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   527篇
  免费   99篇
  国内免费   76篇
化学   394篇
晶体学   13篇
力学   19篇
综合类   6篇
数学   39篇
物理学   231篇
  2024年   9篇
  2023年   22篇
  2022年   44篇
  2021年   44篇
  2020年   35篇
  2019年   40篇
  2018年   20篇
  2017年   22篇
  2016年   33篇
  2015年   20篇
  2014年   28篇
  2013年   47篇
  2012年   31篇
  2011年   30篇
  2010年   29篇
  2009年   35篇
  2008年   25篇
  2007年   31篇
  2006年   26篇
  2005年   24篇
  2004年   11篇
  2003年   9篇
  2002年   11篇
  2001年   6篇
  2000年   5篇
  1999年   6篇
  1998年   9篇
  1997年   3篇
  1996年   10篇
  1995年   7篇
  1994年   7篇
  1993年   5篇
  1992年   2篇
  1991年   3篇
  1990年   3篇
  1989年   2篇
  1987年   2篇
  1986年   1篇
  1985年   2篇
  1982年   1篇
  1981年   2篇
排序方式: 共有702条查询结果,搜索用时 15 毫秒
41.
The electronic properties of four divinylanthracene‐bridged diruthenium carbonyl complexes [{RuCl(CO)(PMe3)3}2(μ? CH?CHArCH?CH)] (Ar=9,10‐anthracene ( 1 ), 1,5‐anthracene ( 2 ), 2,6‐anthracene ( 3 ), 1,8‐anthracene ( 4 )) obtained by molecular spectroscopic methods (IR, UV/Vis/near‐IR, and EPR spectroscopy) and DFT calculations are reported. IR spectroelectrochemical studies have revealed that these complexes are first oxidized at the noninnocent bridging ligand, which is in line with the very small ν(C?O) wavenumber shift that accompanies this process and also supported by DFT calculations. Because of poor conjugation in complex 1 , except oxidized 1+ , the electronic absorption spectra of complexes 2+ , 3+ , and 4+ all display the characteristic near‐IR band envelopes that have been deconvoluted into three Gaussian sub‐bands. Two of the sub‐bands belong mainly to metal‐to‐ligand charge‐transfer (MLCT) transitions according to results from time‐dependent DFT calculations. EPR spectroscopy of chemically generated 1+ – 4+ proves largely ligand‐centered spin density, again in accordance with IR spectra and DFT calculations results.  相似文献   
42.
分别在苏打石灰玻璃、Mo箔、无择优取向的Mo薄膜以及(110)择优取向的Mo薄膜四种不同衬底上,采用共蒸发工艺沉积约2 μm厚的Cu(In,Ga)Se2薄膜,用X射线衍射仪测量薄膜的织构,研究衬底对Cu(In,Ga)Se2薄膜织构的影响.在以上四种衬底上沉积的Cu(In,Ga)Se2薄膜的(112)衍射峰强度依次逐渐减弱,(220/204)衍射峰从无到有且强度逐渐增强.在苏打石灰玻璃和Mo箔衬底上的Cu(In,Ga)Se2关键词: 择优取向 Cu(In 2薄膜')" href="#">Ga)Se2薄膜 太阳电池  相似文献   
43.
ThestudyofphotoionizationandphotodissociationprocessesinducedbyintensefemtosecondlaserpuIses(>lo"W/cm')withpolyatomicmoleculesbecomesofinterestbecausesomenewphenomenahavebeenobserved'-3.Sofar,mostoftheinvestigationsfocusontheexperimentalexplorationofphotoionizationprocesses'-'.Butthephotoionizationmechanismofpolyatomicmoleculesinanintensefslaserfieldisstillambiguous'.,.Incontrasttothephotoionizationprocesses,theunderstandingoffragmentationofmolecularionisevenpoorer.Corkumetal,'.,'reportedthef…  相似文献   
44.
姜标  张翱  阚颖 《中国化学》1999,17(3):293-299
Pinanyldioxy styrylboronic ester (1) was employed for asymmetric 1,3-dipolar cycloaddition with nitrile oxides, optically active △2-isoxazolines (3) or 4-hydroxy-△2-isoxazolines (4) were obtained. The effect of different bases on the selectivity of the cycloaddition reaction was studied.  相似文献   
45.
本实验在氨气和氯化氢气体的单喷泉实验基础上设计了集两种气体的制备、收集、验满、尾气处理、气体反应、喷泉实验与试剂回收利用于一体的连续性实验,喷泉部分涉及到的实验原理有氨气与硫酸铜溶液的配位反应、氨气与氯化钴溶液的沉淀反应、无色酚酞溶液和酸性对硝基苯酚溶液在碱性环境下的变色反应,以及氯化铁和硫氰化钾在弱酸性条件下的反应等。本实验的主要仪器装置由团队自行设计、定制,操作简便,玻璃活塞还可控制喷发顺序,实现多色多样喷泉,伴随氯化铵生成时的袅袅白烟,云蒸霞蔚,煞是壮观。另外,我们设计了多角度的互动方案,针对不同程度知识背景的受众传授知识,让参观者真切感受到化学的魅力。  相似文献   
46.
