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   6491篇
  免费   1053篇
  国内免费   673篇
化学   4818篇
晶体学   57篇
力学   320篇
综合类   16篇
数学   719篇
物理学   2287篇
  2024年   11篇
  2023年   178篇
  2022年   174篇
  2021年   257篇
  2020年   314篇
  2019年   293篇
  2018年   241篇
  2017年   232篇
  2016年   360篇
  2015年   342篇
  2014年   388篇
  2013年   466篇
  2012年   610篇
  2011年   650篇
  2010年   408篇
  2009年   413篇
  2008年   400篇
  2007年   384篇
  2006年   312篇
  2005年   282篇
  2004年   195篇
  2003年   179篇
  2002年   154篇
  2001年   109篇
  2000年   95篇
  1999年   113篇
  1998年   94篇
  1997年   89篇
  1996年   83篇
  1995年   68篇
  1994年   57篇
  1993年   48篇
  1992年   58篇
  1991年   37篇
  1990年   27篇
  1989年   28篇
  1988年   18篇
  1987年   12篇
  1986年   8篇
  1985年   11篇
  1984年   5篇
  1983年   3篇
  1982年   6篇
  1981年   2篇
  1980年   1篇
  1957年   2篇
排序方式: 共有8217条查询结果,搜索用时 15 毫秒
101.
Liu Y  Cui L  Guan F  Gao Y  Hedin NE  Zhu L  Fong H 《Macromolecules》2007,40(17):6283-6290
Uniform nylon 6 nanofibers with diameters around 200 nm were prepared by electrospinning. Polymorphic phase transitions and crystal orientation of nylon 6 in unconfined (i.e., as-electrospun) and a high T(g) (340 degrees C) polyimide confined nanofibers were studied. Similar to melt-spun nylon 6 fibers, electrospun nylon 6 nanofibers also exhibited predominant, meta-stable gamma crystalline form, and the gamma-crystal (chain) axes preferentially oriented parallel to the fiber axis. Upon annealing above 150 degrees C, gamma-form crystals gradually melted and recrystallized into the thermodynamically stable alpha-form crystals, which ultimately melted at 220 degrees C. Release of surface tension accompanied this melt-recrystallization process, as revealed by differential scanning calorimetry. For confined nanofibers, both the melt-recrystallization and surface tension release processes were substantially depressed; gamma-form crystals did not melt and recrystallize into alpha-form crystals until 210 degrees C, only 10 degrees C below the T(m) at 220 degrees C. After complete melting of nano-confined crystals at 240 degrees C and recrystallization at 100 degrees C, only alpha-form crystals oriented perpendicular to the nanofiber axis were obtained. In the polyimide-confined nanofibers, the Brill transition (from the monoclinic alpha-form to a high temperature monoclinic form) was observed at 180-190 degrees C, which was at least 20 degrees C higher than that in unconfined nylon 6 at approximately 160 degrees C. This, again, was attributed to the confinement effect.  相似文献   
102.
聚吡咯水杨酸修饰电极的电化学行为及水杨酸含量测定   总被引:10,自引:0,他引:10  
李春光  崔刚 《分析化学》1994,22(9):922-924
本用电化学方法制备了聚吡咯-水杨酸修饰电极;并进行了电化学行为的研究,经电化学处理该是电极对水杨酸根具有选择性响应,响应线性范围在1.0×10^-^5-1.0×10^-^3mol/L之间。电极斜率为40mV/pC,该电极具有较好的稳定性,响应时间在180-300s之间;电极寿命可达60d。  相似文献   
103.
In this work, we used the hydrothermal method to synthesize Eu3+ ion-doped cubic BaF2 nanorods, which is a luminescent material. The clubbed structures were well crystallized and exhibited face-centred cubic structures, as indicated by powder X-ray diffraction, scanning electron microscopy, electron diffraction, and transmission electron microscopy. The luminescent properties were studied, and local symmetry surrounding Eu3+ ions and electronic transition processes included. The results indicated that Eu3+ occupied only one C4ν site in nanorods.  相似文献   
104.
Zeolite T membranes were synthesized on tubular porous mullite tubes by hydrothermal synthesis. The membranes selectively permeated carbon dioxide from CO2/CH4 and CO2/N2 mixtures with high separation performances, which were due to combined effects of molecular sieving and competitive adsorption.  相似文献   
105.
