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   1880篇
  免费   110篇
  国内免费   402篇
化学   1906篇
晶体学   27篇
力学   32篇
综合类   37篇
数学   96篇
物理学   294篇
  2024年   3篇
  2023年   14篇
  2022年   68篇
  2021年   63篇
  2020年   68篇
  2019年   56篇
  2018年   52篇
  2017年   91篇
  2016年   88篇
  2015年   70篇
  2014年   94篇
  2013年   183篇
  2012年   115篇
  2011年   104篇
  2010年   98篇
  2009年   105篇
  2008年   120篇
  2007年   113篇
  2006年   100篇
  2005年   123篇
  2004年   87篇
  2003年   67篇
  2002年   69篇
  2001年   60篇
  2000年   39篇
  1999年   50篇
  1998年   41篇
  1997年   39篇
  1996年   40篇
  1995年   16篇
  1994年   28篇
  1993年   15篇
  1992年   26篇
  1991年   17篇
  1990年   18篇
  1989年   18篇
  1988年   14篇
  1987年   5篇
  1986年   4篇
  1985年   1篇
  1984年   1篇
  1982年   5篇
  1981年   1篇
  1980年   1篇
  1977年   1篇
  1974年   1篇
排序方式: 共有2392条查询结果,搜索用时 15 毫秒
201.
SiCp尺寸对SiCp/Cu基复合材料抗磨性能的影响   总被引:8,自引:1,他引:8  
以纳米级(30nm)、亚微米级(130nm)、微米级(14μm)3种粒径的SiCp和微米级(10μm)铜粉为原料,用冷压烧结和热挤压方法制备了纳米、亚微米和微米级SiCp/Cu复合材料,考察了SiCp尺寸对SiCp/Cu复合材料抗磨性能的影响.结果表明,不同尺寸的SiCp颗粒作为增强相均能显著改善铜基复合材料的抗磨性能;随着SiCp尺寸的增大,SiCp/Cu复合材料的抗磨性能提高幅度显著增大,但偶件磨损表面的犁削加剧;以微米级SiCp为原料制备的SiCp/Cu复合材料的抗磨性能最佳,但其导致偶件40Cr钢犁削作用显著加剧.从摩擦副整体的摩擦磨损性能角度而言,宜采用SiCp尺寸为130nm的SiCp/Cu复合材料同40Cr钢组成摩擦副.  相似文献   
202.
刘海弟  陈运法 《无机化学学报》2010,26(12):2195-2202
研究了以聚乙二醇为模板剂、正硅酸乙酯(TEOS)为硅源制备铁掺杂的多孔二氧化硅的方法。开发了一步完成多孔材料制备和掺杂的新工艺。研究了不同的铁元素掺杂量对样品性能的影响。采用低温氮吸附、SEM、FTIR、XRD方法表征了样品的比表面、孔结构和表面基团等信息。最优样品比表面大于700 m2·g-1、孔容大于1 mL·g-1。研究了所制备的多孔材料和双氧水共同降解水中苯酚的能力,研究发现负载铁的催化剂可以在很宽的pH值范围内(3~8)和双氧水协同使用,这可能是因为铁元素被牢固负载于多孔二氧化硅的骨架上,避免了其在高pH值下发生的水解反应。  相似文献   
203.
根据卟啉类试剂的特性,从其在分析化学中的显色性、荧光性、超分子特性、电化学活性等方面,简要综述了近几年来卟啉类试剂在分析化学中的应用进展情况.  相似文献   
204.
纤维素基水处理剂研究进展   总被引:1,自引:0,他引:1  
根据纤维素基水处理剂的结构特点对其进行了分类和划分,从载体形态、接枝链与载体接枝方法、功能吸附/脱附基团选取及功能化方法、吸附/脱附性能的影响因素和脱附方法等五个方面综述了国内外在该领域的研究现状;并对其发展前景进行了展望.  相似文献   
205.
Ethene and two kinds of nitrating reagents (HNO3 and N2O5) were included in respective molecular systems, which progressed through a two‐stage electrophilic and free radical nitrosubstitution, resulting in the corresponding nitroethene compounds. Subsequent halogenation (using Cl2 and Br2) and amination (using ammonia) were then performed, also by electrophilic and radical substitution, to produce the target 1,1‐diamino‐2,2‐dinitroethene (FOX‐7) derivatives. All transition state species were identified using a two‐ or three‐structure Synchronous Transit‐Guided Quasi‐Newton between the Cartesian coordinates of the related molecular systems at specific reaction stages. The modeling results suggest that N2O5 is the better agent for nitration and bromine is suitable for use in halogenation. The comparable activation energies throughout the reaction stages were considered to imply the most feasible pathways of FOX‐7 synthesis. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010  相似文献   
206.
