全文获取类型
收费全文 | 14440篇 |
免费 | 2415篇 |
国内免费 | 1662篇 |
专业分类
化学 | 7712篇 |
晶体学 | 249篇 |
力学 | 570篇 |
综合类 | 98篇 |
数学 | 804篇 |
物理学 | 9084篇 |
出版年
2024年 | 38篇 |
2023年 | 131篇 |
2022年 | 317篇 |
2021年 | 351篇 |
2020年 | 461篇 |
2019年 | 432篇 |
2018年 | 423篇 |
2017年 | 412篇 |
2016年 | 584篇 |
2015年 | 508篇 |
2014年 | 563篇 |
2013年 | 1511篇 |
2012年 | 752篇 |
2011年 | 902篇 |
2010年 | 705篇 |
2009年 | 915篇 |
2008年 | 917篇 |
2007年 | 918篇 |
2006年 | 877篇 |
2005年 | 764篇 |
2004年 | 693篇 |
2003年 | 718篇 |
2002年 | 631篇 |
2001年 | 470篇 |
2000年 | 559篇 |
1999年 | 416篇 |
1998年 | 341篇 |
1997年 | 275篇 |
1996年 | 247篇 |
1995年 | 194篇 |
1994年 | 208篇 |
1993年 | 171篇 |
1992年 | 158篇 |
1991年 | 126篇 |
1990年 | 107篇 |
1989年 | 95篇 |
1988年 | 76篇 |
1987年 | 58篇 |
1986年 | 76篇 |
1985年 | 66篇 |
1984年 | 68篇 |
1983年 | 17篇 |
1982年 | 34篇 |
1981年 | 41篇 |
1980年 | 32篇 |
1979年 | 26篇 |
1978年 | 21篇 |
1977年 | 22篇 |
1976年 | 18篇 |
1973年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
251.
Summary Further to Gilpin's observations in liquid chromatography of the irreversible transformation of alkyl grafts, following the replacement of an organic mobile phase by an aqueous one, we describe some gas chromatographic experiments which lead to similar (log Vs, I/T) plots, as a consequence of the same solvent release process.We use paraffin films on siliceous supports or hydroxylated liquid substrates or C22-alkyl bonded silica. These experiments demonstrate that this irreversible transition and the melting-like reversible transition are completely different phenomena. They confirm the existence of at least three kinds of monomeric alkyl films. 相似文献
252.
负载型无铬超细铁基变换催化剂的制备和催化性能 总被引:11,自引:0,他引:11
以镁铝尖晶石为载体,以过渡金属氧化物为助剂,用吸附γ-Fe2O3胶体法制备了负载型无铬铁基变换催化剂.TEM,XRD,BET和活性测试结果表明,采用胶体负载法制备的变换催化剂,其活性组分Fe3O4以分立的超细微颗粒分布在镁铝尖晶石载体表面上,颗粒之间存在一定的间隔.过渡金属氧化物NiO或V2O5能够进入Fe3O4晶格形成固溶体,起到代替氧化铬的作用,提高催化活性.负载型催化剂FeNi/MgAl2O4(m(NiO)/m(Fe2O3)=3%)在汽/气比为1和空速为2000h-1的反应条件下,CO转化率在400和350℃时分别为95%和80%;在高空速和低汽/气比条件下也具有很好的催化性能.稳定性实验结果表明,该催化剂
具有良好的热稳定性和一定的抗硫能力.与非负载型催化剂相比,负载型催化剂具有更为优越的催化性能. 相似文献
253.
