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   9762篇
  免费   946篇
  国内免费   892篇
化学   8313篇
晶体学   44篇
力学   933篇
综合类   157篇
数学   468篇
物理学   1685篇
  2024年   33篇
  2023年   125篇
  2022年   361篇
  2021年   339篇
  2020年   442篇
  2019年   358篇
  2018年   360篇
  2017年   357篇
  2016年   504篇
  2015年   442篇
  2014年   480篇
  2013年   1052篇
  2012年   590篇
  2011年   537篇
  2010年   394篇
  2009年   445篇
  2008年   422篇
  2007年   533篇
  2006年   456篇
  2005年   437篇
  2004年   380篇
  2003年   322篇
  2002年   309篇
  2001年   219篇
  2000年   223篇
  1999年   198篇
  1998年   182篇
  1997年   161篇
  1996年   135篇
  1995年   124篇
  1994年   76篇
  1993年   105篇
  1992年   92篇
  1991年   62篇
  1990年   51篇
  1989年   34篇
  1988年   35篇
  1987年   33篇
  1986年   28篇
  1985年   27篇
  1984年   24篇
  1983年   8篇
  1982年   13篇
  1981年   13篇
  1980年   15篇
  1979年   14篇
  1978年   10篇
  1976年   9篇
  1973年   10篇
  1972年   6篇
排序方式: 共有10000条查询结果,搜索用时 9 毫秒
181.
用三乙胺盐酸盐与酚醛环氧树脂开环反应合成了一种水溶性聚合物,研究了相转移催化剂、反应时间、反应温度、开环顺序等条件对反应程度的影响。研究了开环反应中丙烯酸及三乙胺盐酸盐与酚醛环氧树脂的比例对产物的水溶性及感兴性能的影响。  相似文献   
182.
本文研究了噻二唑偶氮二甲氨基苯甲酸与Cu(Ⅱ)显色反应条件,确定在pH3.0~4.5范围形成蓝紫色络合物,组成比为1:1,摩尔吸光系数ε=4.55×10~4L·mol~(-1)·cm~(-1),1gβ=7.32。应用拟定的方法测定天然水中微量铜,获得满意的结果。  相似文献   
183.
Difference and double-difference near-infrared DO-D and HO-H stretching overtone (2nuOD and 2nuOH) spectroscopy and a rigorous (physically substantiated) band deconvolution technique were applied to reveal three different kinds of inherent (interstitial) structures of liquid water, which determine its high density (compared to ice lh under ambient conditions), its compressibility (under hydrostatic pressure, up to 300MPa), and its high fragility (manifested under temperature variation). Our data processing allowed the rigorous discrimination of up to six vibrational components. On the basis of an extensive comparative analysis combined with available structural data (X-ray and neutron scattering) and molecular dynamics (MD) simulations for liquid water, as well as with experimental and computed data for small non-tetrahedrally arranged water clusters, the major four components could be ascribed to: i) The basic lh icelike substructure; ii) the temperature-dependent remote interstitial "defects" due to tetrahedral displacements (primarily responsible for transport properties); iii) the interstitial "defects" most probably arranged in quasiplanar noncyclic tetramers (totally absent in the ice structure); and iv) the interstitial "defects" formed with increasing pressure, probably arranged in cubic water octamers and composed of two pairs of noncyclic and cyclic tetramer fragments. The latter structures include, essentially, bent hydrogen bonds stabilized by resonance effects.  相似文献   
184.
The transport properties of separating membranes MF-4SK are studied during electrolysis of H2O in solutions of KOH. The effective diffusion coefficients of molecules of KOH and H2O and the transfer coefficients of ions K+ and OH? and molecules of H2O are measured at KOH concentrations reaching 11 M, currents reaching 0.31 A cm?2, at ambient temperature and at 80°C. In contact with a KOH solution in the concentration interval 0.1 to 11 M, the membranes that initially swelled in H2O lose a considerable fraction of water that was present in them and the overall volume of clusters and solution-filled channels in them noticeably decreases. The coefficients of transfer by current of ions K+ out of anodic compartment into cathodic and the OH? ions in the reverse direction, respectively, happen to be equal to about 0.6 and 0.4 at ambient temperature and 0.8 and 0.2 at 80°C. The coefficients of transfer of water molecules out of the anodic volume into the cathodic volume in the process of electrolysis happen to be in the limits 1.6–1.9 at ambient temperature and in the limits 2.2–2.8 at 80°C. The effective diffusion coefficients of molecules of KOH and H2O at moderate concentrations of KOH (5.6 M) amount to ~2.6 × 10?7 and 30 × 10?7 cm2s?1 at ambient temperature and ~4 × 10?7 and 61 × 10?7 cm2s?1 at 80°C, respectively. At a high concentration of KOH (~10 M) these quantities substantially diminish.  相似文献   
185.
