Intramolecular energy transfer mechanism between ligands in ternary rare earth complexes with aromatic carboxylic acids and 1,10-phenanthroline

A series of binary and ternary rare earth (Gd, Eu, Tb) complexes with aromatic acids and 1,10-phenanthroline have been synthesized. The lowest triplet state energies of ligands have been obtained by measuring the phosphorescence spectra of binary gadolinium complexes. By comparing the phosphorescence spectra of binary complexes with those of ternary ones, it is found that there exists another intramolecular energy transfer process from the aromatic acids to 1,10-phenanthroline besides the intramolecular energy transfer process between the aromatic acids and the central rare earth ions. The intramolecular energy transfer efficiencies have been calculated by determining phosphorescence lifetimes of binary and ternary gadolinium complexes. The luminescence properties of corresponding europium and terbium complexes are in agreement with the prediction based on energy transfer mechanism. (C) 1998 Elsevier Science S.A. All rights reserved.

Compatibilizing effects and mechanism of compatibilization of LLDPE/PEO blends by EAA

The compatibilizing effects of the compatibilizer, ethylene-acrylic acid random copolymer (EAA), on linear low density polyethylene (LLDPE)/poly(ethylene oxide) (PEO) blends and the mechanism of compatibilization of the blends have been studied. Morphology and microstructures as characterized by SEM, DMA, DSC and IR show that EAA can act as an effective compatibilizer, and the mechanism of compatibilization is due to the compatibility of amorphous phases between EAA and LLDPE, and intermolecular interaction between the carboxylic groups in EAA. and the ethereal oxygens in PEG.

Deformation process and mechanism of HDPE/LDPE blends

Blends of HDPE in more LDPE, with appropriate heat treatment, produce a dispersion of separate entities of HDPE in a matrix of LDPE. The system offered an especially favourable means of studying the deformation of melt-crystallized lamellae. It has been found that sheaf-like spherulites are transformed under tensile deformation into hourglass shapes i.e. a double cone aligned along the drawing direction with origin in the center of the object. This is a consequence of different modes of deformation according to the relation of an individual lamella to the tensile axis. The work shows that the lamellae have not undergone melting and recrystallization in the deformation process at room temperature.

Investigation of mechanism of nephelauxetic effect

By using the chemical bond theory of dielectric description and electronic structure of 3d elements, the mechanism of nephelauxetic effect is studied, and the main factors responsible for this effect are identified. These are: the covalency of chemical bond, polarizabilities of ligand bond volume for the host and the valence and spin state of the center ion. Relationships between these factors are given, and the results are discussed. (C) 1996 Elsevier Science Ltd. All rights reserved.

Crystal structure and mechanism of (Z)-1-[2-(phenyl-bromide-chloride)vinyl]-1-cyclohexanol

The crystal structure and mechanism of the title molecule are described. This crystal is orthorhombic, belonging to space group PC21/B with a=1,002 1(2) nm, b=1.483 0(3) nm, c=2.173 6(4) nm, V=3.230 39(2) nm(3), Z=2, D-c=1.80 g/cm(3), R=0.069 3. The structure was solved by direct method. The tin atom of the title compound exists in two distorted-trigonal-bipyramidal geometry, defined by two carbon, one bromide, one chloride and one oxygen atoms leading to a five-membered chelate ring. In the structure, the five-membered ring containing the intermolecular O-->Sn has a half chair conformation.

Studies of catalyzed reaction mechanism between co-polyether (THF/EO) and N-100 by NMR - Interaction and complex formation between reactants and catalysts

To elucidate the mechanism of the catalyzed reaction of co-polyether (EO/THF) with N-100, the interaction and complex formation between reactants and catalysts were investigated by means of NMR spectroscopy. It is shown that the resonance peak of isocyanate carbon splits into two parts when the solutions of N-100 and co-polyether were mixed. The disappearing of proton resonance peak of hydroxyl group in NMR spectra when dibutyltin dilaurate(DBTDL) were added to the copolyether(THF/EO) solution indicates the complex formation, This interaction appears to be a bonding of tin to the oxygen of hydroxyl and make the hydrogen of the hydroxyl group very mobile and active, then exchange with other protons, In the case of triphenyl bismuth(TPB), the high field shift and intensity enhancement of proton peak were observed, which suggest a nucleophilic attack of the bismuth to the hydroxyl hydrogen.

Iron(II)-8-quinolinol/MCM-41-catalyzed phenol hydroxylation and reaction mechanism

Iron(II)-8-quinolino/MCM-41 is prepared. Its catalysis is studied in phenol hydroxylation using H2O2 (30%) as oxidant. The experiment shows that Iron(II)-8-quinolinol/MCM-41 has good catalytic activity and desired stability. Based on cyclic voltammetry, ESR, and UV-visible spectra studies of iron(II)-8-quinolinol complex in liquid phase, a radical substitution mechanism is proposed and used to demonstrate the experimental facts clearly. (C) 1997 Academic Press.

