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   2456篇
  免费   317篇
  国内免费   168篇
化学   672篇
晶体学   9篇
力学   625篇
综合类   26篇
数学   364篇
物理学   1245篇
  2024年   2篇
  2023年   21篇
  2022年   39篇
  2021年   52篇
  2020年   55篇
  2019年   57篇
  2018年   49篇
  2017年   49篇
  2016年   51篇
  2015年   43篇
  2014年   110篇
  2013年   190篇
  2012年   124篇
  2011年   133篇
  2010年   133篇
  2009年   165篇
  2008年   183篇
  2007年   169篇
  2006年   185篇
  2005年   146篇
  2004年   153篇
  2003年   109篇
  2002年   99篇
  2001年   73篇
  2000年   66篇
  1999年   52篇
  1998年   69篇
  1997年   56篇
  1996年   49篇
  1995年   47篇
  1994年   34篇
  1993年   21篇
  1992年   26篇
  1991年   26篇
  1990年   25篇
  1989年   17篇
  1988年   16篇
  1987年   9篇
  1986年   8篇
  1985年   9篇
  1984年   6篇
  1983年   3篇
  1982年   5篇
  1981年   1篇
  1980年   1篇
  1978年   3篇
  1977年   1篇
  1973年   1篇
排序方式: 共有2941条查询结果,搜索用时 31 毫秒
101.
Rayleigh–Taylor instability of a heavy fluid supported by a lighter one through porous medium, in the presence of a uniform, horizontal and oscillating magnetic field is studied. The fluids are taken as viscous (obeying Darcy's law), uniform, incompressible, and infinitely conducting. The amplitude of the oscillating part of the field is taken to be small compared with its steady part. The dispersion relation is obtained in the form of a third-order differential equation, with time as the independent variable and with periodic coefficients, for the vertical displacement of the surface of separation of the two fluids from its equilibrium position. The oscillatory magnetic field of frequency ωω and steady part H0H0 has a stabilizing influence on a mode of disturbance which is unstable in a steady magnetic field of strength H0H0. It is found that the oscillatory magnetic field and porosity of the porous medium have stabilizing effects, while the medium permeability has a destabilizing influence on the considered system. For a constant value of any of these physical parameters, the system has been found to be unstable (for small wavenumbers) as well as stable afterwards after a definite wavenumber value. The marginal stability case of parametric resonance holds when M1=M2=0M1=M2=0 (and hence m=0m=0), in which the characteristic exponents, and the corresponding solutions for uu break down, is also investigated in detail. It is found, to order ??, that the effect of an oscillating magnetic field has no stabilizing influence on a disturbance which is marginally stable in the steady magnetic field; while to order ?2?2, and when the magnetic field oscillates, a resonance between this mode of disturbances and the oscillating field leads to instability when ρ2>ρ1ρ2>ρ1. It is found also, in this resonant case, that all the constant or varied physical parameters, mentioned above, have destabilizing influences on the considered system. Finally, the other two resonance points appear in non-porous media (i.e., when m=±iωm=±iω and m=±2iωm=±2iω), are disappeared here due to the presence of the porous medium.  相似文献   
102.
Metallic glass (MG) is amorphous and has some outstanding properties such as ultrahigh strength, superior elasticity, and excellent thermo-plasticity. However, as MG is relatively new to the metal family, the relationship between its physical properties and amorphous structure is still unclear. This article aims to provide an insightful discussion through a comprehensive review about the investigations in the past few decades on the scientific mechanisms of this class of material. The discussion of the paper will include the following key aspects: (1) the formation mechanism of an amorphous structure through glass transition, (2) the structural characterization and models, (3) the micromechanics of plastic event and shear band, and (4) the correlation between the amorphous structure and its mechanical properties.  相似文献   
103.
