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121.
Micromechanics of cleavage fracture initiation in ferritic steels by carbide cracking 总被引:1,自引:0,他引:1
Cleavage fracture in ferritic steels is often initiated in brittle carbides randomly distributed in the material. The carbides break as a result of a fibre loading mechanism in which the stress levels in the carbides are raised, as the surrounding ferrite undergoes plastic deformation. The conditions in the vicinity of the nucleated micro-crack will then determine whether the crack will penetrate or be arrested by the ferrite. The ferrite is able to arrest nucleated cracks through the presence of mobile dislocations, which blunt and shield the microcrack and thus lowers the stresses at the crack tip. Hence, the macroscopic toughness of the material directly depends on the ability of the ferrite to arrest nucleated micro-cracks and in turn on the plastic rate sensitivity of the ferrite. The initiation of cleavage fracture is here modelled explicitly in the form of a micro-crack, which nucleates in a brittle carbide and propagates into the surrounding ferrite. The carbide is modelled as an elastic cylinder or in a few cases an elastic sphere and the ferrite as an elastic viscoplastic material. The crack growth is modelled using a cohesive surface, where the tractions are governed by a modified exponential cohesive law. It is shown that the critical stress, required to propagate a microcrack from a broken carbide, increases with decreasing plastic rate sensitivity of the ferrite. The results also show that a low stress triaxiality and a high aspect ratio of the carbide promote the initiation of cleavage fracture from a broken carbide. 相似文献
122.
The complexation behavior of Aldrich humic acid (AHA) and a modified humic acid (AHA-PB) with blocked phenolic hydroxyl groups for trivalent lanthanides (Ln) is compared, and their influence on the mobility of Ln(III) in an aquifer is analyzed. As speciation technique, capillary electrophoresis (CE) was hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). For metal loading experiments 25 mg L−1 of AHA and different concentrations (cLn(Eu+Gd) = 100–6000 μg L−1) of Eu(III) and Gd(III) in 10 mM NaClO4 at pH 5 were applied. By CE-ICP-MS, three Ln-fractions, assumed to be uncomplexed, weakly and strongly AHA-complexed metal can be detected. For the used Ln/AHA-ratios conservative complex stability constants log βLnAHA decrease from 6.33 (100 μg L−1 Ln3+) to 4.31 (6000 μg L−1 Ln3+) with growing Ln-content. In order to verify the postulated weaker and stronger humic acid binding sites for trivalent Eu and Gd, a modified AHA with blocked functional groups was used. For these experiments 500 μg L−1 Eu and 25 mg L−1 AHA and AHA-PB in 10 mM NaClO4 at pH-values ranging from 3 to 10 have been applied. With AHA-PB, where 84% of the phenolic OH-groups and 40% of the COOH-groups were blocked, Eu complexation was significantly lower, especially at the strong binding sites. The log β-values decrease from 6.11 (pH 10) to 5.61 at pH 3 (AHA) and for AHA-PB from 6.01 (pH 7) to 3.94 at pH 3. As a potential consequence, particularly humic acids with a high amount of strong binding sites (e.g. phenolic OH- and COOH-groups) can be responsible for a higher metal mobility in the aquifer due to the formation of dissolved negatively charged metal-humate species. 相似文献
123.
Jonas Boström Valera Veryazov Francesco Aquilante Thomas Bondo Pedersen Roland Lindh 《International journal of quantum chemistry》2014,114(5):321-327
An algorithm for computing analytical gradients of the second‐order Møller–Plesset (MP2) energy using density fitting (DF) is presented. The algorithm assumes that the underlying canonical Hartree–Fock reference is obtained with the same auxiliary basis set, which we obtain by Cholesky decomposition (CD) of atomic electron repulsion integrals. CD is also used for the negative semidefinite MP2 amplitude matrix. Test calculations on the weakly interacting dimers of the S22 test set (Jure?ka et al., Phys. Chem. Chem. Phys. 2006, 8, 1985) show that the geometry errors due to the auxiliary basis set are negligible. With double‐zeta basis sets, the error due to the DF approximation in intermolecular bond lengths is better than 0.1 pm. The computational time is typically reduced by a factor of 6–7. © 2013 Wiley Periodicals, Inc. 相似文献
124.
In this paper, we present a smoothing technique which can be understood as a Quasi-Newton method. The idea of this preconditioner is that it approximates the symbol of the inverse Hessian, which has smoothing behavior. This symbol is derived analytically for the Stokes equations and investigated numerically for a flow with a Reynolds number of 80. The resulting symbol is then approximated by differential operators, which will lead to a method similar to Sobolev Smoothing. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
125.
126.
