STUDY ON DEPOSITION POTENTIALS OF LITHIUM AND SODIUM-IONS AND DEPOLARIZATION IN BINARY CHLORIDE

Deposition potentials of Lithium and Sodium ions have been measured in binary chloride systems (LiCl-KCl, NaCl-KCl) by I-V curve method, to provide a theoretical base for preparing high purity Al-Li alloy by electrolysis in molten salt. The changes of free energy and enthalpy were calculated in terms of depolarization values on Al cathode. Thermodynamic meaning of depolarization was discussed in details and the empirical relation between binary alloy type and depolarization type was proposed. It is shown for the first time that the presence of a third element in Al-Li alloy can strengthen depolarization of Li ion at Al alloy cathode and give foundation for preparing high purity Al-Li-M ternary alloy. The effect of LiCl concentration on deposition potentials of Li ion at Al cathode in KCl-LiCl melt was studied and average active coefficient of LiCl was obtained.

A SIMPLE METHOD FOR PREDICTION OF GAS-PERMEABILITY OF POLYMERS FROM THEIR MOLECULAR-STRUCTURE

A method for the prediction of gas permeabilities (P) through polymers from their chemical structure has been developed on the basis of the ratio of molar free volume to molar cohesive energy, V(f)/E(coh). The permeation of small gas molecules through polymer membranes is dependent on the chain packing density measured by V(f) and segmental motion of polymer chains measured by E(coh). But no simple relationship between P and V(f) or E(coh) alone was found. The permeability data of more than 60 polymers covering 7 orders of magnitude for six gases have been treated with linear regression analysis. All plots of log P vs. V(f)/E(coh) gave good straight lines. It is also found that a linear relationship holds when plotting both the intercepts and slopes of log P vs. V(f)/E(coh) lines against square of the diameters of gas molecules. Therefore, the permeabilities of all the non-swelling gases through a great variety of polymers can be estimated using two correlations above. Moreover, this method is more accurate than others in the literature and may found useful for the selection of gas separation or barrier membrane materials.

SPECTROPHOTOMETRIC DETERMINATION OF LANTHANUM AND SUM OF OTHER LIGHT RARE-EARTHS BY FLEXIBLE TOLERANCE SIMPLEX-METHOD

The absorptivities of color elements in a mixture can be obtained by using Gauas' elimination with selection of principal element in matrix to the standards. These values can be applied to flexible tolerance simplex method to give the composition of samples. In the exprimental design and data treatment, an effort was made to minimize the errors of results according the principal of optimization. When the difference of absorptivities of color material is significant to the exprimental error, the pr...

Research on crustal structure and lithosphere property in the Okinawa Trough area

A mass of geological, geophysical and geochemical data and information from the Okinawa Trough area are collected for comprehensive research in the study area from East China to Okinawa Trough and then to Ryukyu Island Are region. According to the seismic tomography result (P and S wave) and the processing result of free-air and Bouguer gravity anomaly and magnetic anomaly data in the study area, the comprehensive interpretation is carried out. The Moho depth distribution of the study area is obtained by the inversion calculation based on gravity data using the Harmonious Series method. The crust properties are analyzed. Meantime, some Cenozoic basalt data from Kuandian (NE China), Hannuoba (North China), Minxi (South China), Penghu Islands (Taiwan Strait), Okinawa Trough and Japan Island Arc regions are chosen to make the comparison research on element- isotopes. The result indicates that the lithosphere thickness in the Okinawa Trough area has obviously decreased, where a Low -velocity layer of upper-mantle has reached the Moho interface and the metasometized asthenosphere has formed. The research result on element- isotopes shows that the characteristic of the crust in the Okinawa Trough area is different from that in East China area and the Ryukyu Island Arc area. It is considered that the crust in the Okinawa Trough area belongs to the transition type, which is quite similar to the feature of the oceanic crust.

