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   2069篇
  免费   249篇
  国内免费   161篇
化学   1472篇
晶体学   22篇
力学   84篇
综合类   14篇
数学   163篇
物理学   724篇
  2024年   3篇
  2023年   32篇
  2022年   52篇
  2021年   58篇
  2020年   66篇
  2019年   60篇
  2018年   81篇
  2017年   60篇
  2016年   114篇
  2015年   106篇
  2014年   123篇
  2013年   185篇
  2012年   153篇
  2011年   147篇
  2010年   151篇
  2009年   140篇
  2008年   134篇
  2007年   125篇
  2006年   108篇
  2005年   83篇
  2004年   54篇
  2003年   71篇
  2002年   60篇
  2001年   39篇
  2000年   39篇
  1999年   28篇
  1998年   26篇
  1997年   20篇
  1996年   22篇
  1995年   9篇
  1994年   6篇
  1993年   11篇
  1992年   8篇
  1991年   9篇
  1990年   8篇
  1989年   11篇
  1988年   5篇
  1987年   9篇
  1986年   5篇
  1985年   6篇
  1984年   4篇
  1983年   5篇
  1982年   3篇
  1981年   6篇
  1980年   3篇
  1977年   6篇
  1976年   3篇
  1975年   3篇
  1972年   4篇
  1971年   3篇
排序方式: 共有2479条查询结果,搜索用时 93 毫秒
91.
This article discusses the effect of water fraction on the rheological properties of waxy crude oil emulsions including gel point, yield stress, viscosity, and thixotropy. The experimental results reveal that the rheological behaviors of the w/o emulsion samples all intensify with the increase of water volume fraction within 60%. Of more significance is that a correlation for w/o emulsions between yield stress and water volume fraction is put forward with an average relative error of 6.75%. In addition, some mainstream viscosity prediction models of w/o emulsions are evaluated, and Elgibaly model is the best-fit for the emulsions in this study.  相似文献   
92.
以胜利褐煤为研究对象,利用FT-IR等手段,用灰分、不同湿度下的平衡复吸水含量等,系统研究了不同相对湿度下K+、Na+、Ca2+、Mg2+的水合作用对胜利褐煤平衡复吸水含量的影响。结果表明,相同浓度不同类型的金属离子与煤样的交换能力的趋势为Ca2+Na+K+Mg2+。金属离子对胜利褐煤平衡复吸水含量影响力的顺序为Mg2+Ca2+Na+≈K+。相对湿度高时,平衡复吸水含量的主要控制因素为游离水分子之间的分子作用力;相对湿度中等时,平衡复吸水含量的主要控制因素为金属水簇与毛细管之间的毛细管作用力;相对湿度低时,平衡复吸水含量的主要控制因素为金属离子的水合作用。  相似文献   
93.
Ligand place‐exchange (LPE) reactions are extensively applied for the post‐functionalization of monolayer‐protected gold clusters (MPCs) by using excessive incoming ligands to displace initial ones. However, the modified MPCs are often enlarged or degraded; this results in ill‐defined size‐dependent properties. The growth of MPCs essentially involves an unprotected surface that is subsequently has gold atoms added or is fused with other gold cores owing to collision. Reported herein is a guideline for the selection of solvents to suppress unwanted MPC growth. Favorable solvents are those with significant affinity to gold or with low solubility for desorbed ligands because these properties retard LPE reactions and minimize the time available for unprotected gold cores. This finding provides a general and convenient approach to regulate the size of functionalized MPCs.  相似文献   
94.
The unique physical and chemical properties of room-temperature ionic liquids(RTILs) have recently received increasing attention as solvent alternatives for possible application in the field of nuclear industry, particularly in liquid-liquid separations of radioactive nuclides. We investigated solvent extraction of U(VI) from aqueous solutions into a commonly used ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([C4mim][NTf2]) using trioctylphosphine oxide(TOPO) as an extractant. The effects of contact time, TOPO concentration, acidity, and nitrate ions on the U(VI) extraction are discussed in detail. The extraction mechanism was proposed based on slope analysis and UV-Vis measurement. The results clearly show that TOPO/[C4mim][NTf2] provides a highly efficient extraction of U(VI) from aqueous solution under near-neutral conditions. When the TOPO concentration was 10 mmol/L, the extraction of 1 mmol/L U(VI) was almost complete( 97%). Both the extraction efficiency and distribution coefficient were much larger than in conventional organic solvents such as dichloromethane. Slope analysis confirmed that three TOPO molecules in [C4mim][NTf2] bound with one U(VI) ion and one nitrate ion was also involved in the complexation and formed the final extracted species of [UO2(NO3)(TOPO)3]+. Such a complex suggests that extraction occurs by a cation-exchange mode, which was subsequently evidenced by the fact that the concentration of C4mim+ in the aqueous phase increased linearly with the extraction percent of U(VI) recorded by UV-Vis measurement.  相似文献   
95.
