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   1928篇
  免费   133篇
  国内免费   6篇
化学   1630篇
晶体学   13篇
力学   43篇
数学   94篇
物理学   287篇
  2023年   12篇
  2022年   45篇
  2021年   54篇
  2020年   40篇
  2019年   56篇
  2018年   30篇
  2017年   27篇
  2016年   89篇
  2015年   60篇
  2014年   77篇
  2013年   151篇
  2012年   160篇
  2011年   195篇
  2010年   120篇
  2009年   85篇
  2008年   137篇
  2007年   120篇
  2006年   103篇
  2005年   68篇
  2004年   76篇
  2003年   61篇
  2002年   69篇
  2001年   31篇
  2000年   35篇
  1999年   24篇
  1998年   14篇
  1997年   13篇
  1996年   15篇
  1995年   8篇
  1994年   8篇
  1993年   18篇
  1992年   5篇
  1991年   6篇
  1990年   6篇
  1989年   4篇
  1988年   4篇
  1987年   7篇
  1986年   3篇
  1985年   6篇
  1984年   4篇
  1983年   2篇
  1981年   3篇
  1980年   3篇
  1979年   4篇
  1978年   3篇
  1976年   1篇
  1975年   1篇
  1974年   1篇
  1972年   2篇
  1971年   1篇
排序方式: 共有2067条查询结果,搜索用时 15 毫秒
1.
Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS2, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec?1 and a charge transfer resistance (Rct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer.  相似文献   
2.
3.
Burn‐in is a widely used method to improve the quality of products or systems after they have been produced. In this paper, we consider the problem of determining the optimal burn‐in time and optimal work size maximizing the long‐run average amount of work saved per time unit in the computer applications. Assuming that the underlying lifetime distribution of the computer has an initially decreasing or/and eventually increasing failure rate function, an upper bound for the optimal burn‐in time is derived for each fixed work size and a uniform (with respect to the burn‐in time) upper bound for the optimal work size is also obtained. Furthermore, it is shown that a non‐trivial lower bound for the optimal burn‐in time can be derived if the underlying lifetime distribution has a large initial failure rate. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   
4.
To study living anionic polymerization, 3‐(triethylsilyl)propyl isocyanate (TEtSPI) monomer was synthesized by hydrosilylation of allylamine with triethylsilane and treatment of the resulting amine with triphosgene. The polymerization of TEtSPI was performed with sodium naphthalenide (Na‐Naph) as an initiator and in the absence and presence of sodium tetraphenylborate (NaBPh4) as an additive in tetrahydrofuran (THF) at ?78 and at ?98 °C. A highly stabilized amidate anion for living polymerization of isocyanates was generated for the first time with the combined effect of the bulky substituent and the shielding action of the additive NaBPh4, extending the living character at least up to 120 min at ?98 °C. Even the anion could exist at ?78 °C for 10 min. A block copolymer, poly(n‐hexyl isocyanate)‐b‐poly[(3‐triethylsilyl)propyl isocyanate]‐b‐poly(n‐hexyl isocyanate), was synthesized with quantitative yields and controlled molecular weights via living anionic polymerization in THF at ?78 °C for TEtSPI and ?98 °C for n‐hexyl isocyanate, respectively, with Na‐Naph with three times of NaBPh4 as a common ion salt. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 933–940, 2004  相似文献   
5.
