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   8917篇
  免费   1665篇
  国内免费   955篇
化学   6037篇
晶体学   89篇
力学   744篇
综合类   70篇
数学   1145篇
物理学   3452篇
  2024年   22篇
  2023年   194篇
  2022年   253篇
  2021年   320篇
  2020年   354篇
  2019年   332篇
  2018年   291篇
  2017年   280篇
  2016年   429篇
  2015年   418篇
  2014年   457篇
  2013年   638篇
  2012年   754篇
  2011年   842篇
  2010年   557篇
  2009年   538篇
  2008年   620篇
  2007年   482篇
  2006年   526篇
  2005年   386篇
  2004年   324篇
  2003年   256篇
  2002年   243篇
  2001年   205篇
  2000年   194篇
  1999年   202篇
  1998年   191篇
  1997年   179篇
  1996年   173篇
  1995年   141篇
  1994年   123篇
  1993年   116篇
  1992年   92篇
  1991年   69篇
  1990年   75篇
  1989年   61篇
  1988年   45篇
  1987年   35篇
  1986年   34篇
  1985年   22篇
  1984年   18篇
  1983年   14篇
  1982年   15篇
  1981年   3篇
  1980年   8篇
  1979年   2篇
  1975年   1篇
  1959年   1篇
  1957年   2篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
The polycondensation of decafluorobenzophenone with hexafluorobisphenol A was modified by the addition of a molecular sieve dehydrating apparatus to the refluxing reaction system. This modification promoted the polymerization and enabled the reactions to be conducted in milder conditions and completed in a shorter time, thereby depressing side reactions such as branching and crosslinking. The resulting fluorinated poly(arylene ether ketone)s (FPAEK) were free of gel particles and possessed the designed molecular weights. This modified procedure was also suitable for introducing crosslinkable pentafluorostyrene (FSt) moieties into the polymers at the chain ends and/or inside the chain with the vinyl group of FSt being pendant. The resulting FSt containing fluorinated poly(arylene ether ketone)s (FPAEK‐FSt) can then be thermally crosslinked at 100 °C in the presence of 1% benzoyl peroxide (BPO) or at 250 °C without any initiator. The glass‐transition temperatures (Tg's) of FPAEK increased with increasing molecular weight and leveled off at about 147 °C for the polymer with a number‐average molecular weight of 18,600 Da, whereas the values were not apparently affected by the addition of FSt units. However, crosslinking of the FPAEK‐FSt resulted in an approximate 30 °C increase of the Tg. Spin‐coating FPAEK‐FSt onto silicon wafers followed by crosslinking gave films with excellent thermal stability, physical strength, and adhesion to the substrate as well as good reproducibility in terms of film preparation and optical properties. The refractive index and birefringence of the films measured at a wavelength of 1.55 μm were 1.502 and 2.5 × 10?3, respectively. © 2002 Government of Canada. Exclusive worldwide publication rights in the article have been transferred to Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4205–4216, 2002  相似文献   
102.
铕掺杂BaPbO3的EXAFS研究   总被引:3,自引:0,他引:3  
采用扩展X射线吸收精细结构方法,研究了铕掺杂BaPbO3多晶粉末中Eu,Pb两种原子的近邻结构。Eu的掺杂,导致八面体中金属Pg,Eu的配位数降低。  相似文献   
103.
A simple, sensitive, and rapid method using gas chromatography (GC)-mass spectrometry (MS) is developed for the simultaneous separation and identification of the active ingredients of Liqusticum Chuanxiong Hort (Chuanxiong). Ten phthalic anhydride derivatives (PADs) are identified in Chuanxiong as 3-butylphthalide, 3-butylidenephthalide, 3-butylidene-4-hydroxyphthalide, senkyunolide A, neocnidilide, Z-ligustilide, E-ligustilide, senkyunolide F, senkyunolide-H, and senkyunolide-I. The existence of ferulic acid and vanillin in Chuanxiong extract is also demonstrated. Further identification of these compounds is performed by thin-layer chromatography, high-performance liquid chromatography (HPLC), and HPLC-MS analysis. This is the first report of the separation and determination of the PADs in Chuanxiong by GC-MS.  相似文献   
104.
缓慢炭化部分氧化对制备煤质活性炭的影响   总被引:5,自引:0,他引:5  
研究了炭化升温速度、炭化低温区引入空气部分氧化对活性炭制备过程中炭化阶段、炭化物结构、活性炭性能等的影响。结果表明,炭化时低温部分氧化可提高炭化物得率,使炭化物微晶的d002值升高和Lc值减小;而较慢的炭化升温速度有利于制备优质活性炭。缓慢炭化、部分氧化可以在一定程度上控制炭化路径,使炭化向生成取向性差、难石墨化、各向同性、呒定形炭多的炭化物的方向进行;并讨论了它们控制炭化的作用机理。以此为指导,  相似文献   
105.
