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   4607篇
  免费   306篇
  国内免费   1106篇
化学   5053篇
晶体学   16篇
力学   174篇
综合类   47篇
数学   208篇
物理学   521篇
  2024年   14篇
  2023年   50篇
  2022年   138篇
  2021年   184篇
  2020年   206篇
  2019年   146篇
  2018年   115篇
  2017年   143篇
  2016年   185篇
  2015年   159篇
  2014年   185篇
  2013年   289篇
  2012年   329篇
  2011年   220篇
  2010年   232篇
  2009年   314篇
  2008年   439篇
  2007年   289篇
  2006年   312篇
  2005年   276篇
  2004年   235篇
  2003年   200篇
  2002年   151篇
  2001年   141篇
  2000年   144篇
  1999年   115篇
  1998年   113篇
  1997年   104篇
  1996年   112篇
  1995年   92篇
  1994年   89篇
  1993年   86篇
  1992年   55篇
  1991年   39篇
  1990年   24篇
  1989年   23篇
  1988年   16篇
  1987年   18篇
  1986年   9篇
  1985年   5篇
  1984年   6篇
  1983年   1篇
  1982年   7篇
  1981年   2篇
  1980年   1篇
  1979年   3篇
  1976年   2篇
  1971年   1篇
排序方式: 共有6019条查询结果,搜索用时 15 毫秒
31.
Polypropylene microporous membranes were treated with plasma in a mixture of N2 and H2 (1:2 in volume). Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and ultra-violet (UV) spectra demonstrated the success of grafting amino groups. The density of the polar amino groups on the membrane surface is about 0.59 μmol/cm^2. The as-treated membranes were successively applied to the in situ synthesis of oligonucleotides and an average coupling yield was more than 98%. The surface feature of the treated membrane is suggested to be responsible for its advantage over a glass slide.  相似文献   
32.
The sulfonated poly(ether ether ketone sulfone) (SPEEKS)/heteropolyacid (HPA) composite membranes with different HPA content in SPEEKS copolymers matrix with different degree of sulfonation (DS) were investigated for high temperature proton exchange membrane fuel cells. Composite membranes were characterized by Fourier transfer infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR band shifts suggested that the sulfonic acid groups on the copolymer backbone strongly interact with HPA particles. SEM pictures showed that the HPA particles were uniformly distributed throughout the SPEEKS membranes matrix and particle sizes decreased with the increment of copolymers' DS. The holes were not found in SPEEKS‐4/HPA30 (consisting of 70% SPEEKS copolymers with DS = 0.8 and 30% HPA) composite membrane after composite membranes were treated with boiling water for 24 h. Thermal stabilities of the composite membranes were better than those of pure sulfonated copolymers membranes. Although the composite membranes possessed lower water uptake, it exhibited higher proton conductivity for SPEEKS‐4/HPA30 especially at high temperature (above 100 °C). Its proton conductivity linearly increased from 0.068 S/cm at 25 °C to 0.095 S/cm at 120 °C, which was higher than 0.06 S/cm of Nafion 117. In contrast, proton conductivity of pure SPEEKS‐4 membrane only increased from 0.062 S/cm at 25 °C to 0.078 S/cm at 80 °C. At 120 °C, proton conductivity decreased to poor 0.073 S/cm. The result indicated that composite membranes exhibited high proton conductivity at high temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1967–1978, 2006  相似文献   
33.
The direct methanol fuel cell (DMFC) has the potential to replace lithium‐ion rechargeable batteries in portable electronic devices, but currently experiences significant power density and efficiency losses due to high methanol crossover through polymer electrolyte membranes (PEMs). Numerous publications document the synthesis and characterization of new PEMs for the DMFC. This article reviews this research, transport phenomena in PEMs, and experimental techniques used to evaluate new PEMs for the DMFC. Although many PEMs do not show significant improvements over Nafion®, the benchmark PEM in DMFCs, experimental results show that several new PEMs exhibit lower methanol crossover at similar proton conductivities and/or higher DMFC power densities. These results and recommendations for future research are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Parts B: Polym Phys 44: 2201–2225, 2006  相似文献   
34.
The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006  相似文献   
35.
A series of sulfonated poly(aryl ether ether ketone ketone)s statistical copolymers with high molecular weights were synthesized via an aromatic nucleophilic substitution polymerization. The sulfonation content (SC), defined as the number of sulfonic acid groups contained in an average repeat unit, could be controlled by the feed ratios of monomers. Flexible and strong membranes in sodium sulfonate form could be prepared by the solution casting method, and readily transformed to their proton forms by treating them in 2 N sulfuric acid. The polymers showed high Tgs, which increased with an increase in SC. Membranes prepared from the present sulfonated poly(ether ether ketone ketone) copolymers containing the hexafluoroisopropylidene moiety (SPEEKK‐6F) and copolymers containing the pendant 3,5‐ditrifluoromethylphenyl moiety (SPEEKK‐6FP) had lower water uptakes and lower swelling ratios in comparison with previously prepared copolymers containing 6F units. All of the polymers possessed proton conductivities higher than 1 × 10?2 S/cm at room temperature, and proton conductivity values of several polymers were comparable to that of Nafion at high relative humidity. Their thermal stability, oxidative stability, and mechanical properties were also evaluated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2299–2310, 2006  相似文献   
36.
The method of condensed matter physics is applied to reason out the problem of Na transport through a biological membrane. A similiarity of gating process in Na ion channel to the superionic phase transition is discussed. A possible microscopic mechanism is suggested.  相似文献   
37.
Both homogeneous and asymmetric polyethersulfone (PES) membranes were prepared by solvent casting. The sorption and permeation behavior of CO2, O2, and N2 using these two kinds of cast PES membranes and commercially available homogeneous PES film was investigated to extract the pressure dependence of gas permeability and the permselectivity for CO2 relative to N2, and to confirm the validity of the working assumption that a skin layer in an asymmetric membrane can be essentially replaced by a thick homogeneous dense membrane. The pressure dependence of the mean permeability coefficient to CO2 in homogeneous membranes obeys the dual-mode mobility model. The ideal separation factor for CO2 relative to N2 at an upstream pressure of 0.5 MPa attains ca. 40, while the permeability to CO2 is about 2.7 Barrer at the same upstream pressure. The same separation factor in asymmetric membranes amounts to 35. The diffusion behavior for the skin layer in an asymmetric membrane with a thin skin layer can be simulated approximately by that in a homogeneous dense membrane. © 1993 John Wiley & Sons, Inc.  相似文献   
38.
本文研究了用于示波电位滴定的PVC膜电极,成功地用于中和、络合及沉淀滴定,并探讨了它们在药物分析中的应用。所研究电极见表1。实验部分一仪器与试剂 SR-071型双踪示波器,213型铂片电极  相似文献   
39.
穿过液膜的自发电势振荡   总被引:2,自引:0,他引:2  
An artificial membrane consisting of pricramic acid in nitrobenzene was used as an oil phase imposed between two aqueous phases. The right one contained trimethyl-slearylammonium chloride and aicohol; and the left contained sucrose solution (or H_2O). We found that this system exhibited rhythmic oscillation of electrical potential. The amplitude of the oscillations was between 20—150 mV. The oscillations were observed even when ethyl alcohol was absent in the aqueous of trimethylslearylammonium Chloride, and the increase in amplitude of oscillation with time was found to be less in the presence of sucrose. Some of the expremental results have been explained.  相似文献   
40.
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