Shear induced molecular alignments of a side-chain liquid crystalline polyacetylene containing biphenyl mesogens

Mesomorphic properties of a side chain liquid crystalline polyacetylene, poly(11-{[(4'-heptyloxy-4-biphenylyl)carbonyl]oxy}-1-undecyne) (PA9EO7), are investigated using polarized optical microscope, X-ray diffraction, and transmission electron microscope. Polymer PA9EO7 forms enantiotropic smectic A and smectic B phases. It also exhibits an additional high order smectic phase, a sandwich structure consisting of different molecular packing of biphenyl mesogenic moieties from that of alkyl spacers and terminals, when it is prepared from its toluene solution. Shearing the polymer film at its smectic A phase generates banded texture with the alignment of the backbones parallel to the direction of shear force. While at its high order smectic phase, the mesogen pendants of the polymer are arranged parallel to the direction of shear. The different mesomorphic behaviors arise from different molecular alignments influenced by the fluidity.

Theoretical representation of shear and pressure influence on the phase separation behavior of PVME/PS mixture

In the framework of lattice fluid model, the Gibbs energy and equation of state are derived by introducing the energy (E-s) stored during flow for polymer blends under shear. From the calculation of the spinodal of poly(vinyl methyl ether) (PVME) and polystyrene (PS) mixtures, we have found the influence of E., an equation of state in pure component is inappreciable, but it is appreciable in the mixture. However, the effect of E, on phase separation behavior is extremely striking. In the calculation of spinodal for the PVME/PS system, a thin, long and banana miscibility gap generated by shear is seen beside the miscibility gap with lower critical solution temperature. Meanwhile, a binodal coalescence of upper and lower miscibility gaps is occurred. The three points of the three-phase equilibrium are forecasted. The shear rate dependence of cloud point temperature at a certain composition is discussed. The calculated results are acceptable compared with the experiment values obtained by Higgins et at. However, the maximum positive shift and the minimum negative shift of cloud point temperature guessed by Higgins are not obtained, Furthermore, the combining effects of pressure and shear on spinodal shift are predicted.

Shear induced mixing/demixing: Blends of homopolymers, of homopolymers plus copolymers, and blends in solution

Shear may shift the phase boundary towards the homogeneous state (shear induced mixing, SIM), or in the opposite direction (shear induced demixing, SID). SIM is the typical behavior of mixtures of components of low molar mass and polymer solutions, SID can be observed with solutions of high molar mass polymers and polymer blends at higher shear rates. The typical sequence with increasing shear rate is SIM, then occurrence of an isolated additional immiscible area (SLD), melting of this island into the main miscibility gap, and finally SIM again. A three phase line originates and ends in two critical end points. Raising pressure increases the shear effects. For copolymer containing systems SID is sometimes observed at very low shear rates, preceding the just mentioned sequence of shear influences.

Shear-induced spiral-like morphology of a main-chain liquid crystalline poly(aryl ether ketone)

The shear-induced spiral-like morphology of a main-chain thermotropic liquid crystalline poly(aryl ether ketone) is observed and characterized by means of polarizing light microscopy, atomic force microscopy, transmission electron microscopy and electron diffraction techniques. The spiral-like texture is formed during shearing in the temperature range of liquid crystalline to isotropic transition (335-340 degreesC), and dispersed discontinuously in the mosaic matrix. Electron diffraction results indicate that the spiral exhibits orthorhombic lateral packing of the crystals and homeotropic alignment of the molecules. The spiral formation process and possible affecting factors are discussed.

Irreversible capacity loss of graphite electrode in lithium-ion batteries

The irreversible capacity loss of the carbon electrode in lithium-ion batteries at the first cycle is caused mostly by surface film growth. We inspected an unknown irreversible capacity loss (UICL) of the natural graphite electrodes. The charge/discharge behavior of graphite and meso-phase carbon microbeads heat-treated at 2800 degrees C (MCMB28) as the materials of the carbon anode in the lithium-ion battery were compared. It was found that the capacity loss of the natural graphite electrode in the first cycle is caused not only by surface film growth, but also by irreversible lithium-ion intercalation on the new formed surface at the potential range of lithium intercalation, while the capacity loss of the MCMB28 electrode is mainly originated from surface film growth. The reason for the difference of their irreversible capacity losses of these two kinds of carbon material was explained in relation to their structural characteristics. (C) 1997 Published by Elsevier Science S.A.