Extraction of Nitraria tangutorum seed oil by supercritical carbon dioxide and determination of free fatty acids by HPLC/APC/IMS with fluorescence detection

The seed oil from Nitraria tangutorum samples was obtained by supercritical carbon dioxide extraction methods. The extraction parameters for this methodology, including pressure, temperature, particle size and extraction time, were optimized. The free fatty acids in the seed oil were separated with a pre-column derivation method and 1,2-benzo-3,4-dihydrocarbazole-9-ethyl-p-toluenesulfonate (BDETS) as a labeling regent, followed by high-performance liquid chromatography (HPLC) with fluorescence detection. The target compounds were identified by mass spectrometry with atmospheric pressure chemical ionization (APCI in positive-ion mode). HPLC analysis shows that the main compositions of the seed oil samples were free fatty acids (FFAs) in high to low concentrations as follows: linoleic acid, oleic acid, hexadecanoic acid and octadecanoic acid. The assay detection limits (at signal-to-noise of 3:1) were 3.378-6.572 nmol/L. Excellent linear responses were observed, with correlation coefficients greater than 0.999. The facile BDETS derivatization coupled with mass spectrometry detection allowed the development of a highly sensitive method for analyzing free fatty acids in seed oil by supercritical CO2 extraction. The established method is highly efficient for seed oil extraction and extremely sensitive for fatty acid profile determination. (C) 2007 Elsevier B.V. All rights reserved.

Determination of free fatty acids in bryophyte plants and soil by HPLC with fluorescence detection and identification by online MS

A method for the determination of long and short chain free fatty acids (FFAs), using 1-[2-(ptoluenesulfonate)-ethyll-2-phenylimidazole-[4,5-f-9,10-phenanthrene (TSPP) as labeling reagent, has been developed. Identification of FFA derivatives was carried out by HPLC-MS with atmospheric pressure chemical ionization (APCI) in positive ion mode. Gradient elution on an Agilent Eclipse XDB-C-8 column gave good separation of the derivatives. Excellent linear responses were observed and good compositional data could be obtained from as little as 200 mg of bryophyte plants and soil samples. Facile TSPP derivatization coupled with HPLC-APCI-MS analysis allowed the development of a highly sensitive method for the quantitative analysis of trace level of FFAs from biological and natural environmental samples.

Determination of free fatty acids in soil and bryophyte plants by precolumn derivatization via HPLC with fluorescence detection and tandem mass spectrometry (HPLC-MS/MS)

A sensitive method for the determination of 30 kinds of free fatty acids (FFAs, C-1-C-30) with 1-[2-(p-toluenesulfonate)-ethyl]-2-phenylimidazole-[4,5-f] 9,10-phenan- threne (TSPP) as labeling reagent and using high performance liquid chromatography with fluorescence detection and identification by online postcolumn mass spectrometry with atmospheric pressure chemical ionization (APCI) source in positive-ion mode (HPLC/MS/APCI) has been developed. TSPP could easily and quickly label FFAs in the presence of K2CO3 catalyst at 90 degrees C for 30 min in N,N-dimethylformamide (DMF) solvent, and maximal labeling yields close to 100% were observed with a 5-fold excess of molar reagent. Derivatives were stable enough to be efficiently analyzed by high performance liquid chromatography. TSPP was introduced into fatty acid molecules and effectively augmented MS ionization of fatty acid derivatives and led to regular MS and MS/MS information. The collision induced cleavage of protonated molecular ions formed specific fragment ions at m/z [MH](+)(molecular ion), m/z [M'+CH2CH2](+)(M' was molecular mass of the corresponding FFA) and m/z 295.0 (the, mass of protonated molecular core structure of TSPP). Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C-8 column (4.6 x 150 mm, 5 mu m, Agilent) with a good baseline resolution in combination with a gradient elution. Linear ranges of 30 FFAs are 2.441 x 10(-3) to 20 mu mol/L, detection limits are 3.24 similar to 36.97 fmol (injection volume 10 mu L, at a signal-to-noise ratio of 3, S/N 3:1). The mean interday precision ranged from 93.4 to 106.2% with the largest mean coefficients of variation (R.S.D.) < 7,5%. The mean intraday precision for all standards was < 6.4% of the expected concentration. Excellent linear responses were observed with correlation coefficients of > 0.9991. Good compositional data could be obtained from the analysis of extracted fatty acids from as little as 200 mg of bryophyte plant samples.Therefore, the facile TSPP derivatization coupled with HPLC/MS/APCI analysis allowed the development of a highly sensitive method for the quantitation of trace levels of short and long chain fatty acids from biological and natural environmental samples.

