首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   3840篇
  免费   649篇
  国内免费   436篇
化学   2842篇
晶体学   48篇
力学   402篇
综合类   40篇
数学   477篇
物理学   1116篇
  2024年   15篇
  2023年   65篇
  2022年   174篇
  2021年   173篇
  2020年   206篇
  2019年   193篇
  2018年   151篇
  2017年   171篇
  2016年   225篇
  2015年   185篇
  2014年   238篇
  2013年   323篇
  2012年   269篇
  2011年   275篇
  2010年   232篇
  2009年   223篇
  2008年   211篇
  2007年   220篇
  2006年   197篇
  2005年   179篇
  2004年   171篇
  2003年   189篇
  2002年   120篇
  2001年   90篇
  2000年   70篇
  1999年   51篇
  1998年   46篇
  1997年   52篇
  1996年   30篇
  1995年   37篇
  1994年   29篇
  1993年   14篇
  1992年   13篇
  1991年   16篇
  1990年   15篇
  1989年   9篇
  1988年   11篇
  1987年   6篇
  1986年   6篇
  1985年   4篇
  1984年   4篇
  1983年   5篇
  1982年   2篇
  1981年   2篇
  1979年   2篇
  1978年   1篇
  1977年   1篇
  1963年   1篇
  1959年   1篇
  1936年   1篇
排序方式: 共有4925条查询结果,搜索用时 0 毫秒
21.
Different types of silanized polyurethanes (SPUR) were prepared in two ways: the first type (a), by reacting a polyether diol with an isocyanatesilane and the second type (b) by reacting it with diisocyanate (IPDI) and afterwards with aminosilane. These systems are able to cure with atmospheric moisture and, as a consequence, a tridimensional hybrid structure is formed where the inorganic and organic phases are bonded with covalent bonds. The evolution of the curing process in both systems has been monitored by means of Fourier transform infrared spectroscopy, through the changes observed in the carbonyl stretching vibration region. The results obtained show that the SPURs of kind (b) present stronger hydrogen bonding interactions as a consequence of urea groups present in the final structure. Moreover, given the proximity of both urethane and urea groups to alkoxysilane end groups, during the alkoxysilane curing process these groups are forced to approximate themselves even further and therefore the reticulation process leads to an increase of the self association of urethane and urea groups.Finally, DSC has been used to measure Tg values of the systems studied before and after the curing process. The obtained results have confirmed the main conclusions obtained in FTIR analysis.  相似文献   
22.
张丽圆  王磊 《中国化学》2006,24(11):1605-1608
Immobilized copper(Ⅱ) in organic-inorganic hybrid materials catalyzed Ar-N coupling of arylboronic acids with imidazoles has been developed. Arylboronic acids reacted with imidazoles smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper(Ⅱ) catalyst (10 mol%) in methanol without any additives and bases. The reactions generated the corresponding cross-coupling products in good yields. Furthermore, silica-supported copper can be recovered and recycled by a simple filtration procedure and used for five consecutive trials without decreases in activity.  相似文献   
23.
Three types of single-chain hydrocarbon fluorocarbon hybrid bolaamphiphiles were synthesized.They readily formed different kinds of organized supramolecular assemblies,including vesicles,tapes,and micellar fibers,in aqueous solution.The aggregates morphology was characterized by transmission electron microscopy (TEM) after negative staining.The superstructures of these aggregates seemed to be determined by the geometry and the head group's properties of the corresponding amphiphiles.  相似文献   
24.
The immobilization of copper in organic-inorganic hybrid materials catalyzing the Ullmann reaction has been described. Phenols reacted with aryl iodides, aryl bromides and aryl chlorides smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper catalyst. The protocol involved the use of DMSO as the solvent, and potassium fluoride as the base. The reactions generated the corresponding cross-coupling products in good to excellent yields. Furthermore, the silica-supported copper could be recovered and recycled by a simple filtration of the reaction solution and used for 10 consecutive trials without loss of its reactivity.  相似文献   
25.
Inorganic-organic hybrids have been synthesized by incorporation of the inorganic component of Ti(OC2H5)4 into the organic polymer of ethyl cellulose. The inorganic-organic hybrids did not dissolve in toluene used as a solvent for the starting materials. The ethanol was formed as a by-product of the alcoholysis condensation reaction between Ti(OC2H5)4 and ethyl cellulose. These results suggest that ethoxy groups of Ti(OC2H5)4 react with hydroxy groups of ethyl cellulose to form cross-linking bonds of –O–Ti–O–. The reaction of Ti(OC2H5)4 with ethyl cellulose was further investigated by Fourier transform infrared (FT-IR) spectroscopy. The FT-IR spectroscopic experiments revealed that the Ti–O bond state of Ti(OC2H5)4 was changed by refluxing a toluene solution of Ti(OC2H5)4 with ethyl cellulose. The inorganic-organic hybrids have an interesting dielectric property; their dielectric constant is higher than that of ethyl cellulose and that of a simple mixture of TiO2 and ethyl cellulose.  相似文献   
26.
