Crystallization behavior of blends of high-density polyethylene with novel linear low-density polyethylene

Blends of high-density polyethylene (HDPE) with novel linear low-density polyethylene (LLDPE) samples in the whole range of compositions were investigated by means of differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). The LLDPEs are ethylene/octene-1 copolymers prepared with a single-site catalyst, with a narrower distribution of branches compared to Ziegler-Natta type polymers. It was found that cocrystallization or separate crystallization in the blends profoundly depends on the content of branches in the LLDPE, while the critical branch content of the novel LLDPE for separate crystallization is much lower than that of commercial LLDPE (prepared with Ziegler-Natta catalysts). This implies that the miscibility of linear and branched polyethylene is also affected by the distribution of branches. The marked expansion of the unit cell in cocrystals, which are formed by HDPE with the novel LLDPE, indicates that the branches are included in the crystal lattice during the cocrystallization process. The result is very helpful to understand the phenomenon that the unit cell dimensions of commercial branched polyethylene are larger than those of linear polyethylene.

The crystal structure and drawing-induced polymorphism in poly(aryl ether ketone)s .1. Poly(oxybiphenyl-4-4'-diyloxy-1,4-phenylenecarbonyl-1,3-phenylenecarbonyl-1,4-phenylene)

Crystal structure and polymorphism induced by uniaxial drawing of a poly(aryl ether ketone) [PEDEKmK] prepared from 1,3-bis(4-fluorobenzoyl)benzene and biphenyl-4,4'-diol have been investigated by means of transmission electron microscopy (TEM), electron diffraction (ED), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC) techniques. The melting and recrystallization process in the temperature range of 250-260 degrees C, far below the next melting temperature (306 degrees C), was identified and found to be responsible for the remarkable changes in lamellar morphology. Based on WAXD and ED patterns, it was found that crystal structure of isotropic-crystalline PEDEKmK obtained under different crystallization conditions (melt-crystallization, cold-crystallization, solvent-induced crystallization, melting-recrystallization, and crystallization from solution) keeps the same mode of packing, i.e., a two-chain orthorhombic unit cell with the dimensions a = 0.784 nm, b = 0.600 nm, and c = 4.745 nm (form I). A second crystal modification (form II) can be induced by uniaxial drawing above the glass transition temperature, and always coexists with form I. This form also possesses an orthorhombic unit cell but with different dimensions, i.e., a = 0.470 nm, b = 1.054 nm, c = 5.064 nm. The 0.32 nm longer c-axis of form II as compared with form I is attributed to an overextended chain conformation due to the expansion of ether and ketone bridge bond angles during uniaxial drawing. The temperature dependence of WAXD patterns for the drawn PEDEKmK suggests that form II can be transformed into the more stable form I by relaxation of overextended chains and relief of internal stress at elevated temperature in absence of external tension.

Genome-wide analysis of restriction-modification system in unicellular and filamentous cyanobacteria

Cyanobacteria are an ancient group of gram-negative bacteria with strong genome size variation ranging from 1.6 to 9.1 Mb. Here, we first retrieved all the putative restriction-modification (RM) genes in the draft genome of Spirulina and then performed a range of comparative and bioinformatic analyses on RM genes from unicellular and filamentous cyanobacterial genomes. We have identified 6 gene clusters containing putative Type I RMs and 11 putative Type II RMs or the solitary methyltransferases (MTases). RT-PCR analysis reveals that 6 of 18 MTases are not expressed in Spirulina, whereas one hsdM gene, with a mutated cognate hsdS, was detected to be expressed. Our results indicate that the number of RM genes in filamentous cyanobacteria is significantly higher than in unicellular species, and this expansion of RM systems in filamentous cyanobacteria may be related to their wide range of ecological tolerance. Furthermore, a coevolutionary pattern is found between hsdM and hsdR, with a large number of site pairs positively or negatively correlated, indicating the functional importance of these pairing interactions between their tertiary structures. No evidence for positive selection is found for the majority of RMs, e. g., hsdM, hsdS, hsdR, and Type II restriction endonuclease gene families, while a group of MTases exhibit a remarkable signature of adaptive evolution. Sites and genes identified here to have been under positive selection would provide targets for further research on their structural and functional evaluations.

