全文获取类型
收费全文 | 1305篇 |
免费 | 135篇 |
国内免费 | 147篇 |
专业分类
化学 | 1073篇 |
晶体学 | 12篇 |
力学 | 56篇 |
综合类 | 33篇 |
数学 | 66篇 |
物理学 | 347篇 |
出版年
2024年 | 1篇 |
2023年 | 18篇 |
2022年 | 43篇 |
2021年 | 66篇 |
2020年 | 51篇 |
2019年 | 52篇 |
2018年 | 23篇 |
2017年 | 44篇 |
2016年 | 56篇 |
2015年 | 48篇 |
2014年 | 58篇 |
2013年 | 169篇 |
2012年 | 67篇 |
2011年 | 54篇 |
2010年 | 47篇 |
2009年 | 72篇 |
2008年 | 58篇 |
2007年 | 58篇 |
2006年 | 67篇 |
2005年 | 47篇 |
2004年 | 55篇 |
2003年 | 57篇 |
2002年 | 116篇 |
2001年 | 34篇 |
2000年 | 31篇 |
1999年 | 22篇 |
1998年 | 20篇 |
1997年 | 17篇 |
1996年 | 16篇 |
1995年 | 16篇 |
1994年 | 18篇 |
1993年 | 10篇 |
1992年 | 21篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1988年 | 9篇 |
1987年 | 2篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 5篇 |
1982年 | 8篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有1587条查询结果,搜索用时 281 毫秒
41.
Changes in the hybrid state of atomic orbitals of nitrogen and p-character of LEP, which occur under the effect of saturated hydrocarbon radicals and polar substituents in aliphatic amines, differ substantially. Therefore, the effect of the both substituents on the basicity constants of amines cannot be described by the single formal type of interaction. The anomalous changes in the basicity in the series of primary, secondary, and tertiary alkylamines, which are discussed in the literature, and the correlations pK
BH+ = f(*) and G
B = f(*) are, in fact, imaginary, because the alkyl radicals at the N atom do not manifest the electron-donor properties. 相似文献
42.
M. Menning C. Schelle A. Duran J.J. Damborena M. Guglielmi G. Brusatin 《Journal of Sol-Gel Science and Technology》1998,13(1-3):717-722
Glass-like sol-gel coatings have been investigated as corrosion protective coatings on stainless steel. Magnesium- and borosilicate coatings with thickness of about 100–700 nm and methyl-modified SiO2 coatings with a thickness of about 2 m were deposited on stainless steel plates by dip-coating. The coatings were densified between 400°C and 500°C in different atmospheres (N2, air) for 1 h. The corrosion protection against gaseous attack was investigated by accelerated corrosion tests, at 800°C in air for 1 h. A corrosion protection factor was calculated from the relation Fe/Fe2O3, determined by XRD on the surface of coated and uncoated samples. Methyl-modified SiO2 coatings showed a protection factor, which was 2 orders of magnitude higher than for the other coatings. Electrochemical investigations were performed on samples submerged in a NaCl solution for 200 h. The corrosion propagation, polarization resistance and impedance vector were measured. For accelerated corrosion tests, polarization intensity curves were determined for high potentials of up to 1 V. Again excellent results were obtained for the methyl-modified SiO2 coatings, which remained passive for 200 h. Results of the salt spray corrosion test, however, showed no corrosion protection by the sol-gel coatings. After 2000 h in the salt spray chamber the steel was corroded and the coatings peeled off. It is concluded that for the further development of these coatings an improved interfacial passivation will be required. 相似文献
43.
The synthesis and comprehensive characterization of a purely sterically stabilized latex with narrow size distribution is
reported. By use of non-ionic initiators no chemically bound surface charges are generated. Stabilization of the particles
is achieved through use of a non-ionic surfactant having a double bond in the hydrophobic part which is chemically bound to
the surface. Analysis of the latex particles thus generated by transmission electron microscopy, disc centrifugation, and
small-angle X-ray scattering (SAXS) reveals that the size distribution is narrow (standard deviation between 6 and 10%). SAXS
furthermore demonstrates that the surfactant is located in a thin layer on the surface. The interaction of the particles is
purely repulsive as shown by the analysis of the turbidity of the latex. The systems obtained herein may serve as model systems
of water-borne purely sterically stabilized colloid particles.
