全文获取类型
收费全文 | 2313篇 |
免费 | 349篇 |
国内免费 | 388篇 |
专业分类
化学 | 2089篇 |
晶体学 | 67篇 |
力学 | 289篇 |
综合类 | 31篇 |
数学 | 17篇 |
物理学 | 557篇 |
出版年
2024年 | 3篇 |
2023年 | 24篇 |
2022年 | 68篇 |
2021年 | 88篇 |
2020年 | 113篇 |
2019年 | 90篇 |
2018年 | 66篇 |
2017年 | 78篇 |
2016年 | 117篇 |
2015年 | 110篇 |
2014年 | 114篇 |
2013年 | 209篇 |
2012年 | 143篇 |
2011年 | 144篇 |
2010年 | 133篇 |
2009年 | 131篇 |
2008年 | 144篇 |
2007年 | 146篇 |
2006年 | 142篇 |
2005年 | 131篇 |
2004年 | 134篇 |
2003年 | 121篇 |
2002年 | 127篇 |
2001年 | 74篇 |
2000年 | 76篇 |
1999年 | 40篇 |
1998年 | 52篇 |
1997年 | 45篇 |
1996年 | 46篇 |
1995年 | 31篇 |
1994年 | 26篇 |
1993年 | 18篇 |
1992年 | 14篇 |
1991年 | 16篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 8篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
排序方式: 共有3050条查询结果,搜索用时 203 毫秒
101.
《Analytical letters》2012,45(18):2892-2904
A spectrofluorimetric method has been developed for trace amount of aluminum(III) by using a novel Schiff base, N,N′-bis(salicylidene)-1,4-diaminobuthane (BUTAS), and 4-methyl-2-aminophenol (OAP). Since the aluminum complexes are generally fluorescent, aluminum(III) increases the fluorescence intensity of BUTAS-OAP by formation of Al-BUTAS-OAP complex. The fluorescence of the complex is measured at an excitation wavelength of 410 nm with an emission at 526 nm. Aluminum(III) can be detected within a concentration limit of 0.11–1.62 ppb and the lowest detection limit being 0.07 ppb. The proposed method was applied to diluted hemodialysis solution and spectrofluorimetric data was compared with data of standard pharmacopoeia method. 相似文献
102.
Dr. Cédric Boulho Dr. Harmen S. Zijlstra Alexander Hofmann Prof. Dr. Peter H. M. Budzelaar Prof. Dr. Sjoerd Harder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17450-17459
Reaction of (TBBP)AlMe ? THF with [Cp*2Zr(Me)OH] gave [(TBBP)Al(THF)?O?Zr(Me)Cp*2] (TBBP=3,3’,5,5’‐tetra‐tBu‐2,2'‐biphenolato). Reaction of [DIPPnacnacAl(Me)?O?Zr(Me)Cp2] with [PhMe2NH]+[B(C6F5)4]? gave a cationic Al/Zr complex that could be structurally characterized as its THF adduct [(DIPPnacnac)Al(Me)?O?Zr(THF)Cp2]+[B(C6F5)4]? (DIPPnacnac=HC[(Me)C=N(2,6‐iPr2?C6H3)]2). The first complex polymerizes ethene in the presence of an alkylaluminum scavenger but in the absence of methylalumoxane (MAO). The adduct cation is inactive under these conditions. Theoretical calculations show very high energy barriers (ΔG=40–47 kcal mol?1) for ethene insertion with a bridged AlOZr catalyst. This is due to an unfavorable six‐membered‐ring transition state, in which the methyl group bridges the metal and ethene with an obtuse metal‐Me‐C angle that prevents synchronized bond‐breaking and making. A more‐likely pathway is dissociation of the Al‐O‐Zr complex into an aluminate and the active polymerization catalyst [Cp*2ZrMe]+. 相似文献
103.
104.
