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41.
M. Valkeapää Y. Katsumata T. Motohashi R.S. Liu H. Yamauchi 《Journal of solid state chemistry》2007,180(5):1608-1615
A comparative study on the oxidation and charge compensation in the AxCoO2−δ systems, A=Na (x=0.75, 0.47, 0.36, 0.12) and Li (x=1, 0.49, 0.05), using X-ray absorption spectroscopy at O 1s and Co 2p edges is reported. Both the O 1s and Co 2p XANES results show that upon removal of alkali metal from AxCoO2−δ the valence of cobalt increases more in LixCoO2−δ than in NaxCoO2−δ. In addition, the data of O 1s XANES indicate that charge compensation by oxygen is more pronounced in NaxCoO2−δ than in LixCoO2−δ. 相似文献
42.
J. Zsakó 《Journal of Thermal Analysis and Calorimetry》1996,46(6):1845-1864
Four many curves methods, viz. calculation techniques based on Eqs (30), (31), (34) and (36), respectively, for deriving kinetic parameters from several TG curves recorded with different heating rates are tested on two sets of theoretical TG curves. The maximum reaction rate temperature and conversion, as well as the approximate formulae used for their calculation are discussed. Some aspects of the kinetic compensation effect are analysed. The final conclusion is that the use of the many curves methods is not reasonable. 相似文献
43.
It follows from an analysis of the error levels of TG evaluation methods that it is a conceptual error to disregard the analogies
of mass, energy and momentum streams of subordinate partial processes. This error is bypassed by means of the introduced method
of dimensionless analysis and by determining the characteristic, constants-like data of thermal processes by using the measured
data directly. These methods are very suitable for increasing the consistency of the calculated results by seeking for similarity,
even in comparisons of measurements made under very different conditions and for emphasizing the differences too, quantitatively.
With this new interpretation of TG processes, the idea of the kinetic compensation effect becomes only a consequence of the
discussed conceptual error.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
44.
Guo X Shuang S Wang X Dong C Pan J Aboul-Enein HY 《Biomedical chromatography : BMC》2004,18(8):559-563
The interaction of rutin and venoruton (troxerutin), with alpha-, beta- and gamma-cyclodextrin (CD), hydroxypropyl-beta-cyclodextrin (HP-beta-CD) and methyl-beta-cyclodextrin (M-beta-CD) was investigated by reversed-phase thin layer chromatography on polyamide plates. A mobile phase consisted of NH(4)OH; NH(4)Cl buffer solution containing various CD concentrations (pH = 9.7, 20 degrees C) was used as mobile phase. The equilibrium constants (K(f)) and the retention factor (R(f)) were determined and used to study the inclusion process. The in fluence of CDs on the solubility of rutin and venoruton was characterized by R(M) values and the increasing hydrophilicity of drugs. The results show that the inclusion capacity of cyclodextrins follows the order HP-beta-CD > M-beta-CD > beta-CD > gamma-CD, and rutin is more easily included by the studied cyclodextrins than venoruton. In addition, the thermodynamic parameters (Delta H, Delta S) for the formation of complexes were obtained from the van't Hoff equation, displaying the enthalpy-entropy compensation effect. 相似文献
45.
Riccardo Baron Daniel Trzesniak Alex H de Vries Andreas Elsener Siewert J Marrink Wilfred F van Gunsteren 《Chemphyschem》2007,8(3):452-461
Thermodynamic data are often used to calibrate or test amomic-level (AL) force fields for molecular dynamics (MD) simulations. In contrast, the majority of coarse-grained (CG) force fields do not rely extensively on thermodynamic quantities. Recently, a CG force field for lipids, hydrocarbons, ions, and water, in which approximately four non-hydrogen atoms are mapped onto one interaction site, has been proposed and applied to study various aspects of lipid systems. To date, no extensive investigation of its capability to describe salvation thermodynamics has been undertaken. In the present study, a detailed picture of vaporization, solvation, and phase-partitioning thermodynamics for liquid hydrocarbons and water was obtained at CG and AL resolutions, in order to compare the two types or models and evaluate their ability to describe thermodynamic properties in the temperature range between 263 and 343 K. Both CG and AL models capture the experimental dependence of the thermodynamic properties on the temperature, albeit a systematically weaker dependence is found for the CG model. Moreover, deviations are found for solvation thermodynamics and for the corresponding enthalpy-entropy compensation for the CG model. Particularly water/oil repulsion seems to be overestimated. However, the results suggest that the thermodynamic properties considered should be reproducible by a CG model provided it is reparametrized on the basis of these liquid-phase properties. 相似文献
46.
