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   36527篇
  免费   5584篇
  国内免费   3653篇
化学   25551篇
晶体学   363篇
力学   2227篇
综合类   244篇
数学   4295篇
物理学   13084篇
  2024年   73篇
  2023年   743篇
  2022年   909篇
  2021年   1251篇
  2020年   1433篇
  2019年   1304篇
  2018年   1125篇
  2017年   1028篇
  2016年   1589篇
  2015年   1556篇
  2014年   1950篇
  2013年   2513篇
  2012年   3222篇
  2011年   3229篇
  2010年   2192篇
  2009年   2065篇
  2008年   2217篇
  2007年   1981篇
  2006年   1863篇
  2005年   1559篇
  2004年   1312篇
  2003年   995篇
  2002年   907篇
  2001年   747篇
  2000年   703篇
  1999年   841篇
  1998年   695篇
  1997年   639篇
  1996年   708篇
  1995年   605篇
  1994年   552篇
  1993年   473篇
  1992年   452篇
  1991年   364篇
  1990年   324篇
  1989年   236篇
  1988年   216篇
  1987年   199篇
  1986年   142篇
  1985年   156篇
  1984年   135篇
  1983年   116篇
  1982年   80篇
  1981年   59篇
  1980年   49篇
  1979年   32篇
  1978年   26篇
  1976年   27篇
  1975年   31篇
  1974年   23篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
981.
A study has been made of the adsorption, interaction, and spreading of mixtures of anionic and cationic surfactants at the aqueous solution/polyethylene (PE) interface. When a drop of an aqueous solution of an anionic or cationic hydrocarbon-chain surfactant is placed on a highly hydrophobic PE film (contact angle of water > 90 degrees ), it spreads to an area very little larger than that of a drop of water of the same volume. If the anionic and cationic hydrocarbon-chain surfactant solutions are mixed prior to being applied to PE film, synergism is small, if any, and the reproducibility of the experimental results is poor. However, when the cationic and anionic aqueous solutions are applied on the PE film in a sequential manner, a remarkable synergism in spreading is observed and the results are very reproducible. The area spread by an aqueous solution of the anionic-cationic mixture may be more than 400 times that of aqueous solutions of the same volume and surfactant concentration of the individual surfactant components. Previous work in this laboratory on surfactant systems showing synergism in spreading on PE film, but only weak interaction at the aqueous solution/air interface, showed that the synergy was due to changes at the aqueous solution/PE interface and not to the changes at the aqueous solution/air or PE/air interface. Investigation of the adsorption behavior at the aqueous solution/solid interface of two of the anionic-cationic mixtures studied here indicates the reason for differences in spreading behavior observed with different anionic-cationic mixtures. The more similar the adsorption tendencies at the solid/aqueous solution interface of the anionic and cationic surfactants, and the closer their adsorption to an equimolar monolayer there, the stronger their interaction there and the greater their enhancement of the spreading. A mechanism is proposed for the synergy in spreading observed, based upon the difference between the surface tension in the precursor film at the spreading interface and that at the top of the spreading drop.  相似文献   
982.
Novel naphthalocyanine (Nc) nanotubes with special wall structures were fabricated by a template method using Nc molecules as building blocks. Thermal stabilization of the ordered columnar structures of the tetrakis(tert-butyl)naphthalocyanine (Ni-BNc) molecules, induced from the pi-pi interactions in the nanoscale channels of an alumina template, resulted in Nc nanotubes with walls consisting of well-ordered Nc molecular disks. Further thermal treatment of Ni-BNc at 600 degrees C produced carbonized Nc nanotubes containing ordered columnar, graphitic wall structures with the graphene disks arranged perpendicular to the tube axis. These nanotubes may be useful for extending the application of Nc molecules for nanodevice fabrication.  相似文献   
983.
The two families of intermetallic phases REAuAl4Ge2 (1) (RE=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb) and REAuAl4(AuxGe1−x)2 (2) (x=0.4) (RE=Ce and Eu) were obtained by the reactive combination of RE, Au and Ge in liquid aluminum. The structure of (1) adopts the space group R-3m (CeAuAl4Ge2, , ; NdAuAl4Ge2, , ; GdAuAl4Ge2, , ; ErAuAl4Ge2, , ). The structure of (2) adopts the tetragonal space group P4/mmm with lattice parameters: , for EuAuAl4(AuxGe1−x)2 (x=0.4). Both structure types present slabs of “AuAl4Ge2” or “AuAl4(AuxGe1−x)2” stacking along the c-axis with layers of RE atoms in between. Magnetic susceptibility measurements indicate that the RE atoms (except for Ce and Eu) possess magnetic moments consistent with +3 species. The Ce atoms in CeAuAl4Ge2 and CeAuAl4(AuxGe1−x)2 (x=0.4) appear to be in a mixed +3/+4 valence state; DyAuAl4Ge2 undergoes an antiferromagnetic transition at 11 K and below this temperature exhibits metamagnetic behavior. The Eu atoms in EuAuAl4(AuxGe1−x)2 (x=0.4) appear to be in a 2+ oxidation state.  相似文献   
984.
Using four basis bets, (6‐311G(d,p), 6‐31+G(d,p), 6‐31++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for the dimers CH2O? HF, CH2O? H2O, CH2O? NH3, and CH2O? CH4. The structures of CH2O? HF, CH2O? H2O, and CH2O? NH3 are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the H atoms of CH2O and lone pair(s) on the F atom in HF, the O atom in H2O, or the N atom in NH3. In contrast with the above three dimers, for CH2O? CH4, because there is not a π‐type hydrogen bond to bend its linear hydrogen bond, the structure of CH2O? CH4 is noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD (T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005  相似文献   
985.
