全文获取类型
收费全文 | 847篇 |
免费 | 130篇 |
国内免费 | 209篇 |
专业分类
化学 | 1033篇 |
晶体学 | 15篇 |
力学 | 4篇 |
综合类 | 5篇 |
物理学 | 129篇 |
出版年
2024年 | 2篇 |
2023年 | 13篇 |
2022年 | 20篇 |
2021年 | 28篇 |
2020年 | 41篇 |
2019年 | 29篇 |
2018年 | 30篇 |
2017年 | 35篇 |
2016年 | 31篇 |
2015年 | 39篇 |
2014年 | 43篇 |
2013年 | 77篇 |
2012年 | 59篇 |
2011年 | 38篇 |
2010年 | 47篇 |
2009年 | 43篇 |
2008年 | 47篇 |
2007年 | 64篇 |
2006年 | 46篇 |
2005年 | 52篇 |
2004年 | 45篇 |
2003年 | 59篇 |
2002年 | 49篇 |
2001年 | 28篇 |
2000年 | 26篇 |
1999年 | 21篇 |
1998年 | 25篇 |
1997年 | 24篇 |
1996年 | 23篇 |
1995年 | 24篇 |
1994年 | 21篇 |
1993年 | 17篇 |
1992年 | 14篇 |
1991年 | 6篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1975年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有1186条查询结果,搜索用时 15 毫秒
1.
Several phenoxy-imine ligands bearing o-trityl group in phenoxy moiety RN=CHArOH (Ar = C6H2(CPh3)tBu, R = 2,6-Me2C6H3 ( L 1 H ); 2,6-iPr2C6H3 ( L 2 H ); 3,5-(CF3)2C6H3 ( L 3 H ); 3,5-(OMe)2C6H3 ( L 4 H ); CHPh2 ( L 5 H ); CPh3 ( L 6 H )) were synthesized and characterized by1H NMR and 13C NMR spectroscopy. The vanadium complexes based on these ligands LVCl2(THF)2 ( 1–6 ) were synthesized via conventional transmetalation reaction in moderate to high yields. Complexes 1–6 were fully characterized by FT-IR, elemental analyses and the molecular structures of 1 , 2 ·H2O, (2 ·H2O ) 2 (μ-Cl) 2 , 4 , and 5 were confirmed by X-ray crystallographic analysis in which the six-coordinated vanadium centers are in a typical octahedral geometry. Upon activation with Et2AlCl in toluene, complexes 1–6 showed high activities in ethylene polymerization affording polymers with moderate molecular weight (5.9–11.8 × 104 Da). Moreover, in hexane or CH2Cl2, 1–6 /Et2AlCl exhibited enhanced activities. When activated with MAO or MMAO in toluene, these complexes showed relatively low activities but afforded polymers with ultra-high molecular weight (up to 3.30 × 106 Da). 1–6 /Et2AlCl also showed high activities in ethylene/1-hexene copolymerization at room temperature giving moderate molecular-weight polymers (6.5–11.4 × 104 Da) with co-monomer incorporation being of 6.0 ~ 7.8%. 相似文献
2.
In this paper, we report the conducting and electrochemical properties of a homogeneous V2O5-SiO2 xerogel composite obtained from the simultaneous polymerization in both inorganic components (Si-O and V-O based polymers) forming an interpenetrating polymer network, where a mutual “solubility” due to cross-links and entanglements was observed. The presence of V2O5 inside the silica matrix has a strong effect on electrical conductivity; measurements showed room temperature conductivity almost 1000 times higher than what is found in the literature. In addition, the electrochemical behavior is quite similar to that found in V2O5 xerogel. Moreover, the effects of thermal treatment on the conducting and electrochemical properties were investigated. It was found that both properties were improved with no significant effect on V2O5 xerogel layered structure. 相似文献
3.
4.
本文研究了新席夫碱吡哆醛缩邻氨基酚的合成及其分析应用,提出了钒(V)的分光光度测定法,该法简便,灵敏,选择性好。 相似文献
5.
Mitsuru Ueda Tetsuya Abe Mitsuo Oda 《Journal of polymer science. Part A, Polymer chemistry》1992,30(9):1993-1998
Aromatic poly(thioether ketone)s were prepared by the direct polycondensation of aromatic dicarboxylic acids with aryl compounds containing ether or sulfide structures using phosphorus pentoxide/methanesulfonic acid (PPMA) as a condensing agent and solvent. Polycondensation proceeded smoothly and produced aromatic poly(thioether ketone)s with inherent viscosities up to 0.73 dL/g. The synthesis of substituted aryl ketones by the reaction of substituted benzoic acids with aryl compounds in PMMA was studied in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(thioether ketone)s showed a 10% weight loss in air and nitrogen at around 450 and 460°C, respectively. © 1992 John Wiley & Sons, Inc. 相似文献
6.
