全文获取类型
收费全文 | 2699篇 |
免费 | 465篇 |
国内免费 | 269篇 |
专业分类
化学 | 568篇 |
晶体学 | 130篇 |
力学 | 228篇 |
综合类 | 11篇 |
数学 | 644篇 |
物理学 | 1852篇 |
出版年
2024年 | 7篇 |
2023年 | 35篇 |
2022年 | 90篇 |
2021年 | 60篇 |
2020年 | 63篇 |
2019年 | 70篇 |
2018年 | 72篇 |
2017年 | 67篇 |
2016年 | 100篇 |
2015年 | 88篇 |
2014年 | 131篇 |
2013年 | 326篇 |
2012年 | 156篇 |
2011年 | 214篇 |
2010年 | 161篇 |
2009年 | 218篇 |
2008年 | 194篇 |
2007年 | 170篇 |
2006年 | 146篇 |
2005年 | 111篇 |
2004年 | 96篇 |
2003年 | 93篇 |
2002年 | 107篇 |
2001年 | 62篇 |
2000年 | 100篇 |
1999年 | 75篇 |
1998年 | 81篇 |
1997年 | 46篇 |
1996年 | 30篇 |
1995年 | 42篇 |
1994年 | 27篇 |
1993年 | 13篇 |
1992年 | 25篇 |
1991年 | 12篇 |
1990年 | 16篇 |
1989年 | 12篇 |
1988年 | 19篇 |
1987年 | 13篇 |
1986年 | 13篇 |
1985年 | 13篇 |
1984年 | 12篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 6篇 |
1976年 | 6篇 |
1973年 | 2篇 |
排序方式: 共有3433条查询结果,搜索用时 31 毫秒
61.
Nb4W13O47, a member of the solid solution series Nb8−nW9+nO47 (0?n?5), crystallizes in a threefold superstructure of the tetragonal tungsten bronze structure. While the oxidation of this reduced phase at TOX=1200 °C leads to a separation into the thermodynamically stable phases, lower oxidation temperatures result in products that comprise new structural elements and ordering variants. The characterization of the oxidation products obtained at TOX=1000 °C was performed by scanning transmission electron microscopy applying a high-angle annular dark field detector. At the selected imaging conditions (Z contrast), not only the metal positions are revealed by this technique but valuable additional information about the elemental distribution can be obtained simultaneously. 相似文献
62.
Irmgard Kalf 《Journal of organometallic chemistry》2006,691(10):2277-2285
Enantiomerically pure cationic complexes were obtained via cyclopalladation of primary amines and subsequent addition of a chelating ethylendiamine ligand. No diastereomeric resolution was observed upon combining these cations with racemic mandelate or hydratropate anions, but four less popular products, namely three double salts and a solid solution, were obtained and structurally characterized. For one of the double salts, the alternative ionic compounds based on different stereoisomers of the same residues were synthesized independently: The conventional racemic solid and both diastereomeric salts formed by enantiopure cations and anions were studied by single crystal X-ray diffraction. Lattice energy calculations confirm that the diastereomeric salts differ significantly; formation of the partially racemic double salt, however, is energetically favourable and precludes resolution. 相似文献
63.
Oxygen Atom Adsorption and Diffusion on Pd Low-index Surfaces and (311) Stepped Surface 总被引:2,自引:0,他引:2
Introduction Atom adsorption on transition metal surfaces has attracted special attention as a base for understanding the fundamental processes of oxidative catalysis. Particularly interesting is the adsorption and diffusion of oxygen on well-defined metal surfaces. An oxygen covered palladium surface, for example, plays a central role in several important reactions such as oxidation of carbon monoxide and ammonia. In particular, the (100), (111), (110) surfaces and the interactions with oxyge… 相似文献
64.
本工作采用溴加成法、酚解法、FTIR法及臭氧裂解法分别测定了五种不饱和蒸气压下聚合的PVC样品(u-PVC)和五种商品PVC样品(s-PVC)的总双键、总不稳定氯、孤立双键和内部双键的含量.通过研究结构缺陷和PVC的平均分子量及脱HCl速率的相互关系,揭示了不饱和总双键值,总不稳定氯和孤立双键含量彼此的相关性是建立在它们分别与1/M_n的相关性基础之上,从而得出了这三种定量值测得的主要都是端基烯丙基氯结构.根据三者对脱HCl速率的良好线性相关性,首次提出了端基烯丙基氯结构在HCl催化作用下异构化成内部烯丙基氯从而成为脱HCl速率主要原因的机理. 相似文献
65.
