COORDINATION CHEMISTRY AND SUPERCONDUCTIVITY

Analysing the coordination state of copper ions in cuprate superconductors, it is found that the larger the energy splitting between d(x2-y2) and d(z2) orbitals of Cu or the higher the energy of the d(x2-y2) orbital, the higher the Tc. Thus, appropriate coordination structures and strong-field ligands must be chosen for expanding the energy splitting and increasing the energy of the d(x2-y2) orbital when searching for new high-Tc superconductors. Summarizing the experimental results of ESR and XPS, it is considered that the [Cu2+ - O open-square-box 2- - Cu3+] resonance exists in cuprate superconductors and the electron field breathing mode is present. Analysing the mechanism and the relationship between the coordination state of Cu and Tc, we consider that the two dimensional Cu-O planes are responsible for the superconductivity of YBa2Cu3O7-y.

Cold event at 5 500 a BP recorded in mud sediments on the inner shelf of the East China Sea

A 700-year record (1.0-1.5 a resolution) of the East Asian winter monsoon (EAWM), based on grain-size analysis and AMS(14)C dating of Core EC2005 from the inner-shelf mud wedge of the East China Sea (ECS), was compared with the Dongge stalagmite delta O-18 record during the mid-Holocene. The upper muddy section of Core EC2005 has been formed mainly by suspended sediments derived from the Changjiang (Yangtze) River mouth since 7.3 ka BP. High precipitation and a strengthened EAWM might have played key roles in the high sedimentation rate (1 324-1 986 cm/ka) between 5.9-5.2 ka BP. The EAWM strengthened when the Asian summer monsoon weakened, especially around 5 500 a BP, which corresponded to a worldwide cold event. The EAWM during the mid-Holocene shows statistically significant solar periodicities at 62 and 11 a. The 5 500 a BP cold event might be resulted from orbital forcing and changes in solar activity.

Evolution and variability of the East Asian summer monsoon during the Pliocene: Evidence from clay mineral records of the South China Sea

The Late Pliocene is thought to be characterized by the simultaneous intensification of both the East Asian winter monsoon (EAWM) and East Asian summer monsoon (EASM). However, the evolution of the EASM during the Pliocene remains still controversial and only little is known about the dynamics of the EASM during the Pliocene on orbital time scales. Here we use clay mineral assemblages in sediments from Ocean Drilling Program (ODP) Site 1143 in the southern South China Sea (SCS) to obtain proxy records of past changes in the EASM climate during the Pliocene. Provenance analysis suggests that illite, chlorite and kaolinite originated mainly from the Mekong River drainage area. Smectite was derived mainly from the Indonesian islands. The kaolinite/illite ratio and the chemical index of alteration (CIA) of siliciclastic sediments allowed us to reconstruct the history of chemical weathering and physical erosion of the Mekong River drainage area and thus, the evolution of,the EASM during the Pliocene. Our clay minerals proxy data suggests a stronger EASM during the Early Pliocene than during the Late Pliocene. We propose that the long-term evolution of the EASM has been driven by global cooling rather than the uplift of the Tibetan Plateau. Spectral analysis of kaolinite/ illite ratio displays a set of strong periodicities at 100 ka, 30 ka, 28 ka, 25 ka, and 22 ka. with no clear obliquityrelated signal. Our study suggests that the Pliocene EASM intensity on orbital time scales is not only controlled by the Northern Hemisphere summer insolation, but also strongly influenced by equatorial Pacific ENSO-like ocean atmosphere dynamics. (C) 2010 Elsevier B.V. All rights reserved.

A unified criterion for initiation of sediment motion and inception of sheet flow under water waves

A unified criterion is developed for initiation of non-cohesive sediment motion and inception of sheet flow under water waves over a horizontal bed of sediment based on presently available experimental data. The unified threshold criterion is of the single form, U-o = 2 pi C[1 + 5(T-R/T)(2)](-1/4), where U-o is the onset velocity of sediment motion or sheet flow, T is wave period, and C and T-R are the coefficients. It is found that for a given sediment, U-o initially increases sharply with wave period, then gradually approaches the maximum onset velocity U-o = 2 pi C and becomes independent of T when T is larger. The unified criterion can also be extended to define sediment initial motion and sheet flow under irregular waves provided the significant wave orbital velocity and period of irregular waves are introduced in this unified criterion.

