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61.
Shampa Kandoi Jeff Greeley Marco A. Sanchez-Castillo Steven T. Evans Amit A. Gokhale James A. Dumesic Manos Mavrikakis 《Topics in Catalysis》2006,37(1):17-28
A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition
pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT)
calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004)
3910]. Results from reaction kinetics experiments show that the rate of H2 production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by
the presence of CO or H2 with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers
derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives
insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the
effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH3OH→H2COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol
is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species. 相似文献
62.
Photocatalytic activities for water decomposition were examined for photocatalysts using hexa- and octa-titanates and TiO2(B) with different tunnel space in the structure. Using RuO2 as promoter, M2Ti6O13 (M = Li, Na, K, Rb) showed the stoichiometric production of Hz and O2 except for Li, whereas H2Ti8O17 and TiO2(B) had very low activity producing only hydrogen as a product. The effects of promoters on Na2Ti6O13 showed that the activity increased in the order of RuO2 > RuO2 + IrO2 > IrO2 > RuO2 + Pt > MnO2. These effects along with other related ones are discussed: it emerges that the presence of the tunnels is important for the achievement of high photocatalytic activity. 相似文献
63.
A decomposition algorithm for scheduling problems based on timed automata (TA) model is proposed. The problem is represented as an optimal state transition problem for TA. The model comprises of the parallel composition of submodels such as jobs and resources. The procedure of the proposed methodology can be divided into two steps. The first step is to decompose the TA model into several submodels by using decomposable condition. The second step is to combine individual solution of subproblems for the decomposed submodels by the penalty function method. A feasible solution for the entire model is derived through the iterated computation of solving the subproblem for each submodel. The proposed methodology is applied to solve flowshop and jobshop scheduling problems. Computational experiments demonstrate the effectiveness of the proposed algorithm compared with a conventional TA scheduling algorithm without decomposition. 相似文献
64.
65.
针对海绵城市径流总量控制目标,提出一种在城市规划体系中控制性详细规划和修建性详细规划阶段分解落实年径流总量控制率的方法。在控制性详细规划阶段分解径流总量控制指标时,分步骤先后确定各项低影响开发措施的面积率和下沉深度;在修建性详细规划阶段,配合径流总量控制指标分解结果,给出适宜的各项低影响开发措施的技术实施导则,以保证各单项指标的正确实施,并以某项目为例介绍了技术实施导则的构建方法。 相似文献
66.
Platinum-based catalysts, for the electro-oxidation of methanol, have been made by thermal decomposition of chloride precursors onto titanium mesh. The catalysed electrodes were successfully operated in acidic methanol electrolytes. Electrochemical characterisation has been carried out using cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic polarisations. A complete analysis of the electrochemical results showed that the preliminary performance of the catalysed titanium mesh was comparable to that achieved with carbon-supported PtRu catalysts. The catalysts formed on titanium mesh by thermal decomposition also exhibited dimensional stability. Catalysed titanium mesh therefore appears to be a promising alternative to carbon-supported catalysts for certain fuel cell applications. 相似文献
67.
68.
介绍和评述了诊断含能材料热分解和推进剂燃烧波结构的方法、仪器和研究进展,以及含能材料和推进剂热分解和燃烧波结构的研究结果,探讨了燃烧机理研究方法的发展方向。提出需要不断完善和更新推进剂燃烧的诊断方法,以获得更为全面的接近真实条件下推进剂燃烧的有效信息。附参考文献14篇。 相似文献
69.
T.V. Choudhary A.K. Santra C. Sivadinarayana B.K. Min C.-W. Yi K. Davis D.W. Goodman 《Catalysis Letters》2001,77(1-3):1-5
Ammonia decomposition on Ir(100) has been studied over the pressure range from ultrahigh vacuum to 1.5 Torr and at temperatures ranging from 200 to 800 K. The kinetics of the ammonia decomposition reaction was monitored by total pressure change. The apparent activation energy obtained in this study (84 kJ/mol) is in excellent agreement with our previous studies using supported Ir catalysts (Ir/Al2O3 82 kJ/mol). Partial pressure dependence studies of the reaction rate yielded a positive order (0.9±0.1) with respect to ammonia and negative order (–0.7 ±0.1) with respect to hydrogen. Temperature-programmed desorption data from clean and hydrogen co-adsorbed Ir(100) surfaces indicate that ammonia undergoes facile decomposition on both these surfaces. Recombinative desorption of N2 is the rate-determining step with a desorption activation energy of 63 kJ/mol. Co-adsorption data also indicate that the observed negative order with respect to hydrogen pressure is due to enhancement of the reverse reaction (NH
x
+ H NH
x+1, x=0–2) in the presence of excess H atoms on the surface. 相似文献
70.
针对离散Hopfield 神经网络(DHNN) 的权值设计问题, 提出一种改进型学习算法, 并在DHNN动力学分析的基础上设计该学习算法. 利用矩阵分解的方法(MD) 得到正交矩阵, 并采用得到的正交矩阵直接计算DHNN的权值矩阵. 通过该学习算法得到的权值矩阵, 可以很好地存储训练样本的信息, 使测试样本收敛到稳定点. 该学习算法不需要进行分块计算, 减少了计算步骤和计算量, 降低了网络的迭代次数, 从而提高了网络运行速度. 最后, 将该学习算法应用于水质评价, 验证了其有效性和可行性. 相似文献