全文获取类型
收费全文 | 5720篇 |
免费 | 822篇 |
国内免费 | 384篇 |
专业分类
化学 | 3961篇 |
晶体学 | 109篇 |
力学 | 338篇 |
综合类 | 19篇 |
数学 | 581篇 |
物理学 | 1918篇 |
出版年
2024年 | 19篇 |
2023年 | 125篇 |
2022年 | 143篇 |
2021年 | 141篇 |
2020年 | 261篇 |
2019年 | 194篇 |
2018年 | 160篇 |
2017年 | 157篇 |
2016年 | 354篇 |
2015年 | 293篇 |
2014年 | 360篇 |
2013年 | 373篇 |
2012年 | 297篇 |
2011年 | 387篇 |
2010年 | 356篇 |
2009年 | 382篇 |
2008年 | 370篇 |
2007年 | 419篇 |
2006年 | 355篇 |
2005年 | 264篇 |
2004年 | 278篇 |
2003年 | 205篇 |
2002年 | 131篇 |
2001年 | 123篇 |
2000年 | 128篇 |
1999年 | 93篇 |
1998年 | 97篇 |
1997年 | 95篇 |
1996年 | 64篇 |
1995年 | 40篇 |
1994年 | 35篇 |
1993年 | 40篇 |
1992年 | 26篇 |
1991年 | 24篇 |
1990年 | 17篇 |
1989年 | 21篇 |
1988年 | 24篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 14篇 |
1984年 | 5篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1978年 | 3篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1969年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有6926条查询结果,搜索用时 125 毫秒
1.
H.-J. Sue E. I. Garcia-Meitin N. A. Orchard 《Journal of Polymer Science.Polymer Physics》1993,31(5):595-608
The fracture behavior of a core-shell rubber (CSR) modified epoxy is investigated using both fracture mechanics and microscopy tools. The CSR-modified epoxy is found to be toughened via numerous line-array cavitations of the CSR particles, followed by plastic flow of the epoxy matrix. The toughening effect via the above craze-like damage process is found to be as effective as that of the well-known widespread rubber cavitation/matrix shear yielding mechanisms. The conditions for triggering the craze-like damage appear to be both stress state and rubber concentration dependent. The type of rubber tougheners utilized also plays a critical role in triggering this rather unusual craze-like damage in epoxy systems. © 1993 John Wiley & Sons, Inc. 相似文献
2.
J rgen Rosenqvist Kristina Axe Staffan Sj berg Per Persson 《Colloids and surfaces. A, Physicochemical and engineering aspects》2003,220(1-3):91-104
The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition −O2C---Cn---CO2−; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles. 相似文献
3.
The reaction mechanism of the l-proline-catalyzed α-aminoxylation reaction between aldehyde and nitrosobenzene has been investigated using density functional theory (DFT) calculation. Our calculation results reveal following conclusions [1]. The first step that corresponds to the formation of C–O bond, is the stereocontrolling and rate-determining step [2]. Among four reaction channels, the syn-attack reaction channel is more favorable than that of the anti one, and the TS-ss channel dominates among the four channels for this reaction in the step of C–O bond formation [3]. The intermolecular hydrogen bond between the acidic hydrogen of l-proline and the N atom of the nitrosobenzene in an early stage of the process catalyzes very effectively the C–O bond formation by a large stabilization of the negative charge that is developing at the O atom along the electrophilic attack [4]. The effect of solvent decreases the activation energy, and also, the calculated energy barriers are decrease with the enhancement of dielectric constants for C–O bond formation step. These results are in good agreement with experiment, and allow us to explain the origin of the catalysis and stereoselectivity for l-proline-catalyzed α-aminoxylation of aldehyde reaction. The addition of H2O to substituted imine proline, intermolecular proton-transfer steps, and the l-proline elimination process were also studied in this paper. 相似文献
4.
5.
The ring opening of the oxadiaziridine by cleavage of the N-N bond has been theoretically investigated by SCF calculations improved with limited CI. The possible competition of this reaction with the better known ones (N-O bond cleavage, inversion of the N atom) is discussed. The chemical implications of the formation of a new type of 1,3-dipole are examined. 相似文献
6.