The electroosmotic peristaltic flow of modified hybrid nanofluid in presence of entropy generation has been presented in this thermal model. The Hall impact and thermal radiation with help of nonlinear relations has also been used to modify the analysis. The assumed flow is considered due to a non-uniform trapped channel. The properties of modified hybrid nanofluid model are focused with interaction of three distinct types of nanoparticles namely copper (Cu), silver (Ag) and aluminum oxide (Al2O3). The mathematical modeling and significances of entropy generation and Bejan number are identified. With certain flow assumptions, the governing equations are attained for optimized peristaltic electroosmotic problem. Widely used assumptions of long wave length and low Reynolds number reduced the governing equations in ordinary differential equations. The ND solver is flowed for the solution process. The physical significant of results is observed by assigning the numerical values to parameters.  相似文献   
27.
综述了近年来C60及其卤化衍生物在阴离子聚合中的研究进展。在阴离子聚合中,C60可以直接与反应而进入主链,形成超枝化结构;C60可作为阴离子聚合的偶联剂,形成星形和线形结构;C60阴离子可以引发阴离子聚合。介绍了偶联产物结构控制的方法,以及偶联产物的稳定性。氯化富勒烯也可以作为阴离子聚合的偶联剂,生成星形结构聚合物。  相似文献   
28.
The coloration of glass via melting techniques presents some unique problems with respect to the reproducibility, toxicology and economics of certain colors, especially if the market demands are highly variable. This is also the case for consumer products such as crystal glass and tableware. Traditionally, the decoration of crystal glasses is performed by laborious manual techniques, which are costly and do not meet modern market requirements. Alternatively, spraying of colored lacquers is a highly flexible and valuable tool for the development of new products. Sol-gel type hybrid coatings provide several advantages compared to conventional organic systems like high abrasion resistance, almost perfect adhesion, refractive index matching and sufficient stability in dishwashing procedures. The solubility of organic dyes in the hybrid matrix is sufficient for intense colors even at rather low layer thicknesses, which on the other hand convey the high brilliance of the base material. The development of transparent, translucent and opaque hybrid coatings for crystal glass has been completed in the last few years and the production of partially coated articles has started recently. The synthesis and properties of the coating material are reviewed and the industrial process and first market results are also outlined.  相似文献   
29.
In this work, the sol–gel technique was used to prepare a new organic–inorganic hybrid from Epoxidized Natural Rubber (ENR-50) and Titanium dioxide (TiO2) by blending different content of titania precursors (10, 30, and 50 wt%) with an ENR-50 matrix. A wide range of analyses was conducted to understand the nature of this hybrid and also to evaluate its potential uses in applications required high refractive index such as micro optical and optoelectronic devices. Results indicated that the ring-opening reaction of epoxide groups in ENR-50 increased with the increase of titania content in the hybrid resulting a strong bonding between titania and ENR-50 through TiOC bond, which was observed in FTIR spectrum at 1027–1028 cm−1. It is also observed a slight decrease in the intensity of the amorphous peak along with a new crystalline peak appeared at 2θ = 23 and 27° due to the crystalline nature of titania. The hybrids showed three thermal degradation steps in the range of temperature 76 to 769 °C due to the existence of the Ti moieties with the mixture of polymer chains, which in turn shifted the Tg at 24.3, 26.9 and 28.1 °C for the hybrid at 10, 30, and 50 wt% TiO2 compared to the Tg of ENR-50 at −18.4 °C respectively. The morphology of the ENR-50 showed clear changes during of the synthesis of ENR-50/TiO2 hybrids, these changes were proven by SEM, TEM, and AFM analyses. Uv–Vis results showed that the higher wavelength peak at 293 nm has shifted to 296, 298 and 300 nm for the hybrid at 10, 30, and 50 wt% TiO2 respectively due to the strong interaction between titania precursors and ENR-50 matrix. Furthermore, the hybrids showed good optical transparency in the visible light range.  相似文献   
30.
A novel one-dimensional (1D) coordination polymer [{Cu(2,2′-bpy)}6(Mo6O22)][GeMo12O40]·H2O (2,2′-bpy=2,2′-bipyridine), which represents the first example of 1D organic-inorganic hybrid based on a Keggin-type heteropolyanion [GeMo12O40]4− and an unprecedented isopolyanion [Mo6O22]8−, has been hydrothermally synthesized and characterized by single crystal X-ray diffraction. Crystal data: C60H50Cu6GeMo18N12O63, monoclinic, P21/c, a=13.9344(3), b=20.0329(3), c=17.2151(3) Å; β=94.0220(10)°, V=4793.70(15) Å3, T=293(2) K; Z=2.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号