气相色谱分离多环芳香环境污染物用固定相的应用进展

综述了几种气相色谱固定相包括聚硅氧烷、液晶、冠醚、环糊精、离子液体及纤维填充固定相,在分离多环芳香烃(PAHs)、多环芳香化合物(PACs)及多氯联苯(PCBs)等环境污染物中的应用进展,展望了此类固定相的应用前景(引用文献64篇)。     

Electric-field gradients at Ta impurities in Sc2O3 semiconductor

In this work we present an ab initio study of Ta-doped Sc₂O₃ semiconductor. Calculations were performed at dilute Ta impurities located at both cationic sites of the host structure, using the Augmented Plane Wave plus Local Orbitals (APW+lo) method. The structural atomic relaxations and the electric-field gradients (EFG) were studied for different charge states of the cell in order to simulate different ionization states of the double-donor Ta impurity. From the results for the EFG tensor at Ta impurity sites and the comparison with experimental results obtained using the Time-Differential γ–γ Perturbed-Angular-Correlations technique we could determined the structural distortions induced by the Ta impurity and the electronic structure of the doped-semiconductor.     

Ab initio study of the EFG tensor at Cd impurities in Sc2O3 semiconductor

We present an ab initio study of diluted Cd impurities localized at both cation sites of the semiconductor Sc₂O₃. The electric-field-gradient (EFG) tensor at Cd impurities located at both cationic sites of the host structure was determined from the calculation of the electronic structure of the doped system. Calculations were performed with the full-potential augmented-plane wave plus local orbitals (APW+lo) method within the framework of the density functional theory. We studied the atomic structural relaxations and the perturbation of the electronic charge density induced by the impurities in the host system in a fully self-consistent way. We showed that the Cd impurity introduces an increase of 8% in the nearest oxygen neighbors bond-lengths, changing the EFG sign for probes located at the asymmetric cation site. The APW+lo predictions for the charged state of the Cd impurity were compared with EFG results existent in the literature, coming from time-differential γ–γ perturbed-angular-correlations experiments performed on ¹¹¹Cd-implanted Sc₂O₃ powder samples. From the excellent agreement between theory and experiment, we can strongly suggest that the Cd acceptor impurities are ionized at room temperature. Finally, we showed that simple calculations like those performed within the point-charge model with antishielding factors do not correctly describe the problem of a Cd impurity in Sc₂O₃.     

Electromagnetic properties of low lying levels in75As

Theg-factors of the 265 and 280 keV levels have been measured to be 0.61±0·16 and 0·30±0·05 respectively. The PAC technique was used for the measurements. In addition, the half-life of the 280 keV level has been remeasured to beT _1/2=0·32±0·02 ns using γ-γ delayed coincidences. Electromagnetic properties of the various levels calculated on the core-particle coupling model agree with the experimental results. The results are compared with other existing theoretical calculations.     

Polymorphic Phase Transformation in In2La and CeIn2

Nuclear quadrupole interactions of ¹¹¹Cd probes in In₂La and CeIn₂ were measured using perturbed angular correlation of gamma rays (PAC). Near room temperature, a single non-axially symmetric quadrupole interaction was observed in each compound, with ω ₀ = eQV _zz /ℏ = 78.8(2) Mrad/s and η = 0.312(1) for In₂La at 11°C and ω ₀ = 80(1) Mrad/s and η = 0.29(2) for CeIn₂ at 34°C. The observed non-axial symmetry is consistent with the reported CeCu₂ structure of the phases. The non-axially symmetric interactions were replaced completely by axially symmetric interactions (η = 0) at 524°C, with ω ₀ = 101.0(1) Mrad/s in In₂La and ω ₀ = 96.9(4) Mrad/s in CeIn₂. The change in symmetry is attributed to a polymorphic phase transformation. Based on symmetry information from the quadrupole interaction and on chemical arguments, it is proposed that high-temperature phases of In₂La and CeIn₂ both have the AlB₂ (C32) structure.     