Near-Space Wide-Swath Radar Imaging With Multiaperture Antenna

Near-space, defined as the altitude region between 20 and 100 km, offers many capabilities that are not accessible for low Earth-orbit (LEO) satellites or airplanes because it is above storm and not constrained by orbital mechanics and high fuel consumption. Hence, a high flying speed can be obtained for the maneuvering vehicles operating in near-space. This offers a promising solution to simultaneous high-resolution and wide-swath synthetic aperture radar (SAR) imaging. As such, one near-space wide-swath SAR imaging technique is presented in this letter. The system configuration, signal model, and imaging scheme are described. An example near-space SAR system is designed, and its imaging performance is analyzed. Simulation results show that near-space maneuvering vehicle SAR indeed seems to be a promising solution to wide-swath SAR imaging.

On the nonlinear integral transform of an ocean wave spectrum into an along-track interferometric synthetic aperture radar image spectrum

We present a new nonlinear integral transform relating the ocean wave spectrum to the along-track interferometric synthetic aperture radar (AT-INSAR) image spectrum. The AT-INSAR, which is a synthetic aperture radar (SAR) employing two antennas displaced along the platform's flight direction, is considered to be a better instrument for imaging ocean waves than the SAR. This is because the AT-INSAR yields the phase spectrum and not only the amplitude spectrum as with the conventional SAR. While the SAR and AT-INSAR amplitude spectra depend strongly on the modulation of the normalized radar cross section (NRCS) by the long ocean waves, which is poorly known, the phase spectrum depends only weakly on this modulation. By measuring the phase difference between the signals received by both antennas, AT-INSAR measures the radial component of the orbital velocity associated with the ocean waves, which is related to the ocean wave height field by a well-known transfer function. The nonlinear integral transform derived in this paper differs from the one previously derived by Bao et al. [1999] by an additional term containing the derivative of the radial component of the orbital velocity associated with the long ocean waves. By carrying out numerical simulations, we show that, in general, this additional term cannot be neglected. Furthermore, we present two new quasi-linear approximations to the nonlinear integral transform relating the ocean wave spectrum to the AT-INSAR phase spectrum.

The effect of some triazole derivatives as inhibitors for the corrosion of mild steel in 1 M hydrochloric acid

Corrosion inhibition by some new triazole derivatives on mild steel in 1 M hydrochloric acid solutions has been investigated by weight loss test, electrochemical measurement, scanning electronic microscope analysis and quantum chemical calculations. The results indicate that these compounds act as mixed-type inhibitors retarding the anodic and cathodic corrosion reactions and do not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. The studied compounds following the Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The effect of molecular structure on the inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were calculated. (C) 2009 Published by Elsevier B.V.

2,3,5-triphenyl-2H-tetrazolium chloride and 2,4,6-tri(2-pyridyl)-s-triazine on the corrosion of mild steel in HCl

Electrochemical measurement, quantum chemical method, and scanning electron microscopy (SEM) were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) and 2,4,6-tri(2-pyridyl)-s-triazine(TPT) on the corrosion of mild steel in 1mol.L-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mechanism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal was protected from aggressive corrosion by the addition of TTC and TPT.

Aminic nitrogen-bearing polydentate Schiff base compounds as corrosion inhibitors for iron in acidic media: A quantum chemical calculation

Quantum chemical calculations based on DFT method were performed on three polydentate Schiff base compounds (PSCs) used as corrosion inhibitors for iron in acid media to determine the relationship between the molecular structure of PSC and inhibition efficiency. The structural parameters, such as the frontier molecular orbital energy HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital), the charge distribution of the studied inhibitors, the absolute electronegativity (chi) values, and the fraction of electrons (Delta N) transfer from inhibitors to iron, were also calculated and correlated with inhibition efficiencies. The results showed that the inhibition efficiency of PSCs increased with the increase in E-HOMO and decrease in E-LUMO-E-HOMO; and the areas containing N atoms are most possible sites for bonding the metal iron surface by donating electrons to the metal. (C) 2007 Elsevier Ltd. All rights reserved.

Nicotinic acid as a nontoxic corrosion inhibitor for hot dipped Zn and Zn-Al alloy coatings on steels in diluted hydrochloric acid

The inhibition effect of nicotinic acid for corrosion of hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid was investigated using quantum chemistry analysis, weight loss test, electrochemical measurement, and scanning electronic microscope (SEM) analysis. Quantum chemistry calculation results showed that nicotinic acid possessed planar structure with a number of active centers, and the populations of the Mulliken charge, the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) were found mainly focused around oxygen and nitrogen atoms, and the cyclic of the benzene as well. The results of weight loss test and electrochemical measurement indicated that inhibition efficiency (IE%) increased with inhibitor concentration, and the highest inhibition efficiency was up to 96.7%. The corrosion inhibition of these coatings was discussed in terms of blocking the electrode reaction by adsorption of the molecules at the active centers on the electrode surface. It was found that the adsorption of nicotinic acid on coating surface followed Langmuir adsorption isotherm with single molecular layer, and nicotinic acid adsorbed on the coating surface probably by chemisorption. Nicotinic acid, therefore, can act as a good nontoxic corrosion inhibitor for hot dipped Zn and Zn-Al alloy coatings in diluted hydrochloric acid solution. (c) 2007 Elsevier Ltd. All rights reserved.