Genome-wide analysis of restriction-modification system in unicellular and filamentous cyanobacteria

Cyanobacteria are an ancient group of gram-negative bacteria with strong genome size variation ranging from 1.6 to 9.1 Mb. Here, we first retrieved all the putative restriction-modification (RM) genes in the draft genome of Spirulina and then performed a range of comparative and bioinformatic analyses on RM genes from unicellular and filamentous cyanobacterial genomes. We have identified 6 gene clusters containing putative Type I RMs and 11 putative Type II RMs or the solitary methyltransferases (MTases). RT-PCR analysis reveals that 6 of 18 MTases are not expressed in Spirulina, whereas one hsdM gene, with a mutated cognate hsdS, was detected to be expressed. Our results indicate that the number of RM genes in filamentous cyanobacteria is significantly higher than in unicellular species, and this expansion of RM systems in filamentous cyanobacteria may be related to their wide range of ecological tolerance. Furthermore, a coevolutionary pattern is found between hsdM and hsdR, with a large number of site pairs positively or negatively correlated, indicating the functional importance of these pairing interactions between their tertiary structures. No evidence for positive selection is found for the majority of RMs, e. g., hsdM, hsdS, hsdR, and Type II restriction endonuclease gene families, while a group of MTases exhibit a remarkable signature of adaptive evolution. Sites and genes identified here to have been under positive selection would provide targets for further research on their structural and functional evaluations.

