DFT/TDDFT Studies on the Electronic Structures and Spectral Properties of Rhenium(I) Pyridinybenzoimidazole Complexes

The electronic structures and spectral properties of three Re(I) complexes [Re(CO)(3)XL] (X = Br, Cl; L = 1-(4-5 '-phenyl-1.3,4-oxadiazolylbenzyl)-2-pyridinylbenzoimidazole (1), 1-(4-carbazolylbutyl)-2-pyridinylbenzoimidazole (2), and 2-(1-ethyl benzimidazol-2-yl)pyridi ne (3)) were investigated theoretically. The ground and the lowest lying triplet excited states were full optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. TDDFT/PCM calculations have been employed to predict the absorption and emission spectra starting from the ground and excited state geometries, respectively.

The viscoelastic and viscoplastic behavior of low-density polyethylene

Three series of tensile tests with constant cross-head speeds (ranging from 5 to 200 mm/min), tensile relaxation tests (at strains from 0.03 to 0.09) and tensile creep tests (at stresses from 2.0 to 6.0 MPa) are performed on low-density polyethylene at room temperature. Constitutive equations are derived for the time-dependent response of semicrystalline polymers at isothermal deformation with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical cross-links and lamellar blocks). The network is thought of as an ensemble of meso-regions linked with each other. The viscoelastic behavior of a polymer is modelled as thermally-induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects mutual displacement of meso-domains driven by macro-strains. Stress-strain relations for uniaxial deformation are developed by using the laws of thermodynamics. The governing equations involve five material constants that are found by fitting the observations. Fair agreement is demonstrated between the experimental data and the results of numerical simulation.

Preparation of fully cross-linked CNBR/PP-g-GMA and CNBR/PP/PP-g-GMA thermoplastic elastomers and their morphology, structure and properties

Binary CNBR/PP-g-GMA and ternary CNBR/PP/PP-g-GMA thermoplastic elastomers were prepared by reactive blending carboxy nitrile rubber (CNBR) powder with nanometer dimension and polypropylene functionalized with glycidyl methacrylate (PP-g-GMA). Morphology observation by using an atomic force microscope (AFM) and TEM revealed that the size of CNBR dispersed phase in CNBR/PP-g-GMA binary blends was much smaller than that of the corresponding CNBR/PP binary blends. Thermal behavior of CNBR/PP-g-GMA and CNBR/PP blends was studied by DSC. Comparing with the plain PP-g-GMA, T, of PP-g-GMA in CNBR/PP-g-GMA blends increased about 10degreesC. Both thermodynamic and kinetic effects would influence the crystallization behavior of PP-g-GMA in CNBR/PP-g-GMA blends. At a fixed content of CNBR, the apparent viscosity of the blending system increased with increasing the content of PP-g-GMA. FTIR spectrum verified that the improvement of miscibility of CNBR and PP-g-GMA was originated from the reaction between carboxy end groups of CNBR and epoxy groups of GMA grafted onto PP molecular chains. Comparing with CNBR/PP blends, the tensile strength, stress at 100% strain, and elongation at break of CNBR/PP-g-GMA blends were greatly improved.

Modern spectral estimation of ICP-AES

The inductively coupled plasma atomic emission, spectrometry (ICP-AES) and its signal characteristics were discussed using modem spectral estimation technique. The power spectra density (PSD) was calculated using the auto-regression (AR) model of modem spectra estimation. The Levinson-Durbin recursion method was used to estimate the model parameters which were used for the PSD computation. The results obtained with actual ICP-AES spectra and measurements showed that the spectral estimation technique was helpful for the better understanding about spectral composition and signal characteristics.

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.

