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991.
A model has been developed to study the effects of chemical kinetics on the residue curve maps (RCM) for reactive distillation systems with liquid phase splitting. In the model, chemical reaction can occur in both or only one of the two liquid phases. The heating policy V/V0=H/H0 is applied so that the kinetic effect can be described by a single parameter, the Damköhler number Da. The effects of reaction kinetics on pseudohomogeneous and heterogeneous mixtures have been compared. The properties of their RCMs are the same outside, but are fully different inside the liquid-liquid (L-L) region if they have different chemical equilibrium curves. Inside the L-L region, the chemical equilibrium curve coincides to a unique reactive liquid-liquid tie line in case that the pseudohomogeneous chemical equilibrium curve intersects with the L-L envelope. When the reaction occurs in only one of the two liquid phases, the residue curves inside the L-L region are strongly affected by the L-L envelope, especially at high Da. In the present paper, first an illustrative arbitrary reaction system, and then the reaction of cyclohexene with water to cyclohexanol are analysed with respect to their RCMs. 相似文献
992.
Vessela D. Kortenska Milena P. Velikova Nedyalka V. Yanishlieva Iskra R. Totzeva Vassya S. Bankova Maria C. Marcucci 《European Journal of Lipid Science and Technology》2002,104(1):19-28
The effects of seven (prenyl‐ and methoxy‐) derivatives of cinnamic acid (0.1 mM) on the kinetics of lipid (sunflower oil triacylglycerols, TGSO) bulk phase oxidation at 80 °C have been compared. Synthesis of prenyl cinnamic acid derivatives: 3‐prenyl‐4‐hydroxy‐cinnamic acid (PHC), 3,5‐diprenyl‐4‐hydroxy‐cinnamic acid (DPHC), 2,2‐di‐methyl‐6‐carboxy‐ethenyl‐2H‐benzopyran (DMCB), 2,2‐dimethyl‐6‐carboxy‐ethenyl‐8‐prenyl‐2H‐benzopyran (DCEPB) present in Brazilian propolis has been performed. The monoprenyl derivative (PHC) has been found to exert a higher antioxidant activity as compared to the diprenyl derivative (DPHC). However, cinnamic acid derivatives DMCB and DCEPB have caused no change in the kinetics of TGSO oxidation. The results obtained have been compared with those on related compounds containing a cinnamic acid moiety as a structural feature, such as 4‐hydroxy‐cinnamic (p‐coumaric), 3‐methoxy‐4‐hydroxy‐cinnamic (ferulic) and 3,5‐dimethoxy‐4‐hydroxy‐cinnamic (sinapic) acids, as well as with data on butylated hydroxytoluene (BHT) and α‐tocopherol (αToc). PHC has shown a stronger antioxidant efficiency than BHT, p‐coumaric and ferulic acid, but a weaker antioxidant efficiency than α‐Toc and sinapic acid. The observed antioxidant effect of DPHC was stronger than that of p‐coumaric and ferulic acids and weaker than that of α‐Toc, BHT and sinapic acid. 相似文献
993.
Pramod Kandanarachchi Andrew Guo Dmytro Demydov Zoran Petrovic 《Journal of the American Oil Chemists' Society》2002,79(12):1221-1225
The kinetics and mechanism of the hydroformylation of soybean oil by homogeneous ligand-modified rhodium catalysts were investigated
at 70–130°C and 4000–11,000 kPa. The effects of reaction rates on systematic variations in reaction parameters were evaluated
in order to develop an industrial process to convert vegetable oils to polyaldehydes. The activation energies in the presence
of triphenylphosphine (Ph3P) (61.1±0.8 kJ/mol) (mean±SD) and triphenyl phosphite [(PhO)3P] (77.4±5.0 kJ/mol) were determined. The catalyst was deactivated at temperatures higher than 100°C. An evaluation of the
effects of the reaction parameters on initial rates yielded the rate laws for Ph3P {rate=k [olefin][Rh(CO)2Acac]1.1 [Ph3P]−0.5 (pH2+pCO)1.4, where Rh(CO)2Acac is (acetylacetonato)dicarbonylrhodium (I)} and (PhO)3P {rate=[olefin] [Rh(CO)2Acac]1.2 [(PhO)3P]−0.8 (pH2+pCO)0.9 at total pressures lower than 7000 kPa, and rate =[olefin] [Rh(CO)2Acac]1.2 [(PhO)3P]−0.8(pH2+pCO)1.7 at total pressures higher than 7000 kPa}. 相似文献
994.
M. Saaoudi E. Chassaing M. Cherkaoui M. Ebntouhami 《Journal of Applied Electrochemistry》2002,32(12):1331-1336
Electroless NiP films, with 12 to 16 wt % P, were deposited from a moderately acid solution. Thermogravimetric analysis indicates the presence of occluded hydrogen in the layers, which desorbs upon heating. The amount of incorporated hydrogen decreases when the pH of the solution or the nickel sulfate concentration is increased; by contrast it increases with hypophosphite concentration. Cyclic voltammetry, using an electrochemical quartz crystal microbalance, confirms the existence of parasitic reactions, namely the reduction of protons of the solvent during the cathodic process and oxidation of hydrogen during the dissolution of the layers. This behaviour is in qualitative agreement with the proposed reaction scheme. 相似文献
995.
Ressler Thorsten Wienold Julia Jentoft Rolf E. Neisius Thomas Günter Marco M. 《Topics in Catalysis》2002,18(1-2):45-52
The potentials of X-ray absorption spectroscopy (XAS) (quantitative phase composition and average valence together with a short-range order structure analysis) combined with a time-resolution in the second range make time-resolved (TR-) XAS a powerful tool for investigating the reactivity of solids in catalysis and solid-state chemistry. General aspects of TR-XAS investigations are discussed (i.e., instrumentation, data analysis). In addition, some experiments illustrate how the kinetics of solid-state reactions in heterogeneous catalysis can be elucidated from TR-XAS studies. 相似文献
996.
过渡金属离子液相催化氧化烟气脱硫 总被引:10,自引:1,他引:10
烟气脱硫技术属我国环保市场急需的关键技术。过渡金属离子液相催化氧化烟气脱硫技术可以利用产生的稀硫酸制取石膏、肥料和聚合硫酸铁等多种高附加值的副产品。阐述了烟气脱硫的反应机理、脱硫吸收液和脱硫装置 ,以及吸收液酸度、温度、液气比、气速和入口浓度等因素对脱硫效率的影响。评述了金属离子的协同作用、各种工艺路线及副产物 相似文献
997.
超临界水氧化技术是一种快速彻底降解废水中有机物质的新型处理技术。在超临界水氧化有机物中 ,乙酸被认为是一种中间产物 ,乙酸氧化是反应速率的控制步骤 ,其氧化动力学的研究对反应器设计具有重要意义。大部分研究都集中在动力学参数和反应条件如温度、压力、密度和停留时间上。最近的研究发现加入二氧化锰等催化剂 ,可缓和反应温度、压力条件 ,以达到高效节能的目的。综述了目前在超临界水氧化乙酸动力学方面的研究进展。对连续平推流或间歇反应器中实验数据用幂指数曲线拟合得到的动力学方程表明 ,乙酸氧化为一级反应 相似文献
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