Pei X Fernandes A Mathy B Laloyaux X Nysten B Riant O Jonas AM 《Langmuir : the ACS journal of surfaces and colloids》2011,27(15):9403-9412
Photoresponsive monolayers of hydrophilically substituted azobenzenes have been prepared by reaction on aminosilane monolayers on silicon surfaces. Grafting densities in the 0.2-1.0 molecule/nm(2) range were determined by X-ray reflectometry. The monolayers exhibit reversible photoisomerization, switching from a more hydrophilic trans state to a less hydrophilic cis state upon UV irradiation, in contrast with the usual behavior of most azobenzene monolayers that switch from a less to a more hydrophilic state. This indicates that the wettability is not dominated by the change in the dipole moment of the azobenzene moiety but originates from variations in the composition of the outer surface of the monolayers resulting from the reorientation of the substituent groups. The light-driven change in the water contact angle correlates linearly with the grafting density but remains small. However, the wettability contrast can be increased by forcing the molecules to stand in an improved vertical orientation, either by densifying the underlying aminosilane monolayer or by filling the voids left at the bottom of the layer of grafted azobenzene molecules. 相似文献
127.
Grignard B Vaillant A de Coninck J Piens M Jonas AM Detrembleur C Jerome C 《Langmuir : the ACS journal of surfaces and colloids》2011,27(1):335-342
Superhydrophobic aluminum surfaces with excellent corrosion resistance were successfully prepared by electrospinning of a novel fluorinated diblock copolymer solution. Micro- and nanostructuration of the diblock copolymer coating was obtained by electrospinning which proved to be an easy and cheap electrospinning technology to fabricate superhydrophobic coating. The diblock copolymer is made of poly(heptadecafluorodecylacrylate-co-acrylic acid) (PFDA-co-AA) random copolymer as the first block and polyacrylonitrile (PAN) as the second one. The fluorinated block promotes hydrophobicity to the surface by reducing the surface tension, while its carboxylic acid functions anchor the polymer film onto the aluminum surface after annealing at 130 °C. The PAN block of this copolymer insures the stability of the structuration of the surface during annealing, thanks to the infusible character of PAN. It is also demonstrated that the so-formed superhydrophobic coating shows good adhesion to aluminum surfaces, resulting in excellent corrosion resistance. 相似文献
128.
Rafa? GrubbaAleksandra Wi?niewska Katarzyna BaranowskaEberhard Matern Jerzy Pikies 《Polyhedron》2011,30(7):1238-1243
Reactions of R2P-P(SiMe3)Li with [Cp2MCl2] (M = Zr, Hf) in hydrocarbons yield the related terminal phosphanylphosphido complexes [Cp2M(Cl){(Me3Si)P-PR2-κP1}] (R = iPr and tBu). The solid state structures of [Cp2M(Cl){P(SiMe3)-PiPr2-κP1}] (M = Zr, Hf) were established by single crystal X-ray diffraction studies. The phosphido-P atoms adopt almost planar geometries and the phosphanyl P atoms adopt pyramidal geometries. The reaction of a mixture of (Me3Si)2PLi and Ph2P-P(SiMe3)Li with [CpZrCl3] in toluene yields the dinuclear complex [Cp2Zr2Cl5(Ph2PPPSiMe3)(Li THF DME)]. 相似文献
129.
Functional surfaces and especially the control of surface properties depending on external parameters such as light illumination
have gained increasing importance in the last few years. We present the characterization of polymers from the cycloolefin
(co)polymer class (COC/COP) functionalized with an aminosilane as a basis for the further immobilization of compounds. In
a first step, an assay using AlexaFluor?647 fluorescent dye was used to assess surface homogeneity and reproducibility. A
coefficient of variation of less than 15% for dot-to-dot and less than 25% for chip-to-chip could be achieved. The same amino-functionalized
surfaces were then used to immobilize a biotinylated photolabile linker compound, binding AlexaFluor?647-labeled streptavidin.
The linker was photocleaved with high efficiency at λ = 365 nm and P = 0.15 mW/cm2. Fluorescence measurements show that polymers of the COC/COP class can be used as versatile surfaces for the photoinduced
release of compounds immobilized via photolabile linkers. 相似文献
130.
Jonas T. Hartwig 《Journal of Pure and Applied Algebra》2011,215(10):2352-2377
We define a notion of pseudo-unitarizability for weight modules over a generalized Weyl algebra (of rank one, with commutative coefficient ring R), which is assumed to carry an involution of the form X∗=Y, R∗⊆R. We prove that a weight module V is pseudo-unitarizable iff it is isomorphic to its finitistic dual V?. Using the classification of weight modules by Drozd, Guzner and Ovsienko, we obtain necessary and sufficient conditions for an indecomposable weight module to be isomorphic to its finitistic dual, and thus to be pseudo-unitarizable. Some examples are given, including Uq(sl2) for q a root of unity. 相似文献