全文获取类型
收费全文 | 6355篇 |
免费 | 979篇 |
国内免费 | 416篇 |
专业分类
化学 | 2524篇 |
晶体学 | 199篇 |
力学 | 453篇 |
综合类 | 70篇 |
数学 | 1814篇 |
物理学 | 2690篇 |
出版年
2024年 | 16篇 |
2023年 | 60篇 |
2022年 | 103篇 |
2021年 | 125篇 |
2020年 | 149篇 |
2019年 | 175篇 |
2018年 | 164篇 |
2017年 | 211篇 |
2016年 | 250篇 |
2015年 | 171篇 |
2014年 | 266篇 |
2013年 | 753篇 |
2012年 | 347篇 |
2011年 | 288篇 |
2010年 | 299篇 |
2009年 | 347篇 |
2008年 | 362篇 |
2007年 | 341篇 |
2006年 | 372篇 |
2005年 | 301篇 |
2004年 | 300篇 |
2003年 | 286篇 |
2002年 | 288篇 |
2001年 | 180篇 |
2000年 | 184篇 |
1999年 | 180篇 |
1998年 | 135篇 |
1997年 | 132篇 |
1996年 | 110篇 |
1995年 | 107篇 |
1994年 | 89篇 |
1993年 | 67篇 |
1992年 | 82篇 |
1991年 | 51篇 |
1990年 | 40篇 |
1989年 | 39篇 |
1988年 | 29篇 |
1987年 | 38篇 |
1986年 | 32篇 |
1985年 | 36篇 |
1984年 | 40篇 |
1982年 | 36篇 |
1981年 | 29篇 |
1980年 | 20篇 |
1979年 | 22篇 |
1978年 | 12篇 |
1977年 | 17篇 |
1976年 | 13篇 |
1974年 | 13篇 |
1973年 | 11篇 |
排序方式: 共有7750条查询结果,搜索用时 15 毫秒
121.
Cyclical bifurcated hydrogen bonded structures are proposed for aqueous solutions of hydrofluoric acid and for the bifluoride ion which are consistent with the spectral data. The structure proposed for HF is also applicable to solutions in organic solvents. Raman spectra of tetramethylguanidinium perchlorate suggest that the corresponding Raman spectra of perchloric acid solutions may not be interpreted in terms of a completely dissociated acid. Other evidence including activity coefficient, heat capacity and partial molal volume data suggest that there is some association in relatively dilute perchloric acid solutions between the perchlorate ion and the hydrated proton. This association decreases in concentrated aqueous solutions. 相似文献
122.
Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV10O15 and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV10−xTixO15, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi10O15”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti2+ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10−3 emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T1/2 law, was seen, in sharp contrast to BaV10O15 where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role. 相似文献
123.
一种低磁矩、大功率复合稀土石榴石铁氧体的工艺和性能研究 总被引:4,自引:0,他引:4
为满足低场区几百兆赫的超大功率器件的性能要求,以钇铁石榴石铁氧体为基础,制备了一种低磁矩复合稀土石榴石铁氧体YGd CaVInIG,研究了少量Mn3+替代Fe3+和预烧温度、烧结温度对铁氧体性能和结构的影响。实验表明,以少量Mn3+替代Fe3+可以提高铁氧体电阻率,降低磁损耗和介电损耗。Mn3+掺入量以x为0.04~0.06比较合适,铁氧体最佳予烧温度为1050℃,最佳烧结温度1350~1380℃,保温5h,氧气中烧结,其性能为:4πMs=500±10%kA·m-1,ΔH=5.25~5.55kA·m-1,TC>180℃,tgδe≤0.5×10-5,这种材料适合微波低频段器件性能要求。X射线衍射分析指出,掺Mn3+的YGdCaVInIG铁氧体相变完全,呈单相复合石榴石铁氧体,空间群为I230,点阵常数1.25057~1.25101nm,单胞分子数n为7.75~7.80。 相似文献
124.
125.
126.
