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   127650篇
  免费   20725篇
  国内免费   12462篇
化学   85063篇
晶体学   1413篇
力学   8524篇
综合类   740篇
数学   15072篇
物理学   50025篇
  2024年   434篇
  2023年   2504篇
  2022年   4321篇
  2021年   4828篇
  2020年   4973篇
  2019年   4846篇
  2018年   4231篇
  2017年   3962篇
  2016年   6153篇
  2015年   5847篇
  2014年   7145篇
  2013年   9335篇
  2012年   11235篇
  2011年   11590篇
  2010年   7719篇
  2009年   7444篇
  2008年   7926篇
  2007年   7231篇
  2006年   6564篇
  2005年   5532篇
  2004年   4118篇
  2003年   3256篇
  2002年   2939篇
  2001年   2423篇
  2000年   2208篇
  1999年   2605篇
  1998年   2303篇
  1997年   2174篇
  1996年   2316篇
  1995年   1898篇
  1994年   1799篇
  1993年   1465篇
  1992年   1306篇
  1991年   1213篇
  1990年   995篇
  1989年   728篇
  1988年   595篇
  1987年   484篇
  1986年   458篇
  1985年   401篇
  1984年   297篇
  1983年   202篇
  1982年   183篇
  1981年   124篇
  1980年   84篇
  1979年   48篇
  1978年   34篇
  1976年   37篇
  1975年   33篇
  1974年   45篇
排序方式: 共有10000条查询结果,搜索用时 12 毫秒
21.
The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH4 > N2 > O2 > CO2. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO2 decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO2‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004  相似文献   
22.
Cellulose was dissolved in 6 wt % NaOH/4 wt % urea aqueous solution, which was proven by a 13C NMR spectrum to be a direct solvent of cellulose rather than a derivative aqueous solution system. Dilute solution behavior of cellulose in a NaOH/urea aqueous solution system was examined by laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 6 wt % NaOH/4 wt % urea aqueous solution at 25 °C was [η] = 2.45 × 10?2 weight‐average molecular weight (Mw)0.815 (mL g?1) in the Mw region from 3.2 × 104 to 12.9 × 104. The persistence length (q), molar mass per unit contour length (ML), and characteristic ratio (C) of cellulose in the dilute solution were 6.0 nm, 350 nm?1, and 20.9, respectively, which agreed with the Yamakawa–Fujii theory of the wormlike chain. The results indicated that the cellulose molecules exist as semiflexible chains in the aqueous solution and were more extended than in cadoxen. This work provided a novel, simple, and nonpollution solvent system that can be used to investigate the dilute solution properties and molecular weight of cellulose. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 347–353, 2004  相似文献   
23.
Non-dispersive atomic fluorescence spectrometry (NDAFS) coupled with vapor generation (VG) sample introduction was applied to the determination of the concentrations of hazardous heavy metals, such as arsenic, cadmium, lead and mercury, in seawater, soils and total airborne particulate matter (PM) collected around the Xiamen area in China. Almost 100% sample introduction efficiency was achieved by using thiourea and ascorbic acid for the pre-reduction of As(V) to As(III), K3Fe(CN)6 and tartaric acid for pre-oxidation of Pb(II) to Pb(IV), and masking the interferences arising from the co-existing transition metals to As, Cd, Hg and Pb during their vapor generation process. Moreover, a novel sample pretreatment device was developed to avoid the loss of mercury, lead, cadmium and arsenic during sample pretreatment. With such methods, the detection limit (DL) of arsenic, cadmium, lead and mercury was down to 0.08, 0.03, 0.05, 0.01 ng mL(-1) (3sigma), respectively. The relative standard deviations (RSD, n = 11) for arsenic, cadmium, lead and mercury at 10 ng mL(-1) were 0.9%, 1.6%, 1.3% and 2.0%, respectively. The concentrations of hazardous heavy metals in the environmental samples collected in Xiamen, China are in the range from 0.02 +/- 0.001 ng mL(-1) in seawater to 15.3 +/- 0.2 microg g(-1) in soils. Besides flame/GF-AAS and ICP-AES/MS, VG-NDAFS should be another choice for the determination of hazardous heavy metals in environmental samples.  相似文献   
24.
