全文获取类型
收费全文 | 2716篇 |
免费 | 398篇 |
国内免费 | 315篇 |
专业分类
化学 | 1835篇 |
晶体学 | 104篇 |
力学 | 159篇 |
综合类 | 27篇 |
数学 | 13篇 |
物理学 | 1291篇 |
出版年
2024年 | 2篇 |
2023年 | 15篇 |
2022年 | 47篇 |
2021年 | 62篇 |
2020年 | 85篇 |
2019年 | 90篇 |
2018年 | 86篇 |
2017年 | 74篇 |
2016年 | 113篇 |
2015年 | 118篇 |
2014年 | 113篇 |
2013年 | 369篇 |
2012年 | 178篇 |
2011年 | 181篇 |
2010年 | 137篇 |
2009年 | 147篇 |
2008年 | 168篇 |
2007年 | 164篇 |
2006年 | 196篇 |
2005年 | 117篇 |
2004年 | 112篇 |
2003年 | 118篇 |
2002年 | 131篇 |
2001年 | 89篇 |
2000年 | 80篇 |
1999年 | 68篇 |
1998年 | 52篇 |
1997年 | 36篇 |
1996年 | 34篇 |
1995年 | 37篇 |
1994年 | 29篇 |
1993年 | 21篇 |
1992年 | 34篇 |
1991年 | 20篇 |
1990年 | 9篇 |
1989年 | 8篇 |
1988年 | 10篇 |
1987年 | 12篇 |
1986年 | 13篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 8篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1973年 | 3篇 |
1972年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有3429条查询结果,搜索用时 46 毫秒
101.
Electrosorption of hydrogen into palladium-gold alloys 总被引:1,自引:0,他引:1
M. Łukaszewski K. Kuśmierczyk J. Kotowski H. Siwek A. Czerwiński 《Journal of Solid State Electrochemistry》2003,7(2):69-76
Hydrogen electrosorption into Pd-Au alloys has been studied in acidic solutions (1 M H2SO4) using cyclic voltammetry. Pd-Au electrodes with limited volume were prepared by electrochemical co-deposition. It was found
that the maximum H/(Pd+Au) ratios decrease monotonically with increasing gold content and reach zero at ca. 70 at% Au. Similarly
to the case of Pd limited volume electrodes, two peaks in the hydrogen region, corresponding to two types of sorbed hydrogen,
are observed on voltammograms for Pd-rich alloys. The hydrogen capacity, H/(Pd+Au), measured electrochemically, depends on
the sweep rate in the cyclic voltammetry experiments, which suggests that two different mechanisms for hydrogen desorption
from the Pd-Au alloy are possible. After a strong decrease of Pd concentration at the electrode surface, caused by long cyclic
polarization to sufficiently anodic potentials, the amount of absorbed hydrogen is still significant for alloys initially
rich in Pd. The results obtained from CO adsorption experiments suggest that only Pd atoms are active in the hydrogen absorption/desorption
process.
Electronic Publication 相似文献
102.
103.
Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate 总被引:1,自引:0,他引:1
Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is (28.795 ± 0.182) kJ/mol (298.15 K), and the standard molar enthalpy of formation of the title complex is (-2185.43 ± 13.80) kJ/mol (298.15 K). Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction: an nth-order reaction (Fn) with n=4.28, E1=147.35 kJ/mol, A1=3.63×10^13 s^-1 is followed by a second-order reaction (F2) with E2=212.71 kJ/mol, A2= 1.82 × 10^18 s^-1. 相似文献
104.
Joachim Janssen Holger Rumpf Hartwig Modrow Ralf Rablbauer Georg Frommeyer Josef Hormes 《无机化学与普通化学杂志》2003,629(10):1701-1708
The surface oxidation of FeCr alloys with 18, 28, and 43 mass‐% Cr was investigated in situ using grazing‐incidence X‐ray absorption spectroscopy (GIXAS) at the chromium and iron K‐edges. Oxidation in air was monitored in situ in the temperature range from 290 K to 680 K. The standard GIXAS data analysis is extended for the treatment of a single layer model in order to estimate the chromium concentrations of the oxide layer and of the near‐interface substrate as well as the oxide layer thickness. XANES analysis shows transitions from b.c.c. Fe to corundum type Fe2O3 and from b.c.c. Cr to corundum type Cr2O3. The initial oxide layers are 1.1‐1.4 nm thick and contain 60‐90 mass‐% chromium, while the near‐interface substrate is depleted in Cr. During heating, iron oxide growth dominates up to 560‐600 K. Then the chromium oxide layer loses its passivation effect and Cr oxidation sets in. 相似文献
105.
106.