东天山红山高硫型浅成低温铜-金矿床氧化带的形成机理和硫酸盐矿物的系列发现及意义

Located in the Paleozoic uplift along the southern margin of Tu-Ha basin in eastern Xinjiang, the newly discovered Hongshan Cu-Au deposit occurs in the superimposed Mesozoic volcanic basin upon the north section of later Paleozoic Dananhu-Tousuquan accretionary arc. Kalatage Cu-Au orebelt is controlled by NWW-trend faults, and includes Hongshan and Meiling Cu-Au deposits. The host rocks of Hongshan ore district are mainly rhyolitic-dacitic ignimbrites, whereas Cu-Au mineralization is closely related to quartz porphyry, rhyolitic porphyry and granitic porphyry. Mineralization styles are dominantly veinlet-disseminated and veinlet, occasionally stockwork. The mineral association is chalcopyrite, pyrite, bornite, chalcocite and sphalerite. The hydrothermal alteration consists of silicfication, sericitization, alunitization, pyrophylitization, illitization, hydromuscovitization, and chloritization. Hongshan Cu-Au deposit, on the edge of the desert, is one of the driest areas in eastrn Tianshan. Moreover， the highest temperature has been up to 60℃, and the average rainfall receives only 34.1mm/y. The light rainfall and rapid evaporation in the vicinity of this deposit have allowed the formation of a great variety of water-soluble sulfates. Oxidization zone of this deposit lies on the upper part of primary sulfide orebodies appearing with a depth of 50-60m, which is dominant in sulfate minerals. 1. Based on the field observation, the volcanic and sub-volcanic rock composition, hydrothermal alteration, ore structure and mineralization characteristics, this paper proposed that the Hongshan Cu-Au deposit belongs to a transitional type from high-sulfide epithermal to porphyry Cu-Au deposit, which corresponds with the typical HS-epithermal deposit such as Zijinshan Au-Cu deposit in Fujian Province, SE-China. 2. The Hongshan copper-gold deposit was controlled by the tectonic, stratum, magma activity and volcanic apparatus, whereas Au mineralization is closely related to quartz porphyry, rhyolitic porphyry and fine grained pyritization in hydrothermal activity, and Cu mineralization is closely related to quartz porphyry and hydrothermal explosive breccia. 3. Oxidation zone of Hongshan Cu-Au deposit lies on the upper part of primary sulfide orebodies deposit. 23 sulfate minerals were identified in this work. The results of samples XRD and chemical analysis were furthermore confirmed through thermal, infrared spectrum and mössbauer spectrum analysis. Among those, nine minerals as Ferricopiapite, Cuprocopiapite, Rhomboclase, Parabutlerite, Krausite, Yavapaiite, Metasideronatrite Kroehnkite and Paracoquimbite were founded in China for the first time. And Paracoquimbite was secondly reported in the world (first case reported at 1938 in Chile). 4. EPMA analysis shows that Al impurity in crystal lattice is important to polytype formation of paracoquimbite and coquimbite besides stack fault. 5. Compared with Meiling Cu-Au deposit in the same Kalatage ore belt from the characteristics of δ34S of barite, lithofacies, hydrothermal alteration and homogeneous temperature, Hongshan Cu-Au deposit belongs to the same metallogenic system of HS-epithermal type as Meiling Cu-Au deposit. But Hongshan Cu-Au deposit has less extensive alteration and shallower denudation. 6. Sulfur isotope analyses show that δ34S values of pyrites vary in the range of +1.86‰~+5.69‰, with an average of 3.70‰, mostly in the range of +1.86‰~+3.20‰, and δ34Scp<δ34Spy. Therefore ore-forming fluid of porphyry comes from mantle and was contaminated by the earth’s crust. Sulfur isotope has reached balance in ore-forming process. 7. Sulfur isotope analyses show that δ34S values of sulfates vary in the range of +2.15‰~+6.73‰, with an average of +3.74‰, mostly equals as δ34S values of primary sulfides in Hongshan Cu-Au deposit. So supergene sulfates inherit sulfur of primary sulfide. δ34S values are mostly same in different sulfates. As well as pyrite and chalcopyrite, volcanic hot spring and associated native sulfur underground also provide water medium and sulfur during the formation process of sulfate. 8. According to the EPMA of sample chalcopyrite and pyrite in Hongshan Cu-Au, the value of Cu/Ni is 0.98-34.72, mostly close to the value of 5, which shows that Hongshan deposit is a typical volcanogenic magmaic hypothermal deposit. Au and Ag, Zn, Te and Bi are positive correlation, Cu and Hg, Se, Sb are positive correlation, indicates Au and Cu don’t locate in the factor of mineralization of same mineralization groups. The reasons of gold concentration in the oxidation zone are: 1). Change of redox potential (Eh) makes gold to deposit from the liquid of mineralization zone; 2). PH is one of the most factors of gold’s deposition; 3). Soluble complex and colloid of gold can be adsorbed easily. 9. The biotite and hornblende K-Ar isotopic ages from the wall rock－quartz diorite, biotite granite and monzonite granite are 231.99±3.45Ma, 237.97±2.36Ma and 296.53±6.69Ma respectively. The ore-bearing rhyolitic breccia lava contains breccia of the biotite granite which indicates the volcanism and related Cu-Au mineralization occurred later than the granite, possibly in Mesozoic. K-Ar ages of granitoids in Sanya, Baishiquan and Hongliugou area and Molybdenite Re-Os age of Baishan Mo deposit all are in Triassic. Besides late Paleozoic magmatism, igneous magmatic event of Mesozoic was widespread in eastern Tianshan. 10. The K-Ar age dating indicates that the K-Ar age of Voltaite occurred below surface 1m is 56.02±3.98Ma, K-Ar age of Ferricopiapite occurred below surface 1.5m is 8.62±1.12Ma, K-Ar age of Yavapaiite occurred below surface 14 m is 4.07±0.39Ma, and K-Ar age of Voltaite occurred below surface 10 m is 14.73±1.73Ma. So the age interval of oxidation zone of Hongshan copper-golden bed is between 60 -3.38Ma. Oxidization occurred at Caenozoic era (from 65Ma), which can be identified through comparing with different deposits oxidation zone in other countries. The coupling between global tectonic event and climatic change event which occur from Caenozoic era has some effect on epigeosphere system, which can act on the surface of bed oxidation zone similarly. It induces that the age mentioned above coincide with collision of India-Asia and multistage uplifting of Qinhai-Tibet Plateau happened subsequently. Bed oxidation zone is the effect and record of collision and uplifting of Tibet Plateau. The strong chemical weathering of surface accumulation to which was leaded by PETM event occurred Paleocene and Eocene is the reason of Voltaite sharply rises. On the contrary, Ferricopiapite formed due to the global cold weather. The predecessor did much research through biota, isotopes, susceptibility, but this paper try to use different sulfate mineral instead of climatic change. So the research of sulfate minerals not only indicates a great deal of oxidized zone feature, but also the intergrowth of sulfate minerals may be used to trace paleoenviroment and paleoclimate of oxidation zone. 11. Analysis of the information of alteration and mineralization features of four bore cores, induced activity polarization well logging and Eh-4 geophysical section, deep mineralization anomaly objects of Hongshan ore districts shows low resistance, middle and high polarization, measurements of Eh-4 consecutive conductance section show the existing of concealed porphyry ore body deeper than 450m, on the top of and around rock body there are low resistance body ranged from 100-300Ω•m, this area may be the ore-bearing part. In a word, Hongshan Cu-Au deposit deposit is a combine of upper HS-style epithermal Au deposit and deeper porphyry mineralization system. It has great potential to find large HS-style epithermal-porphyry Au-Cu deposits. This paper consists of seven chapters and twenty seven sections. The geological character of deposit is basic condition in this work. Constitute of oxidation zone, research of sulfate mineral, relation between oxidation and primary zone, K-Ar ages of potassic sulfate are key parts of thesis. Genesis of ore deposit is the further expansion of this research. Analysis of ore-controlling factors is the penetration above basic. Analysis of potential is application of exploration.