过程分析化学的提出与进展

文中对过程分析化学(PAC)的应用进行了全面评述,主要包括PAC的一般概念、特征、五个阶段和各种应用技术以及发展前景。     

Investigation of dynamic processing on aluminum floc aggregation:Cyclic shearing recovery and effect of sulfate ion

The floc formation and re-aggregation potential and the effects of sulfate on coagulation by AlCl3, polyaluminum chloride (PAC), and Al13 species using a photometric dispersion analyzer (PDA) are in- vestigated. It is found that the recovery level from shearing is the highest for the Al13 species. This is likely a result of increased collision efficiency due to more effective charge neutralization. The ex- perimental results show that sulfate has a significant effect on coagulation and promoting aggregation of hydrolyzed species for the Al13 species. It results in significant improvement of the coagulation effi- ciency through an electrostatic patch effect. The results further indicate that zeta potential of the parti- cle suspension is not the only indicator for the coagulant efficiency when precipitate formation sig- nificantly improves coagulation.     

Enhancing electrochemical preparation of polyaluminum chloride by a magnetic field

A novel effective method for preparing polyaluminum chloride (PAC) with high content of Al₁₃ polymer through conventional electrolysis coupled with rare earth Nd-Fe-B magnetic field was introduced. The content of Al₁₃ polymer in PAC synthesized by this method was highly influenced by the electrobath voltage (E), the magnetic flux density (B), the current density (i) and the distance between the two adjacent electrodes (d_adj). A total aluminum concentration (Al_T) in the PAC solution of 0.8 mol l⁻¹ was obtained when the E, B and i was 2.2 V, 0.4 T and 3.2 A dm⁻², respectively. The optimum d_adj and circulating flow (Q_f) were 20 mm and 23.7 l h⁻¹. With accelerated mass transfer rate by external magnetic field and high Q_f, this process had the advantages of forming more Al(OH)₄⁻ as the precursor of Al₁₃ polymer and inhibiting the concentration polarization more obviously than conventional electrolysis process. Under the optimum conditions, the amount of Al₁₃ polymer in PAC accounted for 82.3% of the Al_T (Al_T = 0.8 M, basicity = 2.2), which was higher than that of PAC prepared by other methods.     

Perturbed angular correlation study of Ta-doped PbTi1−xHfxO3 compounds

In this work, the hyperfine quadrupole interaction at Ta-doped PbTi_1−xHf_xO₃ polycrystalline samples is studied for the first time. Powders with x=0.25, 0.50 and 0.75 were prepared and characterized by X-ray diffraction analysis. Perturbed Angular Correlation (PAC) analyses were done as a function of temperature, using low concentration ¹⁸¹Ta nuclei as probes. In the ferroelectric and paraelectric phases of these compounds two sites were occupied by the probes. For each site the quadrupole frequency, asymmetry and relative distribution width parameters were obtained as a function of temperature above and below the Curie temperature (T_C). One of these sites was assigned to the regular Ti–Hf site, while the other one was assigned to some kind of defect. The behavior of the hyperfine parameters as a function of temperature was analyzed in terms of a recent published phase diagram and the presence of disorder below and above T_C. For the three compositions measured, the obtained hyperfine parameters present discontinuities which correspond to the ferroelectric–paraelectric phase transition. In both phases it was found broad frequency distributed interactions. The disorder in the electronic distribution would be responsible for the broad line width of the hyperfine interaction.     

Hyperfine Fields at the Cd Site in La0.67Cd0.25MnO3 CMR Manganites

Although Cd and Ca ions have the same valence and cation size, their incorporation into vacancy-doped La manganites induce different properties. While the incorporation of Ca leads to high Tc up to 250 K and induces a metallic-like behaviour, the incorporation of Cd severely reduces Tc and promotes insulator-like behaviour. In this work, the Cd hyperfine fields have been measured with the Perturbed Angular Correlations (PAC) technique after implantation and annealing of ^111m Cd in La–Cd–MnO₃ samples. The PAC results are compared with measurements of the resistivity and magnetization performed on the same samples. The mixed La and Mn site Cd occupancy is suggested as a possibility to explain the properties of the La–Cd–MnO₃ system.