Reyer J Dijkstra Hans F.M Boelens Freek Ariese Cees Gooijer 《Analytica chimica acta》2004,519(2):129-136
In column liquid chromatography (LC) coupled to conventional Raman spectroscopy (RS) removal of the spectral background of the eluent is often demanding, because of the strong signals of the organic modifier. A new chemometrical method is proposed, called the eluent background subtraction (EBS) method, which can correct for small shape and intensity differences of the eluent spectra. The variations in the eluent spectra are modelled using principal component analysis (PCA). The PCA loading vectors are subsequently used for eluent background correction of the elution spectra of the analyte. The loading vectors are fitted under these spectra by an asymmetric least-squares method. This method was successfully applied under various experimental conditions and performed much better than conventional background correction methods. Analyte detectability was improved by (weighted) averaging of all elution spectra and smoothing via a p-spline function. 相似文献
47.
We develop a second‐order accurate Navier–Stokes solver based on r‐adaptivity of the underlying numerical discretization. The motion of the mesh is based on the fluid velocity field; however, certain adjustments to the Lagrangian velocities are introduced to maintain quality of the mesh. The adjustments are based on the variational approach of energy minimization to redistribute grid points closer to the areas of rapid solution variation. To quantify the numerical diffusion inherent to each method, we monitor changes in the background potential energy, computation of which is based on the density field. We demonstrate on a standing interfacial gravity wave simulation how using our method of grid evolution decreases the rate of increase of the background potential energy compared with using the same advection scheme on the stationary grid. To further highlight the benefit of the proposed moving grid method, we apply it to the nonhydrostatic lock‐exchange flow where the evolution of the interface is more complex than in the standing wave test case. Naive grid evolution based on the fluid velocities in the lock‐exchange flow leads to grid tangling as Kelvin–Helmholtz billows develop at the interface. This is remedied by grid refinement using the variational approach. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
48.
49.
A picosecond widely tunable deep-ultraviolet laser for angle-resolved photoemission spectroscopy
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We develop a picosecond widely tunable laser in a deep-ultraviolet region from 175 nm to 210 nm,generated by two stages of frequency doubling of a 80-MHz mode-locked picosecond Ti:sapphire laser.A β-BaB2O4 walk-off compensation configuration and a KBe2BO3F2 prism-coupled device are adopted for the generation of second harmonic and fourth harmonics,respectively.The highest power is 3.72 mW at 193 nm,and the fluctuation at 2.85 mW in 130 min is less than ±2%. 相似文献
50.
Combining the experimental research with the simulation calculation, the error evaluation for Zernike polynomials fitting (ZPF) based phase compensation of digital holographic microscopy (DHM) is performed. The obtained results show that the reconstructed phase with high precision can be obtained by ZPF phase compensation algorithm. Moreover, the phase error for ZPF based phase compensation algorithm increases with both the variation of object height and object transverse area, the larger variation of object height, the larger of phase error, and the larger of object transverse area, the faster increase of RMS phase error. To decrease the error of ZPF phase compensation algorithm, it is required to ensure one of the variations of object height and object transverse area to be a small value. Importantly, the proposed method supplies a useful tool for the error evaluation of phase compensation algorithm. 相似文献