黄土高原中部60万年来黄土—古土壤序列有机碳同位素研究

Vegetation is very sensitive to climate change. Carbon isotopes in paleosol have been widely used to contruct the propotion of plants using C3 and C4 photosynthetic pathways. δ13C of Loess organic matter were analyzed on the loess- paleosols samples from Jingchuan sections and Luochuan S4—S5 sequence. This paper presents a long carbon isotope time series, covering the last 600kyr. δ13C record of Loess organic matter in Jingchuan is correlated with marine oxygen isotope records. Basing on former research work, this paper discusses temperature, rainfall and P CO2 effect on δ13Corg value. In the interglacial periods, carbon isotope is more sensitive than other proxies and indicates several climate fluctuations. The main conclusions are as follows: 1. Obtained δ13C composition from paleosols and loess sediments in Jingchuan range of -20.0‰ to -24.6‰, the maximum biomass of C4 is 35%, indicating a C3 and C4 mixed steppe with C3 dominated. C4 plant is not always expansion during paleosols periods. The minimum values of Jingchuan section appeared in S4 soil, and the vegetation was almost pure C3 plant at that time. δ13Corg value in S5-2 is also lower than loess in S5, reaching the minimum valus of S5 soil. 2. PCO2 variation has little impact on δ13Corg value in interglacial periods for the last 600kyr. The correlation between δ13Corg value curve and magnetic susceptibility curve as proxy of summer monsoon in general, means summer monsoon drive C4 plant expansion during glacial and interglacial. 3. The lowerδ13Corg values in S4 and S5-2 appear at Jingchuan and Luochuan, suggest origin from woodland or C3 grassland. Whatever vegetation it is, indicate strengthened East Asian summer monsoon and increase of precipitation. C4 plant percentage is lower in S5-1 and S1 which have stronger summer monsoon, than S0 and S2. And it also indicates increase of precipitation.δ13Corg values has not always non-linearity correlation with summer monsoon. 4. The maximum entroy spectral analysis of δ13C values of the last 600kyr indicates there is 21 kyr cycles in Loess sequence. It means that summer monsoon in the Chinese Loess Plateau also has the precession cycles like its origin low latitude.