Antioxidant capacity and lipophilic content of seaweeds collected from the Qingdao coastline

Lipophilic extracts from 16 species of seaweeds collected along the Qingdao coastline were screened and evaluated for their antioxidant activities (AA) using the beta-carotene-linoleate assay system. The diethyl ether soluble extracts of all selected seaweeds exhibited various degrees of antioxidative efficacy in each screen. The highest antioxidant capacities among the tested samples were observed for Rhodomela confervoides and Symphyocladia latiuscula and were comparable with that of the well-known antioxidant butylated hydroxytoluene and greater than that of propyl gallate. The lipophilic content of all 16 samples and the chemical composition of 4 selected seaweeds, R. confervoides and S. latiuscula, which had higher AA, Laminaria japonica, which had intermediate AA, and Plocamium telfairiae, which had lower AA, were analyzed by gas chromatography and gas chromatography-mass spectrometry, respectively. Fatty acids and alkanes were found. The present data indicated an increase in antioxidative property with increasing content of unsaturated fatty acid. The result of this study suggests that seaweeds can be considered as a potential source for the extraction of lipophilic antioxidants, which might be used as dietary supplements or in production in the food industry. This is the first report on the antioxidant activities of lipophilic extracts from seaweeds.

Evaluation of 28 marine algae from the Qingdao coast for antioxidative capacity and determination of antioxidant efficiency and total phenolic content of fractions and subfractions derived from Symphyocladia latiuscula (Rhodomelaceae)

The extracts obtained from 28 species of marine algae were evaluated for their antioxidant activity (AA) versus the positive controls butylated hydroxytoluene (BHT), gallic acid (GA), and ascorbic acid (AscA). Most of the tested samples displayed antioxidant activity to various degrees. Among them, the extract of Symphyocladia latiuscula exhibited the strongest AA, which was comparable to BHT, GA, and AscA in radical scavenging activity, as shown in the DPPH (alpha,alpha-diphenyl-beta-picrylhydrazyl) assay, and higher than those of the positive controls in beta-carotene-linoleate assay system. In addition, the ethyl acetate-soluble fraction isolated from the crude extract of S. latiuscula exhibited the highest antioxidant activity in both assay systems. This fraction was further fractionated into seven subfractions (F1-F7) by vacuum liquid chromatography (VLC). F1 and F4 were found to be the most effective subfractions in scavenging DPPH radical assay and in the beta-carotene-linoleate assay, respectively. The total phenolic content (TPC) and reducing power (RP) for all of the extracts, fractions, and subfractions (F1-F7) were also determined. The TPC of the 28 extracts ranged from 0.10 to 8.00 gallic acid equivalents (mg/g seaweed dry weight) while the RP ranged from 0.07 to 11.60 ascorbic acid equivalents (mg center dot g(-1) seaweed dry weight). Highly positive relationships between AA and TPC as well as between AA and RP were found for the extracts and fractions, while for the subfractions F1-F7 only weak or no such relations were found. The results obtained from this study indicate that further analysis is needed of those marine algal species that contain the most antioxidant activity in order to identify the active principles.

Growth characters and photosynthetic capacity of Gracilaria lemaneiformis as a biofilter in a shellfish farming area in Sanggou Bay, China

Experiments on growth characters and ecological functions of the macroalgae Gracilaria lemaneiformis, collected from south China, were conducted in polyculture areas of kelp and filter-feeding bivalve in Sanggou Bay in Weihai City, Shandong, in north China from May 2002 to May 2003. The results of 116 days cultivation showed that the average wet weight of alga increased 89 times from 0.1 to 8.9 kg rope(-1), with an average specific growth rate ( based on wet weight) of 3.95% per day. The most favorable water layer for its growth was 1.0 - 1.8 m below the surface in July and August, with an average specific growth rate of 8.2% per day in 30-day experiments. Photosynthetic activity changed seasonally, with an average of 7.3 mg O-2 g dw(-1) h(-1). The maximum rate (14.4 mg O-2 g dw(-1) h(-1)) was recorded in July, or 19.3 mg CO2 g dw(-1) h(-1), while the minimum (0.40 mg CO2 g dw(-1) h(-1)) was in April. This study indicated that the culture of G. lemaneiformis is an effective way to improve water quality where scallops are cultivated intensively.