合成了9种具L-氨基酸衍生物结构的介晶化合物(I-Ⅲ,Ⅳab,Ⅴa,b,Ⅵa,b)、4种氨基酸衍生物(A1-4)和6种介晶化合物(M1-6).新化合物(Ⅰ-Ⅲ,Ⅳa,b,Ⅴa,b,Ⅵa,b,A4,M3-6)的化学结构通过IR、1HNMR和元素分析证实;并用偏光显微观察和DSC分析研究了其相变行为,结果表明有8种化合物(M3-6,Ⅵa,b,Ⅴb,Ⅵb)呈现液晶相变。测定了它们的比旋光度。通过X射线衍射研究了化合物Ⅵh120~130℃和Ⅵb170~180℃的近晶结构,Ⅵb显,Ⅵb呈。测定了化合物Ⅳb的电滞回线,证明其具铁电性。 相似文献
254.
We report a comprehensive theoretical study on the decarbonylation of acetaldehyde by Fe+ and Cr+. Various intermediates, transition states, and products involved in the decarbonylation reactions are fully optimized at the B3LYP/6-311+G(2df,2pd) level of theory. The potential energy surfaces (PESs) corresponding to [M,O,C2,H4]+(M=Cr and Fe) are examined in detail using B3LYP and CCSD(T) methods, respectively. The validity of these theoretical methods is calibrated with respect to the available thermochemical data. Calculations suggest that the Cr+ mediated decarbonylation of acetaldehyde takes place in four steps on the sextet surface: encounter complexation, C-C activation, aldehyde H-shift, and nonreactive dissociation, in good accordance with the Co+ mediated decarbonylation of acetaldehyde [Zhao, Zhang, Guo, Wu, Lu, Chem. Phys. Lett. 2005, 414, 28], while for the Fe+/acetaldehyde system decarbonylation can occur on both the quartet and the sextet PESs. The quartet pathway, which experiences spin-orbit coupling between the two surfaces, is energetically more favorable; whereas along the sextet decarbonylation coordinate several high-energy barriers are revealed. The theoretical results are compared with the experimental product kinetic energy and angular distributions of decarbonylation of acetaldehyde by Fe+ and Cr+ measured using a crossed-beam technique [Sonnenfroh, Farrar, J. Am. Chem. Soc. 1986, 108, 3521]. 相似文献
255.
256.
Ruiz E Rodríguez-Fortea A Cano J Alvarez S Alemany P 《Journal of computational chemistry》2003,24(8):982-989
The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data. 相似文献
257.
Muhammad Ilyas Sarwar Sonia Zulfiqar Zahoor Ahmad 《Colloid and polymer science》2007,285(15):1733-1739
Fluoro-aramid-based sol/gel-derived nanocomposites were synthesized by condensing a mixture of 4,4′-(hexafluoro-isopropylidene)dianiline
and 1,3-phenylenediamine with terephthaloylchloride (TPC) in dimethylacetamide. TPC was added in slight excess to produce
amide chains with carbonyl chloride end groups and then replaced with alkoxy groups using aminophenyltrimethoxysilane to develop
bonding with the silica network. Mechanical, dynamic mechanical thermal, water absorption and morphological measurements were
carried out on the thin hybrid films. Increase in the tensile strength and modulus was observed as compared to pristine polyamide.
The thermal decomposition temperature was found in the range of 400–500 °C. The water absorption was found to be reduced with
higher silica content. The glass transition temperature and the storage moduli increased with increasing silica concentration.
The maximum increase in the T
g value (345 °C) was observed with 20 wt% silica. Scanning electron microscopy revealed the uniform distribution of silica
in the matrix with an average particle size ranging from 8 to 50 nm. 相似文献
258.
259.
260.
Effects of metal surfaces, such as aluminium, silver and gold, on the melting behavior and thermal polymerization of long-chain diynoic acids having a diacetylene group at different positions were investigated by thermal analyses using DSC, TG and other methods. The surface effects of metals were significant in the order of Ag, Al and Au. These effects are attributable to the anchoring of carboxyl group on the surface by chemisorption, which leads to unfavorable condition for polymerization of heptadeca-2,4-diynoic acid. In the case of tricosa-10,12-diynoic acid, containing a flexible methylene chain, inserted between COOH and C≡C?C≡C groups, the anchoring of COOH on the metal surface causes rather favorable effect on the polymerization. 相似文献