全文获取类型
收费全文 | 5187篇 |
免费 | 648篇 |
国内免费 | 980篇 |
专业分类
化学 | 5647篇 |
晶体学 | 46篇 |
力学 | 29篇 |
综合类 | 39篇 |
数学 | 155篇 |
物理学 | 899篇 |
出版年
2024年 | 32篇 |
2023年 | 276篇 |
2022年 | 191篇 |
2021年 | 190篇 |
2020年 | 384篇 |
2019年 | 292篇 |
2018年 | 191篇 |
2017年 | 228篇 |
2016年 | 241篇 |
2015年 | 216篇 |
2014年 | 247篇 |
2013年 | 332篇 |
2012年 | 292篇 |
2011年 | 301篇 |
2010年 | 239篇 |
2009年 | 273篇 |
2008年 | 297篇 |
2007年 | 299篇 |
2006年 | 264篇 |
2005年 | 264篇 |
2004年 | 244篇 |
2003年 | 236篇 |
2002年 | 228篇 |
2001年 | 146篇 |
2000年 | 137篇 |
1999年 | 119篇 |
1998年 | 86篇 |
1997年 | 93篇 |
1996年 | 82篇 |
1995年 | 72篇 |
1994年 | 57篇 |
1993年 | 54篇 |
1992年 | 46篇 |
1991年 | 28篇 |
1990年 | 26篇 |
1989年 | 19篇 |
1988年 | 18篇 |
1987年 | 15篇 |
1986年 | 10篇 |
1985年 | 21篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 10篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有6815条查询结果,搜索用时 31 毫秒
21.
The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH4 > N2 > O2 > CO2. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO2 decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO2‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004 相似文献
22.
Styrene (STY) is now produced industrially in fairly large quantities by the dehydrogenation of ethylbenzene (EB) using promoted iron oxide catalyst with superheated steam.In this case, small amount of carbon dioxide formed as a by-product was known to inhibit the catalytic activity of commercial catalyst. Recently, there have been some reports which carbon dioxide showed positive effects to promote catalytic activities on the reaction over several catalysts.In this study, we attempted to combine the dehydrogenation of EB to STY with the carbon dioxide shift-reaction. The combine reaction (EB + CO2 → STY + H2O + CO) can be considered as one of the ways of using CO2 resources and can yield simultaneously STY and Carbon oxide.Alumina oxide catalysts such as Al2O3, Na2O/Al2O3 and K2O/Al2O3 were prepared by the usual impregnation method with an aqueous solution of NaNO3 and KNO3, and then calcined at 650℃ for 5 h in a stream of air. The reaction condition is 600℃, flow of CO2 38ml/mon and space velocity (EB) 1.28h-1. 相似文献
23.
S.A. Masti A.K. Sharma P.N. Vasambekar A.S. Vaingankar 《Journal of magnetism and magnetic materials》2006
Magnetization and permeability of polycrystalline ferrites with general formula CdxMg1−xFe2−yCryO4 (x=0, 0.2, 0.4, 0.6, 0.8, 1.0; y=0, 0.05 and 0.10) were studied. Study of saturation magnetization reveals that the Neel's two-sublattice model exists upto x=0.4, for y=0, 0.05 and 0.1 and a three-sublattice model (YK-model) is predominant for x>0.4 and y=0, 0.05 and 0.10. The saturation magnetization and magnetic moment were found to decrease with the increase in Cr3+ contents, which is attributed to the dilution of B–B site interaction. Variation of initial permeability with temperature revealed the long-range ferromagnetic ordering in the compounds with x=0.4. The sample with x?0.4 and y=0, 0.05 and 0.10 showed peaking behavior near Curie temperature, which is attributed to the decrease of anisotropy constant K1 to zero. Low-frequency dispersion of initial permeability suggests domain wall displacement. Addition of Cd2+ resulted in a sharp decrease in Curie temperature. With the addition of Cr3+, initial permeability was found to decrease. 相似文献
24.
W.F. Wang 《Journal of Quantitative Spectroscopy & Radiative Transfer》2004,86(4):437-444
It is shown that by including the second term of Magnus expansion, improved convergence can be achieved for the non-perturbative pressure broadening formalism proposed by Neilson and Gordon (J. Chem. Phys. 58 (1973) 4131). The present method was applied to the line broadening calculations of CO in a bath of Ar. 相似文献
25.
A new type of phosphino-phosphonium ylide ligand bearing a chiral sulfinyl center affords a P,C-chelated palladium(II) complex with a resolved asymmetric ylidic carbon atom. According to 31P NMR analysis of the crude material, the diastereoselectivity of the complexation at room temperature is ca. 7:1. In the crystal state, an X-ray diffraction analysis of one epimer reveals a quasi C2-symmetric chloro-bridged dinuclear structure, where the (S) configuration of the sulfur atom induces a (S) configuration of the ylidic carbon atom. A in situ Pd(0) catalyst generated from the phosphino-ylide and Pd(PPh3)4 promotes allylic substitution of 3-acetoxy-1,3-diphenylpropene by sodium malonate in 70% yield and 5% e.e. 相似文献
26.
27.
本文利用比较原理以及一种特殊变换研究了一类非线性退化方程的混合问题,得到了这类复杂问题解的渐进性质。 相似文献
28.
Shahla Yekta 《Journal of fluorine chemistry》2004,125(4):517-525
New partially fluorinated binaphthols were obtained using a copper-catalyzed oxidative coupling. The corresponding enantiomerically pure compounds were prepared by fractional crystallization of the corresponding bis(menthyl)carbamates. Nucleophilic aromatic substitution using oxygen- and carbon-based nucleophiles resulted in functionalized derivatives without concomitant racemization. The titanium(IV) complexes of these ligands are catalytically active in the asymmetric oxidation of sulfides. 相似文献
29.
Homogeneously prepared tosylcelluloses (TC) with degrees of substitution (DS) of DSTos 0.1–1.8 were used as intermediates for the synthesis of methylaminocelluloses (MAC) by nucleophilic substitution with methylamine. TC with DSTos up to 1.1 were shown to be valuable intermediates for selective synthesis of MAC with DSMA varying from 0.1 to approximately 1. No nucleophilic substitution was observed at higher DSTos. At the chosen reaction conditions (60 °C, 48 h) residual tosyl moieties remained unchanged and little hydrolysis took place. The samples obtained were characterized by means of elemental analysis, FTIR and 13C CP/MAS NMR spectroscopy. 13C CP/MAS NMR spectroscopy was found to be an efficient tool for quantification of DSMA. Furthermore, the swelling behaviour in water was investigated and preliminary tests concerning the bilirubin adsorption capacity of MAC were carried out. 相似文献
30.
Polyethyleneimine (PEIM) samples crosslinked by a commercial epoxy resin (Epon 828) were prepared, and their adsorption capacity for acidic gases was studied. The swelling and deswelling characteristics of the crosslinked samples were also examined as part of this program. Reactivation of these adsorbents could be carried out by heat, or by a combination of heat and treatment in dilute alkalies. 相似文献