压力和铁含量对铁方镁石(Mg1-xFex)O(x<=0.25)弹性常数影响的第一性原理研究

By first principle methods based on density functional theory (DFT),the equation of state(EOS) and elastic constants of both periclase and ferropericlase are calculated. The pressure and iron doping effects on the elastic constants of ferropericlase are investigated systematically. Firstly, we calculate the elastic constants of periclase and compare the obtained results with experimental data and other theoretical calculations, which shows a encouraging consistence and demonstrates the practicability of first-principle methods. Secondly, by adding iron into periclase crystal model, we build up ferropericlase with iron contents ranging from 0% to 25% mole percent. The corresponding elastic constants are calculated in a large pressure range(0~120GPa). Emphatically, the strong correlation of 3d electrons in transitional elements, such as iron, is difficult to treat in first-principle methods for a long time. The current solution is to make additional correction. During the initial stage of this study, the strong correlation of 3d electrons in iron is not considered, and we observed that addition of iron decreases the volume of ferropericlase, which is totally contradictory to the experimental data. By applying LDA+U approximation in order to solve the strongly correlated 3d electron of iron, we observed the expansion of volume by iron as expected. On the basis of the LDA+U approximation, the elastic constants of ferropericlase are calculated. After a detailed analysis of data obtained from theoretical calculations, we have reached the following conclusions:(1)pressure imposes positive effects on all elastic constants, and the degree of effects is C11>C12>C44. (2) Iron has no distinctive effects on C11 and C12, although some fluctuations are observed around 60GPa. However, iron has obvious softening effects on C44 The softening effects on C44 are intensified as pressure increases. Above the 100GPa, the effects increase greatly, even surpasses the pressure's positive effects in ferropericlase crystal models with iron mole percent of having 12.5%, 18.75% and 25% iron content. (3)As to the modulus deprived from elastic constants, iron has no effect on the adiabatic bulk module BS, only a little fluctuation around 60GPa. We find iron's softening effects on shear modulus G. (4)We find out that, compared with low iron content, elastic constants with iron content approaching 25mole% is consistently fluctuated，which may be caused by the limitations of the LDA+U approximation method itself. (5)We investigate the pressure and Fe doping effects on elastic anisotropy factor（A=(2C44+C12-C11)/C11） of ferropericlase and find out that iron contents will lower the critical isotropic pressure. At the same pressure, when the pressure is below the isotropic pressure, iron softens the anisotropy factor ; when pressure surpasses the isotropic pressure, iron increases the anisotropy factor.

黄土高原22万年来的黑碳记录和古火灾害历史重建

The term black carbon is used to describe a relatively inert and ubiquitous form of carbon, comprising a range of materials from char and charcoal to element or graphite carbon produced by the incomplete combustion of fossil fuels and biomass. Due to its inertness, the BC in soils, lacustrine and marine sediments and ice can persist over a long period of time. So BC signatures in geological deposits can be used as evidence of natural fires happened in their surroundings. To study the temporal and spatial changes in paleofires over the Chinese Loess Plateau, black carbon concentrations were analyzed on the loess-paleosol samples from three sections including Lijiayuan, Lingtai and Weinan along a north-south transect. Using the orbitally-tuned time-scales of the sections, the black carbon sedimentation rates (BCSR) were calculated. Meanwhile, with objective to document fine resolution fire history during late Pleistocene and Holocene periods, we measured BC concentrations of loess-paleosol samples at dense sampling intervals since 28 ka BP. in Lijiayuan section. The BCSR of the samples were also calculated. In addition, we also conducted observation on black carbon morphologies to examine their sources. Based on the results, the following remarks can be concluded: 1. In the last two glacial cycles, the BCSR values in glacial periods are 2-3 times higher than in interglacial periods, and the BCSR variability has a relatively strong precession-associated 23 kyr period, suggesting that the glacial cold-dry climate conditions were apt to induce natural fires over the Loess Plateau, 2. Comparison of the BCSR records among the three loess sections demonstrates that natural fire occurrence was much more intensive and frequent in the northern and interglacial periods. 3. Pollen records and carbon isotope analyses of organic matter have shown that the Loess Plateau was covered by an Artemisia-dominated grassland vegetation both during glacial and interglacial periods, So grassland fires were the dominant fire types in the Plateau, which is also corroborated by the observation of black carbon morphology. In addition, statistics and comparison of BC particle sizes among the sections demonstrated that BC records probably reflected local fires. 4. According to previous studies about the effect of fires on vegetation changes, we considered that the fires might play an important role in the expansion of grassland during glacial periods, besides the control of climate changes. 5. The high resolution black carbon record in Lijiayuan section has shown that the BCSR series well documented Younger dryas (YD) and Heinrich (HI和H2) events, suggesting that natural fires in the northwestern part of Chinese Loess Plateau could regularly respond to the millennial scale climate oscillation.

