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   9560篇
  免费   1068篇
  国内免费   1675篇
化学   9488篇
晶体学   48篇
力学   209篇
综合类   75篇
数学   344篇
物理学   2139篇
  2024年   20篇
  2023年   103篇
  2022年   233篇
  2021年   331篇
  2020年   377篇
  2019年   312篇
  2018年   261篇
  2017年   285篇
  2016年   407篇
  2015年   369篇
  2014年   411篇
  2013年   750篇
  2012年   658篇
  2011年   554篇
  2010年   516篇
  2009年   630篇
  2008年   739篇
  2007年   593篇
  2006年   593篇
  2005年   553篇
  2004年   490篇
  2003年   447篇
  2002年   354篇
  2001年   285篇
  2000年   284篇
  1999年   235篇
  1998年   222篇
  1997年   188篇
  1996年   188篇
  1995年   154篇
  1994年   149篇
  1993年   137篇
  1992年   100篇
  1991年   67篇
  1990年   51篇
  1989年   55篇
  1988年   39篇
  1987年   34篇
  1986年   27篇
  1985年   11篇
  1984年   23篇
  1983年   8篇
  1982年   13篇
  1981年   8篇
  1980年   6篇
  1979年   9篇
  1978年   4篇
  1977年   8篇
  1976年   5篇
  1975年   3篇
排序方式: 共有10000条查询结果,搜索用时 140 毫秒
81.
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   
82.
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   
83.
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   
84.
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   
85.
Efficient vectorial processes such as the transduction of bioenergy and signals are characteristics that strikingly distinguish living systems from inanimate materials. Recent developments in biophysical and biochemical techniques have provided new information about the structure, dynamics and interaction of biomolecules involved in vectorial life processes at multiple length and temporal scales. This wealth of data makes it possible to carry out theoretical and computational studied of key mechanistic questions associated with complex life processes at an unprecedented level. Using two “vectorial biomolecular machines”, myosin and cytochrome c oxidase, as examples, we discuss the identification of interesting and biologically relevant questions that require thorough theoretical analysis. Technical challenges and recent progress related to these theoretical investigations are briefly summarized  相似文献   
86.
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   
87.
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   
88.
尚小明  汤国庆  张桂兰  陈文驹 《光学学报》1996,16(10):1371-1378
报道了以N2激光为泵浦光源,获得激发态分子内质子转移(ESIPT)分子HBO的激光输出现象。其激光转换效率约为17%,调谐范围为495~540nm,最强的输出波长在510nm。以HBO的激发态分子内质子转移的光物理和光化学过程为基础,建立了HBO产生激光的动态模型,数值模拟了在宽带和窄带情况下激光输出的光谱特性和时间特性,理论计算值与实验观测值很好相符,同时证实了激发态分子内质子转移分子的激光脉冲宽度依赖于激发态分子内质子转移分子的酮式异构体的基态S′0的寿命  相似文献   
89.
The limiting molar conductances ° of deuterium chloride DCl in D2O were determined as a function of pressure and temperature in order to examine the proton-jump mechanism in detail. The excess deuteron conductances °E(D +), as estimated by the equation [°E(D +) = °(DCl/D 2 O) – °(KCl/D 2 O)], increases with an increase in the pressure and temperature as well as the excess proton conductance [°E(H +) = °(HCl/H 2 O) – °(KCl/H 2 O)]. The isotope effect on the excess conductances, however, depends on the pressure and temperature contrary to the model proposed by Conway et al.: °E(H +)/°E(D +) decreases with increasing pressure and temperature. The magnitude of the decrease with pressure becomes more prominent at lower temperature. These results are discussed in terms of the pre-rotation of adjacent water molecules, the bending of hydrogen bonds with pressure, and the difference in strength of hydrogen bonds between D2O and H2O.  相似文献   
90.
Considering a system ofN identical interacting particles, which obey Fermi-Dirac or Bose-Einstein statistics, we derive new formulas for correlation functions of the type (whereB j is diagonal in the free-particle states) in the thermodynamic limit. Thereby we apply and extend a superoperator formalism, recently developed for the derivation of long-time tails in semiclassical systems. As an illustrative application, the Boltzmann equation value of the time-integrated correlation functionC(t) is derived in a straightforward manner. Due to exchange effects, the obtained t-matrix and the resulting scattering cross section, which occurs in the Boltzmann collision operator, are now functionals of the Fermi-Dirac or Bose-Einstein distribution.  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