全文获取类型
收费全文 | 1581篇 |
免费 | 21篇 |
国内免费 | 404篇 |
专业分类
化学 | 1726篇 |
晶体学 | 8篇 |
力学 | 22篇 |
综合类 | 2篇 |
数学 | 3篇 |
物理学 | 245篇 |
出版年
2024年 | 3篇 |
2023年 | 62篇 |
2022年 | 24篇 |
2021年 | 25篇 |
2020年 | 30篇 |
2019年 | 26篇 |
2018年 | 16篇 |
2017年 | 26篇 |
2016年 | 36篇 |
2015年 | 37篇 |
2014年 | 46篇 |
2013年 | 117篇 |
2012年 | 76篇 |
2011年 | 72篇 |
2010年 | 72篇 |
2009年 | 131篇 |
2008年 | 131篇 |
2007年 | 160篇 |
2006年 | 127篇 |
2005年 | 85篇 |
2004年 | 93篇 |
2003年 | 68篇 |
2002年 | 45篇 |
2001年 | 47篇 |
2000年 | 52篇 |
1999年 | 43篇 |
1998年 | 38篇 |
1997年 | 33篇 |
1996年 | 33篇 |
1995年 | 31篇 |
1994年 | 26篇 |
1993年 | 33篇 |
1992年 | 23篇 |
1991年 | 26篇 |
1990年 | 17篇 |
1989年 | 21篇 |
1988年 | 14篇 |
1987年 | 11篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 13篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1976年 | 2篇 |
1972年 | 2篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1966年 | 2篇 |
排序方式: 共有2006条查询结果,搜索用时 15 毫秒
1.
Tanja Vidaković-Koch Tamara Miličić Luka A. Živković Hoon Seng Chan Ulrike Krewer Menka Petkovska 《Current Opinion in Electrochemistry》2021
The nonlinear frequency response analysis (NFRA) can be seen as an extension of electrochemical impedance spectroscopy. NFRA gives a full and detailed representation of the system response and can establish a connection between model parameters and the experimentally observed phenomena. In this article, different theoretical NFRA approaches and the most recent application examples are discussed. A simple electrochemical example is used to showcase the benefits and disadvantages of analyzing the system response by using different approaches. In addition, it was shown how to extract experimental harmonic values and analyze them. 相似文献
2.
Nagendranath Mahata V. Vishwanathan 《Journal of molecular catalysis. A, Chemical》1997,120(1-3):267-270
Kinetics of vapor phase hydrogenation of phenol to cyclohexanone over Pd/MgO system has been studied in a flow microreactor under normal atmospheric pressure. The reaction rate is found to be negative order with respect to the partial pressure of phenol and has increased from −0.5 to 0.5 with increasing temperature (473 to 563 K). The apparent activation energy (Ea) of the process is found to be close to 65 kJ per mol. On the basis of kinetic results a surface mechanism is proposed. 相似文献
3.
F. Gugumus 《Polymer Degradation and Stability》2006,91(11):2698-2714
Formation of carboxylic acids at a constant rate can be easily explained. It seems to result from the formation and decomposition of α,γ-keto-hydroperoxides. Formal kinetics based on formation and decomposition of these structural units is in agreement with the experimental findings. The activation energy deduced from the calculations is negligible, in agreement with the experimental data showing the constant rate to be practically temperature independent. Comparison of the acids with the hydroperoxides and ketones formed initially shows that the rate of oxygen addition to alkyl radicals is significantly smaller than in low molecular mass liquids. The same conclusion is reached on comparing directly the acids formed on decomposition of α,γ-keto-hydroperoxides in polyethylene melt and in hexadecane. The rate of oxygen addition in polyethylene melt is closer to 2 × 105 than to 6 × 105 (s−1) that is valid in hexadecane.It is possible to attribute the relatively small amount of aldehydes that might be formed at a constant rate to different reactions of alkoxy radicals that are not in a cage with other radicals. These alkoxy radicals result from the addition of peroxy radicals to unsaturated bonds. This addition is followed mainly by epoxide formation and simultaneous release of an alkoxy radical. 相似文献
4.