Unimolecular fragmentation patterns of the molecular ions of selected lactams and sultams bearing alkoxymethyl group at the nitrogen atom were studied. The main common fragmentation reaction observed for all compounds studied in this work is the elimination of an aldehyde molecule. This reaction is considered to proceed via two different mechanisms. For lactams, hydrogen rearrangement within an alkoxymethyl group is observed, which leads to the appropriate N-methyl derivatives. For sultams, transfer of the methyl group to the nitrogen and oxygen atoms, proceeding through an ion-neutral complex, dominates. Another important fragmentation channel characteristic exclusively for lactams is the loss of an alkyl radical. This process takes place within the N-alkoxymethyl moiety, yielding the appropriate protonated ion of N-formyllactams. This process is accompanied by relatively high kinetic energy release. 相似文献
7.
B.M. Huerta-Martínez F.J. Medellín-Rodríguez R. Cedillo García 《European Polymer Journal》2005,41(3):519-525
Compatibility mechanisms between EVA and complex heterophasic iPP-EPx copolymers have been studied as a function of EP content. Systematic studies were made in order to characterize the thermal, morphological and mechanical behavior, before and after blending a series of PP-EPx/EVA concentrations. Multiple melting, proportional to the EP content, was observed for the neat copolymers and an explanation was given for its evolution in terms of rejection-like secondary crystallization. After blending with EVA, the generation of a single Tg was taken as an indication of compatibility between both polymers. A morphological transition toward compatibility was first determined at 20 wt.% EVA which was in correlation with a morphological change from isolated spherical domains to interconnected voids. A second morphological transition from interconnected voids to fibrous crystals was observed above 40 wt.% EVA. This last transition marked the beginning of compatibility. Overall, the evolution of blends was explained in terms of the nature of the complex heterophasic copolymers. Tensile mechanical studies were also consistent with morphological changes. Increases in the x content in EPx and in EVA concentration worked in favor of impact resistance. 相似文献
8.
Jay K. Kochi 《Angewandte Chemie (International ed. in English)》1988,27(10):1227-1266
The broad varieties of organic and organometallic reactions merge into a common unifying mechanism by considering all nucleophiles and electrophiles as electron donors (D) and electron acceptors (A), respectively. Comparison of outer-sphere and inner-sphere electron transfers with the aid of Marcus theory provides the thermochemical basis for the generalized free energy relationship for electron transfer (FERET) in Equation (37) and its corollaries in Equations (43) and (44) that have wide predictive applicability to electrophilic aromatic substitutions, olefin additions, organometallic cleavages, etc. The FERET is based on the conversion of the weak nucleophile–electrophile interactions extant in the ubiquitous electron donor—acceptor (EDA) precursor complex [D, A] to the radical ion pair [D⊕, A?], for which the free energy change can be evaluated from the charge-transfer absorption spectra according to Mulliken theory. FERET analysis thus indicates that the charge-transfer ion pairs [D⊕, A?] are energetically equivalent to the transition states for nucleophile/electrophile transformations. The behavior of such ion pairs can be directly observed immediately following the irradiation of the charge-transfer bands of various EDA complexes with a 25-ps laser pulse. Such studies confirm the radical ion pair [Arene⊕, NO2] as a viable intermediate in electrophilic aromatic nitration, as presented in the electron-transfer mechanism between arenes and the nitryl cation (NO) electrophile. 相似文献
9.
Abstract On the basis of experimental results obtained in the present and some other works a model of melting of rare gas solids within bubbles formed in a crystalline metal matrix as a result of ion implantation is proposed. Rare gas solid is supposed to melt on heating at the expense of the bubble volume expansion by emission of a dislocation loop. On this basis the melting temperature can be estimated as one which is enough to provide for a pressure inside a bubble sufficient for the initiation of the dislocation loop punching. Values of melting temperatures obtained in this way are in good agreement with available experimental data. 相似文献
10.
Uri. Goldberg 《International Journal of Computational Fluid Dynamics》2013,27(1):27-38
A new topography-parameter-free turbulence closure, based on a transport equation for the pseudo eddy viscosity, is described. The model is tested against experimental data of several flow cases across the Mach number range and compared to Menter's single equation model and to the Spalart-Allmaras model. The main conclusion is that the new closure outperforms the other two models in both low and high speed flows. 相似文献