The voltammetric behavior of a glassy carbon electrode modified with multiwalled carbon nanotubes (MWCNTs) and Au particles was studied in alkaline medium towards the electrooxidation of some carbohydrates used as model compounds. The influence of carbohydrate concentration and scan rate on peak potentials, peak currents, etc., observed at the modified electrode was evaluated and critically discussed. The Au particles dispersed into multiwalled carbon nanotubes structures showed favorable electrocatalytic and analytical properties towards the electrooxidation of xylose and glucose molecules. Atomic force microscopy performed on the resulting modified electrode showed a well‐efficient 3D distribution of Au active particles having sharp‐edged and elongated grains along bundles of the MWCNTs. The three‐dimensional MWCNT‐Au composite structure of the catalyst act as a promoter to enhance the diffusive character of recorded currents and probably also increases the rate of the heterogeneous electron transfer of the electrooxidation process considered.  相似文献   
104.
A highly efficient strategy for the formation of medium‐sized‐ring ethers and amines based on a gold‐catalyzed cascade reaction, involving enynyl ester isomerization and intramolecular [3+2] cyclization, has been developed. Various multisubstituted medium‐sized‐ring unsaturated ethers and amines were obtained through this transformation. This method represents one of the relatively few transition metal catalyzed intramolecular cycloaddition reactions for medium‐sized ring synthesis.  相似文献   
105.
螯合辅助溶剂挥发共组装法制备的炭-氧化铝复合材料为载体,分别使用水、乙醇或二者混合物为氯铂酸的分散介质,浸渍制备炭-氧化铝复合材料负载Pt催化剂.通过XRD,N2物理吸附以及TEM表征可知,乙醇作为浸渍溶剂时,最有利于Pt的分散,而混合溶剂浸渍制备的催化剂Pt颗粒最大.2-氧-4-苯基丁酸乙酯不对称加氢反应结果表明,氯铂酸水溶液浸渍得到的催化剂Pt纳米粒子的粒径有利于获得高的光学选择性,催化剂经辛可尼丁修饰后,以乙酸为反应溶剂,可获得最高84.8%的光学选择性.此外,该催化剂重复利用性能优异,可以重复利用22次,活性没有下降.  相似文献   
106.
基于氮掺杂碳载铁复合物的锌空电池氧阴极催化剂   总被引:1,自引:0,他引:1  
迫在眉睫的环境和能源问题推动人类探索可行、可靠和可再生的能源技术.锌-空气电池和氢氧燃料电池等器件显示出高能量转换效率,但是仍有许多难题有待克服,例如阴极侧上缓慢的氧还原反应(ORR),以及高昂的成本极大地限制了铂基催化剂在商业上的广泛应用.因此,开发高性能的廉价ORR催化剂具有重要意义.过渡金属碳氮化合物(M-N-C, M=Co, Fe等)成为最有希望替代铂基催化剂的一类材料, M-N-C催化剂可以通过直接热解含有过渡金属、氮和碳物种的前驱体合成.然而热解时金属原子易团聚,多孔结构不能被有效地控制,导致相对较差的催化活性.目前, MOF衍生的催化剂在能源转化和储存技术中得到了广泛的关注,其具有丰富的氮含量、高比表面积和可调的孔道结构等特点.本文报道了一种简便可靠可控的合成铁氮共掺杂碳十二面体纳米结构催化剂的方法,并作为阴极电催化剂用于锌空气电池中,测试结果证实,合成的铁氮共掺杂的纳米碳具有与铂基材料相当的活性和更加优异的稳定性.表面吸附了的邻菲罗啉铁的ZIF-8在碳化过程中,氮基团能够结合铁形成Fe Nx结构单元,因此可得到铁氮共掺杂的电催化剂.粉末X射线衍射,扫描电镜证实ZIF-8的成功合成.经过热解得到的催化剂中Fe Nx或Fe Cx衍射峰较弱,表明样品中铁含量较低,存在部分无定型铁.通过拉曼光谱分析发现,引入的邻菲罗啉在热解过程中诱导了缺陷的形成,所以Fe-NCDNA-0的ID/IG比值明显高于NC.同时ID/IG随着铁含量的增加而减少,这是因为铁可以诱导石墨化,诱导效应随着铁含量的增加而增加.分析氮气吸附-脱附等温线得出,引入邻菲罗啉之后,比表面积增加;而铁的引入因其占据了微孔结构,导致比表面积下降.同时电镜证实Fe-NCDNA-2具有较大的形貌扭曲,使得该材料具有较大的比表面积.