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   6957篇
  免费   709篇
  国内免费   1483篇
化学   7246篇
晶体学   182篇
力学   278篇
综合类   55篇
数学   14篇
物理学   1374篇
  2024年   21篇
  2023年   133篇
  2022年   157篇
  2021年   201篇
  2020年   243篇
  2019年   230篇
  2018年   166篇
  2017年   211篇
  2016年   293篇
  2015年   293篇
  2014年   369篇
  2013年   659篇
  2012年   461篇
  2011年   475篇
  2010年   381篇
  2009年   369篇
  2008年   404篇
  2007年   424篇
  2006年   476篇
  2005年   390篇
  2004年   438篇
  2003年   387篇
  2002年   323篇
  2001年   228篇
  2000年   206篇
  1999年   181篇
  1998年   182篇
  1997年   155篇
  1996年   127篇
  1995年   115篇
  1994年   94篇
  1993年   64篇
  1992年   55篇
  1991年   52篇
  1990年   28篇
  1989年   30篇
  1988年   34篇
  1987年   14篇
  1986年   14篇
  1985年   13篇
  1984年   8篇
  1983年   4篇
  1982年   5篇
  1981年   6篇
  1980年   8篇
  1979年   4篇
  1978年   3篇
  1977年   3篇
  1975年   4篇
  1973年   4篇
排序方式: 共有9149条查询结果,搜索用时 31 毫秒
111.
Excess molar enthalpies of binary mixtures for tributyl phosphate (TBP)+methanol/ethanol were measured with a TAM air Isothermal calorimeter at 298.15 K and ambient. The results for xTBP+(1–x)CH3OH are negative in the whole range of composition, while the values for xTBP+(1–x)C2H5OH change from positive values at low x to small negative values at high x. The experimental results have been correlated with the Redlich–Kister polynomial. IR spectra of the mixtures were measured to investigate the effect of hydrogen bonding in the mixture.  相似文献   
112.
一种新的磷酸根离子敏感电极研究   总被引:5,自引:0,他引:5  
一种新的磷酸根离子敏感电极研究肖丹,俞汝勤,李军,袁孔铨(湖南大学化学化工系,长沙,410082)关键词磷酸根,离子选择电极,磷酸二氢根磷酸根离子浓度的测定在化学化工、环境保护、生命科学和临床医学等领域有着重要的意义。对磷酸根离子敏感电极的研究和探索...  相似文献   
113.
The intercalation of some amines (aniline, benzylamine, cyclohexylamine,piperidine, pyridine, pyrazine and piperazine) into -titaniumphosphate, Ti(HPO4)H2O,has been investigated by the batch method and/or by exposing the host to thevapour of the amines. The changes in the interlayer distance of the solidduring the intercalation process was followed by X-ray powder diffraction.The new intercalates were characterised by chemical and thermal analysis.Materials with a monolaminar and/or bilaminar arrangement of amine moleculesin the phosphate interlayer region are obtained depending on the nature ofthe amine. Due to steric hindrance, saturated phases are not obtained forall amines studied. The thermal decomposition of the intercalates (nitrogenatmosphere), takes place in three stages: dehydration, removal of amines andcondensation of the hydrogenphosphate to pyrophosphate groups.  相似文献   
114.
In contrast to aluminum alkyls, alkyl aluminum halides such as EtAlCl2 react with crown ethers to form cation-anion pairs which exhibit the liquid clathrate effect. Specifically, [12-C-4·AlCl2][AlCl3Et] and [18-C-6·AlCl2][AlCl3Et] have been isolated and characterized by X-ray diffraction techniques. The cations show aluminum in an octahedral environment made up of four of the oxygen atoms from the crown and two chlorine atoms. The 12-C-4 derivative crystallizes in the monoclinic space group P21/c with cell constants of a=7.497(4), b=22.121(8), c=12.339(5) Å, =94.99(3)o, and Z=4 for =1.43 g cm–3. Least-squares refinement based on 1413 observed reflections led to a final conventional R value of 0.093. The 18-C-6 complex belongs to the triclinic space group P1 with a=8.414(4), b=12.193(6), c=12.394(6) Å, =73.14(4), =86.07(4), =81.52(4)o, and Z=2 for =1.45 g cm–3. Refinement based on 2605 observed reflections led to R=0.063. The complex aluminum-containing species are related to a class of compounds called aluminoxanes.  相似文献   
115.