Using a theory recently developed for the interpretation of activity coefficients of 1:1 electrolytes up to high concentrations in aqueous solution at 25°C, we have analysed available data for aqueous sodium chloride solutions up to saturation in the temperature range 273.15–573.15 K. The approach, which is based on Kirkwood-Buff theory and uses the truncated Poisson-Boltzmann equation to obtain the required information about the various ion-ion radial distributions, is able to fit the results to high accuracy with minimum of parameters, viz, three, of which one is the distance of closest approach, the other two relate to ion-solvent interactions and/or higher order terms in the ion-ion interaction. 相似文献
127.
Hilary E. Kent Terence H. Lilley Peter J. Milburn Michael Bloemendal Gus Somsen 《Journal of solution chemistry》1985,14(2):101-115
Enthalpies of dilution of the N-acetyl amides of glycine, L-alanine, L-valine, L-leucine, and L-phenylalanine, dissolved in N,N-dimethylformamide (DMF) as a solvent have been measured at 25°C. The results obtained have been analyzed to give the enthalpic interaction (or virial) coefficients of the solutes and these are compared with information previously obtained in aqueous systems. There are marked differences in the interaction properties in the two solvents and, while the additivity approach of Savage and Wood is applicable to the solutes in water it is not suitable for representing the interactions in DMF. A correlation is presented between the enthalpic second virial coefficients in DMF and the propensity of side-chains to be in proximity in globular proteins. 相似文献
128.
Valentino J. Stella Venkatramana M. Rao Erika A. Zannou 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):29-33
The purpose of this paper is to share some recent observations on the pharmaceuticaluses and properties of Captisol® or SBE7M--CD in controlled porosity osmotic pump tablets (CP-OPT) and the underlying mechanism/sthat lead to apparent zero-order drug release pattern. It would have been simple toattribute the apparent zero-order release mechanism/s of poorly water-soluble drugsfrom CP-OPTs and pellets utilizing Captisol®as both a solubilizing andosmotic agent, to purely osmotic and diffusional components. However, the mechanismmay be more related to a counterbalancing of physical properties as the concentration of Captisol®changes within the matrix. Specifically, the initial concentration of Captisol®within a core is 0.3–0.4M. When this drops to lower values an osmotic pressure drop occurs across the membrane. Therefore, drug release should not follow apparent zero-order kinetics if all the drug is solubilized. However, as the viscosity within the tablet also drops, the apparent diffusion coefficient of both Captisol® and drug increases. Therefore, it appears that there is an initial resistance (hydraulic pressure) to fluid flow from the tablet through the rate-limiting microporous membrane. This resistance decreases so that even as osmotic pressure and concentration differences drop with time, counterbalancing faster release occurs. Osmotic driving force appears to be the most important initial driving force but a diffusional component becomes more significant with time. 相似文献
129.
Darja?Rudan-Tasic Cveto?KlofutarEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(7):773-784
Summary. The freezing temperatures of dilute aqueous solutions of some poly(oxyethylene) glycols (PEG, HO–(CH2CH2O)
n
–H, n varying from 4 to 117) were measured over a solute to solvent mass ratio from 0.0100 to 0.3900. The second and third osmotic virial coefficient (A
22 and A
222) of poly(oxyethylene) glycols in aqueous solution were determined. The molecular weight dependence of the second virial coefficient can be described by a simple relation A
22=2×10–5
M
n
1.86, and the third virial coefficient is A
222=0.038A
22
2. The activity coefficients of the solute were calculated using the Gibbs-Duhem equation as applied by Bjerrum. From the osmotic and activity coefficients the excess Gibbs energies of solution, as well as the respective partial molar functions of solute and solvent and the virial pair interaction coefficients for the excess Gibbs energies were estimated. The second and the third osmotic virial coefficients are correlated with the Mc-Millan-Mayer virial coefficients. 相似文献
130.
Interpolation formulas are presented to reproduce the rate coefficients for vibrational–translational energy exchange and dissociation for the N + N2 collision process. The original data have been obtained by quasiclassical method in a detailed way, including the effect of molecular rotation. The fitting procedure results are compared with original data and the related error is evaluated. Comparison with global experimental dissociation results is also presented. 相似文献