α-Al2O3纳米粒子对Co-Ni合金异常共沉积电化学行为的影响 总被引:1,自引:0,他引:1
为了研究在电化学复合共沉积过程中,惰性纳米粒子和金属离子、电极表面的相互作用,以及由此产生的对合金电化学共沉积行为的影响.本文从两个吸附过程出发: 电解液中的金属离子和H+在纳米粒子表面的吸附;纳米粒子迁移到阴极表面,在电极表面的吸附.采用Zeta电势和稳态极化以及电化学交流阻抗(EIS)研究了纳米Al2O3粒子和电解液中的金属离子,和电极表面的相互作用,进而分析了纳米粒子对Co2+和Ni2+还原沉积的影响规律.通过对阻抗数据的拟合,讨论了Al2O3纳米粒子对等效电路中各物理参数的影响.在H+和不同金属离子在纳米粒子上发生竞争吸附的基础上,提出了纳米粒子和合金共沉积的可能反应历程. 相似文献
107.
A. V. Piskunov A. V. Lado G. A. Abakumov V. K. Cherkasov O. V. Kuznetsova G. K. Fukin E. V. Baranov 《Russian Chemical Bulletin》2007,56(1):97-103
Oxidation of amalgamated magnesium metal with 3,6-di-tert-butyl-o-benzoquinone (1) in different aprotic organic solvents afforded magnesium catecholate and bis-o-semiquinolate complexes. The catecholate derivatives of magnesium CatMgL2 (Cat is the 3,6-di-tert-butyl-o-benzoquinone dianion, L = THF or Py) were synthesized in high yields in pyridine and tetrahydrofuran, respectively. The reactions
in diethyl ether or dimethoxyethane produced hexacoordinated metal bis-o-semiquinolates SQ2MgLn (SQ is the 3,6-di-tert-butyl-o-benzoquinone radical anion, L = Et2O, n = 2; L = DME, n = 1). The reaction with the use of toluene as the solvent gave a magnesium bis-o-semiquinolate complex containing the coordinated unreduced o-quinone molecule. The molecular structures of the [CatMgPy2]2 and SQ2Mg·DME complexes were established by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 92–98, January, 2007. 相似文献
108.
Guerreiro C. T. R. Ribeiro C. A. Crespi M. S. Torres C. 《Journal of Thermal Analysis and Calorimetry》2002,67(2):419-424
Magnesium ion was reacted with 5,7-dibromo-, 5,7-dichloro-, 7-iodo-and 5-chloro-7-iodo-8-hydroxyquinoline, in acetone/ammonium
hydroxide medium under constant stirring to obtain (I) Mg[(C9H4ONBr2)2]·2H2O; (II) Mg[(C9H4ONCl2)2]·3H2O; (III) Mg[(C9H5ONI)2]·2H2O and (IV)Mg[(C9H4ONICl)2]·2.5H2O complexes. The compounds were characterized by elemental analysis, IR spectra, ICP, TG-DTA and DSC.
Through thermal decomposition residues were obtained and characterized, by X-ray diffractometry, as a mixture of hexagonal
MgBr2 and cubic MgO to the (I) compound at 850°C; cubic MgO to the (II), (III) and (IV) compounds at750, 800 and 700°C, respectively.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
109.
Summary Electrography and paper chromatography were combined to analyse rapidly metallic alloys in an almost non destructive technique. Using anodic dissolution the sample is applied on the start point of the chromatographic paper. Known ketones-HCl-water mixtures are usually used as solvents to analyse electrospots of different alloys and metal coatings and a separate electrospottest is recommended for Cr. Results of qualitative analysis of some steels, Cu–Ni, and Pb alloys are presented. 相似文献
110.
Interactions of water and methanol with a mixture of copper and zinc metals: a theoretical <Emphasis Type="Italic">ab initio</Emphasis> study 总被引:1,自引:0,他引:1
Ab initio cluster quantum chemical calculations at the Hartree–Fock and second-order Møller–Plesset perturbation theory levels were carried out to mimic the interactions of water and methanol with a mixture of Cu and Zn metals. It was shown that both molecular and dissociative adsorption of methanol on a mixture of Cu and Zn metal catalyst are preferred over the corresponding adsorptions of water. Estimated transition-state structures for dissociation of methanol into CH·3 and OH· lie about 9.0 and 22.0 kcal/mol higher compared to the dissociated (forward reaction) and molecular adsorption (reverse reaction) complexes, respectively. Based on distinct radicals' bond energies with the active sites of the catalyst considered, it is suggested that hydrogen molecules could be formed through a chain of homogeneous reactions of methyl radicals released into the gas phase with the water and/or methanol molecules. 相似文献