Capacity of soil to protect organic carbon and biochemical characteristics of density fractions in Ziwulin Haplic Greyxems soil

Physical protection is one of the important ways to stabilize organic carbon in soils. In order to understand the role of soils as a carbon sink or source in global climatic change and carbon cycles and properly manage soils as a carbon sink, we ought to know how many organic carbon (OC) in a given soil could be protected. By a density fractionation approach and ultrasonic technique, each soil sample was divided into three fractions: free light fraction (free-LF), occluded fraction (occluded-LF) and heavy fraction (HF). The obtained fractions were analyzed for total OC content, carbohydrate content and recalcitrant OC content. The results showed: (i) In the whole soil profile, dominance of OC consistently decreased in the following order: HF, free-LF, occluded-LF. This suggested that OC in soils were mostly protected. From 0-10 to 60-80 cm horizons, the OC in free-LF decreased from 25.27% to 3.72%, while OC in HF they were increased from 72.57% to 95.39%. The OC in occluded-LF was between 2.16% and 0.89%. (ii) Organic carbon recalcitrance in free-LF was similar to that in HF, and was even higher than that in HF below the surface horizon. This suggested that free-LF was not always the most fresh and non-decomposed fraction. OM quality of HF was higher than that of free-LF in the surface 10 cm below, namely the protected OM had higher quality than free OM in these horizons.

南海张裂大陆边缘数值模拟研究

The South China Sea (SCS) is one of the largest marginal seas in the western Pacific, which is located at the junction of Eurasian plate, Pacific plate and Indian-Australian plate. It was formed by continent breakup and sea-floor spreading in Cenozoic. The complicated interaction among the three major plates made tectonic movement complex and geological phenomena very rich in this area. The SCS is an ideal place to study the formation and evolution of rifted continental margin and sea-floor spreading since it is old enough to have experienced the major stages of the basin evolution but still young enough to have preserved its original nature. As the demand for energy grows day by day in our country, the deep water region of the northern continental margin in the SCS has become a focus of oil and gas exploration because of its huge hydrocarbon potential. Therefore, to study the rifted continental margin of the SCS not only can improve our understanding of the formation and evolution processes of rifted continental margin, but also can provide theoretical support for hydrocarbon exploration in rifted continental margin. This dissertation mainly includes five topics as follows: (1) Various classic lithosphere stretching models are reviewed, and the continuous non-uniform stretching model is modified to make it suitable for the case where the extension of lithopheric mantle exceeds that of the crust. Then simple/pure shear flexural cantilever model is applied to model the basement geometries of SO49-18 profile in the northern continental margin of the SCS. By fitting the basements obtained by using 2DMove software with modeling results, it is found that the reasonable effective elastic thickness is less than 5km in this region. According to this result, it is assumed that there is weak lower crust in the northern continental margin in the SCS. (2) We research on the methods for stretching factor estimation based on various lithosphere stretching models, and apply the method based on multiple finite rifting model to estimate the stretching factors of several wells and profiles in the northern continental margin of the SCS. (3) We improve one-dimension strain rate inversion method with conjugate gradient method, and apply it to invert the strain rate of several wells in the northern continental margin of the SCS. Two-dimension strain rate forward modeling is carried out, and the modeling results show that effective elastic thickness is a key parameter to control basin’s geometry. (4) We simulate divergent upwelling mantle flow model using finite difference method, and apply this newly developed model to examine the formation mechanism of the northwest and central sub-basin in the SCS. (5) We inverse plate thickness and basal temperature of oceanic lithosphere using sea-floor ages and bathymetries of the North Pacific and the North Atlantic based on varied-parameters plate model, in which the heat conductivity, heat capacity and coefficient of thermal expansion depend on temperature or depth. A new empirical formula is put forward based the inversed parameters, which depicts the relation among sea-floor age, bathymetry and heat flow. Then various similar empirical formulae, including the newly developed one, are applied to examine the sea-floor spread issue in the SCS based on the heat flow and bathymetry data of the abyssal sub-basin.