Experimental and theoretical investigation of the adsorption behaviour of new triazole derivatives as inhibitors for mild steel corrosion in acid media

Three triazole derivatives (4-chloro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (CATM), 4-methoxyl-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (MATM) and 4-fluoro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (FATM)) have been synthesized as new inhibitors for the corrosion of mild steel in acid media. The inhibition efficiencies of these inhibitors were evaluated by means of weight loss and electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and polarization curves. Then the surface morphology was studied by scanning electron microscopy (SEM). The adsorption of triazole derivatives is found to obey Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The relationship between molecular structure of these compounds and their inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were computed. (c) 2007 Elsevier Ltd. All rights reserved.

Electrochemical and quantum chemical study of purines as corrosion inhibitors for mild steel in 1 M HCl solution

The purines and its derivatives, such as, guanine, adenine, 2,6-diaminopurine, 6-thioguanine and 2,6-dithiopurine, were investigated as corrosion inhibitors for mild steel in 1 M HCl solution by weight loss measurements, electrochemical tests and quantum chemical calculations. The polarization curves of mild steel in the hydrochloric acid solutions of the purines showed that both cathodic and anodic processes of steel corrosion were suppressed. The Nyquist plots of impedance expressed mainly as a depressed capacitive loop with different compounds and concentrations. For all these purines, the inhibition efficiency increased by increasing the inhibitor concentration, and the inhibition efficiency orders are 2,6-dithiopurine > 6-thioguanine > 2,6-diaminopurine > adenine > guanine with the highest inhibiting efficiency of 88.0% for 10(-3) M 2,6-dithiopurine. The optimized structures of purines, the Mulliken charges, molecular orbital densities and relevant parameters were calculated by quantum chemical calculations. The quantum chemical calculation results inferred that the adsorption belong to physical adsorption, which might arise from the pi stacking between the pi electron of the purines and the metal surface. (C) 2008 Elsevier Ltd. All rights reserved.

Theoretical study on adsorption of Na+ and Na+(H2O)(n) (n=1-6) on a clean Si(111) surface

To model the adsorption of Na+ in aqueous solution on the semiconductor surface, the interactions of Na+ and Na+(H2O)(n) (n = 1-6) with a clean Si(111) surface were investigated by using hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The Si(111) surface was described with Si8H12, Si16H20, and Si22H21 Cluster models. The effect of the basis set superposition error (BSSE) was taken into account by applying the counterpoise (CP) correction. The calculated results indicated that the interactions between the Na+ cation and the dangling bonds of the Si(111) surface are primarily electrostatic with partial orbital interactions. The magnitude of the binding energies depends weakly on the adsorption sites and the size of the clusters. When water molecules are present, the interaction between the Nal and Si(I 11) surfaces weakens and the binding energy has the tendency to saturate. On a Si22H21 cluster described surface, the optimized Na+-surface distance for Na+(H2O)(5) adsorbed at on-top site is 4.16 angstrom and the CP-corrected binding energy (MP2) is -35.4 kJ/mol, implying a weakly adsorption of hydrated Na+ cation on clean Si(111) surface.