5.
在程序升温条件下 ,用DSC研究了标题化合物的放热分解反应动力学 .用线性最小二乘法、迭代法以及二分法与最小二乘法相结合的方法 ,以积分方程、微分方程和放热速率方程拟合DSC数据 .在逻辑选择建立了微分和积分机理函数的最可几一般表达式后 ,用放热速率方程得到相应的表观活化能 (Ea)、指前因子 (A)和反应级数 (n)的值 .结果表明 :该反应的微分形式的经验动力学模式函数、Ea 和A值分别为 (1-α) 0 .44、2 30 .4kJ/mol和 10 18.16s-1.借助加热速率和所得动力学参数值 ,提出了标题化合物放热分解反应的动力学方程 .该化合物的热爆炸临界温度为 30 2 .6℃ .上述动力学参数对分析、评价标题化合物的稳定性和热变化规律十分有用 . 相似文献
6.
F. Gugumus 《Polymer Degradation and Stability》2007,92(1):143-157
The experimental kinetics for γ-lactone formation shows more complexity than that for acids. Nonetheless, it can be concluded to the existence of a constant rate of formation from the beginning of the experiments with polyethylene melts. There is an additional term contributing to γ-lactone formation in the initial stages that is cubic in processing time. In the advanced stages of processing, in the high temperature range (170-200 °C), the concentration of γ-lactones increases linearly with the processing time.There are many mechanisms susceptible to give γ-lactones on polyethylene melt processing. Some of them are based on decomposition of intermediates formed directly on chain propagation. This is so for the α,γ-keto-hydroperoxides in 4-position to hydroxyl groups. Since decomposition of these intermediates is very fast, the reaction might account for a constant rate of γ-lactone formation from the beginning of polyethylene processing. Decomposition of the α,δ-keto-hydroperoxides formed on intramolecular reactions on chain propagation is not so fast as that of the α,γ-keto-hydroperoxides. Nonetheless, it might account for part of the delayed formation of γ-lactones. The same is valid for the mechanisms based on peroxidation of aldehydes and γ-hydroxy trans-vinylene groups that involve intermediates that are formed on polyethylene peroxidation. They might be important for explaining the cubic term as well as γ-lactone formation in the advanced stages of polyethylene processing. 相似文献
7.
用解偏振光强法和差示扫描量热法(DSC)分别研究了聚甲醛和聚甲醛助剂P的等温结晶动力学和非等温结晶动力学。探讨了助剂P对聚甲醛的结晶成核作用。 相似文献
8.
用ESR方法研究了红薯淀粉在γ射线预辐照下,产生的淀粉自由基特性及其室温下的自由基衰减动力学反应。结果表明在室温条件下,淀粉自由基的相对浓度随辐射剂量的增大而增加。自由基相对浓度的室温衰减用二级反应动力学处理,求得了衰减速率常数和淀粉自由基反应的半衰期。 相似文献
9.
Kinetic studies of PET glycolysis by diethylene glycol (DEG), dipropylene glycol (DPG), glycerol (Gly) and mixtures of these glycols have shown, in a previous study, that the order of reactivity of the glycols differs according to the conditions of temperature and catalysis. Indeed, their global reactivity depends both on their chemical reactivity and physico-chemical properties.Glycolysis of model polyesters which are liquid at the reaction temperature, which allows us to overcome the problem of the polyesters' solubility, were studied to compare the chemical reactivity of these glycols. Three oligoesters were synthesized from dimethyl terephthalate and three different glycols namely triethylene glycol, ethylene glycol and hexanediol to form, respectively, PE3T, OET and PTHD.Results showed that the order of reactivity of the glycols is the same for PET, OET and PTHD but different for PE3T. Indeed, DPG without catalyst has a particular and unexpected behaviour: its reactivity seems to be strongly influenced by the presence of oxygen atoms in the chain. 相似文献
10.
Santanu Bhattacharya Basudeb Saha Amitava Dutta Pradyot Banerjee 《Coordination chemistry reviews》1998,170(1):47-74
This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed. 相似文献