全文获取类型
收费全文 | 1540篇 |
免费 | 519篇 |
国内免费 | 1207篇 |
专业分类
化学 | 635篇 |
晶体学 | 7篇 |
力学 | 113篇 |
综合类 | 40篇 |
数学 | 2090篇 |
物理学 | 381篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 19篇 |
2021年 | 37篇 |
2020年 | 26篇 |
2019年 | 14篇 |
2018年 | 10篇 |
2017年 | 23篇 |
2016年 | 16篇 |
2015年 | 34篇 |
2014年 | 154篇 |
2013年 | 168篇 |
2012年 | 193篇 |
2011年 | 121篇 |
2010年 | 334篇 |
2009年 | 250篇 |
2008年 | 372篇 |
2007年 | 278篇 |
2006年 | 153篇 |
2005年 | 100篇 |
2004年 | 63篇 |
2003年 | 98篇 |
2002年 | 53篇 |
2001年 | 137篇 |
2000年 | 183篇 |
1999年 | 105篇 |
1998年 | 45篇 |
1997年 | 19篇 |
1996年 | 27篇 |
1995年 | 56篇 |
1994年 | 57篇 |
1993年 | 41篇 |
1992年 | 14篇 |
1991年 | 11篇 |
1990年 | 21篇 |
1989年 | 15篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
排序方式: 共有3266条查询结果,搜索用时 31 毫秒
51.
Mono salicylaldiminato vanadium(Ⅲ) complexes(1a-1f)[RN = CH(ArO)]VCl2(THF)2(Ar = C6H4(1a-1e),R = Ph,1a;R = p-CF3Ph,1b;R = 2,6-Me2Ph,1c;R = 2,6-iPr2Ph,1d;R = cyclohexyl,1e;Ar = C6H2tBu2(2,4),R = 2,6-iPr2Ph, 1f) and bis(salicylaldiminato) vanadium(Ⅲ) complexes(2a-2f)[RN = CH(ArO)]2VCl(THF)x(Ar = C6H4(2a-2e),x = 1 (2a-2e),R = Ph,2a;R =p-CF3Ph,2b;R = 2,6-Me2Ph,2c;R = 2,6-iPr2Ph,2d;R = cyclohexyl,2e;Ar = C6H2tBu2(2,4),R = 2,6-iPr2Ph,x = 0,2f) have been evaluated as the active catalysts for ethylene/1-hexene copolymerization in the presence of Et2AlCl.The ligand substitution pattern and the catalyst structure model significantly influenced the polymerization behaviors such as the catalytic activity,the molecular weight and molecular weight distribution of the copolymers etc.The highest catalytic activity of 8.82 kg PE/(mmolV·h) was observed for vanadium catalyst 2d with two 2,6-diisopropylphenyl substituted salicylaldiminato ligands.The copolymer with the highest molecular weight was obtained by using mono salicylaldiminato vanadium catalyst 1f having ligands with tert-butyl at the ortho and para of the aryloxy moiety. 相似文献
52.
53.
54.
55.
A novel simple but effective initiating system of H2O/AlCl3 /veratrole (VE) has been developed to synthesize high molecular weight polyisobutylene (PIB) at elevated temperatures via cationic polymerization of isobutylene (IB) in solvent mixture of hexane/methylene dichloride (n-Hex/CH2Cl2 = 2/1, V/V). VE played very important roles in decreasing cationicity of the growing chain ends, suppressing side reactions of chain transfer and termination during polymerization, leading to production of high molecular weight PIBs. PIBs with high yields, having very high weight-average molecular weight (Mw ) of 1117000 and 370000 g/mol could be synthesized with H2O/AlCl3 /VE initiating system at VE concentration of 5.4 mmol/L at 80 and 60℃ respectively. Molecular weight of PIB increased remarkably with increasing VE concentration. The reaction order with respect to VE concentration was determined to be 3.52 via FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance (ATR) immersion probe. The negative reaction order of VE was consistent with its retarding effect on IB polymerization by interacting with the propagating species. Molecular weight of PIB decreased with increasing polymerization temperature. The activation energy for polymerization degree (EDP ) could be determined to be around 23 kJ/mol when VE concentration was 5.4 mmol/L or 6.4 mmol/L. 相似文献
56.
Star-shaped oligothiophenes with hexakis(fluoren-2-yl)benzene (HFB) as cores were designed and synthesized. Grafting thiophene units to HFB results in a bond flattening of the core, and makes the molecules a flipping-twist shape. Their thermal, photophysical and electrochemical properties were studied. Highly cross-linked conjugated polymers can be produced by electropolymerization of T1-T3. 相似文献
57.
