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991.
992.
激光促进甲醇在杂多化合物上的表面反应 总被引:1,自引:0,他引:1
利用红外光谱 (IR)、程序升温脱附 (TPD)和激光促进表面反应 (L SSR)技术 ,研究了甲醇吸附于杂多化合物 H3PMo1 2 O40 · x H2 O、H3PW1 2 O40 · x H2 O、H6 PMo6 W6 O40 · x H2 O表面上所形成体系的振动结构、化学吸附形态和光促表面反应规律 .实验结果表明 ,在各固体材料表面上甲醇同时发生分子吸附和解离吸附 ,且在室温条件下体系即发生显著的光促表面反应 ;与甲醇吸附强度和吸附量相比 ,反应体系的振动结构对 L SSR效率起着更重要的作用 .根据表征和反应结果 ,分析了体系中活性物种的产生途径 ,并给出了反应机理的模型 相似文献
993.
994.
995.
The structure of the conformationally flexible 2-fluoroethanal molecule (CH2FCHO, FE) in the ground (S0) and lowest excited triplet (T1) and singlet (S1) electronic states was investigated by ab initio quantum-chemical methods. The FE molecule in the S0 state was found to exist as two conformers, viz., as cis (the F—C—C—O angle is 0°) and trans (the F—C—C—O angle is 180°) conformers. On going both to the T1 and S1 states, the FE molecule undergoes substantial structural changes, in particular, the CH2F top is rotated with respect to the core and the carbonyl CCHO fragment becomes nonplanar. The potential energy surfaces for the T1 and S1 states are qualitatively similar, viz., six minima in each of the excited states of FE correspond to three pairs of mirror-symmetrical conformers. Based on the potential energy surfaces calculated for the FE molecule in the T1 and S1 states, the one-dimensional problems on the torsion and inversion nuclear motions as well as the two-dimensional torsion-inversion problems were solved. 相似文献
996.
Inverse gas chromatography (IGC) was applied to characterize the surface energy of organically modified silicates (ormosils) by measuring the interaction of molecular organic probes with the ormosil surface. Ormosils were prepared by the sol-gel method by the reaction of TEOS (tetraethoxysilane), PDMS (polydimethylsiloxane) and different types of silica (Aerosil 130, Aerosil 200 and Aerosil 380). The isosteric heat of adsorption, q
st, and the dispersive component of the surface energy, s
D, were estimated by using the retention volume of different nonpolar and polar probes at infinite dilution. The dispersive component shows an increase as the specific surface area of the silica is increased from 29.6 mJ/m2 to 51.4 mJ/m2 at 60°C. Such values are lower than that obtained for aerosil particles meaning that PDMS chains impede the interaction with silanol groups located on the silica surface. The specific interaction parameter, ISP, and the enthalpy of specific adsorption, H
a
SP, of polar probes on the ormosil surface were also measured in order to obtain the acid-base character of ormosil surface. The H
a
SP, was correlated with the donor, DN, and the acceptor, AN, numbers of the probes to quantify the acidic, K
A, and the basic, K
B, parameters of the substrate surface. The obtained results suggest that the silica particles were covered by PDMS chains in a different way depending on the type of silica used. The values of K
A and K
B suggest that the ormosil surface is amphoteric, with predominantly acceptor electron sites. 相似文献
997.
Influences of Heating Condition and Substrate-Surface Roughness on the Characteristics of Sol-Gel-Derived Hydroxyapatite Coatings 总被引:6,自引:0,他引:6
A prepared transparent HA solution was coated on Ti6Al4V substrates by a spin-coating technique. The crystallization of the sol-gel-derived HA coated on the metallic substrates could be done at relatively low firing temperatures (as low as 600°C). The characteristics of the HA-coated layer were dependent on the surface roughness of substrates and heating conditions such as firing temperature, holding time, heating rate, and atmosphere. The heat treatment at a slow heating rate (<2°C/min.) and a long heating time (>10 hrs) at 600°C in air produced the uniform surface and improved the crystallinity. The HA layer coated on 20 m grit-blasted substates was more uniform and had fever cracks after firing, compared with that coated on 100 m grit-blasted rougher substrates. 相似文献
998.
SiO2–Al2O3 aerogels and xerogels with a Si to Al molar ratio r
Si/Al varying from 0.25 to 20, were made by sol-gel process in acidic conditions at pH 2 and respectively dried by the CO2 supercritical method and by solvent evaporation. The Al precursor was also chelated with ethylacetoacetate, which made it possible to study the structure and texture of such gels in conditions favorable to the formation of mixed Al–O–Si bonds. Nitrogen adsorption isotherms according to the Brunauer, Emmett and Teller method (BET), 27Al magic angle spinning nuclear magnetic resonance (27Al MAS-NMR), Fourier Transformed Infrared Spectroscopy (FTIR) and Infrared absorbance spectra after Temperature Programmed Desorption (TPD) of pyridine, showed that the Si–O infrared asymmetric stretching vibration and the Bronsted acidity relative to the Lewis acidity, depended on the ratio of AlIV to Si atoms. 相似文献
999.
A procedure for pH-metric determination of the limiting adsorption of OH groups (A
OH) by FeIII, ZrIV, CrIII, and InIII oxyhydroxide hydrogels from 0.1 and 1.0 M solutions of NaCl is described. Data on the molecular area occupied by a single OH group on the hydrogel surface (S
OH) and the S
spec values, which were calculated from A
OH and S
OH, are presented. The S
spec value does not depend on the pH of hydrogel precipitation; the true S
spec value can be determined only from sorption of the OH groups at the actual point of zero charge of the hydrogel. The A
OH values for hydrogels were found to change only slightly during aging of hydrogels in electrolyte solutions. 相似文献
1000.
Chistyakov A. L. Stankevich I. V. Gambaryan N. P. Akhrem I. S. 《Russian Chemical Bulletin》2001,50(1):29-34
Fragments of the potential energy surfaces (PES) of the systems [C3H8 + CBr3
+] and [C3H8 + Br2CBr+·Br2AlBr2
–] were simulated by the MNDO/PM3 method. Energy minima corresponding to weakly bound adducts of propane molecule with the CBr3
+ cation or neutral complex CBr3
+·AlBr4
– were found on the PES's of both systems. These are adducts with the coordination of a H atom of the methylene group of the propane molecule to the electrophile at the Br atom carrying the largest positive charge. As the fragments of the adducts are brought close together, the coordinated H atom migrates to the C atom of the CBr3
+ fragment. The potential barriers of these migrations were found to be low for both systems. The reactions proceed without formation of cyclic intermediates or transition states typical of the Olah mechanism. 相似文献