The desorption behavior of a surfactant in a linear low‐density polyethylene (LLDPE) blend at elevated temperatures of 50, 70, and 80 °C was studied with Fourier transform infrared spectroscopy. The composition of the LLDPE blend was 70:30 LLDPE/low‐density polyethylene. Three different specimens (II, III, and IV) were prepared with various compositions of a small molecular penetrant, sorbitan palmitate (SPAN‐40), and a migration controller, poly(ethylene acrylic acid) (EAA), in the LLDPE blend. The calculated diffusion coefficient (D) of SPAN‐40 in specimens II, III, and IV, between 50 and 80 °C, varied from 1.74 × 10?11 to 6.79 × 10?11 cm2/s, from 1.10 × 10?11 to 5.75 × 10?11 cm2/s, and from 0.58 × 10?11 to 4.75 × 10?11 cm2/s, respectively. In addition, the calculated activation energies (ED) of specimens II, III, and IV, from the plotting of ln D versus 1/T between 50 and 80 °C, were 42.9, 52.7, and 65.6 kJ/mol, respectively. These values were different from those obtained between 25 and 50 °C and were believed to have been influenced by the interference of Tinuvin (a UV stabilizer) at elevated temperatures higher than 50 °C. Although the desorption rate of SPAN‐40 increased with the temperature and decreased with the EAA content, the observed spectral behavior did not depend on the temperature and time. For all specimens stored over 50 °C, the peak at 1739 cm?1 decreased in a few days and subsequently increased with a peak shift toward 1730 cm?1. This arose from the carbonyl stretching vibration of Tinuvin, possibly because of oxidation or degradation at elevated temperatures. In addition, the incorporation of EAA into the LLDPE blend suppressed the desorption rate of SPAN‐40 and retarded the appearance of the 1730 cm?1 peak. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1114–1126, 2004  相似文献   
6.
Anilines react with epoxides in dioxane at 180°C in the presence of a catalytic amount of a ruthenium catalyst along with tin(II) chloride to afford 2-substituted indoles in moderate to good yields.  相似文献   
7.
The mathematical model for predicting the precision, limit of detection (LOD) and range of quantitation (ROQ) in a competitive enzyme-linked immunosorbent assay (ELISA) proposed by Hayashi et al. (Anal. Chem., 2004, 76, 1295) was validated. The model describes the relative standard deviation (RSD) of concentration estimates by the RSDs of pipetting volumes of analyte, enzyme-conjugated antigen, antibody and substrate solutions, and the standard deviation (SD) of inherent absorbances between the wells in an ELISA plate. For 6 kinds of direct competitive ELISA kits, the LOD and ROQ predicted by the model agreed well with those obtained by experiments with real samples. It was also confirmed that the model is applicable to the prediction of uncertainty that depends on the pipetting error of the viscous antiserum solution. The model was demonstrated to be useful for estimating the LOD and ROQ of competitive ELISA.  相似文献   
8.
We theoretically investigated a digitally tunable laser with a chirped ladder filter and a ring resonator to obtain a wide wavelength tuning range covering the whole C- or L- band. The clear relation between the tuning range and laser structure, especially the ladder filter, is described analytically. The introduction of a chirped structure into a ladder filter is effective in achieving both wide tunability and a stable lasing mode. A numerical simulation based on multimode rate equations shows that a tuning range of over 40 nm and a mode suppression ratio over 40 dB can be achieved by introducing a chirped ladder filter.  相似文献   
9.
Polyvinyl alcohol (PVA) nanofibers containing Ag nanoparticles were prepared by electrospinning PVA/silver nitrate (AgNO3) aqueous solutions, followed by short heat treatment, and their antimicrobial activity was investigated for wound dressing applications. Since PVA is a water soluble and biocompatible polymer, it is one of the best materials for the preparation of wound dressing nanofibers. After heat treatment at 155 °C for 3 min, the PVA/AgNO3 nanofibers became insoluble, while the Ag+ ions therein were reduced so as to produce a large number of Ag nanoparticles situated preferentially on their surface. The residual Ag+ ions were reduced by subsequent UV irradiation for 3 h. The average diameter of the Ag nanoparticles after the heat treatment was 5.9 nm and this value increased slightly to 6.3 nm after UV irradiation. It was found that most of the Ag+ ions were reduced by the simple heat treatment. The PVA nanofibers containing Ag nanoparticles showed very strong antimicrobial activity. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2468–2474, 2006  相似文献   
10.
Kum  Jun Sig  Kim  Sam Jin  Shim  In Bo  Kim  Chul Sung 《Hyperfine Interactions》2004,158(1-4):169-173
It is shown that in-situ 166mHo (I = 7) in a spherical single crystal of HoF3 can be used as sensitive internal thermometer to thermally detect NMR (NMR-TDNO) from the 100% abundant stable 165Ho (I = 7/2) nuclei. In addition, new 166mHo NMRON results are reported. Both the 166mHo NMRON and 165Ho NMR-TDNO spectra show three distinct quadrupolar split sub-resonances, in zero applied field. The data is used to make estimates of the Ho magnetic moments and quadrupole parameters for the 166mHo and 166mHo sites.  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