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   2620篇
  免费   243篇
  国内免费   271篇
化学   2024篇
晶体学   38篇
力学   461篇
综合类   3篇
数学   97篇
物理学   511篇
  2024年   1篇
  2023年   28篇
  2022年   43篇
  2021年   69篇
  2020年   138篇
  2019年   93篇
  2018年   93篇
  2017年   131篇
  2016年   162篇
  2015年   122篇
  2014年   135篇
  2013年   275篇
  2012年   142篇
  2011年   162篇
  2010年   143篇
  2009年   173篇
  2008年   154篇
  2007年   161篇
  2006年   168篇
  2005年   138篇
  2004年   120篇
  2003年   89篇
  2002年   65篇
  2001年   52篇
  2000年   42篇
  1999年   42篇
  1998年   31篇
  1997年   22篇
  1996年   25篇
  1995年   16篇
  1994年   29篇
  1993年   14篇
  1992年   13篇
  1991年   10篇
  1990年   9篇
  1989年   4篇
  1988年   8篇
  1987年   3篇
  1986年   1篇
  1985年   1篇
  1984年   2篇
  1982年   2篇
  1981年   1篇
  1957年   2篇
排序方式: 共有3134条查询结果,搜索用时 15 毫秒
71.
Free vibration problems of lattice sandwich beams under several typical boundary conditions are investigated in the present paper. The lattice sandwich beam is transformed to an equivalent homogeneous three-layered sandwich beam. Unlike the traditional analytical model in which the rotation angles of the face sheets and the core are assumed the same, different rotation angles are considered in this paper to characterize the real response of sandwich beams. The analytical solutions of the natural frequencies for several typical boundary conditions are obtained. The effects of material properties and geometric parameters on the natural frequencies are also investigated.  相似文献   
72.
Several urea-inserted organo-polyoxometalates (POMs) derived from polyoxotungstovanadate [P2V3W15O61]9− were prepared. The insertion of the carbonyl into the polyoxometallic framework activates the urea toward Hydrogen-bond catalysis. This was shown on the Friedel-Crafts arylation of trans-β-nitrostyrene. Modelling shows that the most stable form of the organo-POMs features a cis-trans arrangement of the two N−H bonds, but that the likely catalytically active trans-trans form is accessible at room temperature. Finally, it is possible that the oxo substituents next to the vanadium atoms may help the approach of the nucleophile via H-bonding.  相似文献   
73.
As alternative hydrophobic adsorbent for DNA adsorption, supermacroporous cryogel disks were synthesized via free radical polymerization. In this study, we have prepared two kinds of cryogel disks: (i) poly(2‐hydroxyethyl methacrylate‐N‐methacryloyl‐l ‐tryptophan) [p(HEMA‐MATrp)] cryogel containing specific hydrophobic ligand MATrp; and (ii) monosize p(HEMA‐MATrp) particles synthesized via suspension polymerization embedded into p(HEMA) cryogel structure to obtain p(HEMA‐MATrp)/p(HEMA) composite cryogel disks. These cryogel disks containing hydrophobic functional group were characterized via swelling studies, Fourier transform infrared spectroscopy, elemental analysis, surface area measurements and scanning electron microscopy. DNA adsorption onto both p(HEMA‐MATrp) cryogel and p(HEMA‐MATrp)/p(HEMA) composite cryogels was investigated. Maximum adsorption of DNA on p(HEMA‐MATrp) cryogel was found to be 15 mg/g polymer. Otherwise, p(HEMA‐MATrp)/p(HEMA) composite cryogels significantly increased the DNA adsorption capacity to 38 mg/g polymer. Composite cryogels could be used repeatedly without significant loss on adsorption capacity after 10 repetitive adsorption–desorption cycles. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
74.
《Mendeleev Communications》2021,31(5):706-708
Acyclovir release from its composites with unmodified silica at pH 1.6 and 7.4 follows zero order kinetics for two days. Modification of the silica matrix with phenyl groups leads to dramatic decrease in the drug release level at pH 7.4 compared with pH 1.6 as well as to heterogeneous phase state of acyclovir in the phenyl modified composite with high loading of the drug.  相似文献   
75.
Zn‐Al‐salicylic nanohybrid layers have been prepared and used as fillers for polyvinyl alcohol (PVA). Nanohybrid layers of a broad absorption area in UV region were completely and uniformly dispersed in a continuous polymer matrix. PVA and PVA nanohybrid composite (NHC) films were exposed to UV irradiation. Thermal properties (diffusivity, effusivity, and conductivity) of both have been measured through photoacoustic technique before and after UV irradiation. Thermal parameters of PVA suffered from a quick deterioration with UV exposure due to reduction of the phonon mean free path as a result of molecular chain scissions. However, significant stability in such parameters of NHC has been obtained under the influence of UV irradiation. This thermal properties stability may be an important step on the way of obtaining photostable polymer NHC. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   
76.