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

Phenol hydroxylation by iron(II) phenanthroline: The reaction mechanism

Phenol hydroxylation catalyzed by iron(II)-1,10-phenanthroline is investigated through kinetics, ESR, W-Vis as well as cyclic voltammogram studies. The optimum reaction conditions are obtained for diphenols production. Radical substitution mechanism is first proposed to explain the effects of pH, reaction medium and other factors on the phenol hydroxylation with H2O2 as oxidant, and found that the coexisting of iron(II)-1,10-phenanthroline and iron(III)-1,10-phenanthroline is the key for phenol hydroxylation to occur with H2O2 as oxygen donor.

Synthesis and thermo-decomposition mechanism of rare earth complexes with phenylacetic acid

Rare earth complexes with phenylacetic acid (LnL(3) . nH(2)O, Ln is Ce, Nd, Pr, Ho, Er, Yb and Y, L is phenylacetate, n = 1-2) were prepared and characterized by elemental analysis, IR spectroscopy, chemical analysis, and X-ray crystal structure. The mechanism of thermal decomposition of the complexes was studied by means of TG-DTG, DTA and DSC. The activation energy and enthalpy change for the dehydration and melting processes were determined.

Toughening mechanism of polymer blends: Influence of voiding ability of dispersed-phase particles

The parameters which effect the cavitation strain of polymer blends toughened with a shear yield mechanism have been studied by analysis of the stress acted on the equatorial plane of dispersed-phase particles. As a result, the cavitation strain of polymer blends depends on the Young's modulus and the Poisson's ratio of the dispersed-phase particles and the matrix and also on the break stress of dispersed-phase particles. We tried to provide a criterion for selecting the materials used as dispersed-phase particles which can effectively enhance the toughness of polymer blends. (C) 1996 John Wiley & Sons, Inc.

IONIC-CONDUCTION OF A NOVEL COMB POLYMER ELECTROLYTE BASED ON MALEIC-ANHYDRIDE COPOLYMER WITH OLIGO-OXYETHYLENE SIDE-CHAINS

A comb-shaped polymer (BM350) with oligo-oxyethylene side chains of the type -O(CH2CH2O)(7)CH3 was prepared from methyl vinyl ether/maleic anhydride copolymer. Homogeneous amorphous polymer electrolyte complexes were made from the comb polymer and LICF(3)SO(3) by solvent casting from acetone, and their conductivities were measured as a function of temperature and salt concentration. Maximum conductivity close to 5.08 X 10(-5) Scm(-1) was obtained at room temperature and at a [Li]/[EO] ratio of about 0.12. The conductivity which displayed non-Arrhenius behaviour was analyzed using the Vogel-Tammann-Fulcher equation and interpreted on the basis of the configurational entropy model. The results of mid-IR showed that the coordination of Li+ to side chains made the C-O-C band become broader and shift slightly. X-ray photoelectron spectroscopy analysis indicated that the oxygen atoms in the two situations could coordinate to Li+ and this coordination resulted in the reduction of the electron orbit binding energy of F and S.

MECHANISM OF IRON INHIBITION BY STEARIC-ACID LANGMUIR-BLODGETT MONOLAYERS

Using the Langmuir-Blodgett (LB) technique, stearic acid (SA) monolayers were deposited onto the surface of an iron (Fe) electrode to study the inhibition effect and the mechanism of SA in a neutral medium. Molecular orientation and the number of deposited monolayers of SA were shown to have marked effects on inhibition of Fe corrosion. The inhibition mechanism depended mainly on blocking.

TEMPERATURE EFFECT ON IMPACT FRACTURE-TOUGHNESS AND FRACTURE MECHANISM OF PHENOLPHTHALEIN POLY(ETHER KETONE)

Phenolphthalein poly(ether ketone) (PEK-C) was tested using an instrumented impact tester to determine the temperature effect on the fracture toughness K-c and critical strain energy release rate G(c). Two different mechanisms, namely the relaxation processes and thermal blunting of the crack tip were used to explain the temperature effect on the fracture toughness. Examination of the fracture surfaces revealed the presence of crack growth bands. It is suggested that these bands are the consequence of variations in crack growth along crazes that are formed in the crack tip stress field. As the crack propagates, the stress is relaxed locally, decreasing the growth rate allowing a new bundle of crazes to nucleate along which the crack advances.

STUDIES ON COMPATIBILIZATION OF POLYPROPYLENE THERMOPLASTIC POLYURETHANE BLENDS AND MECHANISM OF COMPATIBILIZATION

This paper reports a study of compatibilization and the mechanism of compatibilization of polypropylene (PP)/thermoplastic polyurethane (TPU) blends with maleated polypropylene (PP-MA) and its graft copolymer with polyethylene oxide (PEO), (PP-MA)-g-PEO.