Received: 23 December 1997 Accepted: 18 May 1998 相似文献
44.
A. D. Dubonosov V. P. Rybalkin Ya. Yu. Vorob’eva V. A. Bren’ V. I. Minkin S. M. Aldoshin V. V. Tkachev A. V. Tsukanov 《Russian Chemical Bulletin》2004,53(10):2248-2252
It was shown by electron absorption spectroscopy and X-ray diffraction analysis that steric strains in photochromic 2-(N-acyl-N-arylaminomethylene) benzo[b]thiophen-3(2H)-one molecules ortho-substituted in the N-phenyl ring increase the quantum yield of the N→O photoinduced rearrangement in accord with an increase in the steric constant of the ortho-substituent.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2151–2155, October, 2004. 相似文献
45.
The partial molal volumes of Li+, Na+, K+, Rb+, Cs+, Cl–, Br–, I–, and NO
3
-
in DMSO at 25°C have been determined from ultrasonic vibration potential data and density data for solutions of uni-univalent electrolytes. Hepler's semiemprirical equation has been used to split ionic partial molal volumes into geometric and electrostrictive contributions. The results obtained in this work confirm the conclusion of our previous studies, namely, that the contribution of electrostriction is essentially determined by the properties of that layer of atoms, 0.3 to 0.4 nm thick, in contact with the ion and by the degree of steric hindrance of the poles of the dipole of the solvent molecule. On the other hand, the geometric contribution depends on the size of the solvent molecule and also on the arrangement of the solvent molecules about the ions. It is shown that the geometric contribution to the partial molal volume of ions is largely increased when ions cannot come close enough to the poles of the solvent-molecule dipole, owing to steric hindrance. 相似文献
46.
Eriko Sato Per B. Zetterlund Bunichiro Yamada 《Journal of polymer science. Part A, Polymer chemistry》2004,42(23):6021-6030
α‐(2‐Methyl‐2‐phenylpropyl)acrylate (RS‐2) was examined as a C? C bond‐cleavage type addition–fragmentation chain transfer (AFCT) agent in the benzene solution polymerizations of styrene (St), ethyl methacrylate (EMA), and cyclohexyl acrylate (CHA) with the objective of achieving efficient macromonomer synthesis by radical polymerization. The AFCT efficiency was evaluated in terms of the decrease in the number‐average molecular weight (Mn) upon the addition of the AFCT agent and the number of unsaturated end groups introduced per chain (f). The AFCT efficiency was rationalized by the consideration of the relative importance of AFCT as an end‐forming event and the competition between ‐fragmentation and crosspropagation as adduct radical reaction pathways. In St and EMA polymerizations at 60 °C, RS‐2 resulted in higher f values and lower Mn values than methyl α‐(2‐methyl‐2‐carbomethoxypropyl)acrylate (MMA‐2), and this suggested the facilitation of ‐fragmentation due to the expulsion of the more stable cumyl radical from the RS‐2 adduct radical. Higher f values were observed for MMA‐2 than for RS‐2 in CHA polymerization because of unsaturated end group formation by ‐fragmentation of midchain radicals. However, RS‐2 resulted in lower Mn values for poly(CHA) than MMA‐2 because of a smaller contribution of crosspropagation. Retardation in the presence of the AFCT agents was affected by the balance between b‐fragmentation and crosspropagation and by the addition rate of the propagating radical to the AFCT agent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6021–6030, 2004 相似文献
47.
48.
49.
为了探寻电流脉冲泄流时,设备的接地是否有效可靠,用FDTD法分析了脉冲泄流时均一土壤、分层土壤及局部改善土壤的电导率对冲击接地阻抗(TGR)的影响。结果表明:大地电导率对冲击接地阻抗的影响很大;对均一土壤,TGR随大地电导率的增大而减小,大地电导率越大,TGR对接地体的埋深越不敏感。对分层土壤,接地体要埋在大地电导率大的土壤层中,且不要靠近交界面;局部改善大地导电性能对降低TGR效果明显,TGR对改善区域的体积非常敏感,而当电导率大于一定值时,大地电导率的再增加,对TGR的影响不明显。 相似文献
50.