苏丹被动裂谷盆地的油气成藏机理和成藏模式

The research area of this paper covers the maximum exploration projects of CNPC, including Blocks 1/2/4 and Block 6 of the Muglad basin and the Melut basin in Bocks 3/7 in Sudan. Based on the study of the evolution history of the Central African Shear Zone (CASZ), structural styles and filling characteristics of the rift basins, it is put forward that the rift basins in Sudan are typical passive rift basins undergoing the strike-slip, extension, compression and inversion since the Cretaceous. The three-stage rift basins overlapped obliquely. The extension and rifting during the Early Cretaceous is 50-70% of the total extension. The features of the passive rift basins decided that there is a single sedimentary cycle and one set of active source rocks within the middle. Influenced by the three-stage rifting and low thermal gradient, hydrocarbon generation and charging took place very late, and the oil pool formation mechanism is very unique from the Lower Cretaceous rift sequences to the Paleogene. The reservoir-seal assemblages are very complicated in time and space. The sealing capacity of cap rocks was controlled by the CASZ. In general the oils become heavier towards the CASZ and lighter far away. The oil biodegradation is the reason causing the high total acid number. The determination of effective reservoir depth ensures that all discovered fields up to now are high-production fields. The propagation and growth of boundary faults in the rift basins can be divided into a simple fault propagation pattern and a fault growth-linkage pattern. It is firstly found that the linkage of boundary fault segments controls the formation of petroleum systems. Three methods have been established to outline petroleum systems. And a new classification scheme of rift-type petroleum system has been put forward: pre-rift, syn-rift (including passive and active) and post-rift petroleum systems. This scheme will be very important for the further exploration of rift basins. This paper firstly established the formation models of oil pools for the passive rift basins in Sudan: the coupling of accommodation zones and main plays for the formation of giant fields. The overlapping of late rifting broke the anticlines to be several fault-blocks. This process determined that anti-fault blocks are the main traptypes in the cretaceous sequences and anticlines in the Paleogene. This can explain why the traptypes are different between the Muglad and Mefut basins, and will provide theoretic guidance for the exploration strategy. The established formation mechanism and models in this paper have had great potential guidance and promotion for the exploration in Sudan, and resulted in significant economic and social benefit. A giant field of 500 million tons oil in place was found 2003. The cost in Blocks 3/7 is only 0.25