《Surface and interface analysis : SIA》2006,38(9):1257-1265
Four vanadium oxide layers on mineral TiO2(001)‐anatase supports with different thickness (3–33 Å) were prepared with reactive d.c. magnetron sputtering and were extensively studied with photoelectron spectroscopy. Al Kα radiation and 150 eV synchrotron radiation were used as excitation sources. The evolution of the 2p, 3s and 3p core level line shapes of V and Ti as a function of the vanadium oxide thickness was studied, as well as the O1s and O2s core lines and the valence band. All the V2p spectra of the deposited vanadium oxide layers consist of at least 60% V5+, the rest being V4+. The V3p region is complicated by multiplet splitting, which prevents the determination of the vanadium oxidation state. The V3p multiplet splitting is different for the two excitation energies. No reduction of the titania support surface due to the vanadium oxide deposition was observed. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
7.
8.
G.T. Chandrappa N. Steunou S. Cassaignon C. Bauvais P.K. Biswas J. Livage 《Journal of Sol-Gel Science and Technology》2003,26(1-3):593-596
Vanadium oxide nanotubes (VO
x
-NT) have been prepared by mixing hexadecylamine with V2O5·nH2O gels. This procedure was followed by an hydrothermal treatment (150–180°C, 2–7 days) which leads to a large quantity of VO
x
-NT. SEM and XRD analysis have been used to optimize the temperature and reaction time required for production of VO
x
-Nt and morphology of the nanotubes investigated by TEM. 相似文献
9.
A method for the direct determination of volatile and non-volatile nickel and vanadium compounds in crude oil without previous treatment using direct solid sampling graphite furnace atomic absorption spectrometry is proposed. The crude oil samples were weighed directly onto solid sampling platforms using a microbalance and introduced into a transversely heated solid sampling graphite tube. In previous work of our group losses of volatile nickel and vanadium compounds have been detected, whereas other nickel and vanadium compounds were thermally stable up to 1300 and 1600 °C, respectively. In order to avoid this problem different chemical modifiers (conventional and permanent) have been investigated. With 400 μg of iridium as permanent modifier, the signal started to drop already after two atomization cycles, possibly because of an interaction of nickel (which is a catalyst poison) with iridium. Twenty micrograms of palladium applied in each determination was found to be optimum for both elements. The palladium was deposited on the platform and submitted to a drying step at 150 °C for 75 s. After that the sample was added onto the platform and submitted to the furnace program. The influence of sample mass on the linearity of the response and on potential measurement errors was also investigated using four samples with different nickel content. For the sample with the lowest nickel concentration the relationship between mass and integrated absorbance was found to be non-linear when a high sample mass was introduced. It was suspected that the modifier had not covered the entire platform surface, which resulted in analyte losses. This problem could be avoided by using 40 μL of 0.5 g L−1 Pd with 0.05% Triton X-100. Calibration curves were established with and without modifier, with aqueous standards, oil-in-water emulsions and the certified reference material NIST SRM 1634c (trace metals in residual fuel oil). The sensitivity for aqueous standards and emulsions was close to that for SRM 1634c, making possible the use of aqueous standards for calibration. The limits of detection and quantification obtained for nickel and vanadium under this condition were found to be 0.02 and 0.06 μg g−1, respectively, for both elements, based on 10 mg of sample. Nickel and vanadium were determined in the samples with (total Ni and V) and without the use of Pd (thermally stable compounds), and the concentration of volatile compounds was calculated by difference. The results were compared with those obtained by high-resolution continuum source graphite furnace atomic absorption spectrometry by emulsion technique; no significant differences were found for total Ni and V at the 95% confidence level according to a Student's t-test. 相似文献
10.
J. P. Doumerc J. M. Cocciantelli J. C. Grenier M. Pouchard P. Hagenmuller 《无机化学与普通化学杂志》1993,619(4):748-752
Magnetic susceptibility of V2O5 and of the α-, ?-, δ- and γ-LixV2O5 bronzes prepared either at high or at room temperature has been measured between liquid helium and ambient temperature. The results are representative of the localized character of the V4+ ion d-electron and, for high enough x-values, of the existence of antiferromagnetic interactions in a low dimensional system. The intrachain exchange integral J has been determined using the Bonner/Fischer model for Heisenberg chains with S = 1/2 spin. It is larger for the γ- than for the δ-phase. This result as well as the occurrence of long range ordering below TN ≈ 130 K in the γ-phase may be ascribed to ordering of V4+ and V5+ ions in the former bronze and to the random distribution of V4+ ions in the latter one. 相似文献