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941.
942.
We report here how the hydration of complex surfaces can be efficiently studied, thanks to recent advances in classical molecular density functional theory. This is illustrated on the example of the pyrophyllite clay. After presenting the most recent advances, we show that the strength of this implicit method is that: (1) it is in quantitative or semi-quantitative agreement with reference all-atom simulations (molecular dynamics here) for both the solvation structure and energetics, and (2) the computational cost is two to three orders of magnitude less than in explicit methods. The method remains imperfect in that it locally overestimates the polarisation of water close to hydrophylic sites of the clay. The high numerical efficiency of the method is illustrated and exploited to carry out a systematic study of the electrostatic and van der Waals components of the surface–solvent interactions within the most popular force field for clays, CLAYFF. Hydration structure and energetics are found to weakly depend upon the electrostatics. We conclude on the consequences of such findings on future force-field development.  相似文献   
943.
The accumulation of microdamage in trabecular bone tissue is suspected of being a predictive indicator of osteoporosis diagnosis. To quantify this microdamage, the Dynamic AcoustoElastic Testing (DAET) method measures the Time Of Flight (TOF) and amplitude variations of transmitted ultrasound (US) pulses, while the bone sample is submitted to a low frequency sinusoidal hydrostatic pressure (opening/closing of microcracks). However, DAET is both sensitive to viscoelastic properties changes and microcracks density. To verify the microcracks density contribution on DAET results, a numerical approach is proposed. Multliple configurations of microdamaged trabecular bone-tissue-like mesh have been simulated. A 2D pseudo-spectral time domain numerical model was then developed to simulate linear wave propagation in heterogeneous solids. The influence of the microcracks number and orientation on the US TOF was particularly investigated. Results are discussed and compared with experimental data obtained from DAET measurements in trabecular bone samples.  相似文献   
944.
The existence of quantum states of matter in a gravitational field was demonstrated recently in the Institut Laue–Langevin (ILL), Grenoble, in a series of experiments with ultra cold neutrons (UCN). UCN in low quantum states is an excellent probe for fundamental physics, in particular for constraining extra short-range forces; as well as a tool in quantum optics and surface physics. The GRANIT is a follow-up project based on a second-generation spectrometer with ultra-high energy resolution, permanently installed in ILL. It has been constructed in framework of an ANR grant; and will become operational in 2011.  相似文献   
945.
We construct an explicit filtration of the ring of algebraic power series by constructible sets, measuring the complexity of these series. As an example of use of this, we give a bound on the dimension of the set of algebraic power series of bounded complexity lying on an algebraic variety defined over the field of power series.  相似文献   
946.
Sputter-deposited Al/CuO multilayers capable of highly energetic reactions have been the subject of intense studies for tunable initiation and actuation. Designing high performance Al/CuO-based initiator devices definitively requires reliable prediction of their ignition and reaction kinetics including self-heating or ageing as a function of heating rate and environmental conditions. The paper proposes a heterogeneous reaction model integrating an ensemble of basic mechanisms (oxygen diffusion, structural transformations, polymorphic phase changes) that have been collected from recent experimental investigations. The reaction model assumes that the rate of reaction is limited by the transport of oxygen across the growing layer of Al2O3 separating Al and CuO. Importantly, we show that the model predicts reasonably all exotherms through a wide range of temperature (ambient – 1000°C), all resulting from a pure diffusion process as experimentally observed for such Al/CuO multilayers. The model shows how the temperature ramp affects the structure of the multilayer and especially the growth of alumina-based interfacial regions. It highlights the importance of the interfacial chemistry evolution such as the native mixture of AlxCuyOz transformation into a thin amorphous alumina, and the polymorphic phase transformation of this latter. The first one occurring at ~350°C results in a loss of continuity of the interface leading to the accelerated redox reaction whereas the second one occurring between 500 and 600°C produces a denser barrier to oxygen diffusion leading to the stop of redox reaction. We finally use the model to simulate thermal annealing as usually performed in accelerated ageing experiments. We theoretically observe and experimentally validate that a two weeks exposure of the multilayers at 200°C starts degrading the multilayers thermal properties whereas when the temperature remains below 200°C, the material keeps its entire integrity.  相似文献   
947.
α-Trifluoromethyl azocanes are accessible from 2-(trifluoropropan-2-ol) piperidines by metal-free ring-expansion involving a bicyclic azetidinium intermediate. The opening of the azetidinium intermediate was achieved by various nucleophiles (amines, alcoholates, carboxylates, phosphonates, halides and pseudo-halides) with an excellent regio- diastereo- and enantioselectivity and in good yields. The relative configuration of the piperidines and azocanes were assigned and the deprotected azocanes offer opportunities for further derivatization.  相似文献   
948.
A textbook dysprosium dinuclear complex based on acetylacetone ligands, [Dy2(acac)42-acac)2(H2O)2], has been synthesized and fully characterized. This simple dimeric lanthanide complex shows well-resolved solid-state luminescence and behaves as a single-molecule magnet under zero DC field. A seminal crystal-field approach is used to marry both magnetism and luminescence in the frame of an energetic picture.  相似文献   
949.
Switchable materials are increasingly considered for implementation in devices or multifunctional composites leading to a strong need in terms of reliable synthetic productions of well-defined objects. Here, an innovative and robust template-free continuous process was developed to synthesize nanoparticles of a switchable coordination polymer, including the use of supercritical CO2, aiming at both quenching the particle growth and drying the powder. This all-in-one process offers a 12-fold size reduction in a few minutes while maintaining the switching properties of the selected spin crossover coordination polymer.  相似文献   
950.
Known for excellent stability, porosity and functionality, the high-valent Zr4+ metal–organic frameworks (Zr-MOFs) still meets synthetic challenge in modulating the strength of Zr-Ocarboxylate linkage. Herein we explore the unusual coordination dynamics of fluorinated Zr-MOFs by designing two trifluoromethyl modified ligands with distinct geometry preference to form a family of thermodynamic and kinetic products. The low-connecting kinetic Zr-MOFs possess substitutable coordination sites to endow Zr6-cluster with extra dynamic behaviors, thus opening a post-synthetic pathway to sequential reassembly/disassembly processes. Comprehensive factors, including ligand geometry, Zr6-cluster connectivity, acid modulator and reaction temperature/concentration, have been studied for controllable syntheses. The stability, hydrophobicity and gas adsorption/separation properties of obtained Zr-MOFs are explored. This work sheds light on the understanding of the dynamic coordination chemistry of Zr-MOFs beyond strong Zr−O bond, which poses a versatile platform for modification and functionalization of Zr-MOFs.  相似文献   
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