粘土粒径及形态结构对粘土胶性能的影响   总被引:7,自引:1,他引:7  
用超声波和离心方法将3种来源不同的粘土样品按粒分径分级,测定各级分粒径比表面积和结构,并制备相应级分的粘土胶进行物理力学性能测试,结果表明,在一定范围内,粘土粒径的变化仅对粘土胶的某些力学性能产生物明显的影响,而粘土粒子以其独特的形态结构对粘土胶产生显著的补强作用。  相似文献   
47.
Anion–π interactions have been widely studied as new noncovalent driving forces in supramolecular chemistry. However, self‐assembly induced by anion–π interactions is still largely unexplored. Herein we report the formation of supramolecular amphiphiles through anion–π interactions, and the subsequent formation of self‐assembled vesicles in water. With the π receptor 1 as the host and anionic amphiphiles, such as sodium dodecylsulfate (SDS), sodium laurate (SLA), and sodium methyl dodecylphosphonate (SDP), as guests, the sequential formation of host–guest supramolecular amphiphiles and self‐assembled vesicles was demonstrated by SEM, TEM, DLS, and XRD techniques. The intrinsic anion–π interactions between 1 and the anionic amphiphiles were confirmed by crystal diffraction, HRMS analysis, and DFT calculations. Furthermore, the controlled disassembly of the vesicles was promoted by competing anions, such as NO3?, Cl?, and Br?, or by changing the pH value of the medium.  相似文献   
48.
The influence of the substitution of Ga atoms for Co atoms in DyCo2 compounds on magnetocaloric properties has been investigated. A series of DyCo2−xGax alloys with x=0, 0.03, 0.06, 0.1, 0.15, and 0.2 was prepared by the arc-melting method for this investigation. Experimental results revealed that the Ga substitution for Co in DyCo2 can form a single phase with the cubic Laves phase structure up to x=0.2. As the Ga content x increases, the lattice parameter and the Curie temperature Tc increases from 143 to 196 K linearly. The maximum magnetic entropy changes in a low field change of 0-1.5 T, increasing from 8.24 to 10.61 J/K kg when the Ga content x increases from 0 to 0.03, but decreasing gradually to 3.51 J/K kg as the Ga content further increases to x=0.2. All the samples show a relatively large magnetic entropy change with very small hysteresis loss.  相似文献   
49.
Amino acid ester substituted polyphosphazenes are osteoactive benefiting from their phosphorus‐containing chemical structure, which highlights interests in bone tissue engineering. To correlate their chemical structures with cell activities, in this study, poly[(ethyl alanato)0.3(ethyl glycinato)0.7phosphazene] (PAGP) and poly[(ethyl phenylalanato)0.3(ethyl glycinato)0.7phosphazene] (PPGP) are synthesized to carry out studies on cell osteogenic differentiation. In the non‐contact culture manner, bone mesenchymal stromal cells (BMSCs) are cultured in transwell chambers containing PAGP or PPGP films, while the cells and the materials do not contact. In the contact culture manner, BMSCs are cultured on the PAGP or PPGP films. In the meantime, solutions containing PAGP or PPGP degradation products (i.e., phosphate, ammonium, and corresponding amino acids) are applied for cell culture using inorganic phosphate (Pi) ion as control. Thus, the influences from substrate surface and degradation products can be identified separately. The results reveal that both the phosphorus‐containing surface of PAGP and PPGP films and their degradation products play significant roles in regulating cell behaviors. In comparison with PAGP, PPGP seems able to provide relatively stable phosphorus‐containing surface to strengthen the cell‐scaffold interaction because of its slower degradation rate and higher Young's modulus, leading to greater promotion in osteogenic differentiation via contact effect.  相似文献   
50.
Nd-Fe-B/FeCo多层纳米复合膜的结构和磁性   总被引:4,自引:0,他引:4       下载免费PDF全文
敖琪  张瓦利  张熠  吴建生 《物理学报》2007,56(2):1135-1140
制备了Nd28Fe66B6/Fe50Co50多层纳米复合磁性薄膜,对溅射态和650℃退火处理15 min试样的相成分分析和微结构的观察显示,溅射态薄膜呈非晶态,经650℃退火处理15 min后,薄膜主要相成分为硬磁性Nd2Fe14B相和软磁性相FeCo(110)相.Nd2Fe14B相呈柱状,其易磁化c轴垂直于膜面,尺寸约10 nm.在硬磁性相和软磁性相之间存在少量富Nd相和非晶态,富Nd相大小约7 nm.磁性测量和分析表明,1)该系列薄膜退火态具有垂直于膜面的磁晶各向异性.2)对于固定厚度(10 nm)层Nd-Fe-B和不同厚度(tFeCo=1—100 nm)层FeCo多层纳米复合膜,剩磁随软磁相FeCo 厚度的增加快速增加,而矫顽力则减小.当tFeCo=5 nm时,最大磁能积达到200 kJ/m3. 3)硬磁相Nd-Fe-B层和软磁相FeCo层之间交换耦合导致剩磁和磁能积增强. 关键词: Nd-Fe-B/FeCo多层纳米复合膜 交换耦合 磁各向异性  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