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51.
Simple and convenient methods for determining surface chemical composition of lignocellulosic materials are described. The
methods are based on vapor phase fluorine surface derivatization with either trifluoro acetic anhydride (TFAA), tri-fluoro
ethanol (TFE) or pentafluorophenyl hydrazine (PFPH) and subsequent Electron Spectroscopy for Chemical Analysis (ESCA). Model
cellulosic surfaces with well defined functionalities were used to optimize the derivatization reaction conditions. Detection
and accessibility of surface hydroxyl functional groups were investigated in cotton and regenerated cellulose as models. Carboxymethyl
cellulose (CMC) was used as a model surface for detection and quantification of carboxylic acid groups. Theoretical conversion
curves for derivatization reactions were calculated and used to evaluate the extent of the reactions on the model surfaces.
It was found that the conversion was higher for the regenerated cellulose and CMC than for cotton. The protocols developed
using the model surfaces were applied to a case study on wood fibers with different degrees of complexity, namely dissolving
and chemithermomechanical (CTMP) pulp. Untreated and oxygen-plasma modified pulps were compared with respect to the surface
composition of functional groups. According to the derivatization reactions, functionalities containing oxygen were significantly
increased on the plasma-treated samples. The effect of the treatment was found to be dependent on the type of pulp. Fluorine
derivatization is shown to be an unambiguous method for clear assessment of the chemical functionalities of cellulosic surfaces. 相似文献
52.
Gudrun Thter 《Mathematical Methods in the Applied Sciences》2002,25(10):875-894
The Neumann problem is crucial in mathematical physics. Nevertheless, as far as cylindrical domains are concerned there is still the open question how to construct solutions to data in usual Sobolev spaces since the standard Kondratiev theory does not apply. In this paper that unsatisfactory gap is filled and moreover, data with polynomial asymptotic behaviour are considered. As interesting special case we find solutions with bounded Dirichlet integral. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
53.
Sølvi Storsæter 《Surface science》2006,600(10):2051-2063
The heats of adsorption of different C1 and C2 molecules assumed to be present during the initial steps of the Fischer-Tropsch synthesis and activation energies for elementary steps envisioned to occur in the synthesis are calculated for Co by using the unity bond index-quadratic exponential potential (UBI-QEP) method. The preexponential factors for the elementary steps are calculated from transition-state theory, and the rate constants are calculated according to the Arrhenius equation. The activation barrier for hydrogenation of CO is found to be lower compared to hydrogen assisted dissociation of CO, which has a smaller activation barrier than direct dissociation of CO. The reaction steps with high activation barriers are eliminated. Based on this elimination two sets of elementary steps for formation of C1 and C2 alkenes and alkanes in the Fischer-Tropsch synthesis are established: one based on hydrogen assisted CO dissociation (carbide mechanism) and one based on CO hydrogenation (CO insertion mechanism). In addition, one mechanism of producing CO2 from the water-gas shift reaction is proposed. The resulting mechanisms are combined and used in the microkinetic model, which are fitted to experimental results at methanation conditions (T = 483 K or 493 K, p = 1.85 bar and H2/CO = 10) over a Co/Al2O3 Fischer-Tropsch catalyst. A good tuning is obtained by adjusting the C-Co and H-Co binding strengths. The microkinetic modelling based on these assumptions indicates that CO is mainly converted through hydrogenation of CO and that C2 compounds are mainly produced by insertion of CO into a metal-methyl bond. Thus, from the surface coverages and reaction rates predicted by the microkinetic modelling the mechanism can be further reduced to only include the CO insertion mechanism. Hydrogenation of CHO to CH2O is found to be the rate determining initiation step, and insertion of CO into a metal-methyl bond is found to be the rate determining step for chain growth. By using the UBI-QEP method for calculation of activation energies, the activation barriers for dissociation of CO and hydrogenation of surface carbon are found to be too large for the carbide mechanisms to occur. However, experimental data or another theoretical method is necessary in order to support or disprove the calculated activation energies in this work. 相似文献
54.
Ph. Hägler B. Pire L. Szymanowski O.V. Teryaev 《The European Physical Journal C - Particles and Fields》2002,24(2):261-270
We study Pomeron-Odderon interference effects giving rise to charge and single-spin asymmetries in diffractive electroproduction
of a pair. We calculate these asymmetries, originating from both longitudinal and transverse polarizations of the virtual photon,
in the framework of QCD and in the Born approximation, in a kinematical domain accessible to HERA experiments. We predict
a sizable charge asymmetry with a characteristic dependence on the invariant mass of the pair, which makes this observable very important for establishing the magnitude of the Odderon exchange in hard processes.
The single-spin asymmetry turns out to be rather small. We briefly discuss future improvements of our calculations and their
possible effects on the results.
Received: 18 July 2002 / Published online: 25 October 2002 相似文献
55.
The direct and the exchange core polarization (ECP) contributions of the conduction electrons to the Knight shift of palladium are evaluated. To obtain the wave functions for the conduction electrons and the partial densities of states at the Fermi surface a KKR energy band calculation was performed. The contributions of the core electrons to the Knight shift were determined by using the moment perturbation method (MP). Electron-electron interactions are taken into account by individual enhancement factors for thed ands electrons. The agreement between the theoretical results and the available experimental data is quite satisfactory. 相似文献
56.
57.
Joachim Käschel 《Proceedings Mathematical Sciences》1992,102(2):155-158
In Venkaiah [1] an algorithm for solving linear optimization problems based on the idea of the projective algorithm of Karmarkar,
is proposed. The essential simplification in the new algorithm is the use of a fixed projection operator. In this way the
algorithm requires onlyO(n
2
) operations to obtain a sufficient exact solution. In this note it is shown that in some special cases the algorithm of Venkaiah
yields a feasible solution that is far from the optimal one. 相似文献
58.
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