A “Mitsubishi emblem” tetrauclear aluminum complex containing two unsymmetric N2O2‐ligands and a symmetric NO3‐ligand as initiator for polymerization of rac‐lactide 下载免费PDF全文
Minggang Hu Fugui Wang Fuzhong Han Qigang Deng Wenhui Ma Hailong Yan Guohua Dong Weiming Song 《Journal of polymer science. Part A, Polymer chemistry》2017,55(12):2084-2091
A novel hydroxy‐, methoxy‐, and phenoxy‐bridge “Mitsubishi emblem” tetranuclear aluminum complex ( 1 ) is synthesized from an unsymmetric amine‐pyridine‐bis(phenol) N2O2‐ligand (H2L1) and a symmetric amine‐tris(phenol) NO3‐ligand (H2L2). Two same configuration chiral nitrogen atoms are formed in the tetranuclear Al complex upon coordination of the unsymmetric tertiary amine ligand to central Al. Complex 1 initiates controlled ring‐opening polymerization (ROP) of rac‐lactide and afford polylactide (PLA) with narrow molecular weight distributions (Mw/Mn = 1.05–1.19). The analysis of 1H NMR spectra of the oligomer indicates that the methoxy group is the initiating group and the ring‐opening polymerization of lactide follows a coordination‐insertion mechanism. The Homonuclear decoupled 1H NMR spectroscopy suggests the isotactic‐rich chains is preferentially formed in PLA. The study on kinetics of the ROP of lactide reveals the homopropagation rate is higher than the cross‐propagation rate, which is in agreement with the observed isotactic selectivity in the ROP of rac‐lactide. The stereochemistry of the polymerization was also supported by activation parameters. The introduction of unsymmetric ligand H2L1 has an effect on stereoslectivity of polymerization. This result may be of interest for the design of multinuclear metal complex catalysts containing functionalized ligands. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2084–2091 相似文献
105.
Acrylate and methacrylate monomers absorbent acrylate foams were prepared based on the method of high internal phase emulsion (HIPE). The influence of reaction conditions on liquid absorption by acrylate foams was studied. The reaction conditions included monomer ratio, cross-linker amount, initiator amount, emulsifier amount, emulsion concentration, emulsification temperature, and the curing time. The reaction conditions were determined to achieve the best liquid absorption by acrylate foams. Acrylate foams were analyzed with Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The results showed that when the monomer ratio was 9:1, cross-linking agent was 30% of monomer amount, initiator amount was 4% of the reactants amount, emulsifier amount was 8% of the reactants amount, the ratio of aqueous phase to oil phase was 32:1, emulsification temperature was 75°C, and curing time was 1.5 h, we could prepare the acrylate foam material with the best liquid absorption. Reaction of monomer and cross-linking agent was confirmed by FTIR analysis. The pore sizes of acrylate foam were between 1 μm and 8 μm according to SEM analysis. This material was very suitable to absorb aqueous fluids. 相似文献
106.
107.
M. Thirumal Dipak Khastgir Nikhil K Singha B. S. Manjunath Y. P. Naik 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(7):704-712
Water blown rigid polyurethane foams (PUF) with organoclay/organically modified nanoclay (ONC) were prepared and their properties such as density, mechanical, morphological, insulation, thermal and flame retardant properties were studied. In this investigation, the ONC content was varied from 1 to 10 parts per hundred of polyol (php) by weight. It was observed that the compressive strength of ONC filled PUF increased up to 3 php of ONC loading and then it decreased. Wide angle X-ray diffraction and transmission electron microscopy studies indicated the exfoliated dispersion of ONC in PUF. The thermal conductivity of ONC filled PUF decreases up to 5 php and then increases. The glass transition temperature (Tg) of PUF decreases on loading of ONC. The TGA analysis shows that there is slight increase in degradation temperature with increase in ONC loading. The flame retardant properties (LOI and flame spread rate) are improved slightly on addition (3 php) of ONC filled PUF. 相似文献
108.
109.
对炭泡沫为支撑骨架的氧化硅气凝胶(SiO2/炭泡沫)和碳化硅(SiC/炭泡沫)复合材料分别采用XRD、SEM、激光导热仪、万能力学试验机进行物相、微观结构、热学及力学性能方面的表征.结果表明:所制备的SiO2/炭泡沫与原炭泡沫相比,具备更高的抗压强度(14.95 MPa)和更低的室温热导率(0.44 W·m-1·K-1).SiC/炭泡沫材料则保持了较高的抗压强度值(14.66 MPa),其在 1 200 ℃下具备极低的高温热导率(2.18W·m-1·K-1).热重分析表明,SiC/炭泡沫在氧化氛围中到610 ℃才发生质量的损失,而内部炭发生完全烧蚀的温度高达844 ℃,这表明该材料的抗氧化性能远好于纯的炭泡沫材料. 相似文献
110.
Pyrrole was polymerized on the surface of titanium foam using FeCl3 as oxidant and the as-synthesized product could be directly used as electrode for supercapacitor. The globular polypyrrole (PPy) particles were firmly loaded on the substrate with high density. The morphology study of PPy film is observed in SEM images, the XRD, FTIR and UV–vis spectra reveal the structure and crystalline of PPy nanoparticles. The electrochemical properties of PPy modified electrode are investigated by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and cycle life techniques. The electrochemical measurements showed such a PPy–Ti electrode had a wide working potential window, a high specific capacitance of 855 F g−1 and excellent cycle stability at a discharge current density of 1 A g−1. 相似文献