Determination of 30 free fatty acids in two famous Tibetan medicines by HPLC with fluorescence detection and mass spectrometric identification

A simple and sensitive high-performance liquid chromatographic (HPLC) method with fluorescence detection and mass spectrometric identification has been developed for analysis of 30 long-chain and short-chain free Fatty acids (FFAs). The fatty acids were derivatized to their esters with 1-[2-(p-toluenesulfonate)ethyl]-2-phenylimidazole-[4,5-f]-9,10-phenanthrene (TSPP) in N,N-dimethylformamide (DMF) at 90 degrees C with anhydrous K2CO3 as catalyst. A mixture Of C-1-C-30 fatty acids was completely separated within 60 min by gradient elution on a reversed-phase C-8 column. Qualitative identification of the acids was performed by atmospheric-pressure chemical ionization mass spectrometry (APCI-MS) in positive-ion mode. The fluorescence excitation and emission wavelengths were 260 and 380 nm, respectively. Quantitative determination of the 30 acids in two Tibetan medicines Gentiana straminea and G. dahurica was performed. The results indicated that the medicines contained many FFAs. Linear correlation coefficients for the FFA derivatives were > 0.9991. Relative standard deviations (RSDs, n = 6) for the fatty acid derivatives were < 3%. Detection limits (at a signal-to-noise ratio of 3:1) were 3.1-38 fmol. When the fatty acid derivatives were determined in the two real samples results were satisfactory and the sensitivity and reproducibility of the method were good.

Analysis of saturated free fatty acids from pollen by HPLC with fluorescence detection

A sensitive method for the determination of free fatty acids using 2-(2-(anthracen-10-yl)-1H-naphtho[2,3-dimidazol-1-yl) ethyl-p-toluenesuIfonate (ANITS) as tagging reagent with fluorescence detection has been developed. ANITS could easily and quickly label fatty acids in the presence of the K2CO3 catalyst at 90 degrees C for 40 min in N,N-dimethylformamide solvent. From the extracts of rape bee pollen samples, 20 free fatty acids were sensitively determined. Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C8 column by HPLC in conjunction with gradient elution. The corresponding derivatives were identified by post-column APCI/MS in positive-ion detection mode. ANITS-fatty acid derivatives gave an intense molecular ion peak at mlz [M+H](+); with MS/MS analysis, the collision-induced dissociation spectra of m/z [M+H](+) produced the specific fragment ions at mlz [M-345](+) and mlz 345.0 (here, m/z 345 is the core structural moiety of the ANITS molecule). The fluorescence excitation and emission wavelengths of the derivatives were lambda(ex) = 250 nm and lambda(em) = 512 nm, respectively. Linear correlation coefficients for all fatty acid derivatives are > 0.9999. Detection limits, at a signal-to-noise ratio of 3 : 1, are 24.76-98.79 fmol for the labeled fatty acids.

Enhancement of atmospheric pressure chemical ionization for the determination of free and glycine-conjugated bile acids in human serum

A highly sensitive and accurate method based on the precolumn derivatization of bile acids (BA) with a high ionization efficiency labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl-benzenesulfonate (BDEBS) coupled with LC/MS has been developed. After derivatization, BA molecules introduced a weak basic nitrogen atom into the molecular core structure that was readily ionized in commonly used acidic HPLC mobile phases. Derivatives were sufficiently stable to be efficiently analyzed by atmospheric pressure chemical ionization (APCI)-MS/MS in positive-ion mode. The MS/MS spectra of BA derivatives showed an intense protonated molecular ion at m/z [M + H](+). The collision-induced dissociation of the molecular ion produced fragment ions at [MH - H2O](+), [MH - 2H(2)O](+), [MH - 3H(2)O](+). The characteristic fragment ions were at m/z 320.8, 262.8, and 243.7 corresponding to a cleavage of N - CO, O - CO, and C - OCC, respectively, and bonds of derivatized molecules. The selected reaction monitoring, based on the m/z [M + H]+ -> [MH - H2O](+), [MH - H2O](+), [MH - 2H(2)O](+), [MH-3H(2)O](+), 320.8, 262.8, and 243.7 transitions, was highly specific for the BA derivatives. The LODs for APCI in a positive-ion mode, at an S/N of 5, were 44.36-153.6 fmol. The validation results showed high accuracy in the range of 93-107% and the mean interday precision for all standards was < 15% at broad linear dynamic ranges (0.0244-25nmol/mL). Good linear responses were observed with coefficients of > 0.9935 in APCI/MS detection. Therefore, the facile BDEBS derivatization coupled with mass spectrometric analysis allowed the development of a highly sensitive and specific method for the quantitation of trace levels of the free and glycine-conjugated BA from human serum samples.

