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   7937篇
  免费   1568篇
  国内免费   977篇
化学   5637篇
晶体学   119篇
力学   470篇
综合类   94篇
数学   872篇
物理学   3290篇
  2024年   34篇
  2023年   252篇
  2022年   405篇
  2021年   399篇
  2020年   463篇
  2019年   439篇
  2018年   356篇
  2017年   329篇
  2016年   448篇
  2015年   456篇
  2014年   485篇
  2013年   653篇
  2012年   732篇
  2011年   717篇
  2010年   510篇
  2009年   474篇
  2008年   450篇
  2007年   399篇
  2006年   336篇
  2005年   310篇
  2004年   259篇
  2003年   209篇
  2002年   190篇
  2001年   158篇
  2000年   115篇
  1999年   150篇
  1998年   115篇
  1997年   96篇
  1996年   95篇
  1995年   79篇
  1994年   66篇
  1993年   48篇
  1992年   36篇
  1991年   46篇
  1990年   42篇
  1989年   26篇
  1988年   23篇
  1987年   19篇
  1986年   14篇
  1985年   13篇
  1984年   2篇
  1983年   3篇
  1982年   6篇
  1981年   7篇
  1980年   5篇
  1978年   2篇
  1964年   1篇
  1959年   2篇
  1957年   2篇
  1936年   1篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
向列相液晶被广泛应用于液晶显示中,但是由于杂质的存在,会导致液晶的驱动电压变大,增加能耗。 为了降低阈值电压和饱和电压,通常向液晶中添加纳米颗粒来提高电光性能。 本文利用水热法制备了表面粗糙和光滑的两种立方体Fe2O3纳米颗粒,其形貌均匀,尺寸约550 nm。 将二者分别掺杂到向列相液晶E7中,结果表明,粗糙立方体Fe2O3/E7复合体系具有比光滑立方体Fe2O3/E7复合体系和向列相液晶E7更优的电光性能,且在掺杂质量分数为0.4%时,其电光性能达到最优,阈值电压和饱和电压分别降低9.9%和11.6%,对比度增大80%,响应时间降低至6.0 ms。 这归因于粗糙立方体Fe2O3具有足够的表面积和表面所带电荷更多,所以会更易吸附体系中的杂质离子和减弱杂质离子的屏蔽作用,从而提高了电光性能。  相似文献   
82.
A novel sulfonated poly(arylene ether) containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N'-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton's reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly (MEA) prepared with the asmade film (706 EW, 100 μm dry thickness) shows better cell performance than Nation 115-MEA in the whole current density range.  相似文献   
83.
Hu  Chuanjiang  Duan  Chunying  Meng  Qingjin  Liu  Yongjiang  Lu  Changsheng  Reng  Xiaoming  Chen  Yijun  Cao  Mi 《Transition Metal Chemistry》2000,25(2):141-144
The mixed-valence molybdovanadate compound Na2(NH4)4[VIVVV 8Mo)O28] · 10H2O [Vanadata(6-)tetradeca--oxotetra-3-oxodi-6-oxoheptaoxo(oxomolybdate) nonatetrammonium disodium, decahydrate] has been synthesized from sodium molybdate(VI) dihydrate and sodium metavanadate dihydrate in aqueous solution by adding NH2OH · HCl. The molecular structure has been determined by X-ray diffraction and is based on the isopolydecavanadate structure. The molybdate atom is crystallographically disordered over 6MO6 octahedral sites. The e.s.r. spectrum clearly indicates that one vanadium atom has the oxidation number +4.  相似文献   
84.
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement. Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the U–O bonds of the uranyl cation. Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users.  相似文献   
85.
N,N-二丁基癸酰胺萃取硝酸有机相结构研究   总被引:1,自引:0,他引:1  
利用界面张力、电导、FT-IR等研究了不同硝酸浓度下萃取有机相的微结构。利用Gaussian曲线拟合处理N,N-二丁基癸酰胺(DBDEA)的羰基吸收峰,结果表明体系中存在多种以氢键结合的物种如DBDEA·HNO3、(DBDEA)2·HNO3等。在较高酸度下有机相中萃取剂分子自组装成小的聚集体-反相胶团,极性核由水、硝酸和萃取剂高电荷密度的极性部分构成。  相似文献   
86.
分析了铅中毒引起的消化系统改变及临床特点。  相似文献   
87.
纳米尺寸团簇NinZrn(n=3~5)的几何结构与成键规律研究   总被引:3,自引:0,他引:3  
根据化学键理论与拓扑原理,设计了团簇NinZrn(n=3-5)的可能几何构型,并用从头算方法进行构型优化,结果表明,由NiZr组成的团簇原子间的Zr-Zr和Zr-Ni键明显较强,而Ni-Ni的成键较弱,并发与NinZrn(n=3-5)团簇电子性质与有机烯烃分子等瓣相似,原子之间的成键按照强弱相间的规则分布。  相似文献   
88.
Photocycloadditionof(4-methyl-7-coumarinyl)OxyaceticAcidPropanediolDiesterandX-rayCrystalStructureofProductDuDa-Ming;WangYong...  相似文献   
89.
Mesostructured silica SBA-15 materials with different structural parameters, such as pore size, pore volume, and wall thickness, etc., were prepared by varying the postsynthesis hydrothermal treatment temperature and adding inorganic salts. The hydrothermal stabilities of these materials in steam (100% water vapor) were systematically investigated using a variety of techniques including powder X-ray diffraction, transmission electron microscopy, nitrogen sorption, and (29)Si solid-state NMR. The effect of the pore size, microporosity or mesoporosity, and wall thickness on the stability was discussed. The results show that all of the SBA-15 materials have a good hydrothermal stability under steam of 600 degrees C for at least 24 h. N(2) sorption measurements show that the Brumauer-Emmett-Teller surface area of SBA-15 materials is decreased by about 62% after treatment under steam at 600 degrees C for 24 h. The materials with thicker walls and more micropores show relatively better hydrothermal stability in steam of 600 degrees C. Interestingly, we found that the microporosity of the mesostructured silica SBA-15 is a very important factor for the hydrothermal stability. To the materials with more micropores, the recombination of Si-O-Si bonds during the high-temperature steam treatment may not cause direct destruction to the wall structure. As a result, SBA-15 materials with more micropores show better stability in pure steam of 600 degrees C. Nevertheless, these materials are easily destroyed in steam of 800 degrees C for 6 h. Two methods to effectively improve the hydrothermal stability are introduced here: one is a high-temperature treatment, and another is a carbon-propping thermal treatment. Thermal treatment at 900 degrees C can enhance the polymerization degree of Si-O-Si bonds and effectively improve the hydrothermal stability of these SBA-15 materials in 800 degrees C steam for 12 h. But, this approach will cause very serious shrinkage of the mesopores, resulting in smaller pore diameter and low surface area. A carbon-propping thermal treating method was employed to enhance the polymerization of Si-O-Si bonds and minimize the serious shrinkage of mesopores at the same time. It was demonstrated to be an effective method that can greatly improve the hydrothermal stability of SBA-15 materials in 800 degrees C steam for 12 h. Furthermore, the SBA-15 materials obtained by using the carbon-propping method possess larger pores and higher surface area after the steam treatment at 800 degrees C compared to the materials from the direct thermal treatment method after the steam treatment.  相似文献   
90.
The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.  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