Polymer‐based crosslinked networks with intrinsic self‐repairing ability have emerged due to their built‐in ability to repair physical damages. Here, novel dual sulfide–disulfide crosslinked networks (s‐ssPxNs) are reported exhibiting rapid and room temperature self‐healability within seconds to minutes, with no extra healing agents and no change under any environmental conditions. The method to synthesize these self‐healable networks utilizes a combination of well‐known crosslinking chemistry: photoinduced thiol‐ene click‐type radical addition, generating lightly sulfide‐crosslinked polysulfide‐based networks with excess thiols, and their oxidation, creating dynamic disulfide crosslinkages to yield the dual s‐ssPxNs. The resulting s‐ssPxN networks show rapid self‐healing within 30 s to 30 min at room temperature, as well as self‐healing elasticity with reversible viscoelastic properties. These results, combined with tunable self‐healing kinetics, demonstrate the versatility of the method as a new means to synthesize smart multifunctional polymeric materials.

  相似文献   

96.
Natural fibers containing components with phenolic hydroxyl groups, such as jute, wool, and silk, can be directly modified by laccase-catalyzed grafting. However, cellulosic fibers like cotton cannot be functionalized in this manner. In this work, we developed a facile two-step method to graft polymers on cotton fabric via laccase catalysis. First, polydopamine (PDA) coating was deposited on the surface of the cotton fabrics via catalysis of laccase/2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) system. Then, the newly formed PDA coating acted as the secondary reaction platform for subsequent laccase-mediated grafting of hydrophobic monomer dodecyl gallate (DG). The oxidation of dopamine (DA) catalyzed with the laccase/TEMPO system was investigated using UV–visible (UV–vis) spectroscopy. The scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) results verified that the PDA was coated on the surface of cotton fibers. Fourier transform infrared (FTIR) spectra indicated that the PDA-coated cotton was successfully grafted with DG (DG-PDA-cotton). According to the weighting method, the grafting percentage was about 1.06%. The hydrophobicity of the DG-PDA-cotton fabrics was greatly improved with a contact angle of 133°. Also, the grafted cotton fabrics show repellency of water-soluble stains like coffee, milk, and tea. This study provides a new strategy for surface modification of cotton by laccase-mediated grafting, which offers the references for the green fabrication of cotton fabrics with improved functionalization.  相似文献   
97.
化石燃料的燃烧和其他人类活动排放了大量的CO2气体,引发了诸多环境问题。电催化CO2还原反应(CO2RR)可以储存间歇可再生能源,实现人为闭合碳循环,被认为是获得高附加值化学品和燃料的有效途径。电催化CO2RR涉及多个电子-质子转移步骤,其中*CO通常被认为是关键中间体。铜由于对*CO具有合适的吸附能,已被广泛证明是唯一能够有效地将CO2还原为碳氢化合物和含氧化合物的金属催化剂。然而,纯Cu稳定性差、产品选择性低、过电位高,阻碍了工业级多碳产品的生产。构筑Cu基串联催化剂是提高CO2RR性能的一种有前途的策略。本文首先介绍电催化CO2RR的反应路线和串联机理。然后,系统地总结铜基串联催化剂对电催化CO2RR的最新研究进展。最后,提出合理设计和可控合成新型电催化CO2RR串联催化剂面临的挑战和机遇。  相似文献   
98.
The photo-induced ultrafast electron dynamics in both anatase and rutile TiO\begin{document}$_{2}$\end{document} are investigated by using the Boltzmann transport equation with the explicit incorporation of electron-phonon scattering rates. All structural parameters required for dynamic simulations are obtained from ab initio calculations. The results show that although the longitudinal optical modes significantly affect the electron energy relaxation dynamics in both phases due to strong Fr?hlich-type couplings, the detailed relaxation mechanisms have obvious differences. In the case of a single band, the energy relaxation time in anatase is 24.0 fs, twice longer than 11.8 fs in rutile. This discrepancy is explained by the different diffusion distributions over the electronic Bloch states and different scattering contributions from acoustic modes in the two phases. As for the multiple-band situation involving the lowest six conduction bands, the predicted overall relaxation times are about 47 fs and 57 fs in anatase and rutile, respectively, very different from the case of the single band. The slower relaxation in rutile is attributed to the existence of multiple rate-controlled steps during the dynamic process. The present findings may be helpful to control the electron dynamics for designing efficient TiO\begin{document}$_{2}$\end{document}-based devices.  相似文献   
99.
Russian Journal of Organic Chemistry - The reduction of 1-(adamantan-1-yl)-2-azidoethan-1-one oxime with LiAlH4 gave racemic 1-(adamantan-1-yl)ethane-1,2-diamine, which was resolved with l-tartaric...  相似文献   
100.
Cai  Mengmeng  Yao  Lijuan  Zhu  Man  Tao  Peng  Nan  Ruihua  Jian  Zengyun 《Journal of Thermal Analysis and Calorimetry》2021,143(4):2911-2918
Journal of Thermal Analysis and Calorimetry - Differential scanning calorimetry was used to investigate the non-isothermal crystallization kinetics of the Fe76.5Nb3B20Cu0.5 glassy alloys. The...  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