The electrochemical behavior of the copper-tyrosine complex has been studied by linear-sweep adsorption voltammetry. In 0.02 mol/L Na2HPO4 buffer solution (pH=9.6), the complex can be adsorped on a hanging mercury drop electrode and reduced at a peak potential of about –0.42 V (vs. SCE). The secondary derivative peak height is linear proportional to the concentration of tyrosine in the range 1.0×10–7–5.0×10–5 mol/L. The detection limit is 5×10–8 mol/L.Project supported by the Provincial Science Foundation of Shandong Province  相似文献   
25.
用中子活化法相对于54Fe(n,P)54Mn反应,在13.50—14.80MeV中子能区测量了Ba(n,x)134Cs,134Ba(n,2n)133Ba,140Ce(n,2n)139Ce,142Ce(n,2n)141Ce和23Na(n,2n)22Na的反应截面.并将所测的结果和其他作者的结果进行了比较,中子能量是用90Zr(n,2n)89m+gZr反应和93Nb(n,2n)92mNb反应截面比法测定的。  相似文献   
26.
We study a generalization of the notion of the chromatic number of a graph in which the colors assigned to adjacent vertices are required to be, in a certain sense, far apart. © 1993 John Wiley & Sons, Inc.  相似文献   
27.
Ronghua Li  Ruiting Chen  Wenji Wang 《Ionics》2002,8(5-6):412-415
Perovskite-type lithium fast ion conductors of Li3xLa0.67−xScyTi1−2yNbyO3 system were prepared by solid state reaction. X-Ray powder diffraction shows that perovskite solid solution form in the ranges of x=0.10, y≤0.10. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10−4 S·cm−1 and 10−5 S·cm−1 at 25 °C respectively. The compositions have low bulk activation energies of about 17 kJ/mol in the temperature ranges of 298 – 523 K and total activation energies of about 37 kJ/mol in the temperature ranges of 298 – 523 K.  相似文献   
28.
α‐Cyclodextrin (α‐CD) has been complexed with various poly(ethylene glycol) (PEG) derivatives in aqueous solution. It has been found that the end groups of PEG derivatives affect the complexation kinetics greatly, but have only a little influence on the thermodynamic behavior. By increasing the hydrophobicity of end groups, the complexation speeds up rapidly. On the other hand, the bulky end groups slow down the threading of polymeric guests into the cavity of CD. By changing the hydrophobicity and the size of end groups, the complexation rate can be adjusted in the range of several orders of magnitudes, which should be quite useful in the design of new supramolecular systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2050–2057, 2006  相似文献   
29.
Recently, molecular imaging has been rapidly developed to studyphysiological and pathological processes in vivo at the cellularand molecular levels. Among molecular imaging modalities, opticalimaging has attracted a major attention for its unique advantages.In this paper, we establish a mathematical framework for multispectralbioluminescence tomography (BLT) that allows simultaneous studiesof multiple optical reporters. We show solution existence, uniquenessand continuous dependence on data as well as the limiting behaviourswhen the regularization parameter approaches zero or when thepenalty parameter approaches infinity. Then, we propose twonumerical schemes for multispectral BLT and derive error estimatesfor the corresponding solutions.  相似文献   
30.
The crystal and molecular structure of the complex containing cobalt-carbon and iron-sulfur cluster cores, (μ-p-CH3C6H4C2S) (μ-n-C3H7S)Fe2(CO)6Co2(CO)6, has been determined by X-ray diffraction method. The crystals are triclinic, space group P&1bar;, with a — 9.139(2), b=9.610(1), c-17.183(2) Å, α = 84.36(1), β-89.45(1), γ=88.15(1)°, V-1501.0 Å3; Z=2, Dc=1.74 g/cm3. R=0.072, Rw=0.081. The results of the structure determination show a cobalt-carbon cluster core formed through the reaction of (μ-p-CH3C6H4C2S)(μ-n-C3H7S)Fe2(CO)6 with Co2(CO)8. In the cobalt-carbon cluster core, the bond length of the original C≡C lengthened to 1.324 Å which is close to the typical value of carbon-carbon double bond. The groups connecting the carbons of the cluster core are in cis position and lie on the opposite side of cobalt atoms. In this complex, the conformation of —SC3H7 is e-type, while that of —SC2C6H4CH3 is a-type.  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