Room temperature ionic liquid (bmim)PF6 was evaluated for recycling an organocatalyst (4S)-phenoxy-(S)-proline for direct asymmetric aldol reactions. The desired aldol products were obtained with good yields up to 93.2% and enantioselectivities up to 88.5%, and isolation of the products by simple extraction allowed recycling the ionic liquid containing the immobilized catalyst in subsequent reactions without significant decrease of yields and enantioselectivities.  相似文献   
106.
 钼基分子筛催化剂,由于不同分子筛的孔道大小及孔道形状不同\r\n,对甲烷芳构化反应表现出不同的催化性能.具有8元环孔道结构的小\r\n孔ERS-7分子筛没有催化活性,说明甲烷的芳构化反应离不开分子筛孔\r\n道的择形作用,较小的孔道中不能生成苯等芳烃.具有10元环孔道结构\r\n的ZSM-5,ZSM-11和ZRP-1三种分子筛具有较好的催化性能,但由于\r\n其孔道大小及孔道形状的差别在催化行为上表现出一定的差异.具有1\r\n0元环和12元环孔道结构的MCM-22分子筛,尤其对苯等轻芳烃而言,催\r\n化性能最佳.具有12元环孔道结构的JQX-1以及中孔分子筛SBA-15,\r\n虽然具有一定的催化性能,但活性较低.研究结果表明,孔道大小与苯\r\n分子动态直径相近或孔道稍大的分子筛是催化甲烷芳构化反应的良好载\r\n体,孔道过大或过小都不利于苯和萘等芳烃的生成.  相似文献   
107.
芥子气模拟剂2-氯乙基乙基硫醚的光催化降解   总被引:4,自引:0,他引:4  
利用连续流动微反、原位红外和GC/MS等手段考察了芥子气模拟剂2-氯乙基乙基硫醚(2-CEES)在P25 TiO2上的光催化降解反应,证实CO2和H2O是这个反应的最终产物.详细的跟踪分析表明,除了CO2和H2O外,在反应的气相混合物中可检测到C2H4、CH3CHO、CH4、CO、HCl和H2S;少量小分子的羧酸、醚和砜;微量C2H5SC2H5、C2H5S2C2H5、C2H5SC2H4Cl和CH2ClCH2Cl等中间产物;在反应后的催化剂表面可检测到C2H5S2C2H5、C2H5SC2H4OH、C4H9S2C2H5和C2H5S2C2H4OH、等物.根据这些结果提出了2-CEES光催化降解的反应机理,推断2-CEES的光催化降解涉及脱氯、C-S键断裂、有机硫化物光聚合和裂解等复杂过程最终转化为CO2和H2O.认为各种硫物种在表面的积聚引起了催化剂的缓慢失活.  相似文献   
108.
自由体积与亲水性对环氧涂层防护性能的影响   总被引:5,自引:1,他引:5  
报道了涂层聚合物自由体积和亲水性对涂层腐蚀防护性能影响的初步研究结果.实验表明,相对于自由体积,树脂的亲水性是决定树脂吸水率的更主要因素.低亲水性涂层腐蚀防护性能的提高主要源自到达涂层/金属界面的水量的显著降低.但由于采用活性酯固化的环氧树脂涂层中水通道的尺寸相对较大,水合离子扩散较容易,因此该类涂层覆盖下的金属基体被润湿部分的腐蚀趋势反而较一般涂层为大.  相似文献   
109.
A cobalt hexacyanoferrate (CoHCF) nanoparticle (size ca. 60 nm) chemically modified electrode (CME) was fabricated and the electrochemical behavior of hemoglobin (Hb) at this nanosized CoHCF CME was studied. In comparison with a bare glassy carbon electrode (GCE) and a general CoHCF CME electrodeposited in a traditional manner, the present nanosized CoHCF CME performed efficiently electrocatalytic reduction for Hb with relatively high sensitivity, stability, and longlife, Combined with liquid chromatography (LC), the nanosized CoHCF CME was used as the electrochemical detector of Hb in the established flow injection analysis-electrochemical determination (FIA-ECD) system. The peak current was a linear function of concentrations in the range from 2.5×10^-8 to 5.0×10^-6mol/L for Hb, with detection limit of 1.4×10^-8 mol/L. The FIA-ECD system has been successfully applied to assess the Hb content of clinic blood samples with advantages of sensitiveness, speediness, easy control and small sample-consumption.  相似文献   
110.
We report the first separation of the enantiomers of hypericin. Their steady-state optical spectra and ultrafast primary photoprocesses are investigated in chiral environments. Within experimental error, there is no difference between the two enantiomers in any of the systems considered. This is consistent with the emerging picture that the rich and extended absorption spectrum of hypericin is not a result of ground-state heterogeneity. It is also consistent with the observation that the spectra and photophysics of hypericin are generally insensitive to environments in which it does not aggregate.  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