence of the average extinction coefficient of the band at 2016 cm-1 on that of the band at 1894 cm-1 is related to irradiation and annealing conditions, which has also been explained by the relaxation of TTMs and the function of irradiation-induced cross-linking on the relaxation.