Complexation of AlIIIby 8-hydroxyquinoline and fluorescence behavior of the quinolinate(s) were studied in reverse micellar systems at low water content, and compared to aqueous media. Two surfactants were used: one was cationic (CTAC: cetyltrimethylammonium chloride) and the other was anionic (AOT: sodium bis(2-ethylhexyl)sulfosuccinate). The results obtained in the CTAC/dichloromethane system (W= [H2O]/[surfactant] = 0.9) showed that complexation occurred very likely in the oil phase and no micellar effect was observed. On the contrary, in the presence of AOT, specific micellar effects were observed due to the presence of the anionic polar heads: stabilization of the positively charged 1:1 and 1:2 chelates, at the expense of the neutral water-insoluble 1:3 chelate which is formed in aqueous solutions under similar conditions;drastic fluorescence enhancement factorsof 120 and 100 in AOT/heptane (W= 1.5) and AOT/dichloromethane (W= 1.6), respectively. Such factors have never been reported so far in either hydroorganic or direct micellar systems. In return, the length of time for the production of the complex(es) is increased because of the microheterogeneity of the medium and the small sizes of the water pools.  相似文献   
116.
孙捷  孙迎春 《中国化学》2004,22(7):661-667
Introduction Inorganic oxide films have attracted a lot of interest in the last several decades. Among them, silicon dioxide films are widely used in modern microelectronics, optics and mechanics. This material has been grown by various methods including thermal oxidation, chemical vapor phase deposition, plasma-enhanced chemical vapor phase deposition, and so on.1,2 Recently, Nagayama et al.3 have reported that SiO2 thin films could be produced by a new chemical method of liquid phase depos…  相似文献   
117.
Quartz-homeotypic gallium (ortho-) phosphate, GaPO4, is of special interest for resonator applications asking for temperature compensated cuts with higher electro-mechanical coupling than quartz and operational temperatures up to 970°C. The crystal microbalance technique, well known for quartz (QCM) which can be used only at moderate temperatures, can now be extended to much higher temperatures using GaPO4 crystals, benefiting from all three advantages mentioned above. Two different experiments were done to demonstrate the advantages of a crystal microbalance based on GaPO4. First, the GaPO4 resonator was used for film thickness determination and compared with a commercial QCM. This experiment demonstrated that the measuring range can be extended by using GaPO4 resonators instead of quartz. The second experiment demonstrates the possibility for thermogravimetric analysis up to 720°C by using a new concept for resonator mounting.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   
118.
Ti接枝MCM-41催化剂的结构设计及化学亲和选择性研究   总被引:3,自引:0,他引:3  
马辉  何静  David G Evans  段雪 《催化学报》2002,23(5):473-476
 用二氯化钛茂作为活性物种的来源,利用Si-MCM-41催化剂表面羟基的反应性,得到了Ti接枝MCM-41催化剂的两种结构模型.结构表征结果表明,Ti接枝MCM-41催化剂不仅长程结构好,孔径分布均一,而且催化剂表面活性中心含量高.两种结构模型催化剂上芳烃羟化反应性能表明,Ti接枝MCM-41催化剂表面的亲水/憎水性可以在较宽的范围内调变,从而可实现控制芳烃羟化的化学亲和选择性.另外,研究结果还表明,Ti接枝MCM-41催化剂具有很好的活性稳定性.  相似文献   
119.
金属离子掺杂对TiO2光催化性能的影响   总被引:14,自引:1,他引:14  
TiO2光催化反应过程涉及光生电荷、电荷迁移、电荷在TiO2表面的反应和溶液体相反应4个顺序相接并相互影响的步骤.在TiO2中掺杂金属离子对以上4个步骤均有重要影响,合理的掺杂可有效地提高其光催化性能.本文综合了国内外此方面的最新研究成果,从提高TiO2光催化性能和优化光催化反应的角度出发,在材料吸光能力、电荷扩散、表面反应、粒径和晶型等方面,全面地分析总结了金属离子掺杂的影响效果和规律性认识,并对TiO2基光催化材料的金属离子掺杂改性研究的未来发展方向提出了建议.文中还简要介绍了相关的掺杂方法和材料表征手段.  相似文献   
120.
The ternary catalyst systems based on activated silica, aluminum alkyl, and titanium tetrachloride were polymerized in an ethylene gas-phase polymerization process, and further studied using ESR spectroscopy. Two types of titanium (III) ESR-active centers were observed and a linear dependence between the concentration of that characterized by a rhombic anisotropic signal with g1 = 1.962, g2 = 1.945, and g3 = 1.913 values and catalyst productivity was found. © 1993 John Wiley & Sons, Inc.  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