HPLC-APCI-MS determination of free fatty acids in Tibet folk medicine Lomatogonium rotatum with fluorescence detection and mass spectrometric identification

A simple and sensitive method for the determination of free fatty acids (FFAs) using acridone-9-ethyl-p-toluenesulfonate (AETS) as a fluorescence derivatization reagent by high performance liquid chromatography (HPLC) has been developed. Free fatty acid derivatives were separated on an Eclipse XDB-C-8 column with a good baseline resolution and detected with the fluorescence of which excitation and emission wavelengths of derivatives were set at lambda(ex) 404 and lambda(em) 440 nm, respectively. Identification of 19 fatty acid derivatives was carried out by online post-column mass spectrometry with an atmospheric pressure chemical ionization (APCI) source under positive-ion detection mode. Nineteen FFAs from the extract of Lomatogonium rotatum are sensitively determined. The results indicate that the plant Lomatogonium rotatum is enriched with an abundance of FFAs and FFAs of higher contents, which mainly focus on even carbon atoms, C-14, C-16, and C-18. The validation of the method including linearity, repeatability, and detection limits was examined. Most linear correlation coefficients for fatty acid derivatives are > 0.9989, and detection limits (at signal-to-noise of 3: 1) are 12.3-43.7 fmol. The relative standard deviations (RSDs) of the peak areas and retention times for 19 FFAs standards are < 2.24% and 0.45%, respectively. The established method is rapid and reproducible for the separation determination of FFAs from the extract of Lomatogonium rotatum with satisfactory results.

复杂介质边界元法数值模拟研究

A major impetus to study the rough surface and complex structure in near surface model is because accuracy of seismic observation and geophysical prospecting can be improved. Wave theory study about fluid-satuated porous media has important significance for some scientific problems, such as explore underground resources, study of earth's internal structure, and structure response of multi-phase porous soil under dynamic and seismic effect. Seismic wave numerical modeling is one of the effective methods which understand seismic propagation rules in complex media. As a numerical simulation method, boundary element methods had been widely used in seismic wave field study. This paper mainly studies randomly rough surface scattering which used some approximation solutions based on boundary element method. In addition, I developed a boundary element solution for fluid saturated porous media. In this paper, we used boundary element methods which based on integral expression of wave equation to study the free rough surface scattering effects of Kirchhoff approximation method, Perturbation approximation method, Rytov approximation method and Born series approximation method. Gaussian spectrum model of randomly rough surfaces was chosen as the benchmark model. The approximation methods result were compared with exact results which obtained by boundary element methods, we study that the above approximation methods were applicable how rough surfaces and it is founded that this depends on and ( here is the wavenumber of the incident field, is the RMS height and is the surface correlation length ). In general, Kirchhoff approximation which ignores multiple scatterings between any two surface points has been considered valid for the large-scale roughness components. Perturbation theory based on Taylor series expansion is valid for the small-scale roughness components, as and are .Tests with the Gaussian topographies show that the Rytov approximation methods improves the Kirchhoff approximation in both amplitude and phase but at the cost of an extra treatment of transformation for the wave fields. The realistic methods for the multiscale surfaces come with the Born series approximation and the second-order Born series approximation might be sufficient to guarantee the accuracy of randomly rough surfaces. It could be an appropriate choice that a complex rough surface can be divided into large-, medium-, and small-scale roughness components with their scattering features be studied by the Kirchhoff or Rytov phase approximations, the Born series approximation, and the perturbation theory, respectively. For this purpose, it is important to select appropriate parameters that separate these different scale roughness components to guarantee the divided surfaces satisfy the physical assumptions of the used approximations, respectively. In addition, in this paper, the boundary element methods are used for solving the porous elastic wave propagation and carry out the numerical simulation. Based on the fluid-saturated porous model, this paper analyses and presents the dynamic equation of elastic wave propagation and boundary integral equation formulation of fluid saturated porous media in frequency domain. The fundamental solutions of the elastic wave equations are obtained according to the similarity between thermoelasticity and poroelasticity. At last, the numerical simulation of the elastic wave propagation in the two-phase isotropic media is carried out by using the boundary element method. The results show that a slow quasi P-wave can be seen in both solid and fluid wave-field synthetic seismograms. The boundary element method is effective and feasible.