基于结构分析地震资料去噪方法研究

With the development of oil and gas exploration, the exploration of the continental oil and gas turns into the exploration of the subtle oil and gas reservoirs from the structural oil and gas reservoirs in China. The reserves of the found subtle oil and gas reservoirs account for more than 60 percent of the in the discovered oil and gas reserves. Exploration of the subtle oil and gas reservoirs is becoming more and more important and can be taken as the main orientation for the increase of the oil and gas reserves. The characteristics of the continental sedimentary facies determine the complexities of the lithological exploration. Most of the continental rift basins in East China have entered exploration stages of medium and high maturity. Although the quality of the seismic data is relatively good, this areas have the characteristics of the thin sand thickness, small faults, small range of the stratum. It requests that the seismic data have high resolution. It is a important task how to improve the signal/noise ratio of the high frequency of seismic data. In West China, there are the complex landforms, the deep embedding the targets of the prospecting, the complex geological constructs, many ruptures, small range of the traps, the low rock properties, many high pressure stratums and difficulties of boring well. Those represent low signal/noise ratio and complex kinds of noise in the seismic records. This needs to develop the method and technique of the noise attenuation in the data acquisition and processing. So that, oil and gas explorations need the high resolution technique of the geophysics in order to solve the implementation of the oil resources strategy for keep oil production and reserves stable in Ease China and developing the crude production and reserves in West China. High signal/noise ratio of seismic data is the basis. It is impossible to realize for the high resolution and high fidelity without the high signal/noise ratio. We play emphasis on many researches based on the structure analysis for improving signal/noise ratio of the complex areas. Several methods are put forward for noise attenuation to truly reflect the geological features. Those can reflect the geological structures, keep the edges of geological construction and improve the identifications of the oil and gas traps. The ideas of emphasize the foundation, give prominence to innovate, and pay attention to application runs through the paper. The dip-scanning method as the center of the scanned point inevitably blurs the edges of geological features, such as fault and fractures. We develop the new dip scanning method in the shap of end with two sides scanning to solve this problem. We bring forward the methods of signal estimation with the coherence, seismic wave characteristc with coherence, the most homogeneous dip-sanning for the noise attenuation using the new dip-scanning method. They can keep the geological characters, suppress the random noise and improve the s/n ratio and resolution. The rutine dip-scanning is in the time-space domain. Anew method of dip-scanning in the frequency-wavenumber domain for the noise attenuation is put forward. It use the quality of distinguishing between different dip events of the reflection in f-k domain. It can reduce the noise and gain the dip information. We describe a methodology for studying and developing filtering methods based on differential equations. It transforms the filtering equations in the frequency domain or the f-k domain into time or time-space domains, and uses a finite-difference algorithm to solve these equations. This method does not require that seismic data be stationary, so their parameters can vary at every temporal and spatial point. That enhances the adaptability of the filter. It is computationally efficient. We put forward a method of matching pursuits for the noise suppression. This method decomposes any signal into a linear expansion of waveforms that are selected from a redundant dictionary of functions. These waveforms are chosen in order to best match the signal structures. It can extract the effective signal from the noisy signal and reduce the noise. We introduce the beamforming filtering method for the noise elimination. Real seismic data processing shows that it is effective in attenuating multiples and internal multiples. The s/n ratio and resolution are improved. The effective signals have the high fidelity. Through calculating in the theoretic model and applying it to the real seismic data processing, it is proved that the methods in this paper can effectively suppress the random noise, eliminate the cohence noise, and improve the resolution of the seismic data. Their practicability is very better. And the effect is very obvious.

Synthesis of 2-butoxy ethanol with narrow-range distribution catalyzed by supported heteropolyacids

A supported heteropolyacid (HPA), H3PMo12O40/SiO2, calcined in vacuum at 150 degrees C, has been shown to be an efficient solid acid catalyst for the synthesis of 2-butoxy ethanol with high selectivity. (C) 2000 Elsevier Science B.V. All rights reserved.

Direct Computation of 3D Shape Invariants and the Focus of Expansion

Structure from motion often refers to the computation of 3D structure from a matched sequence of images. However, a depth map of a surface is difficult to compute and may not be a good representation for storage and recognition. Given matched images, I will first show that the sign of the normal curvature in a given direction at a given point in the image can be computed from a simple difference of slopes of line-segments in one image. Using this result, local surface patches can be classified as convex, concave, parabolic (cylindrical), hyperbolic (saddle point) or planar. At the same time the translational component of the optical flow is obtained, from which the focus of expansion can be computed.