全文获取类型
收费全文 | 7387篇 |
免费 | 759篇 |
国内免费 | 436篇 |
专业分类
化学 | 2202篇 |
晶体学 | 56篇 |
力学 | 593篇 |
综合类 | 34篇 |
数学 | 2367篇 |
物理学 | 2365篇 |
无线电 | 965篇 |
出版年
2024年 | 15篇 |
2023年 | 95篇 |
2022年 | 129篇 |
2021年 | 174篇 |
2020年 | 219篇 |
2019年 | 224篇 |
2018年 | 176篇 |
2017年 | 208篇 |
2016年 | 247篇 |
2015年 | 200篇 |
2014年 | 305篇 |
2013年 | 684篇 |
2012年 | 326篇 |
2011年 | 376篇 |
2010年 | 296篇 |
2009年 | 380篇 |
2008年 | 426篇 |
2007年 | 453篇 |
2006年 | 382篇 |
2005年 | 350篇 |
2004年 | 352篇 |
2003年 | 308篇 |
2002年 | 263篇 |
2001年 | 262篇 |
2000年 | 233篇 |
1999年 | 209篇 |
1998年 | 169篇 |
1997年 | 178篇 |
1996年 | 110篇 |
1995年 | 110篇 |
1994年 | 106篇 |
1993年 | 83篇 |
1992年 | 68篇 |
1991年 | 78篇 |
1990年 | 44篇 |
1989年 | 30篇 |
1988年 | 33篇 |
1987年 | 34篇 |
1986年 | 32篇 |
1985年 | 41篇 |
1984年 | 31篇 |
1983年 | 20篇 |
1982年 | 27篇 |
1981年 | 17篇 |
1980年 | 17篇 |
1979年 | 13篇 |
1978年 | 10篇 |
1977年 | 11篇 |
1974年 | 5篇 |
1973年 | 10篇 |
排序方式: 共有8582条查询结果,搜索用时 890 毫秒
121.
Jörg Kärger 《Adsorption》2003,9(1):29-35
A review is given on the main problems associated with the determination and interpretation of molecular diffusion in zeolites. It is shown that the diffusivities may most decisively depend on the relevant space and time scales of observation, as well as on the physical state under which the measurements are carried out. Special emphasis is given to the microscopic techniques and their most recent evidence on the existence of transport resistances distributed over the intracrystalline space. 相似文献
122.
《Surface and interface analysis : SIA》2005,37(3):316-324
The present work considers the differences between the following two phenomena: equilibrium segregation, which is a thermodynamic phenomenon where the driving force is excess interfacial energy; and non‐equilibrium segregation, which can be produced by phenomenological shocks applied to the solid surface. Fully stabilized cubic yttria‐stabilized zirconia (YSZ) is used as the exemplar for these considerations. Equilibrium segregation in YSZ results in enrichment of the surface and near‐surface layers in constituent elements, typically yttria and impurities. This segregation is an intrinsic material property and has an impact on the performance of zirconia at elevated temperatures. On the other hand, non‐equilibrium segregation leads to a complex distribution of properties (structure and concentration gradients) that are determined by the experimental procedures used rather than being a material property. However, such non‐equilibrium segregation can result in localized structural changes. The present paper also considers the effect of the gas phase on surface properties of metal oxides, including YSZ, and the surface dynamics of YSZ at temperatures below that required to reach equilibrium. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
123.
Transport phenomenon of three sulfonated azo dyes, C.I. Acid Red 88, C.I. Direct Yellow 12, and C.I. Direct Blue 15 into water-swollen cellulose membranes has been analyzed on the basis of parallel transport theory by surface and pore diffusion. Langmuir equation was applied into the mass balance equation to estimate dye concentration in the pores. The results were compared with the results obtained by applying Freundlich equation in our previous papers. The surface diffusivity (D
s) and the pore diffusivity (D
p) for the parallel diffusion model obtained by applying Langmuir equation agreed with those obtained by applying Freudlich equation. The theoretical concentration profiles for parallel diffusion calculated usingD
s andD
p coincided accurately with the experimental data when we applied either Langmuir or Freundlich equations. 相似文献
124.