花岗岩风化土微观结构及其工程地质特性研究

Saprolite is the residual soil resulted from completely weathered or highly weathered granite and with corestones of parent rock. It is widely distributed in Hong Kong. Slope instability usually happens in this layer of residual soil and thus it is very important to study the engineering geological properties of Saprolite. Due to the relic granitic texture, the deformation and strength characteristics of Saprolite are very different from normal residual soils. In order to investigate the effects of the special microstructure on soil deformation and strength, a series of physical, chemical and mechanical tests were conducted on Saprolite at Kowloon, Hong Kong. The tests include chemical analysis, particle size analysis, mineral composition analysis, mercury injection, consolidation test, direct shear test, triaxial shear test, optical analysis, SEM & TEM analysis, and triaxial shear tests under real-time CT monitoring.Based on the testing results, intensity and degree of weathering were classified, factors affecting and controlling the deformation and strength of Saprolite were identified, and the interaction between those factors were analyzed.The major parameters describing soil microstructure were introduced mainly based on optical thin section analysis results. These parameters are of importance and physical meaning to describe particle shape, particle size distribution (PSD), and for numerical modeling of soil microstructure. A few parameters to depict particle geometry were proposed or improved. These parameters can be used to regenerate the particle shape and its distribution. Fractal dimension of particle shape was proposed to describe irregularity of particle shapes and capacity of space filling quantitatively. And the effect of fractal dimension of particle shape on soil strength was analyzed. At the same time, structural coefficient - a combined parameter which can quantify the overall microstructure of rock or soil was introduced to study Saprolite and the results are very positive. The study emphasized on the fractal characteristics of PSD and pore structure by applying fractal theory and method. With the results from thin section analysis and mercury injection, it was shown that at least two fractal dimensions Dfl(DB) and Df2 (Dw), exist for both PSD and pore structure. The reasons and physical meanings behind multi-fractal dimensions were analyzed. The fractal dimensions were used to calculate the formation depth and weathering rate of granite at Kowloon. As practical applications, correlations and mathematical models for fractal dimensions and engineering properties of soil were established. The correlation between fractal dimensions and mechanical properties of soil shows that the internal friction angle is mainly governed by Dfl 9 corresponding to coarse grain components, while the cohesion depends on Df2 , corresponding to fine grain components. The correlations between the fractal dimension, friction angle and cohesion are positive linear.Fractal models of PSD and pore size distribution were derived theoretically. Fragmentation mechanism of grains was also analyzed from the viewpoint of fractal. A simple function was derived to define the theoretical relationship between the water characteristic curve (WCC) and fractal dimension, based on a number of classical WCC models. This relationship provides a new analytical tool and research method for hydraulic properties in porous media and solute transportation. It also endues fractal dimensions with new physical meanings and facilitates applications of fractal dimensions in water retention characteristics, ground water movement, and environmental engineering.Based on the conclusions from the fractal characteristics of Saprolite, size effect on strength was expressed by fractal dimension. This function is in complete agreement with classical Weibull model and a simple function was derived to represent the relationship between them.In this thesis, the phenomenon of multi-fractal dimensions was theoretically analyzed and verified with WCC and saprolite PSD results, it was then concluded that multi-fractal can describe the characteristics of one object more accurately, compared to single fractal dimension. The multi-fractal of saprolite reflects its structural heterogeneity and changeable stress environment during the evolution history.

Isotope Geochemistry of Gold Ore Deposits in the Gezhen Shear Zone, Qiongxi, Hainan Island

Gold deposits hosted in the Gezhen shear zone at Qingxi, Hainan Island occur in the Precambrian metamorphic rock series and are regionally developed in the N-E direction along the tectonic zone. From northeast to southwest are distributed the Tuwaishan-Baoban gold mining district, the Erjia gold mining district and the Bumo gold mining district, making up the most industrially important gold metallogenesis zone on the Hainan Island. Isotope geochemical studies of the typical gold deposits in this metallogen

Heat capacity enhancement and thermodynamic properties of nanostructured amorphous SiO2

The heat capacity of nanostructured amorphous SiO2 (na-SiO2) has been measured by adiabatic calorimetric method over the temperature range 9-354 K. TG and differential scanning calorimeter (DSC) were also employed to determine the thermal stability. Glass transition temperature (T-g) for the two same grain sizes with different specific surface of naSiO(2) samples and one coarse-grained amorphous SiO2 (ca-SiO2) sample were determined to be 1377, 1397 and 1320 K, respectively. The low temperature experimental results show that there are significant heat capacity (C-P) enhancements among na-SiO2 samples and ca-SiO2. Entropy, enthalpy, Gibbs free energy and Debye temperature (theta (D)) were obtained based on the low temperature heat capacity measurement of na-SiO2. The Cp enhancements of na-SiO2 were discussed in terms of configurational and vibrational entropy. (C) 2001 Elsevier Science B.V. All rights reserved.

Enhancement of molar heat capacity of nanostructured Al2O3

The nanosized alumina prepared by the hydrolysis method with an average particle size of 20 nm was characterized by X-ray diffraction. The heat capacity measurements of the prepared sample were carried out using an adiabatic calorimeter in the temperature range from 78 to 370 K. Enhancement of heat capacity was observed in the nanostructured materials as the heat capacity data were compared with those of the corresponding coarse-grained materials. The enhanced heat capacity was discussed on the basis of experiments. Differential scanning calorimetry and thermogravimetry were used to determine the thermal stability of the nanostructured alumina.