The effects of the spin coating process parameters on the thickness of the SiOx layer of the BOPP/SiOx composite film were investigated. When the concentration of tetraethoxysilane (TEOS) increased from 12.5 vol% to 55% vol%, the SiOx thickness increased from about 80 nm to 470 nm. In the sol time range of 1.5 h to 5 h the SiOx layer thickness reached a maximum at about 4 h and the change of the thickness roughly matched the change of the silica colloidal sphere sizes in sol. When the spin-coating speed of the dispensing stage increased from 450 r/min to 500 r/min, the SiOx layer thickness drastically decreased from about 1.67 μm to 400 nm. While the spin-coating speed of the thinning and drying stage went up to 1200 r/min, the SiOx layer thickness was in the range of 330 nm to 390 nm. It was also found that the SiOx layer thickness was almost increased linearly from about 500 nm to 1.02 μm with the ratio of the commercial silica colloidal to the TEOS from 0.2 to 1.0. The water contact angles decreased to about 23.0° for the BOPP/Si-Sol composite film with 1.67 μm SiOx layer and about 4.0° for the BOPP/mixing Si-Sol composite film with 1.02 μm SiOx layer. Compared to BOPP, the light transparency of the BOPP/Si-Sol composite films decreased by about 5.5% with the SiOx layer from about 80 nm to 1.67 μm and by 7.0% for the BOPP/mixing Si-Sol composite film with the SiOx layer from about 350 nm to 1.02 μm respectively. 相似文献
58.
Multiarm star block copolymers hyperbranched polyethylenimine-b-poly(2-hydroxyethyl methacrylate) (HPEI-b-PHEMA) with average 28 PHEMA arms have been prepared by atom transfer radical polymerization (ATRP) of HEMA in a mixed solvent of methanol and water using a core-first strategy. The hyperbranched macroinitiator employed was prepared on the basis of well-defined hyperbranched polyethylenimine with Mw/Mn of 1.04 by amidation with 2-bromo-isobutyryl bromide. The polymerization condition was optimized to prepare star copolymers with narrow dispersity, and the variables included the volume ratio of methanol to water, the molar ratio of initiating site to CuCl and the molar ratio of [CuCl]:[CuBr2]. Under the optimized polymerization condition, the lowest Mw/Mn value of the obtained star copolymers was around 1.3. Kinetic analysis showed that an induction period existed in the polymerization of HEMA. After this induction period, a linear dependence of ln([M]0/[M]t) on time was observed. The obtained HPEI-b-PHEMA could adsorb hydrophilic molecules. The comparison with the star copolymer with hydrophobic core and hydrophilic PHEMA shell verified that both the hydrophilic core and shell could host the hydrophilic guests, but the amidated HPEI core was more effective than the PHEMA shell. 相似文献
59.
Synthesis and ion transport properties of hot-pressed solid polymer electrolytes (SPEs), (1-x) PEO: x KI, where x is the content of KI in wt%, are reported. A hot-press technique has been used for the formation of the polymeric membranes in place of the usual solution cast method. The composition (80PEO:20KI) was identified as the highest conducting polymer electrolyte on the basis of compositional dependent conductivity studies of PEO:KI films. A conductivity enhancement of more than two orders of magnitude from that of the pure PEO was achieved. Materials characterization and ion transport mechanism were explained by using various experimental techniques. 相似文献
60.
To improve the performances of HDPE-based separators, polyether chains were incorporated into HDPE membranes by blending with poly(ethylene-block-ethylene glycol) (PE-b-PEG) via thermally induced phase separation (TIPS) process. By measuring the composition, morphology, crystallinity, ion conductivity, etc, the influence of PE-b-PEG on structures and properties of the blend separator were investigated. It was found that the incorporated PEG chains yielded higher surface energy for HDPE separator and improved affinity to liquid electrolyte. Thus, the stability of liquid electrolyte trapped in separator was increased while the interfacial resistance between separator and electrode was reduced effectively. The ionic conductivity of liquid electrolyte soaked separator could reach 1.28 × 10-3 S.cm-1 at 25℃, and the electrochemical stability window was up to 4.5 V (versus Li + /Li). These results revealed that blending PE-b-PEG into porous HDPE membranes could efficiently improve the performances of PE separators for lithium batteries. 相似文献