A rapid, selective method that utilize 4-(2-Pyridylazo)-resorcinol (PAR)-modified nanometer SiO2 (nanometer SiO2–PAR) as a new solid-phase extractant for preconcentration of trace mercury (II) has been developed. The adsorption property of nanometer SiO2–PAR for metal ions was studied by selectively extracting different metal ions from aqueous solutions. The results revealed an excellent affinity of the nanometer SiO2–PAR for mercury (II) in presence of interfering metal ions at pH 4. The main parameters of solid-phase extraction such as shaking time, elution and sample dilution effect were studied. The extractant shows rapid kinetic sorption, and the adsorption equilibrium of mercury (II) on nanometer SiO2–PAR was achieved in less than 2 min. The adsorbed mercury (II) was easily eluted by 4 mL of 6 mol L−1 HCl. The maximum preconcentration factor was 50. The maximum static adsorption capacity was 276 μmol g−1 at pH 4. The detection limit (3σ) was 0.43 μg L−1 for cold vapor atomic absorption spectrometry (CVAAS), and the relative standard deviation of the eight replicate determinations was 2.4% for the determination of 2.0 μg of Hg(II) in 100 mL water sample. The method was applied to the determination of trace mercury (II) in sample solutions with satisfactory results.  相似文献   
106.
A highly selective ligand exchange reaction is realized in the self-assembled monolayer (SAM) of a triruthenium cluster on a gold electrode surface under precise electrochemical potential control. CO as well as NO molecules, which are known to play key roles in many chemical, biological, and environmental systems, can be efficiently introduced into the SAM by electrochemically tuning the electronic state of the Ru site. These unique surface reactions are more convenient and efficient than conventional ligand exchange reactions in solution and could be used for the elucidation of the electron-transfer mechanism in a biological system as well as in the development of molecular sensors and devices.  相似文献   
107.
超临界流体萃取仪器的研制   总被引:1,自引:1,他引:1  
崔兆杰  张新保 《分析化学》1995,23(12):1462-1466
本文报道了以国产原配件为基础,成功地研制了分析规模的超临界流体萃取仪器、并对仪器性能进行了全面考察,仪器性能稳定,重现性良好(RSD<3.1%),定量线性关系可靠,可满足定量萃取的要求。  相似文献   
108.
链状[NH3CH2CH2NH3]AgAsS4的溶剂热合成及表征   总被引:2,自引:0,他引:2  
利用溶剂热方法合成了链状[NH3CH2CH2NH3]AgAsS4,通过单晶X射线衍射技术对其进行了晶体结构分析,该化合物晶体属单斜晶系,空间群C2/c,晶胞参数a=1.35805(8)nm,b=0.65331(3)nm,c=2.27711(9)nm,β=106.42(3)°,Z=8.化合物具有有趣的梯子状双链结构,该阴离子链由AsS4与AgS3共用顶点交替连接而成,有机阳离子在阴离子链之间存在较强的N—H…S氢键.DSC和Tg分析结果表明化合物在200℃以下是稳定的.  相似文献   
109.
<正> 前文我们报告了含有芳香叔胺基的丙烯酸酯、甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA)在过氧化二月桂酰(LPO)引发下的聚合动力学。从所得的聚合速度方程式及低的聚合活化能,认为DMABMA与LPO形成氧化还原体系而使DMABMA聚合,在本文第Ⅳ报中报道了DMABMA不仅能引发甲基丙烯酸甲酯的聚合,还参与聚甲基丙烯酸甲酯的链中,因此称这种既能参与引发聚合反应,又参与聚合物链中的引发“引发剂单体(initiatomer)”。这种含有可聚合胺引发体系的优点是,用于丙烯酸酯类医用  相似文献   
110.
A novel, water-soluble, cationic PPV derivative poly[(2,5-bis(3-bromotrimethylammoniopropoxy)-phenylene-1,4-divinylene)-alt-1,4-(2,5-bis(2-(2-hydroxyethoxy)ethoxy))phenylene vinylene] (BH-PPV) has been synthesized by a Heck coupling reaction. Multilayered assemblies of the BH-PPV and the sodium salt of hexa(sulfobutyl)fullerenes (C(60)-HS) were fabricated successfully by an alternate deposition technique. The multilayer structures were studied by UV/Vis spectroscopy, small angle X-ray diffraction, and atomic force microscopy. The photoinduced charge transfer property of the self-assembled multilayer film was also measured by a three-electrode cell technique. A steady and rapid cathodic 5.5 microA cm(-2) photocurrent response was measured as the irradiation of the multilayer film was switched on and off. Importantly, the response of on/off cycling is prompt and reproducible. A possible mechanism for the electron-transfer process is proposed.  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