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51.
Dorian Zapp Judith Scheiber Oliver Gerner Edith Fuchs Jakub Dvorak Daniel Mayer Matthias Nemestothy Rupert Steiner 《世界建筑导报》2018,(3)
正科帕卡格拉纳位于新多瑙河12.5公里处,毗邻Reichsbrücke大桥。出于同旧有设计保持协调性考虑,力求能让大楼融入当地环境,迎合自身功能性需要,GERNER GERNER PLUS团队充分考虑现有周边环境,对大楼重新规划设计。新的设计突显建筑的特殊性和重要性,面向河流的立面是科帕卡格拉纳大楼最重要的部分,所以设计的重点也放在了这里。现有的城市中轴线是一个参照物,为了视觉上和氛围上形成一体化城市的感 相似文献
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Mayer JM 《Accounts of chemical research》2011,44(1):36-46
Hydrogen atom transfer (HAT), a key step in many chemical, environmental, and biological processes, is one of the fundamental chemical reactions: A-H + B → A + H-B. Traditional HAT involves p-block radicals such as tert-BuO(?) abstracting H(?) from organic molecules. More recently, the recognition that transition metal species undergo HAT has led to a broader perspective, with HAT viewed as a type of proton-coupled electron transfer (PCET). When transition metal complexes oxidize substrates by removing H(?) (e(-) + H(+)), typically the electron transfers to the metal and the proton to a ligand. Examples with iron-imidazolinate, vanadium-oxo, and many other complexes are discussed. Although these complexes may not "look like" main group radicals, they have the same pattern of reactivity. For instance, their HAT rate constants parallel the A-H bond strengths within a series of similar reactions. Like main group radicals, they abstract H(?) much faster from O-H bonds than from C-H bonds of the same strength, showing that driving force is not the only determinant of reactivity. This Account describes our development of a conceptual framework for HAT with a Marcus theory approach. In the simplest model, the cross relation uses the self-exchange rate constants (k(AH/A) for AH + A) and the equilibrium constant to predict the rate constant for AH + B: k(AH/B) = (k(AH/A)k(BH/B)K(eq)f)(1/2). For a variety of transition metal oxidants, k(AH/B) is predicted within one or two orders of magnitude with only a few exceptions. For 36 organic reactions of oxyl radicals, k(AH/B) is predicted with an average deviation of a factor of 3.8, and within a factor of 5 for all but six of the reactions. These reactions involve both O-H or C-H bonds, occur in either water or organic solvents, and occur over a range of 10(28) in K(eq) and 10(13) in k(AH/B). The treatment of organic reactions includes the well-established kinetic solvent effect on HAT reactions. This is one of a number of secondary effects that the simple cross relation does not include, such as hydrogen tunneling and the involvement of precursor and successor complexes. This Account includes a number of case studies to illustrate these and various other issues. The success of the cross relation, despite its simplicity, shows that the Marcus approach based on free energies and intrinsic barriers captures much of the essential chemistry of HAT reactions. Among the insights derived from the analysis is that reactions correlate with free energies, not with bond enthalpies. Moreover, the radical character or spin state of an oxidant is not a primary determinant of HAT abstracting ability. The intrinsic barriers for HAT reactions can be understood, at least in part, as Marcus-type inner-sphere reorganization energies. The intrinsic barriers for diverse cross reactions are accurately obtained from the HAT self-exchange rate constants, a remarkable and unprecedented result for any type of chemical reaction other than electron transfer. The Marcus cross relation thus provides a valuable new framework for understanding and predicting HAT reactivity. 相似文献
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Silvia Patricia Galíndez‐Nájera Oswaldo Ramos‐Monroy Nora Ruiz‐Ordaz Angélica Salmerón‐Alcocer Cleotilde Juárez‐Ramírez Deifilia Ahuatzi‐Chacón Everardo Curiel‐Quesada Juvencio Galíndez‐Mayer 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》2011,86(4):554-561
BACKGROUND: The impact of mixtures of chloro‐triazinic herbicides, such as atrazine and simazine, on aquatic ecosystems is of environmental concern. To study their biodegradation under various operational conditions, a binary community comprising Stenotrophomonas maltophilia and Arthrobacter sp. attached to the porous support of a packed bed reactor, was evaluated. RESULTS: The genetic analysis of the two atrazine‐degrading strains revealed that genes atzA, atzB, atzC are present in both bacteria, but only S. maltophilia possess atzD. Thus, by cultivating Arthrobacter sp. on these herbicides, cyanuric acid accumulation was observed. When the binary community was cultivated in the biofilm reactor, at all the loading rates probed, both herbicides were entirely removed. However, complete biodegradation of cyanuric acid was not achieved. CONCLUSIONS: Even with a two‐stage reactor, cyanuric acid was only partially removed. This fact could be attributed to the absence, in the second stage, of an easily degradable energy source, required by S. maltophilia for the uptake and cometabolic degradation of the recalcitrant heterocyclic ring. Responding to differences in nutritional conditions prevailing at each reactor stage, local differences in species' predominance were clearly detected by microbiological and molecular biology methods. Copyright © 2010 Society of Chemical Industry 相似文献
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Detrimental electromechanical system interaction that can occur with the standard configuration that connects the armature circuits in series with a single regulated supply and a single tachometer for speed feedback is discussed. Three basic types of disturbance mechanism are studied. An alternative configuration with dual supplies and control systems and which provides highly beneficial electromechanical system interactions is described. These interactions prevent costly gear maintenance problems resulting from vibrations at the two lower-order torsional resonances 相似文献
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