全文获取类型
收费全文 | 10191篇 |
免费 | 1038篇 |
国内免费 | 964篇 |
专业分类
化学 | 5806篇 |
晶体学 | 132篇 |
力学 | 798篇 |
综合类 | 37篇 |
数学 | 548篇 |
物理学 | 4872篇 |
出版年
2024年 | 13篇 |
2023年 | 96篇 |
2022年 | 193篇 |
2021年 | 233篇 |
2020年 | 309篇 |
2019年 | 220篇 |
2018年 | 223篇 |
2017年 | 291篇 |
2016年 | 408篇 |
2015年 | 317篇 |
2014年 | 464篇 |
2013年 | 759篇 |
2012年 | 675篇 |
2011年 | 777篇 |
2010年 | 615篇 |
2009年 | 748篇 |
2008年 | 741篇 |
2007年 | 784篇 |
2006年 | 750篇 |
2005年 | 500篇 |
2004年 | 436篇 |
2003年 | 392篇 |
2002年 | 290篇 |
2001年 | 229篇 |
2000年 | 225篇 |
1999年 | 176篇 |
1998年 | 172篇 |
1997年 | 140篇 |
1996年 | 144篇 |
1995年 | 105篇 |
1994年 | 136篇 |
1993年 | 94篇 |
1992年 | 88篇 |
1991年 | 69篇 |
1990年 | 66篇 |
1989年 | 53篇 |
1988年 | 39篇 |
1987年 | 42篇 |
1986年 | 28篇 |
1985年 | 29篇 |
1984年 | 20篇 |
1982年 | 15篇 |
1981年 | 12篇 |
1980年 | 11篇 |
1979年 | 20篇 |
1978年 | 9篇 |
1975年 | 5篇 |
1973年 | 10篇 |
1971年 | 4篇 |
1970年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
101.
102.
Jörg Teichgräber 《Journal of organometallic chemistry》2005,690(23):5255-5263
The synthesis, characterization, and thermal decomposition behavior of dicopper(I) oxalato complexes L4Cu2(C2O4) (L = CNtBu (2a), CNCMe2CH2tBu (2b), CNC6H3Me2-2,6 (2c)) is reported. 2c can be prepared in a straightforward manner by the reaction of stoichiometric amounts of Cu2O and oxalic acid with four equivalents of CNC6H3Me2-2,6, while those complexes with aliphatic isocyanides are better prepared from a copper(I) oxalato complex with alkine capping ligands (Me3SiCCSiMe3)2Cu2(C2O4) (1) via ligand exchange. Crystallographic and spectroscopic evidence for 2a-c confirms the anticipated dinuclear structure with the oxalate in a μ-1,2,3,4 bridging mode and an essentially σ-character of the terminal isocyanides. In solid form the complexes are stable at room temperature and can be handled in air for some time. Their decomposition was studied by thermal gravimetric analysis coupled with mass spectrometry, and the degradation pathway was shown to depend on the type of isocyanide capping ligand. Decomposition of 2a,b takes place between 150 and 200 °C to give CuCN in a clean process that involves isobutene elimination from the terminal ligands, with elimination of (CN)2 and conversion to elemental copper at higher temperatures. Heating of 2c leads to CuO (and then to Cu2O) via release of the intact isocyanide, CO2, and CO in a well-behaved thermal process around 200-280 °C. 相似文献
103.
N. Bouad 《Journal of solid state chemistry》2004,177(1):221-226
We report in this paper a study of the mechanical alloying (MA) process for the Pb0.65Sn0.35Te alloy. MA has been carried out in a high-energy planetary ball mill. The mechanism of formation has been studied from systematic analyses of mechanically alloyed powders using X-ray diffraction, differential scanning calorimetry and scanning electron microscopy. As it was already observed for the MA of PbTe, this synthesis is associated with an exothermic reaction between the elemental powders. The required time to reach an homogeneous phase Pb0..65Sn0.35Te is 31 h. 相似文献
104.
S Çak?r E Co?kunP Naumov E Biçer? Bulut H ?çbudakO Çak?r 《Journal of Molecular Structure》2002,608(1):101-107
Aspartame adduct of copper(II) chloride Cu(Asp)2Cl2·2H2O (Asp=aspartame) is synthesized and characterized by elemental analysis, FT IR, UV/vis, ESR spectroscopies, TG, DTG, DTA measurements and molecular mechanics calculations. Aqueous solution of the green solid absorbs strongly at 774 and 367 nm. According to the FT IR spectra, the aspartame moiety coordinates to the copper(II) ion via its carboxylate ends, whereas the ammonium terminal groups give rise to hydrogen bonding network with the water, the chloride ions or neighboring carboxylate groups. The results suggest tetragonally distorted octahedral environment of the copper ions. 相似文献
105.
用AM1方法(采用非限制的Hartree-FockUHF计算)研究乙烯与环己-1,3-二烯的热Diels-Alder反应。结果表明反应是放热的且存在两条竞争的路径;协同反应的活化能以及双自由反应速度控制步骤的活化能分别为112.667kJ/mol和78.406kJ/mol。 相似文献
106.