系统的电化学研究表明,氮掺杂有利于增强ORR活性,在引入铁之后形成高效的活性中心会进一步提高催化性能.因此, Fe-NCDNA-2在碱性条件下表现出优异的ORR性能.线性扫描伏安法曲线表明,铁氮共掺杂的材料表现出与Pt/C相似的性能,其中Fe-NCDNA-2的半波电位(E1/2)为0.863 V,比商业Pt/C的电位更正(E1/2=0.841 V).同时, Fe-NCDNA-2具有更加优异的稳定性,测试30000 s后的电流保持率为80%(Pt/C:64%).在中性介质中,合成的材料也展示了较高的ORR活性.Fe-NCDNA-2的E1/2=0.715 V,催化30000 s后电流保持率77%,均优于商业Pt/C催化剂.组装的锌空气电池进一步验证其作为氧还原催化剂实际应用的可行性.相比于以Pt/C为催化剂做空气阴极的电池,以Fe-NCDNA-2组装的电池表现出更高的开路电压,更高的功率密度(184 m Wcm^-2),以及更加优异的充放电循环稳定性.该工作也有利于启发研究人员探索类似的氮掺杂过渡金属碳材料在各种催化上的应用.  相似文献   
107.
A unified low‐temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes—polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho‐condensed arrangements of fused benzene rings—is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas‐phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer‐selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free‐radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry.  相似文献   
108.
The analytical infinite series solution of submicron particle transport in a circular tube bounded by a porous wall, such as a pinhole, is determined under the slip velocity boundary condition, and the solution is verified by using the experimental data in the previous studies for the specific cases. The results show that particle penetration rate increases with the increase of the porous parameter, the axial pressure drop, and the pinhole radius, whereas it decreases with increasing the pinhole length. The penetration rate of nano-particles are more sensitive to the variation of these parameters. However, the differences between the penetrations of particles ranging from 0.3 μm to 1 μm are not evident because the diffusion becomes weak gradually in this size range. In addition, a further comparison is performed between the analytical solution and the existing studies, and approximate expressions are presented for accurate calculation of particle penetration rate through pinholes appearing in porous materials including filter devices and masks.  相似文献   
109.
 在无溶剂及二(2-乙基己基)丁二酸酯磺酸钠(AOT)/异辛烷/磷酸盐缓冲液微乳液体系中,研究了黑曲霉脂肪酶催化红花油水解反应的动力学. 结果表明,无溶剂及微乳液体系中反应的活化能分别为32.205和7.391 kJ/mol. 酶在无溶剂体系中的热稳定性高于微乳液中. 无溶剂及微乳液体系中的表观米氏常数分别为0.135和0.101 mol/L. 在两种体系中,乙醇对水解反应的抑制作用均为竞争性可逆抑制,且均在底物浓度大于0.819 mol/L时出现底物抑制现象. 结合胶团催化理论和酯键水解机理对两种体系中酶水解性能的差异进行了解释.  相似文献   
110.
研磨作为4H碳化硅(4H-SiC)晶片加工的重要工序之一,对4H-SiC衬底晶圆的质量具有重要影响。本文研究了金刚石磨料形貌和分散介质对4H-SiC晶片研磨过程中材料去除速率和面型参数的影响,基于研磨过程中金刚石磨料与4H-SiC晶片表面的接触情况,推导出简易的晶片材料去除速率模型。研究结果表明,磨料形貌显著影响4H-SiC晶片的材料去除速率,材料去除速率越高,晶片的总厚度变化(TTV)越小。由于4H-SiC中C面和Si面的各向异性,4H-SiC晶片研磨过程中C面的材料去除速率高于Si面。在分散介质的影响方面:水基体系研磨液的Zeta电位绝对值较高,磨料分散均匀,水的高导热系数有利于控制研磨过程中的盘面温度;乙二醇体系研磨液的Zeta电位绝对值小,磨料易发生团聚,增大研磨过程的磨料切入深度,晶片的材料去除速率提高,晶片最大划痕深度随之增大。  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