岩石类材料静态、动态拉伸弹性模量测试方法研究——以巴西圆盘试验和霍普金森压杆、效应为手段

As we all know, rock-like materials will absolutely show very different mechanical properties under the compressive stress and tensile stress respectively. Similarly, under the dynamic compressive stress or dynamic tensile stress, the characteristics of the dynamics showed by the rock-like materials also have great differences from the mechanical behavior under static force. Studying their similarities and differences in rock mechanics theory and practical engineering will be of great significance. Generally, there are compression modulus of elasticity and tensile modulus of elasticity corresponding to compressive stress state and the tensile stress state in the rock. Both the two kinds of elastic modulus play an extremely important role in calculation of engineering mechanics. Their reliability directly affects the accuracy and reliability of the calculation results of internal stress field and displacement field of engineering rock mass. At present, it is easy to obtain the compression modulus of elasticity in laboratory; but it is very difficult to determine the tensile modulus of elasticity with direct tensile test due to that direct tensile test is difficult to perform in laboratory in general. In order to solve this problem, this thesis invents and develops several indirect test methods to determine the static or dynamic tensile modulus of elasticity of rock-type materials with high reliability and good interoperability. For the static tensile modulus of elasticity, the analytical stress field solution has been given out for the Brazilian disc under the radial and linear concentration load with Airy stress function method. At the same time, the stress field has been modeled for the Brazilian disc test by using the finite element software of ANSYS and ADINA. The analytical stress field solution is verified to be right by comparatively researching the analytical stress field solution and the numerical stress field solution. Based on the analytical stress field solution, this thesis proposes that a strain gauge is pasted at the Brazilian disc center along the direction perpendicular to the applied force to indirectly determine the static tensile modulus of elasticity, and related measurement theory also has been developed. The method proposed here has good feasibility and high accuracy verified by the experimental results. For the dynamic tensile modulus of elasticity, two measuring methods and theories are invented here. The first one is that the Split Hopkinson Pressure Bar is used to attract the Brazilian disc to generate the dynamic load, make the dynamic tensile stress is formed at the Brazilian disc center; and also a strain gauge is pasted at the Brazilian disc center to record the deformation. The second is that, in the Hopkinson effect phenomenon, the reflection tensile stress wave is formed when the shock wave propagates to the free end of cylindrical rock bar and reflect, which can make the rock bar is under dynamic tensile stress state; and some strain gauges are pasted at the appropriate place on the rock bar to record the strain coursed by the tensile or compressive stress wave. At last, the dynamic tensile modulus of elasticity can be determined by the recorded strain and the dynamic tensile stress which can be determined by related theories developed in this thesis.