The degradation of unsaturated polyesters crosslinked with styrene was performed in sub-critical water (SCW) in the absence and presence of organic additives. The unsaturated polyesters were de-crosslinked by hydrolysis of ester chains to form polystyrene derivatives on SCW treatment at 300 °C. With an increase in treating time, carboxylic acid groups in the polystyrene derivatives were turned into carboxylic anhydride groups in SCW. The de-crosslinking rate was much enhanced on SCW treatment in the presence of hydroxy compounds with a long alkyl chain and alkylamines, while carboxylic acids, benzenesulfonate salts, and quaternary ammonium salts were ineffective even though they had a long alkyl chain. The degree of de-crosslinking was reduced in the presence of diamines and amino acids because re-crosslinking at both ends of the additive molecules proceeded.  相似文献   
186.
The determination of trace elements concentration in water by electrothermal atomic absorption spectrometry (ETAAS) is a common and well established technique in many chemical testing laboratories. However, the evaluation of measurement uncertainty results is not systematically implemented. The paper presents an easy step-by-step example leading to the evaluation of the combined standard uncertainty of copper determination in water using ETAAS. The major contributors to the overall measurement uncertainty are identified due to amount of copper in water sample that mainly depends on the absorbance measurements, due to certified reference material and due to auto-sampler volume measurements. The practical aspects how the traceability of copper concentration in water can be established and demonstrated are also pointed out.  相似文献   
187.
Free-energy-perturbation theory from molecular dynamics calculations has been used to obtain the DeltaG of adjoining cavities' formation in water. The DeltaGs for systems with three, five and seven cavities are compared with that of a single cavity of the same volume, and found to be in good agreement. The conditions under which the analytical formulation of the energy of cavity formation proposed by Pierotti holds are discussed. The data for a single cavity have been tabulated and can lend themselves to a simple numerical implementation in standard quantum chemical packages, which can be used when high accuracy for DeltaG(cav) is required.  相似文献   
188.
Aqueous acrylic-polyurethane dispersions have become one of the major types of materials used in coating, paint and adhesive industries, because of excellent properties and environmental advantages1-5. However, some properties for cured film such as water…  相似文献   
189.
Oxidized chitosan derivatives with various degrees of oxidation (DS, 0.1–1.0) were prepared by the treatment of chitosan with CrO3/aq HClO4 or by the oxidation of ­3‐O‐ and N‐protected chitosan with 30% aq H2O2/Na2WO4 followed by 3‐O‐ and N‐deprotection. The oxidized products were then N‐acetylated with Ac2O in order to improve their water‐solubility. Although the oxidized chitosan derivative of DS 0.28 and the degree of N‐acetylation of chitosan (DA) 38% was insoluble in the pH 3–8 region, that of DS 0.26 and DA 76% was soluble in the neutral pH range. The newly‐prepared acetylated and oxidized chitosan derivatives were found to suppress the chemiluminescence response of inflammatory cells such as canine polymorphonuclear cells (PMNs). Analysis by the surface plasmon resonance method revealed that the bind and release behavior of PMNs to acetylated oxidized chitosan derivatives was similar to that against carboxymethylated chitosan derivatives. The amount of water‐soluble chitosan derivative bound to cytokine IL‐8 was found to be affected by the structural and electronic features of the chitosan substituents in the chitosan chain. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
190.
Cloud point extraction was applied as a method for preconcentration of rhodium after formation of a complex with 2-propylpiperidine-1-carbodithioate (2-PPC), and later determined by flame atomic absorption spectrometry using TritonX-114 as surfactant. Rhodium was complexed with 2-PPC in an aqueous phase and kept for 15 min in a thermostatted bath at 40 °C. Separation of the two phases was accomplished by centrifugation for 15 min at 4000 rpm. The chemical variables affecting the cloud point extraction were optimized and successfully applied to rhodium determination in various water samples. Under optimized conditions, the preconcentration system (100 mL sample) permitted an enhancement factor of 50. The detection limits obtained under optimal conditions was 0.052 ng mL−1. The extraction efficiency was investigated at different rhodium concentrations (7.0–42.0 μg mL−1), and good recoveries (96.42–99.14%) were obtained using this method. It has been applied to the determination of rhodium in water and was compared with reported methods in terms of Student’s ‘t’-test and variance ratio ‘f’-test.  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