Here, we report the synthesis and characterization of a novel 4-arm poly(lactic acid urethane)-maleate (4PLAUMA) elastomer and its composites with nano-hydroxyapatite (nHA) as potential weight-bearing composite. The 4PLAUMA/nHA ratios of the composites were 1:3, 2:5, 1:2 and 1:1. FTIR and NMR characterization showed urethane and maleate units integrated into the PLA matrix. Energy dispersion and Auger electron spectroscopy confirmed homogeneous distribution of nHA in the polymer matrix. Maximum moduli and strength of the composites of 4PLAUMA/nHA, respectively, are 1973.31 ± 298.53 MPa and 78.10 ± 3.82 MPa for compression, 3630.46 ± 528.32 MPa and 6.23 ± 1.44 MPa for tension, 1810.42 ± 86.10 MPa and 13.00 ± 0.72 for bending, and 282.46 ± 24.91 MPa and 5.20 ± 0.85 MPa for torsion. The maximum tensile strains of the polymer and composites are in the range of 5–93%, and their maximum torsional strains vary from 0.26 to 0.90. The composites exhibited very slow degradation rates in aqueous solution, from approximately 50% mass remaining for the pure polymer to 75% mass remaining for composites with high nHA contents, after a period of 8 weeks. Increase in ceramic content increased mechanical properties, but decreased maximum strain, degradation rate, and swelling of the composites. Human bone marrow stem cells and human endothelial cells adhered and proliferated on 4PLAUMA films and degradation products of the composites showed little-to-no toxicity. These results demonstrate that novel 4-arm poly(lactic acid urethane)-maleate (4PLAUMA) elastomer and its nHA composites may have potential applications in regenerative medicine.  相似文献   
77.
In this article, new compounds based on the carbazole scaffold (DMs = DM1 and DM2, constituted by a carbazole unit connected on positions 3 and 6 to a two 4,4′‐dimethoxydiphenylamine groups and differing by the substituent present on the nitrogen heteroatom of the carbazole core) were synthesized and proposed as high‐performance visible light photoinitiators/photosensitizers for both the free‐radical polymerization of methacrylates and the cationic polymerization of epoxides upon visible light exposure using LED@405 nm. Remarkably, DM2 leads to higher final conversions than DM1. In order to study the photophysical and photochemical properties of the carbazole derivatives, different parameters were taken into account such as the light absorption, the steady‐state photolysis, and the fluorescence spectroscopy. Using different techniques such as fluorescence quenching, redox behavior, and cyclic voltammetry, we are able to discuss the photosensitization/photoinitiation reactions providing a full coherent picture of the involved chemical mechanisms. The photosensitization of the carbazole derivatives occurred predominantly via singlet excited states at the rate of the diffusion limit. Upon exposure to laser diode at 405 nm, DMs show high performance in initiating systems for 3D resins. Remarkably, DM2 can also be used in photocomposite synthesis using light‐emitting diode conveyor. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2081–2092  相似文献   
78.
79.
The effect of UV irradiation on the morphology and structure of syndiotactic polypropylene (sPP) is investigated both for pure films and those filled with multiwall carbon nanotubes (MWCNTs). UV treatment causes a structural reorganization of pure sPP films. It seems that the incorporation of MWCNTs has a strong stabilizing effect, with nanotubes acting as a limiter of the UV‐induced chain breakage, especially when a good dispersion of carbon nanotubes in the polymer is achieved. The incorporation of MWCNTs introduces a high concentration of defects in the crystal structure of sPP, which limits the UV‐induced growth of crystallites, and prevents the development and propagation of cracks caused by UV irradiation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   
80.
The mechanical characterization of complex soft matter by quasi-static magnetometry using nanoscopic magnetic probes is demonstrated for model hydrogels doped with two types of elongated magnetic nanoparticles. Chemically crosslinked poly(acrylamide) (PAAm) hydrogels serve as the matrix in which nickel nanorods or weakly magnetized hematite (α-Fe2O3) ellipsoids are embedded as local probes. We investigated the swelling behavior of the ferrogels in order to verify that their equilibrium swelling degree in water is not influenced by the probes, shows a good correlation with the Frenkel–Flory–Rehner model. The proposed magnetomechanical method relies on a correlation between the shear modulus of the PAAm hydrogel matrix and the coercive fields of the corresponding isotropic ferrogels. By extending the Stoner–Wohlfarth model for single-domain blocked magnetic particles by a term for particle rotation in an elastic matrix, information on the shear modulus of the matrix can be obtained. Comparison of the results with the expected relation from rubber elasticity theory illustrates both the general potential as well as the limits of the approach. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  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