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   85790篇
  免费   1719篇
  国内免费   1623篇
化学   30288篇
晶体学   921篇
力学   7150篇
综合类   77篇
数学   32738篇
物理学   17958篇
  2023年   190篇
  2022年   310篇
  2021年   356篇
  2020年   440篇
  2019年   447篇
  2018年   10692篇
  2017年   10528篇
  2016年   6434篇
  2015年   1267篇
  2014年   788篇
  2013年   971篇
  2012年   4469篇
  2011年   11235篇
  2010年   6152篇
  2009年   6500篇
  2008年   7131篇
  2007年   9172篇
  2006年   616篇
  2005年   1629篇
  2004年   1770篇
  2003年   2186篇
  2002年   1261篇
  2001年   429篇
  2000年   452篇
  1999年   285篇
  1998年   292篇
  1997年   245篇
  1996年   301篇
  1995年   221篇
  1994年   172篇
  1993年   174篇
  1992年   109篇
  1991年   112篇
  1990年   94篇
  1989年   108篇
  1988年   87篇
  1987年   82篇
  1986年   84篇
  1985年   82篇
  1984年   61篇
  1983年   51篇
  1982年   51篇
  1981年   48篇
  1980年   50篇
  1979年   46篇
  1914年   45篇
  1913年   40篇
  1912年   40篇
  1909年   41篇
  1908年   40篇
排序方式: 共有10000条查询结果,搜索用时 562 毫秒
971.
The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions. The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations on the Co(II) sorption on γ-Al2O3 in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al2O3 in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly positive influence of HA at low pH on the Co(II) sorption on γ-Al2O3 was attributed to strong surface binding of HA on γ-Al2O3 and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO) x Co2−x . Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al2O3 in the presence of HA.  相似文献   
972.
醋酸乙烯酯在硅橡胶上的辐射接枝研究   总被引:2,自引:0,他引:2  
研究了不同溶剂中的醋酸乙烯酯在硅橡胶上的辐射接技状况及接枝后硅橡胶表面结构情况.结果表明:(1)在硅橡胶-乙酸乙酯-醋酸乙烯酯体系中,接枝有自加速效应;(2)适量加入对苯二酚,接枝诱导期延长,接枝速率下降,凝胶效应消失,辐射接技经验关联式为RP=0.27×[D](-0.560)×[I](0.490)×[C](0.920),接核反应为扩散控制反应;(3)不同的溶剂对硅橡胶接枝有不同的影响,如甲醇发生敏化作用,提高接枝速率,而苯发生惰化作用,降低接枝速率;(4)在合适的甲醇和苯配比时,接枝反应几乎恒速进行,用扫描电镜(SEM)观察断面,接枝区比较均一,出现微相分离.  相似文献   
973.
In this study, a syringe was filled with silica gel loaded with 3-aminopropyltriethoxysilane, for the separation and preconcentration of copper, cadmium and chromium prior to their determination by graphite furnace atomic absorption spectrometry (GFAAS) in seawater. For this purpose, a syringe was filled with 0.5 g of modified silica gel and the sample solution was drawn into the syringe and ejected back again. The analyte elements were quantitatively retained at pH 5. Then, the elements sorbed by the silica gel were eluted with 2.0 M of HCl and determined by GFAAS. At optimum conditions, the recovery of Cu, Cd and Cr were 96-98%. Detection limits (3delta) were 6.6, 7.5 and 6.0 micro g L(-1) for Cu, Cd and Cr, respectively. The elements could be concentrated by drawing and discharging several portions of sample successively but eluting only once. Cu, Cd and Cr added to a seawater sample were quantitatively recovered (>95%) in the range of the 95% confidence level. The method proposed in this paper was compared with a column technique. Optimum experimental conditions, reproducibility, precision and recoveries of both techniques are the same, but the syringe technique is much faster, easier and more practical than the column technique. It is a portable system and allows one to make the sorption process in the source of sample. In addition, the risk of contamination is less than in the column technique.  相似文献   
974.
The adsorption/desorption process of borate was studied at Pt(111) in acidic solution by cyclic voltammetry. A so-called butterfly wave in the cyclic voltammogram of Pt(111) in HClO4 shifted to negative direction upon the addition of boric acid with the disappearance of its sharp spikes. The shift in potential was found to be −57 mV with a tenfold increase of boric acid concentration. This illustrates that this anomalous wave is due to borate adsorption/desorption by a one-electron transfer process. The borate adsorption/desorption wave was observed to shift by −63 mV/pH. At pH>3, the anomalous wave splits forming two separate waves, depending on the pH and the scan rate. The appearance of two waves is assigned to the change in the adsorption mode of borate or the participation of OH in the adsorption process.  相似文献   
975.
Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)2) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)2 and chloroform interacts via hydrogen bonding to oxygens of the acac ligands.  相似文献   
976.
Sun D  Cao R  Sun Y  Bi W  Li X  Wang Y  Shi Q  Li X 《Inorganic chemistry》2003,42(23):7512-7518
The hydrothermal reactions of AgNO(3), 4,4'-bipy, and carboxylate ligands gave rise to three supramolecular architectures, namely [Ag(bipy)].H(2)SIPA.1/2bipy.H(2)O (1), [Ag(bipy)].1/2H(2)btec.H(2)O (2), and [Ag(bipy)](2).H(2)dpstc.2H(2)O (3) (H(3)SIPA = 5-sulfoisophthalic acid, bipy = 4,4'-bipyridine, H(4)btec = 1,2,4,5-benzenetetracarboxylic acid, H(4)dpstc = 3,3',4,4'-tetracarboxydiphenyl sulfone). All complexes are extended from Ag-bipy linear chains by the combination of coordination bonds and supramolecular interactions in two different approaches. Complexes 1 and 3 comprise two-dimensional frameworks. In the two complexes, a one-dimensional ladderlike structure is first formed by the connection of a Ag-bipy chain through hydrogen bonding between a free carboxylate/bipy ligand and weak coordinative interactions between a free carboxylate ligand and silver ion. The ladderlike structure is then extended to a two-dimensional layer architecture by pi...pi interactions between bipy ligands of the Ag-bipy chains. Complex 2 possesses a three-dimensional framework. The free H(2)btec(2)(-) ligands form a two-dimensional layer network by hydrogen-bonding interactions between protonated and deprotonated carboxylate groups; meanwhile, pi.pi interactions between bipy ligands of Ag-bipy chains also result in a two-dimensional layer. The two layers are further connected by weak Ag-O interactions to generate a three-dimensional supramolecular structure.  相似文献   
977.
投料顺序对动态硫化PP/EPDM性能影响及其机理的研究   总被引:12,自引:0,他引:12  
针对PP降解在PP/EPDM动态硫化中对体系产生的不利影响。考察了四种不同投料顺序对PP/EPDM动态硫化物的冲击韧性,加工流动性,交联程度和断面形貌等宏观和微观性能,并进行了不同EPDM含量的动态硫化和非硫化PP/EPDM的性能比较。结果表明,优化投料顺序能实现对动态硫化体系中化学反应对象和化学反应程度的有效干预。  相似文献   
978.
Orientation control of perovskite compounds was investigated by the application of a seed layer prepared from oxide nanosheets. An aqueous suspension of oxide nanosheets was prepared by the exfoliation of a layered compound of KCa2Nb3O10 oxide grains. A seed layer composed of (TBA)Ca2Nb3O10 nanosheets (TBA = tetrabutylammonium) was formed on a glass substrate by simply dip coating it in the suspension. Two kinds of perovskite compounds, LaNiO3 (LNO) and Pb(Zr,Ti)O3 (PZT) with a preferred orientation of (00l) were successfully grown on this seeded glass substrate. In this study, the relation between lattice mismatch and electrical properties is investigated. A large, oriented PZT film with a size of 5 ×4 cm shows an improved P-E hysteresis behavior by use of this orientation control.  相似文献   
979.
We consider a periodic-review inventory replenishment model with an order-up-to-R operating doctrine for the case of deterministic lead times and a covariance-stationary stochastic demand process. A method is derived for setting the inventory safety stock to achieve an exact desired stockout probability when the autocovariance function for Gaussian demand is known. Because the method does not require that parametric time-series models be fit to the data, it is easily implemented in practice. Moreover, the method is shown to be asymptotically valid when the autocovariance function of demand is estimated from historical data. The effects on the stockout rate of various levels of autocorrelated demand are demonstrated for situations in which autocorrelation in demand goes undetected or is ignored by the inventory manager. Similarly, the changes to the required level of safety stock are demonstrated for varying levels of autocorrelation.  相似文献   
980.
This paper studies the optimal operation of an M/E k /1 queueing system with a removable service station under steady-state conditions. Analytic closed-form solutions of the controllable M/E k /1 queueing system are derived. This is a generalization of the controllable M/M/1, the ordinary M/E k /1, and the ordinary M/M/1 queueing systems in the literature. We prove that the probability that the service station is busy in the steady-state is equal to the traffic intensity. Following the construction of the expected cost function per unit time, we determine the optimal operating policy at minimum cost.  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