E.?BertoloEmail author J.?A.?Kilner M.?Sahibzada 《Journal of Solid State Electrochemistry》2004,8(9):585-591
18O/16O isotope exchange depth profiling (IEDP) combined with secondary ion mass spectrometry (SIMS) has been used to measure the oxygen tracer diffusivity of SrCe0.95Yb0.05O3– between 800 °C and 500 °C at a nominal pressure of 200 mbar. The values of D* (oxygen tracer diffusion coefficient) and k (surface exchange coefficient) increase steadily with increasing temperature, and the activation energies are 1.13 eV and 0.96 eV, respectively. Oxygen ion conductivities have been calculated using the Nernst–Einstein equation. The transport number for oxide ions at 769 °C, the highest temperature studied, is only ~0.05. Moreover, SrCe0.95Yb0.05O3– has been studied using impedance spectroscopy under dry O2, wet O2 and wet H2 (N2/10% H2) atmospheres, over the range 850–300 °C. Above ~550 °C, SrCe0.95Yb0.05O3– shows higher conductivity in dry O2 than in wet O2 or wet H2; below that temperature the results obtained for the three atmospheres are comparable. Dry O2 shows the highest activation energy (0.77 eV); the activation energies for wet O2 and wet H2 are identical (0.62 eV).Abbreviations HTPC high-temperature proton conductor - IEDP isotope exchange depth profiling - SIMS secondary ion mass spectrometryPresented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003 相似文献
125.
Martin Gruebele 《Theoretical chemistry accounts》2003,109(2):53-63
Vibrational energy flow in organic molecules occurs by a multiple-time-scale mechanism that can be modeled by a single exponential
only in its initial stages. The mechanism is a consequence of the hierarchical structure of the vibrational Hamiltonian, which
leads to diffusion of vibrational wavepackets on a manifold with far fewer than the 3N−6 dimensions of the full vibrational state space. The dynamics are controlled by a local density of states, which does not
keep increasing with molecular size. In addition, the number of vibrational coordinates severely perturbed during chemical
reaction is small, leading to preservation of the hierarchical structure at chemically interesting energies. This regularity
opens up the possibility of controlling chemical reactions by controlling the vibrational energy flow. Computationally, laser
control of intramolecular vibrational energy redistribution can be modeled by quantum-classical, or by purely quantum-mechanical
models of the molecule and control field.
Received: 26 July 2002 / Accepted: 30 September 2002 / Published online: 2 December 2002
Electronic Supplementary Material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00214-002-0394-2.
Acknowledgements. This work was supported by NSF grant CHE 9986670.
Correspondence to: M. Gruebele e-mail: gruebele@scs.uiuc.edu 相似文献
126.
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
127.
V.?I.?VigdorovichEmail author L.?E.?Tsygankova O.?V.?Alekhina T.?P.?D'yachkova 《Russian Journal of Electrochemistry》2005,41(10):1046-1052
The effect of thiourea (0.5–10 mM) on the kinetics of the hydrogen evolution reaction (HER) at iron and the hydrogen transport through a steel membrane out of ethylene glycol (containing 2 and 10 wt % H2O) and aqueous solutions containing HCl (0.1–0.99 M) with a constant ionic strength equal to unity is studied in parallel experiments. The presence of 0.5 mM of thiourea in the solutions raises the overvoltage of hydrogen evolution, while a subsequent increase in its concentration does not effect the HER kinetics. The dependence of the flux of hydrogen diffusion through the membrane on the thiourea content passes through a maximum. 相似文献
128.
Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C1 and C18 alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (Ds) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C1 and C18 ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate Ds values under various RPLC conditions. The Ds values can be estimated with a mean square deviation of about 25–30%. The agreement between the Ds values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C1 and C18 ligands and that the contribution of each ligand is proportional to the ligand density. 相似文献
129.
Woo-Jin Lee Su-Il Pyun Tae-Hyun Yang Joong-Do Kim Young-Ho Baek Han-Gyu Kim 《Journal of Solid State Electrochemistry》1997,1(2):120-125
Hydrogen transport through a Pd-Ni alloy electrodeposited on a Pd substrate (Pd-Ni/Pd bilayer symmetric electrode) has been
investigated using cyclic voltammetry and a.c. impedance spectroscopy combined with the electrochemical hydrogen permeation
method. The permeation build-up current transients and the measured impedance spectra were analyzed using the time-lag method
for the bilayer electrode and a complex non-linear least squares data-fitting method based upon the derived Faradaic admittance
for the hydrogen absorption into and diffusion through the bilayer electrode under the permeable boundary condition, respectively.
The value of the hydrogen diffusivity in the Pd-Ni layer was lower than that in the Pd layer. Furthermore, the values of the
charge transfer resistance and equilibrium absorption constant for the Pd-Ni/Pd bilayer electrode were higher than those for
the Pd single layer electrode. From the experimental results, the role of the thin Ni(OH)2 film formed on the Pd-Ni layer surface in the hydrogen transport through the Pd-Ni/Pd bilayer electrode is discussed in terms
of its passivating effect and extremely large hydrogen solubility.
Received: 22 January 1997 / Accepted: 15 April 1997 相似文献
130.
本文研究分数扩散过程和其分部积分公式的关系.首先利用Bismut方法给出拉回公式,进而得到分数扩散过程的分部积分公式。反过来,证明了分数扩散过程可由其分部积分公式唯一刻画. 相似文献