黄土-红粘土化学风化与晚新生代气候变化——甘肃平凉白水剖面为例

Late Cenozoic has witnessed a series of climate-environmental change which ends with a transitional shift from greenhouse to icehouse conditions. In last two decades, scientists began to employ the tectonic uplift and its weathering effect to interpret the climatic changes during the late Cenozoic. However, this endeavor has partly been restricted by the lacking of regional and global chemical weathering data. The loess-red clay deposit in the Loess Plateau may record the weathering features of the detritus material from the wide range upwind of the Loess Plateau. Therefore geochemistry of the loess-plaeosol and red clay sequences may provide insights into the regional chemical weathering regime and the connection between the chemical weathering and the late Cenozoic climate-environmental change Here we selected 319 samples from the Baishui section near the Pingliang City, Gansu Province, and analyzed them with X-ray fluorescence. Based on the result, we reconstruct the chemical weathering history of the Baishui section since 6Ma. We chose CIA as the proxy for chemical weathering intensity. The CIA ratio in soil units is higher than in adjacent loess horizons, but lower than in the red clay, in good agreement with the field observation. The CIA ratios of the Baishui section correlates well with the global ice volume fluctuations, indicating that the global cooling may contribute a lot to the chemical weathering variations in Chinese Loess Plateau. There are at least 3 million-year time scale variations that can be identified in the chemical weathering intensity curve, i.e., between 3.3 to 2.1 Ma, 1.7 to 0.9 Ma and from 0.9Ma. We think these may reflect the combined effect of the tectonic uplift and ice sheets on monsoon intensity. Other time scale variations can be also observed. In the period between 2.4 and 0.8 Ma, the CIA record display the 400,000 years cycle, which may be resulted from the Tibetan uplift during the Pliocene-early Pleistocene which have significantly amplified the monsoon response sensitivity to the orbital-scale variations in insolation. From 1.2 Ma, the 100,000 years period became intensifying, and particularly after 0.8 Ma, the earlier monsoon response at 400,000 year periodicity was overwhelmed by the ice sheet forcing at 100,000 year periodicity. These may indicate that the expansions of the Northern Hemisphere ice sheets may have crossed a threshold, which enforce the monsoon responding at the 100,000 year periodicity.

陇西盆地晚第三纪风尘沉积的地层学研究

In Asia, the significant environment changes in Cenozoic include: uplift of Himalayas and Tibetan Plateau, formation Asian monsoon system, Aridification in Central Asia. One of major advances in recent studies of eolian deposit on the Loess Plateau is the verification of the eolian origin for the Late Tertiary Hipparion Red-Earth (also called red-Clay) underlying the Quaternary loess. Thus, the Late Tertiary eolian deposit, which has been proven a nearly continuous terrestrial record and sensitive to climate change, provides us an important archive to understand these above Cenozoic environment events. The deposit in eastern Loess Plateau has been extensively studied, while the property and age of deposit underlying the Quaternary loess in western plateau remains unclear. In this paper, detail investigations were made on the Sedimentology, geochemistry of Longxi section, a typical section in western Loess Plateau, to address its origin, and on micromammalian fossils and magnetostratigraphy to address its age. The main conclusions are presented as following: 1. The sedimentological and geochemical properties in Longxi section are highly similar to typical Quaternary eolian deposit in Loess Plateau. Nearly 100 paleosols are recognized in the field, and the grain size are very fine with the median grain size centered at 4～7μm. There is a good agreement of both major and trace element compositions between Longxi deposit and the Quaternary Loess. The REE distribution patterns of Longxi deposit and the Quaternary loess are remarkably similar in shape, with enrichment LREE and fairly flat HREE profiles and clear negative Eu anomaly. The mangnetic minerals in Longxi deposit are mainly magnetite, hematite and maghematite, which are similar to those of the Hipparion Red-Earth and Quaternary Loess. The major difference among them is that the samples from Longxi section contain more hematite. The characteristics of anisotropy of magnetic susceptibility (AMS) in Longxi deposit is highly consistent with that of Quaternary loess, while values of the major AMS parameters, e.g. anisotropy degree, magnetic foliation and lineation, are significantly lower than those of fluvial and lake deposits. These evidences indicate an eolian origin for the sediment. 2. An investigation of micromammalian fossils was firstly carried out for determining the approximate age of the sequence because of lack of materials for accurate isotope dating. Three fossil assemblages were obtained which indicate a chronological range from the Middle Miocene to Late Miocene. The magnetostratigraphical study suggests that it is a near continuous terrestrial record for the period from 13.23 to 6.23 MaB.P. The obtained chronology is highly consistent with fossils assemblages. This section is the oldest eolian deposit presently known in Loess Plateau. 3. The magnetic susceptibly value is high in paleosols than in surrounded weak-weathered layers, which suggests that it may be a climate index on orbital time scale. While it cannot be used as a proxy to address the long-term, change of climate on tectonic time scale, as content of the magnetic minerals is highly variable in different parts of the section. 4. The appearance of Middle Miocene eolian deposit in the Loess Plateau marks the strengthening of aridification of Central Asia. The high degree of similarity between the geochemical properties of Longxi eolian deposit, Hipparion Red-Earth and Quaternary loess a suggests that a rather similar source provenance. The dust accumulation rate (DAR) of Longxi section, which is widely used as a proxy to document the aridity in source areas in marine and terrestrial record studies, recorded the aridity condition in northwestern China over a period from Middle Miocene to Late Miocene. The DAR of the section shows that the continent aridity remains moderate and relative stable over that period.