特大地震激发地球自由振荡的数值模拟研究

Large earthquakes, such as the Chile earthquake in 1960 and the Sumatra-Andaman earthquake on Dec 26, 2004 in Indonesia, have generated the Earth’s free oscillations. The eigenfrequencies of the Earth’s free oscillations are closely related to the Earth’s internal structures. The conventional methods, which mainly focus on calculating the eigenfrequecies by analytical ways, and the analysis on observations can not easily study the whole processes from earthquake occurrence to the Earth’s free oscillation inspired. Therefore, we try to use numerical method incorporated with large-scale parallel computing to study on the Earth’s free oscillations excited by giant earthquakes. We first give a review of researches and developments of the Earth’s free oscillation, and basical theories under spherical coordinate system. We then give a review of the numerical simulation of seismic wave propagation and basical theories of spectral element method to simulate global seismic wave propagation. As a first step to study the Earth’s free oscillations, we use a finite element method to simulate the propagation of elastic waves and the generation of oscillations of the chime bell of Marquis Yi of Zeng, by striking different parts of the bell, which possesses the oval crosssection. The bronze chime bells of Marquis Yi of Zeng are precious cultural relics of China. The bells have a two-tone acoustic characteristic, i.e., striking different parts of the bell generates different tones. By analysis of the vibration in the bell and the spectrum analysis, we further help the understanding of the mechanism of two-tone acoustic characteristics of the chime bell of Marquis Yi of Zeng. The preliminary calculations have clearly shown that two different modes of oscillation can be generated by striking different parts of the bell, and indicate that finite element numerical simulation of the processes of wave propagation and two-tone generation of the chime bell of Marquis Yi of Zeng is feasible. These analyses provide a new quantitative and visual way to explain the mystery of the two-tone acoustic characteristics. The method suggested by this study can be applied to simulate free oscillations excited by great earthquakes with complex Earth structure. Taking into account of such large-scale structure of the Earth, small-scale low-precision numerical simulation can not simply meet the requirement. The increasing capacity in high-performance parallel computing and progress on fully numerical solutions for seismic wave fields in realistic three-dimensional spherical models, Spectral element method and high-performance parallel computing were incorporated to simulate the seismic wave propagation processes in the Earth’s interior, without the effects of the Earth’s gravitational potential. The numerical simulation shows that, the results of the toroidal modes of our calculation agree well with the theoretical values, although the accuracy of our results is much limited, the calculated peaks are little distorted due to three-dimensional effects. There exist much great differences between our calculated values of spheroidal modes and theoretical values, because we don’t consider the effect the Earth’ gravitation in numerical model, which leads our values are smaller than the theoretical values. When , is much smaller, the effect of the Earth’s gravitation make the periods of spheroidal modes become shorter. However, we now can not consider effects of the Earth’s gravitational potential into the numerical model to simulate the spheroidal oscillations, but those results still demonstrate that, the numerical simulation of the Earth’s free oscillation is very feasible. We make the numerical simulation on processes of the Earth’s free oscillations under spherically symmetric Earth model using different special source mechanisms. The results quantitatively show that Earth’s free oscillations excited by different earthquakes are different, and oscillations at different locations are different for free oscillation excited by the same earthquake. We also explore how the Earth’s medium attenuation will take effects on the Earth’s free oscillations, and take comparisons with the observations. The medium attenuation can make influences on the Earth’s free oscillations, though the effects on lower-frequency fundamental oscillations are weak. At last, taking 2008 Wenchuan earthquake for example, we employ spectral element method incorporated with large-scale parallel computing technology to investigate the characteristics of seismic wave propagation excited by Wenchuan earthquake. We calculate synthetic seismograms with one-point source model and three-point source model respectively. Full 3-D visualization of the numerical results displays the profile of the seismic wave propagation with respect to time. The three-point source, which was proposed by the latest investigations through field observation and reverse estimation, can better demonstrate the spatial and temporal characteristics of the source rupture processes than one-point source. Primary results show that those synthetic signals calculated from three-point source agree well with the observations. This can further reveal that the source rupturing process of Wenchuan earthquake is a multi-rupture process, which is composed by at least three or more stages of rupture processes. In conclusion, the numerical simulation can not only solve some problems concluding the Earth’s ellipticity and anisotropy, which can be easily solved by conventional methods, but also finally solve the problems concluding topography model and lateral heterogeneity. We will try to find a way to fully implement self-gravitation in spectral element method in future, and do our best to continue researching the Earth’s free oscillations using the numerical simulations to see how the Earth’ lateral heterogeneous will affect the Earth’s free oscillations. These will make it possible to bring modal spectral data increasingly to bear on furthering our understanding of the Earth’s three-dimensional structure.

Improving ICP with Easy Implementation for Free Form Surface Matching

Liu, Yonghuai. Improving ICP with Easy Implementation for Free Form Surface Matching. Pattern Recognition, vol. 37, no. 2, pp. 211-226, 2004.