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   7535篇
  免费   1563篇
  国内免费   951篇
化学   5454篇
晶体学   117篇
力学   436篇
综合类   94篇
数学   859篇
物理学   3089篇
  2024年   21篇
  2023年   227篇
  2022年   330篇
  2021年   343篇
  2020年   446篇
  2019年   410篇
  2018年   338篇
  2017年   316篇
  2016年   427篇
  2015年   427篇
  2014年   463篇
  2013年   626篇
  2012年   716篇
  2011年   714篇
  2010年   516篇
  2009年   467篇
  2008年   449篇
  2007年   396篇
  2006年   332篇
  2005年   301篇
  2004年   252篇
  2003年   205篇
  2002年   184篇
  2001年   154篇
  2000年   116篇
  1999年   138篇
  1998年   107篇
  1997年   93篇
  1996年   96篇
  1995年   78篇
  1994年   67篇
  1993年   45篇
  1992年   36篇
  1991年   46篇
  1990年   41篇
  1989年   26篇
  1988年   21篇
  1987年   18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   4篇
  1978年   2篇
  1964年   1篇
  1959年   1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 765 毫秒
181.
Ti基IrO2+Ta2O5阳极在H2SO4溶液中的电解时效行为   总被引:5,自引:0,他引:5  
研究了450 ℃制备所得Ti/70%IrO2 30%Ta2O5(摩尔分数)高寿命阳极在H2SO4溶液电解过程中电极的物理、化学及电化学性能的时效行为.结果发现,整个电解过程可分为“活化”、“稳定”及“失效”三个阶段.在“活化”及“稳定”区内主要发生电极表面活性氧化物的溶解,涂层中IrO2金红石相的(110)、(101)晶面择优取向随电解时间延长而减弱,而(002)晶面择优增强.但是在“失效区”内,各晶面的择优程度却不随电解时间的变化而变化,这表明在“失效区”内氧化物的损失机制发生了变化.电化学阻抗谱测试表明,电极的析氧电化学反应电阻随电解时间的延长发生缓慢而连续的上升,而整个电极的物理阻抗在“失效区”内却发生突升现象.X射线衍射分析(XRD)表明,随电解时间的延长TiO2金红石相的衍射强度增大,达“失效区”时衍射强度发生突升.根据实验现象特别是“失效区”内阳极的时效行为提出高寿命Ti基氧化物涂层阳极的失效机制.  相似文献   
182.
12兆瓦热电气多联产装置的开发   总被引:8,自引:1,他引:8  
介绍了为解决某钢铁企业的中热值煤气,蒸汽和电的短缺而开发的一台12MW的热电气多联产装置,在该系统中,把一台流化床气化炉和一台75t/h循环流化床锅炉结合在一起,从而实现煤气和蒸汽联产,在详细介绍了该装置的设计思想和结构特点的同时,用所建的热电气多联产模型对该装置包括煤气产量,煤气成分,煤气热值和系统运行温度等在内的性能参数进行了预测。  相似文献   
183.
Photocycloadditionof(4-methyl-7-coumarinyl)OxyaceticAcidPropanediolDiesterandX-rayCrystalStructureofProductDuDa-Ming;WangYong...  相似文献   
184.
Intercalated nanocomposites comprised of poly(propylene carbonate) (PPC) and organo-vermiculite (OVMT) was first prepared via direct melt compounding of the alkali-vermiculite intercalated host with PPC in a twin rotary mixer. The dispersion and morphologies of OVMT within PPC were investigated by X-ray diffraction and transmission electron microscopic techniques. The results revealed the formation of intercalated-exfoliated vermiculite sheets in the PPC matrix. Because of the thermally sensitive nature of PPC, thermal degradation occurred during the melt compounding. The degradation led to a deterioration of the mechanical properties of the nanocomposites. Tensile test showed that the yield strength and modulus of the nanocomposites decrease with increasing vermiculite content. The degradation mechanism was discussed according to the results of GPC and TGA measurements.  相似文献   
185.
The high-quality tubular titania MF membranes are successfully prepared by dip-coating techniques and systematically investigated with regard to their corrosive resistances. The experiments show that dispersants PAA and anatase powder were preferably employed to prepare desired suspensions with solid loading 10–15 wt.% and that suspensions properties significantly affect the final membranes quality. The titania MF membranes with pure water permeability 742.42 l m−2 h−1 bar−1 and 0.1 μm pore diameter have been obtained using the prepared suspensions. The corrosion resistance of titania membranes exhibits that the anatase layers are more stable than the alumina supports in boiling corrosive medium and that the poor quality titania MF membranes become more deteriorated due to its top layer pore blockages and fouling layer formation, which provides a wide range of practical application fields in very hash environments with reliable data supports.  相似文献   
186.
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   
187.
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   
188.
使用密度泛函理论B3LYP方法和6-31G(d,p)、6-31+G(d,p)、6-311G(d,p)及6-311+G(d,p)基组,分别对2-C5H10+和1-C5H10+的各种构象进行了几何构型优化,并用B3LYP/6-311G(d,p)进行了频率分析计算.计算预言1-C5H10+具有非平面构型,与以往报导的从头算计算结论相反.在两个自由基阳离子的各种构象的B3LYP几何构型上,进行了B3LYP和UMP2(full)方法的超精细偶合常数计算,得到了比以往更好的结果.  相似文献   
189.
吴萌  吴锋  栾和林  陈人杰 《化学学报》2005,63(9):787-790
使用2,6-二苯基-4-(2,4,6-三苯基-1-吡啶鎓)苯氧内盐染料(Reichardt's Dye)研究锂离子电池中非水电解质溶剂碳酸酯的极性,并测量极性经验参数ET(30)碳酸乙烯酯为48.6,碳酸丙烯酯为46.1,2,3-碳酸丁烯酯为45.7,碳酸二甲酯为39.0,碳酸甲乙酯为37.3,碳酸二乙酯为37.0.LiClO4加入到碳酸酯溶剂中,显色剂受到离子的盐效应影响,表现为溶液体系的ET(30)值增加,极性增大.由于溶液中粒子间的相互作用不同,环碳酸酯与链状碳酸酯极性变化趋势不同.极性大的溶剂易形成Ar-O-…solvent…Li+结构,起到缓冲作用,抑制了显色剂的酚氧基与Li+直接作用.  相似文献   
190.
Chromate conversion coatings (CCCs) on AA7075‐T6 were characterized using scanning electron microscopy, focused ion beam sectioning and scanning transmission electron microscopy with nano‐electron dispersive spectroscopy line profiling. The thickness and composition of the CCC was different at different locations on the heterogeneous microstructure of AA7075‐T6. The coating formed on the matrix phase was much thicker than that formed on the coarse Al–Cu–Mg, Al–Fe–Cu and Mg–Si intermetallic particles. Nano‐electron dispersive spectroscopy line profiling indicated that the coating on the Al–Fe–Cu particles was similar to the CCC formed on the phase matrix, primarily a chromium oxide. However, the coatings on the Al–Cu–Mg and Mg–Si particles were mixed Al/Mg/Cr oxide and Mg oxide, respectively. The growth of CCC followed a linear‐logarithmic kinetic rate law. The observations of this study support the sol‐gel model of CCC formation. Copyright © 2004 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