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171.
利用具有同步辐射源的反射式飞行时间质谱仪,研究甲基环己烷的真空紫外光电离和光解离. 观测到母体离子C7H14+和碎片离子C7H13+,C6H11+,C6H10+,C5H10+,C5H9+,C4H8+,C4H7+和C3H5+的光电离效率曲线. 测定甲基环己烷的电离能为9.80±0.03 eV,通过光电离效率曲线确定其碎片离子的出现势. 在B3LYP/6-31G(d)水平上对过渡态、中间体和产物离子的优化结构进行表征,并使用G3B3方法计算其能量. 提出主要碎片离子的形成通道. 分子内氢迁移和碳开环是甲基环己烷裂解途径中最重要的过程. 相似文献
172.
A model is developed for the formation and propagation of cracks in a material sample that is heated at its top surface, pyrolyses, and then thermally degrades to form char. In this work the sample is heated uniformly over its entire top surface by a hypothetical flame (a heat source). The pyrolysis mechanism is described by a one-step overall reaction that is dependent nonlinearly on the temperature (Arrhenius form). Stresses develop in response to the thermal degradation of the material by means of a shrinkage strain caused by local mass loss during pyrolysis. When the principal stress exceeds a prescribed threshold value, the material forms a local crack. Cracks are found to generally originate at the surface in response to heating, but occasionally they form in the bulk, away from ever-changing material boundaries. The resulting cracks evolve and form patterns whose characteristics are described. Quantities examined in detail are: the crack spacing in the pyrolysis zone; the crack length evolution; the formation and nature of crack loops which are defined as individual cracks that have joined to form loops that are disconnected from the remaining material; the formation of enhanced pyrolysis area; and the impact of all of the former quantities on mass flux. It is determined that the mass flux from the sample can be greatly enhanced over its nominal (non-cracking) counterpart. The mass efflux profile qualitatively resembles those observed in Cone Calorimeter tests. 相似文献
173.
Data envelopment analysis (DEA) is a method for measuring the efficiency of peer decision making units (DMUs), where the internal structures of DMUs are treated as a black-box. Recently DEA has been extended to examine the efficiency of DMUs that have two-stage network structures or processes, where all the outputs from the first stage are intermediate measures that make up the inputs to the second stage. The resulting two-stage DEA model not only provides an overall efficiency score for the entire process, but also yields an efficiency score for each of the individual stages. The current paper develops a Nash bargaining game model to measure the performance of DMUs that have a two-stage structure. Under Nash bargaining theory, the two stages are viewed as players and the DEA efficiency model is a cooperative game model. It is shown that when only one intermediate measure exists between the two stages, our newly developed Nash bargaining game approach yields the same results as applying the standard DEA approach to each stage separately. Two real world data sets are used to demonstrate our bargaining game model. 相似文献
174.
Numerical modelling of acoustic cavitation threshold in water is presented taking into account non-condensable bubble nuclei, which are composed of water vapor and non-condensable air. The cavitation bubble growth and collapse dynamics are modeled by solving the Rayleigh-Plesset or Keller-Miksis equation, which is combined with the energy equations for both the bubble and liquid domains, and directly evaluating the phase-change rate from the liquid and bubble side temperature gradients. The present work focuses on elucidating acoustic cavitation in water with a wide range of cavitation thresholds (0.02–30 MPa) reported in the literature. Computations for different nucleus sizes and acoustic frequencies are performed to investigate their effects on bubble growth and cavitation threshold. The numerical predictions are observed to be comparable to the experimental data in the previous works and show that the cavitation threshold in water has a wide range depending on the bubble nucleus size. 相似文献
175.
