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971.
972.
An experimental and modeling study of irradiated toluene–NOx–air, toluene–benzaldehyde–NOx–air, and cresol–NOx–air mixtures at part-per-million concentrations has been carried out. These mixtures were irradiated at 303 ± 1 K in a 5800-liter Teflon-lined, evacuable environmental chamber, with temperature, humidity, light intensity, spectral distribution, and the concentrations of O3, NO, NO2, toluene, PAN, formaldehyde, benzaldehyde, o-cresol, m-nitrotoluene, and methyl nitrate beingmonitored as a function of time. For the toluene and toluene–benzaldehyde–NOx–air runs a variety of initial reactant concentrations were investigated. Cresol–NOx–air runs were observed to be much less reactive in terms of O3 formation and NO to NO2 conversion rates than toluene–NOx–air runs, with the relative reactivity of the cresol isomers being in the order meta » ortho > para. The addition of benzaldehyde to toluene–NOx–air mixtures decreased the reactivity, in agreement with previous studies. Alternative mechanistic pathways for the NOx photooxidations of aromaticsystems in general are discussed, and the effects of varying these mechanistic alternatives on the model predictions for the toluene and o-cresol–NOx–air systems are examined. Fits of the calculations to most of the experimental concentration–time profiles could be obtained to within the experimental uncertainty for two of the mechanistic options considered. In both cases it is assumed that (1) O2 adds to the OH–toluene adduct ~75% of the time forming, after a further addition of O2, a C7 bicyclic peroxy radical, and (2) this C7 bicyclic peroxy radical reacts with NO ~75% of the time to ultimately form α-dicarbonyls and conjugated γ-dicarbonyls (e.g., methylglyoxal + 2-butene-1,4-dial) and ~25% of the time to form organic nitrates. The major uncertainties in the mechanisms concern (1) the structure of the bicyclicperoxy intermediate, and (2) the γ-dicarbonyl photooxidation mechanism. Good fits to the o-cresol concentration–time profiles in the toluene–NOx runs are obtained if it is assumed that o7-cresol reacts rapidly with NO3 radicals. However, it is observed that the model underpredicts nitrotoluene yields by a factor of ~10, but this is in any case a minor product. It is concluded that further experimental work will be required toadequately validate the assumptions incorporated in the aromatic photooxidation mechanisms presented here.  相似文献   
973.
James D. Wuest 《Tetrahedron》1980,36(16):2291-2296
Two major adducts are formed when diarylketenes react with ethoxyacetylene: cyclobutenones, produced by 2+2 cycloadditions characteristic of all ketenes, and norcaradienes, the unexpected products of 2+2+2 cycloadditions. Simpler vinylketenes in which the vinyl group is not incorporated in an aromatic ring yield only products derived from 2+2 cycloadditions.  相似文献   
974.
975.
Reagent 1 is a useful reagent for carrying out the annelation 2→3.  相似文献   
976.
The present paper is concerned with an evaluation of a piezoelectric energy conversion system in which two columns of piezoelectric ceramic disks are excited axially by means of thin metallic shims stacked alternately with the disks. Mechanical energy output is extracted through the expansion and contraction of the Columns. The treatment is based upon the equivalent circuit approach first suggested by Mason. A lever system is used in making the mechanical impedance transformation between the very high force and small displacement of the piezoelectric columns and the low force and relatively large displacement required for an artificial heart. The role of mass loading in improving the power capability and efficiency of the energy converter is clearly indicated. It is concluded that the theoretical energy output per unit mass of material per cycle and the efficiency of conversion are such as to justify a continued developmental effort.  相似文献   
977.
A precise and rapid transient diffusion experiment has been developed to measure the diffusive permeability of hollow fibers. In this experiment a sealed hollow fiber containing a radioactive solute is exposed sequentially to several well-stirred solute-free reservoirs. This method was used to measure the diffusive permeability of collagen and Cuprophan hollow fibers in an isotonic saline solution for a spectrum of 14C labelled solutes: urea, sucrose and polyethylene glycol (PEG). To study the effect of environment on membrane permeability, collagen membranes were investigated with urea, sucrose and tritiated water in the following solutions with varying ionic strength and hydrogen ion concentration: pH2 HCl, distilled water and pH2 HCl with 0.8 M NaCl.In each environment, the membranes showed the expected decreases in diffusive permeaability with increasing molecular weight. Collagen membranes ranged from 4 (urea) to 40 (PEG) times the permeability of Cuprophan membranes. The Cuprophan data are consistent with results obtained elsewhere using scaled-down dialyzers. In response to environmental changes, the diffusive permeability of collagen membranes changed overall by a factor of 3 with the following rank: pH 2 HCl > distilled water > pH2 HCl and 0.8 M NaCl. The hydraulic permeability of these membranes changed by a factor of 2 but in a different order pH2 HCl > pH2 HCl and 0.8 M NaCl > distilled water. These permeability changes can be explained in terms of the known environmental dependence for the structure of collagen membranes and have been shown to be consistent with trends predicted by simple transport models.  相似文献   
978.
We have run the high-resolution infrared absorption spectrum of 2ν2, ν1, and ν3 of H2Se in the region 5.2 to 3.8 μm. We have identified and fitted approximately 520 transitions in 2ν2, 930 transitions in ν1, and 620 transitions in ν3. Included are transitions from the isotopic species containing selenium isotopes 82, 80, 78, 77, and 76. Using Typke's rotational Hamiltonian, we analyzed all isotopic species simultaneously. Ground-state constants were determined from a simultaneous least-squares fit of 879 distinct ground-state combination differences formed from our data and 109 microwave transitions. Upper-state constants were obtained from least-squares fits of our spectral lines analyzing 2ν2 as a single noninteracting band and analyzing the Coriolis interacting bands ν1 and ν3 simultaneously, keeping the ground-state constants fixed.  相似文献   
979.
The NASA program for applied research and technology (ART) in thermionic energy conversion (TEC) comprises in-house, university-grant, and industrial-contract studies. In a few years this TEC-ART program has produced important results. Although many of these accomplishments are incremental, their integration has yielded performance gains and the knowledge necessary to direct future work. The current emphasis on out-of-core thermionics allows materials and designs previously prohibited by in-core nucleonics and geometrics. The additional degrees of freedom offer new potentialities. But as always high-temperature material effects will determine the level and lifetime of TEC performance: New electrodes must not only raise power outputs but also maintain them regardless of emitter-vapor deposition on collectors. In addition effective electrodes must serve compatibly with hot-shell alloys. Then, of course, space TEC must withstand external and internal high-temperature vaporization problems. And terrestrial TEC must tolerate hot corrosive atmospheres outside and near-vacuum inside. Finally reduction of losses between converter electrodes is essential even though rather demanding geometrics appear to be required for some modes of enhanced operation. In these and other areas from basic material characterizations to possible system definitions, significant progress is being made in the NASA TEC-ART Program.  相似文献   
980.
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