MORPHOLOGY AND DYNAMIC MECHANICAL-PROPERTIES OF AB CROSS-LINKED POLYMERS BASED ON POLYURETHANES

Polyoxypropylene glycol (PPG) (or castor oil) and toluene diisocyanate (TDI) were mixed, and the prepolymer polyurethane (PU) (I) was formed. Vinyl-terminated polyurethane (II) was prepared from (I), and hydroxyethyl acrylate, AB crosslinked polymers (ABCPs) were synthesized from (II) and vinyl monomers such as styrene, methyl methacrylate, vinyl acetate, etc. The dynamic mechanical properties and morphology of ABCPs were measured. The ABCPs based on PPG have double glass transition temperatures (T(g)) on the sigma-vs. temperature curves. They display a two-phase morphology with plastic components forming the continous phase and PU-rich domains forming the separated phase on the electron micrographs. Irregular shapes and a highly polydisperse distribution of PU-rich domain sizes were observed. The crosslink density of ABCPs has a notable effect on the morphology and properties. The average diameter of the PU-rich domains depends on the molecular weight of prepolymer PPG. The highly crosslinked structures will produce large numbers of very small domains. ABCPs based on castor oil show a single T(g) relaxation on the dynamic mechanical spectra. The compatibility between the two components is much better in ABCPs based on castor oil than in those based on PPG, because there is a high crosslink density in the former. Comparison of the dynamic mechanical spectra of ABCP and interpenetrating networks (IPN) based on castor oil with similar crosslink density and composition imply that the two components in ABCP are compatible whereas microphase separation occurs in IPN. An improvement in the compatibility is achieved by the crosslinking between the two networks.

EPITAXIAL CRYSTALLIZATION OF HIGH-DENSITY POLYETHYLENE ON POLYPROPYLENE IN SOLUTION-CAST FILMS

Epitaxial crystallization of high-density polyethylene (HDPE) on isotactic polypropylene (iPP) in solution-cast films has been investigated by electron microscopy. The specimen-tilt technique of electron microscopy has been used to study the structural relationship between HDPE and iPP crystals. HDPE exhibits different crystalline morphologies in the two basic types of iPP spherulite textures, cross-hatched and lathlike regions. In the former, the crystallographic c axis of HDPE lamellae is in the film plane, while in the latter, the c axis of HDPE crystallites is at an angle of about 50-degrees with the normal of the film. In both structural regions of iPP, however, the contact planes of epitaxial growth are (0 1 0) for iPP and (1 0 0) for HDPE.

地震资料叠前储层预测综合研究--以辽中凹陷东二下段浊积扇气藏为例

Reservoir prediction techniques from prestack seismic are among the most important ones for exploration of lithologic hydrocarbon reservoir. In this paper, we set the turbidite fan sandstone reservoir in Liao-Zhong depress as our researching target, and aims to solve the apllication difficulties on pre-stack inversion in the area, where the drilling data is scarce and the reservoir is lateral varied. Meanwhile, AVO analysis and pre-stack inversion for gas-bearing detection is systematically researched. The seismic reflection characters of gas-bearing sandstone in turbidite fan with different fluid content are defined, after analyzing results from AVO seismic simulation and porous fluid replacement of real log data, and under the guides of the seismic characters from classical gas-bearing sandstone reservoir and numerical simulation for complicate gas-bearing sandstone. It is confirmed that detecting gas-bearing sandstone in turbidite fan via AVO technologies is feasible. In terms of AVO analysis, two AVO characters, fluid detection factor and product of intercept and gradient, can effectively identify top and bottom boundaries and lateral range of tuibidite gas sand by comparing real drilling data. Cross-plotting of near and far angle stack data could avoid the correlation existing in P-G analysis. After comparing the acoustic impedance inversions with routine stacked data and AVO intercept, impedance derived from AVO intercept attribute could reduce the acoustic impedance estimating error which is caused by AVO. On the aspect of elastic impedance inversion, the AVO information in the pre-stack gathers is properly reserved by creating partial angle stack data. By the far angle elastic impedance alone, the gas sand, with abnormally low range of values, can be identified from the background rocks. The boundary of gas sand can also be clearly determined by cross-plotting of near and far angle elastic impedances. The accuracy of far angle elastic impedance is very sensitive to the parameter K, and by taking the statistical average of Vp/Vs on the targeted section in key wells, the accuracy of low frequency trends is gurranteed; the intensive absorsion within the area of the gas sand, which tends to push the spectral of seismic data to the lower end, will cause errors on the inversion result of elastic impedance. The solution is to confine the inversion on the interested area by improving the wavelet. On the aspect of prestack AVA simultaneous inversion, the constraint of local rock-physical trends between velocities of P-wave、S-wave and density successfully removes the instability of inversion, thus improves the precision of the resulting elastic parameters. Plenty of data on rock properties are derived via AVO analysis and prestack seismic data inversion. Based on them, the fluid anomaly is analysized and lithological interpretation are conducted. The distribution of gas sand can be consistently determined via various of ways, such as cross-plotting of P and G attributes, near and far partial angle stack data, near and far angle elastic impedances, λρ and Vp/Vs, etc. The shear modulo and density are also reliable enough to be used for lithological interpretation. We successfully applied the AVO analysis and pre-stack inversion techniques to gas detecting for turbidite fan sand reservoir in Liao-Zhong depression.