M.-E. Herrmann H. Brösicke M. Keller E. Mönch H. Helge 《Isotopes in environmental and health studies》2013,49(1):34-35
It is essential to establish whether and how environmental factors affect the reliability of [13C]methacetin breath test (13C-MBT). In 12 healthy volunteers (smokers), a standard 13C-MBT with 75 mg [13C]methacetin was performed twice in random order: on a control day without smoking and on another day with smoking two cigarettes antecedently. A considerable flattening of the curve of the momentary 13C recovery within the expiratory air was observed when the 13C-MBT was performed after smoking. The maximum of the momentary 13C recovery, D max, decreased from 37.20±2.58 to 25.39±2.29% dose/h (p=0.00052). Moreover, the time to reach D max was prolonged after cigarette smoking (26.5±3.1 vs. 16.5±1.9 min, p=0.0199). The curve of the cumulative 13C recovery on the cigarette smoking day appeared to be shifted downwards, and statistically significant differences relative to the control situation were found between the 24th and 75th minute following [13C]methacetin administration. Smoking cigarettes immediately prior to the 13C-MBT diminishes the ability of the liver to handle methacetin, and hence a possibility of such an interaction should be excluded in order to interpret the results of the test correctly. 相似文献
176.
F. A. Akin 《Molecular physics》2013,111(24):3556-3566
ABSTRACTThe structures, ionisation energies (IE), and electron affinities (EA) of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) isomers upon loss and gain of an electron were calculated using density functional theory (DFT) methods. The adiabatic electron affinities (EAad) range from 1 to 2 eV. The vertical detachment energies are between 1.3 and 4.0 eV. The adiabatic ionisation energies (IEad) are in the 9.9–10.2 eV range. The vertical ionisation energies are in the 10.4–10.9 eV range. It is shown that NO2?/NO2 loss would be common in anions and cations, respectively. Isomerisation and N—N bond dissociation accompany cation and anion formation, respectively. The suggested mass spectral fragmentation products for the cations along the S0 surface are 84, 130, and 176 amu, in agreement with earlier mass spectrometry studies. 相似文献
177.
An alkali‐soluble polysaccharide, GM5‐1, from the mycelium of Ganoderma tsugae, was fractionated by the nonsolvent addition method. The weight‐average molecular mass (M w) and intrinsic viscosity ([η]) of fractions were studied by laser light scattering and viscometry with dimethylsulfoxide (DMSO) containing 0.25M LiCl (0.25M LiCl/DMSO) as the solvent at 30°C. The dependences of [η] and the radius of gyration (?S 2?z 1/2) on M w were found to be [η]=9.8×10?2 M w 0.57 (cm3g?1) and ?S 2?z 1/2=1.65×10?2 M w 0.58 (nm) in the M w range from 8.6×105 to 2.6×106. The analysis based on current theories for a wormlike chain showed that the chain conformational parameters of GM5‐1 were 4.2 nm for persistence length (q) and 833 nm?1 for linear mass density (ML) with an obvious excluded volume effect. The results suggested the alkali‐soluble polysaccharide behaves like a semiflexible chain in 0.25M LiCl/DMSO at 30°C. 相似文献
178.
E. Barth I. Tugtekin H. Weidenbach U. Wachter J. Vogt P. Radermacher 《Isotopes in environmental and health studies》2013,49(1-2):209-213
Abstract Breath tests using 13C-labelled substrates require the measurement of 13CO2/12CO2 ratio in breath gas samples. Next to isotope ratio mass spectrometry (IRMS), which is very sensitive but also complex and expensive, alternatively isotope selective nondispersive infrared spectrometry (NDIRS) can be used to determine the 13CO2/12CO2 ratio in expired breath. In this study we compared NDIRS- with IRMS-results to investigate whether the less expensive and very simply to operate NDIRS works as reliable as IRMS. For this purpose we applicated 1-13C-Phenylalanine to patients with advanced liver cirrhosis and healthy volunteers and took duplicated breath samples for IRMS and NDIRS at selected time points. Our data show a good correlation between these two methods for a small number of samples as required for simple breath tests. Longer series, where repeated measurements are required on the NDIRS instrument lead to a decreasing correlation. This indicates the superiority of IRMS concerning 13CO2-kinetics over longer time periods. 相似文献
179.
180.