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61.
Armin C. Schneider Christoph Pasel Michael Luckas Klaus Gerhard Schmidt Jan-Dirk Herbell 《Journal of solution chemistry》2004,33(3):257-273
The single ion activity coefficients of hydrogen and chloride ions in aqueous HCl solutions have been estimated at 25°C at concentrations up to 1 mol-kg–1, using potentiometric measurements with ion-selective electrodes and appropriate calibration procedures. Two methods are described for an internal calibration of the electrodes in the extended Debye–Hückel concentration range. The results are compared to the conventional pH calibration with external buffer solutions. Since the latter calibration method does not account for the liquid junction potential E
J which arises at the reference electrode, the resulting activity coefficients are quite different in HCl solutions of higher concentration. These differences between internal and external calibration decrease significantly, when a correction for E
J is introduced into the conventional pH calibration. Hence, in solutions of higher ionic strength the accuracy of the conventional pH electrode calibration using buffer solutions is very limited, when exact H+ activities are required. The consistency of the results indicates that the liquid junction potentials in the examined systems calculated by the Henderson/Bates approximation are of reasonable precision. 相似文献
62.
The dominant decay modes of charged top-pions (π±t ) are tb or ~b. We consider the single production ofcharged top-pions in association with a top quark via e+ e- annihilation and calculate the production cross section of theprocesses e+ e- → t-bπ+ (tb-π-) at the leading order. We find that it can reach 1.2 fb with reasonable parameter values.The charged top-pions may be detected via the channel tbπ± in the future high energy e+ e- colliders. 相似文献
63.
The behavior of zirconium atoms at the W(100) surface associated with oxygen adsorption at different sample temperatures has been studied by Auger electron spectroscopy (AES), ion scattering spectroscopy (ISS), and the relative change of the work function (Δф) measured by the onset of the secondary electron energy distribution. The results have revealed: (i) adsorption of zirconium onto the W(100) surface followed by the elevation of the sample temperature up to 1710 K in an oxygen partial pressure of 2.7 × 10−4 induces complete diffusion of zirconium atoms into the W(100) substrate; (ii) further exposure of oxygen induces co-existence of oxygen and tungsten on the surface at 1710 K, resulting in a work function of 4.37 eV; (iii) keeping the sample temperature at 1710 K, simple evacuation of the system has resulted in surface segregation of zirconium atoms to the surface to form a zirconium atomic layer on the top-most surface, reducing the work function to 2.7 eV. The results have revealed that this specific behavior of zirconium atoms at high temperature assures, with very good reproducibility, the highly stable performance and long service life of Zr---O/W(100)-emitters in practical use, even in a low vacuum of 10−6 Pa. 相似文献
64.
65.
Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4950-4964
Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with CuI and trigonal bipyramidal with axial halide complexes with [CuIIX]+ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [CuIIX]+ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [CuIIX]+ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007 相似文献
66.
Aurelien Drezet 《Pramana》2007,68(3):389-396
In a paper by Home and Agarwal [1], it is claimed that quantum nonlocality can be revealed in a simple interferometry experiment
using only single particles. A critical analysis of the concept of hidden variable used by the authors of [1] shows that the
reasoning is not correct.
相似文献
67.
本文将布拉格方程推广应用到高聚物的结构研究中,得到了经不同剂量辐照的聚乙烯单晶的长周期,并辅以示差扫描量热法研究了γ-射线辐照对聚乙烯单晶结构的影响. 相似文献
68.
The adsorption of CN on Cu(1 1 1), Ni(1 1 1) and Ni(1 0 0) has been investigated using density functional theory (DFT). While experimental studies of CN on Cu(1 1 1) show the molecular axis to be essentially parallel to the surface, the normally-preferred DFT approach using the generalised gradient approximation (GGA) yields a lowest energy configuration with the C-N axis perpendicular to the surface, although calculations using the local density approximation (LDA) do indicate that the experimental geometry is energetically favoured. The same conclusions are found for CN on Ni(1 1 1); on both surfaces bonding through the N atom is always unfavourable, in contrast to some earlier published results of ab initio calculations for Ni(1 1 1)/CN and Ni(1 0 0)/CN. The different predictions of the GGA and LDA approaches may lie in subtly different relative energies of the CN 5σ and 1π orbitals, a situation somewhat similar to that for CO adsorbed on Pt(1 1 1) which has proved challenging for DFT calculations. On Ni(1 0 0) GGA calculations favour a lying-down species in a hollow site in a geometry rather similar to that found experimentally and in GGA calculations for CN on Ni(1 1 0). 相似文献
69.
Jorge F. J. Coelho Ana M. F. P. Silva Anatoliy V. Popov Virgil Percec Mariana V. Abreu Pedro M. O. F Gonalves M. H. Gil 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):2809-2825
Living radical polymerization of n‐butyl acrylate was achieved by single electron transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionate. The plots of number–average molecular weight versus conversion and ln[M]0/[M] versus time are linear, indicating a controlled polymerization. This methodology leads to the preparation of α,ω‐di(iodo) poly (butyl acrylate) (α,ω‐di(iodo)PBA) macroinitiators. The influence of polymerization degree ([monomer]/[initiator]), amount of catalyst, concentration of suspending agents and temperature were studied. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering (RALLS), a differential viscometer (DV), and refractive index (RI). The methodology studied in this work represents a possible route to prepare well‐tailored macromolecules made of butyl acrylate in an environmental friendly reaction medium. Moreover, such materials can be subsequently functionalized leading to the formation of different block copolymers of composition ABA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2809–2825, 2006 相似文献
70.
A way of determining the flexibility of wood-pulp fibres is developed, which involves i) a precise measurement of the topology
of single-fibres by using a confocal laser scanning microscope and ii) the measurement of the elastic modulus of the fibres
by using a single-fibre fatigue cell. Reported in this paper are the initial results of tests carried out on black spruce
fibres, which have been subjected to three different levels of mechanical refining energy, namely ∼1100, 2300, and 3500 kWh/t.
It is found that the fibre flexibility rises significantly between the first and second energy levels, but it does not change
to the same degree between the second and third ones. The described procedure of measuring the flexibility of fibres may be
used to establish the appropriate refiner energy necessary for the production of a specific grade of paper.
Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 42, No. 1, pp. 115–128, January–February, 2006. 相似文献