分散聚合水基聚苯胺乳胶微球制备与表征   总被引:7,自引:0,他引:7  
水溶性空间稳定剂聚乙烯吡咯烷酮(PVP)存在时,采用分散聚合制备水溶性单分散的聚苯胺(PAn)乳胶粒子,采用透射电子显微镜(TEM)观察粒子形态及尺寸;利用紫外-可见吸收光谱对胶体分散体系进行表征.实验结果表明,当PAn含量较少(w< 16.78%)时, PAn-PVP复合乳胶粒子呈米粒状;当PAn含量较大(w >23.22%)时, PAn-PVP复合乳胶粒子呈球形.  相似文献   
986.
Chemical processing in the stratospheres of the gas giants is driven by incident vacuum ultraviolet (VUV) light. Ethane is an important constituent in the atmospheres of the gas giants in our solar system. The present work describes translational spectroscopy studies of the VUV photochemistry of ethane using tuneable radiation in the wavelength range 112 ≤ λ ≤ 126 nm from a free electron laser and event-triggered, fast-framing, multi-mass imaging detection methods. Contributions from at least five primary photofragmentation pathways yielding CH2, CH3 and/or H atom products are demonstrated and interpreted in terms of unimolecular decay following rapid non-adiabatic coupling to the ground state potential energy surface. These data serve to highlight parallels with methane photochemistry and limitations in contemporary models of the photoinduced stratospheric chemistry of the gas giants. The work identifies additional photochemical reactions that require incorporation into next generation extraterrestrial atmospheric chemistry models which should help rationalise hitherto unexplained aspects of the atmospheric ethane/acetylene ratios revealed by the Cassini–Huygens fly-by of Jupiter.

The vacuum ultraviolet photodissociation dynamics of ethane provide clues for modelling the atmospheric chemistry of the gas giants.  相似文献   
987.
The title compound, [CuCl(CH4N2S)2]·2C11H6N2O·H2O, consists of mol­ecules of a CuI–thio­urea complex, free 4,5‐di­aza­fluoren‐9‐one (dafone) and crystalline water. The planar complex mol­ecule has trigonal coordination geometry around the CuI atom. The dafone and water mol­ecules, which are hydrogen bonded to the CuI complex, are approximately coplanar with this complex. The crystal displays a sheet structure and π–π stacking is observed between neighbouring sheets.  相似文献   
988.
Hu C  Wu K  Dai X  Hu S 《Talanta》2003,60(1):17-24
A simple and effective chemically modified carbon paste electrode (CMCPE) for the simultaneous determination of lead(II) and cadmium(II) was developed in this work. The electrode was prepared by the addition of diacetyldioxime into a carbon paste mixture. Pb2+ and Cd2+ were preconcentrated on the surface of the modified electrode by complexing with diacetyldioxime and reduced at a negative potential (−1.10 V). Then the reduced products were oxidized by differential pulse stripping. The fact that two stripping peaks appeared on the voltammograms at the potentials of −0.65 V (Cd2+) and −0.91 V (Pb2+) demonstrates the possibility of simultaneous determination of Pb2+ and Cd2+. Under the optimized working conditions, calibration graphs were linear in the concentration ranges of 1.0×10−7-1.5×10−5 mol l−1 (Pb2+) and 2.5×10−7-2.5×10−5 mol l−1 (Cd2+), respectively. For 5 min preconcentration, detection limits of 1×10−8 mol l−1 (Pb2+) and 4×10−8 mol l−1 (Cd2+) were obtained at the signal noise ratio (SNR) of 3. To evaluate the reproducibility of the newly developed electrode, the measurements of 5×10−7 mol l−1 Pb2+ and Cd2+ were parallel carried out for six times at different electrodes and the relative standard deviations were 2.9% (Pb2+) and 3.2% (Cd2+), respectively. Interferences by some metals were investigated. Only Ni2+ and Hg2+ apparently affected the peak currents of Pb2+ and Cd2+. The diacetyldioxime modified carbon paste electrode was applied to the determination of Pb2+ and Cd2+ in water samples. The results indicate that this electrode is sensitive and effective for the simultaneous determination of Pb2+ and Cd2+.  相似文献   
989.
采用共沉淀并加法制备了B位掺杂烧绿石型稀土复合氧化物纳米微晶Y2Sn2-xFexO7-δ(x=00~10)。制备的纳米微晶属于立方晶系,Fd3m,晶胞参数与掺杂量呈线性关系。通过Msbauer、TGDTA,气相色谱和γ射线辐照等技术研究了纳米微晶对CO的催化选择性能。结果表明,纳米微晶对CO的催化选择性明显高于一般粉料对CO的选择性;纳米微晶对CO的选择性与掺杂量有关;未辐照的纳米微晶,当掺杂量x=06时,其对CO的选择性为最高,辐照后的纳米微晶,当掺杂量x=04时,其对CO的选择性为最高  相似文献   
990.
合成了E,E-1,4-二[2′,2″-(苯并(口恶)唑基乙烯基)]苯及衍生物共14种,测定了它们的熔点、红外光谱、核磁共振氢谱、紫外吸收光谱和荧光发射光谱、荧光量子产率及激光性能。  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