Limin Chen Ding Ma Barbara Pietruszka Xinhe Bao 《天然气化学杂志》2006,15(3):181-190
Carbon materials were used as supports for Ag catalysts that are prepared using the conventional wet impregnation method, and their catalytic properties for CO selective oxidation in excess hydrogen at temperatures below 483 K were tested. A variety of techniques, e.g. N2 adsorption, XPS, TPD, UV-Vis DRS, TEM and SEM, were used to determine the influence of physical and chemical properties of the carbon on the properties of Ag catalyst. It was found that defects on the carbon surface served as nucleation sites for silver ions, while functional groups on carbon surface induced their reduction to the metallic form. The formation of silver particles on carbon was governed by homogeneous and/or heterogeneous nucleation during the impregnation and subsequent activation processes. The best catalytic performance was obtained with a Ag/carbon black catalyst with a uniform size distribution of silver nanoparticles (about 12 nm), moderate BET surface area (with a mesoporous structure), and a limited amount of carbon-oxygen groups. The research indicates that carbon materials are potentially good supports for silver catalysts for preferential oxidation of CO in excess hydrogen. 相似文献
66.
El-B. Yallaoui 《Periodica Mathematica Hungarica》1991,23(2):109-120
Let X be an abstract set and L a lattice of subsets of X. To each lattice regular measure µ, we associate two induced measures
and
on suitable lattices of the Wallman space IR(L) and another measure µ on the spaceIR(L). We will investigate the reflection of smoothness properties of p onto
,
and µ; and try to set some new criterion for repleteness and measure repleteness. 相似文献
67.
《Magnetic resonance in chemistry : MRC》2018,56(3):190-195
The local distortions and electron paramagnetic resonance parameters for Cu2+ in the mixed alkali borate glasses xNa2O‐(30–x)K2O‐70B2O3 (5 ≤ x ≤ 25 mol%) are theoretically studied with distinct modifier Na2O compositions x. Owing to the Jahn–Teller effect, the octahedral [CuO6]10− clusters show significant tetragonal elongation ratios p ~19% along the C4 axis. With the increase of composition x, the cubic field parameter Dq and the orbital reduction factor k exhibit linearly and quasi‐linearly decreasing tendencies, respectively, whereas the relative tetragonal elongation ratio p has quasi‐linearly increasing rule with some fluctuations, leading to the minima of g factors at x = 10 mol%. The composition dependences of the optical spectra and the electron paramagnetic resonance parameters are suitably reproduced by the linear or quasi‐linear relationships of the relevant quantities (i.e., Dq, k, and p) with x. The above composition dependences are analyzed from mixed alkali effect, which brings forward the modifications of the local crystal‐fields and the electronic cloud distribution around Cu2+ with the variation of the composition of Na2O. 相似文献
68.
The permeabilities of microscale fibrous porous media were calculated using the multiple-relaxation-time (MRT) lattice Boltzmann method (LBM). Two models of the microscale fibrous porous media were constructed based on overlapping fibers (simple cubic, body-centered cubic). Arranging the fibers in skew positions yielded two additional models comprising non-overlapping fibers (skewed simple cubic, skewed body-centered cubic). As the fiber diameter increased, the fibers acted as granular inclusions. The effects of the overlapping fibers on the media permeability were investigated. The overlapping fibers yielded permeability values that were a factor of 2.5 larger than those obtained from non-overlapping fibers, but the effects of the fiber arrangement were negligible. Two correlations were obtained for the overlapping and non-overlapping fiber models, respectively. The effects of the rarefaction and slip flow are also discussed. As the Knudsen number increased, the dimensionless permeability increased; however, the increase differed depending on the fiber arrangement. In the slip flow regime, the fiber arrangement inside the porous media became an important factor. 相似文献
69.
Abstract On radiolysis tris(acetylacetonato) cobalt(III) in aqueous solutions is found to get reduced by reaction with (1) hydrated electrons, (2) H atoms, (3) OH radicals and (4) C2H2OH radicals. The bimolecular rate constants for the first three reactions, determined by competition kinetics are: 4 × 1010, 2.3 × 109 and 4.7 × 109 M?1sec?1 respectively. Absorption spectra of the irradiated solutions indicate the formation of bis(acetylacetonato) cobalt(II) from reaction (1), but not from (3). The total cobaltous yield in air-free solutions is given byG(Co++) = 5.6 and 6.5 at pH 6.5 and 1 respectively. It appears that Geaq- ∽ H + GoH ∽ 2.8 in neutral solutions. Considerations of material balance for the primary yields of radiolysis of water suggest the possibility that the so-called independent H-atoms in neutral solutions are probably excited water molecules or ion-pairs. 相似文献
70.
The photoluminescence (PL) properties of ZrO2 have been measured at different temperatures between 7 and 300 K, using various kinds of ZrO2 specimens: bulk crystal melt-grown by a large solar furnace, thermally oxidized zirconium plate (ZrO2 film crystal on Zr ) and nanocrystals (surface area: 35–45m2/g, diameter: 20–30 nm). The results clarify the deep and shallow energy level structures in the energy gap. Reversible UV-laser-light-induced spectral changes are observed for all of the specimens in different specimen-atmospheres (vacuum and O2 gas). The results elucidate the defect-effects of the PL properties and the PL enhancement mechanism in ZrO2 nanocrystals. 相似文献