The research described in this paper presents a method for chemically modifying the surface of plant photosynthetic membranes
in such a way that electrical contact can be made. Colloidal platinum was prepared, precipitated directly onto thylakoid membranes
from aqueous solution, and entrapped on fiberglass filter paper. This composition of matter was capable of sustained simultaneous
photoevolution of hydrogen and oxygen when irradiated at any wavelength (400–700 nm) in the chlorophyll absorption spectrum.
Experimental data support the interpretation that part of the platinum metal catalyst is precipitated adjacent to the photosystem-I
reduction site of photosynthesis and that electron transfer occurs across the interface between photosystem I and the catalyst.
When contacted with metal electrodes, the thylakoid-platinum combination was capable of generating a sustained flow of current
through an external load resistor. Procedures for preparing this material and experimental data on its catalytic and electronic
properties are presented. Also presented is an analysis of the flow of photocurrent in terms of the interfacial electron transfer
reactions that occur at the interfaces of the components of the assembly. 相似文献
107.
Multi-temperature thermal plasmas have often to be considered to account for the nonequilibrium effects. Recently André et al. have developed the calculation of concentrations in a multi-temperature plasma by artificially separating the partition functions into a product by assuming that the excitation energies are those of the lower levels (electronic, vibration, and rotation). However, at equilibrium, differences, increasing with temperature, can be observed between partition functions calculated rigorously and with their method. This paper presents a modified method where it has been assumed that the preponderant rotational energy is that of the vibrational level v=0 of the ground electronic state and the preponderant vibrational energy is that of the ground electronic state. The internal partition function can then be expressed as a product of series expressions. At equilibrium for N
2
and N
2
+
partition functions the values calculated with our method differ by less than 0.1% from those calculated rigorously. The calculation has been limited to three temperatures: heavy species Th
, electrons Te
, and vibrational T
v
temperatures. The plasma composition has been calculated by minimizing the Gibbs free enthalpy with the steepest descent numerical technique. The nonequilibrium properties have been calculated using the method of Devoto, modified by Bonnefoi and Aubreton. The ratio =Te/Th
was varied between 1 and 2 as well as the ratio
v
=T
v
/T
h
for a nitrogen plasma. At equilibrium the corresponding equilibrium transport properties of Ar and N
2
are in good agreement with those of Devoto and Murphy except for T>10,000 K where we used a different interaction potential for N–N
+
. The effects of v
and e
on thermodynamic and transport properties of N
2
are then discussed. 相似文献
108.
The phase analysis of cryolite (Na3AlF6) and sodium metasilicate (Na2SiO3) was performed by thermal analysis. The eutectic system with a region of two immiscible substances at a concentration of Na2SiO3 between 42.8 and 46.3 mol‐% was identified and the eutectic temperature determined to (886±2) °C. Based on the results of mass‐loss measurements, it was assumed that the introduced Na2SiO3 reacts with Na3AlF6 due to the formation of some nonvolatile stable compounds. The stable reaction products were identified by X‐ray diffraction analysis and IR spectroscopy of the spontaneously cooled samples, which established the formation of NaF and stable amorphous aluminosilicate compounds. 相似文献
109.
Rat V. André P. Aubreton J. Elchinger M.F. Fauchais P. Lefort A. 《Plasma Chemistry and Plasma Processing》2002,22(4):453-474
The calculation of two-temperature transport coefficients in an argon–hydrogen plasma at atmospheric pressure is performed using a new theory of two-temperature transport properties recently presented. The latter takes into account the coupling between electrons and heavy species, coupling neglected in the already existing theories of Devoto and Bonnefoi. Transport coefficients are calculated at two-temperatures, the kinetic temperature of electrons Te being different from that of heavy species Th. This paper is divided into two parts. The first one is related to elastic processes and its aim is to compare the results obtained with this new theory for viscosity , translational thermal conductivities tr
e and tr
h and electrical conductivity with the previous results of Bonnefoi. The composition is calculated with the modified equilibrium constant of van de Sanden et al. and the most recent interaction potential are discussed. As it could be expected the electron translational thermal conductivity and the electrical conductivity calculated when taking into account or not the coupling between electrons and heavy species show non-negligible discrepancies. Besides this comparison, the results also show the drastic influence of the non-equilibrium parameter =Te/Th on the values of , , tr
e, and tr
h. 相似文献
110.
The compositions in the YBa2−xLaxCu3O7−δ (0x0.2) system were prepared by the solid state reaction, employing a novel high-temperature oxygen sintering route. The modified sintering route yields dense slab like microstructures with large grains. The decomposition (incongruent melting) temperature of the YBa2Cu3O7−δ (Y-123) phase was found to shift to higher temperatures with increasing oxygen partial pressure and lanthanum content. Structure remained orthorhombic up to x=0.2 with a decrease in the orthorhombic strain ((b−a)/b). Iodometric titration indicated a systematic increase in the oxygen content with increasing lanthanum content. Thermo-gravimetric studies in various oxygen partial pressures revealed that the oxygen diffusion in to the YBa2Cu3O7−δ (δ>0.5) lattice is an exothermic event and takes place at temperatures not less than 573 K. High-temperature thermal-expansion measurements in air indicated that the nonlinearity in thermal expansion behaviour was reduced by the substitution of lanthanum. 相似文献