A new low molecular mass organogelator 1 containing 2-(2′-hydroxyphenyl)benzoxazole (HPB) group with long alkyl chain was synthesized by the reaction with 5-amino-2-(2′-hydroxy-4′-methylphenyl)benzoxazole and dodecyl isocyanate in THF at room temperature. The reversible gelation ability of 1 was investigated using a heating-cooling method in various organic solvents. The stable organogel was formed from carbon tetrachloride or from cyclohexane at the concentration as low as 0.9%. The self-assembled supramolecular gel structure formed by non-covalent bonding was confirmed with field emission-scanning electron microscope (FE-SEM) exhibiting fibril- or ribbon-shaped structure depending on the solvent used. Regarding the aggregation-induced emission enhancement (AIEE) phenomenon, the optical properties were investigated in its solution and gelled state. The detecting properties of resulting organogel toward nerve gas simulant were monitored by UV-vis and fluorescence spectroscopy. Both color change from colorless to greenish yellow and disruption of gel structure resulting from alteration in intermolecular forces were observed upon the exposure to nerve gas simulant.  相似文献   
207.
A series of Cr(III) dimers were synthesized from a parent compound [Cr2(μ-oxo)21,2-C4O4)2(H2O)4]·2H2O (I) by ligand substitution. The compounds have been analyzed using variable frequency EPR (9–110 GHz) and magnetic susceptibility as a function of field (0–9 T) and temperature (1.9–300 K) to obtain their electronic g-values, exchange energies, and zero-field parameters. The parent compound exhibits a broad maximum around 34 K characteristic of a dimer with antiferromagnetic coupling that fit the Van Vleck susceptibility model well. It was found that the maxima could be tuned from 34 to 80 K by ligand substitution of the waters. Each compound possesses a characteristic color spanning the range of teal to pink. The g-value of each compound was found to be ∼1.98 using spectral simulation. The DMSO derivative is water soluble and has a high LC50 for PC3 cancer cells, suggesting its use as a magnetic resonance imaging agent. X-ray crystal structure of the DMSO derivative [Cr2(μ-oxo)21,2-C4O4)2(C2H6SO)4]·2H2O (II) revealed that the DMSO ligands are equatorial, and the squarate groups bridge the two chromiums. This is in contrast to the previously proposed structure of the parent compound where the water ligands were axial and the equatorial squarate groups did not bridge the chromiums. These compounds are interesting because of their ease of synthesis, and their wide range of magnetic behavior. The compounds are good probes into antiferromagnetic dimer exchange by controlling the ligand field surrounding the superexchange pathway present in the molecule.  相似文献   
208.
Ansamitocin P‐3 is a potent anti‐tumor maytansinoid found in Actinosynnema pretiosum. However, due to the complexity of the fermentation broth of Actinomycete, how to effectively separate ansamitocin P‐3 is still a challenge. In this study, both analytical and preparative high‐performance counter‐current chromatography were successfully used to separate and purify ansamitocin P‐3 from fermentation broth. A total of 28.8 mg ansamitocin P‐3 with purity of 98.4% was separated from 160 mg crude sample of fermentation broth in less than 80 min with the two‐phase solvent system of hexane–ethyl acetate–methanol–water (0.6:1:0.6:1, v/v/v/v). The purity and structural identification were determined by HPLC, 1H NMR, 13C NMR and mass spectroscopy.  相似文献   
209.
The application of nanotechnology in medicine research has significant potential in modern biomedical research,disease diagnosis and therapy.Organic fluorophore-based detection techniques have been widely used as imaging and signal transduction tools for the detection of trace levels of analytes.The photosensitivity of the fluorophores,however,limits their application in such complex environments as living bio-systems where degradation or photobleaching occurs.Inorganic nanoparticles have unique and stable ...  相似文献   
210.
The effects of β‐cyclodextrin containing silicone oligomer(CDS), as a synergistic agent, on the flame retardancy and mechanical properties of intumescent flame retardant polypropylene composites were studied by adding different amounts of CDS in intumescent flame retardants. The limiting oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) were utilized to evaluate the synergistic effects of CDS in the composites. It was found that after a little amount of CDS partially replaced a charring‐foaming agent (CFA) in IFR, LOI values of the composites were enhanced and they obtained a UL‐94 V‐0 rating. IFR system containing 6.25wt% CDS presented the best flame retardancy in PP. The experimental results obtained from LOI and UL‐94, TGA, SEM, and mechanical properties indicated that the combination of CDS and CFA presents synergistic effects in flame retardancy, char formation, and mechanical properties of the composites. This is probably due to different structures of polyhydroxyl macromolecules (CDS and CFA), the existence of dimethyl silicone group in CDS, and the toughness of epoxy silicon chain in CDS. SEM results proved that the interfacial compatibility between IFR and PP was improved by CDS. Copyright © 2009 John Wiley & Sons, Ltd.  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