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91.
K HondaM Yoshimura R UchikadoT Kondo Tata N Rao D.A TrykA Fujishima M WatanabeK Yasui H Masuda 《Electrochimica acta》2002,47(27):4373-4385
Electrochemical characteristics for several redox systems at diamond films with highly ordered nanometer-scale cylindrical pores (‘nano-honeycombs’) were examined with cyclic voltammetry (CV) and electrochemical impedance measurements. The cyclic voltammetric anodic-cathodic peak separations for these nano-honeycomb electrodes were in the same range as those for polished polycrystalline diamond films, indicating that the involvement of the oxygen-terminated surface of the nano-pore walls, which should give rise to large peak separations for certain redox couples was only slight. Moreover, the peak currents in the CV were not enhanced to the extent expected on the basis of the roughness factors of the nano-honeycomb films. Ac impedance plots results indicated the existence of a concentration gradient of the reactant in the nano-pores, which is in agreement with theoretical predictions for charge transfer reactions in porous electrodes. The average concentration of the reactant (Fe2+/3+) inside the nano-pores was a factor of ca. 80 lower than that in the bulk electrolyte. The results of the impedance analysis also indicated an increase in the reaction resistances with decreasing pore diameters. 相似文献
92.
MODELING AND PREDICTIVE CONTROL OF MIMO NONLINEAR SYSTEMS USING WIENER-LAGUERRE MODELS 总被引:1,自引:0,他引:1
Prabirkumar Saha S. H. Krishnan V. S. R. Rao Sachin C. Patwardhan 《Chemical Engineering Communications》2004,191(8):1083-1119
In this work, a Weiner-type nonlinear black box model was developed for capturing dynamics of open loop stable MIMO nonlinear systems with deterministic inputs. The linear dynamic component of the model was parameterized using orthogonal Laguerre filters while the nonlinear state output map was constructed either using quadratic polynomial functions or artificial neural networks. The properties of the resulting model, such as open loop stability and steady-state behavior, are discussed in detail. The identified Weiner-Laguerre model was further used to formulate a nonlinear model predictive control (NMPC) scheme. The efficacy of the proposed modeling and control scheme was demonstrated using two benchmark control problems: (a) a simulation study involving control of a continuously operated fermenter at its optimum (singular) operating point and (b) experimental verification involving control of pH at the critical point of a neutralization process. It was observed that the proposed Weiner-Laguerre model is able to capture both the dynamic and steady-state characteristics of the continuous fermenter as well as the neutralization process reasonably accurately over wide operating ranges. The proposed NMPC scheme achieved a smooth transition from a suboptimal operating point to the optimum (singular) operating point of the fermenter without causing large variation in manipulated inputs. The proposed NMPC scheme was also found to be robust in the face of moderate perturbation in the unmeasured disturbances. In the case of experimental verification using the neutralization process, the proposed control scheme was found to achieve much faster transition to a set point close to the critical point when compared to a conventional gain-scheduled PID controller. 相似文献
93.
94.
Tert‐butyl hydroquinone–based poly(cyanoarylene ether) (PENT) was synthesized by the nucleophilic aromatic substitution reaction of 2,6‐dichlorobenzonitrile with tert‐butyl hydroquinone using N‐methyl‐2‐pyrrolidone (NMP) as solvent in the presence of anhydrous potassium carbonate in a nitrogen atmosphere at 200°C. PENT‐toughened diglycidyl ether of bisphenol A epoxy resin (DGEBA) was developed using 4,4′‐diaminodiphenyl sulfone (DDS) as the curing agent. Scanning electron micrographs revealed that all blends had a two‐phase morphology. The morphology changed from dispersed PENT to a cocontinuous structure with an increase in PENT content in the blends from 5 to 15 phr. The viscoelastic properties of the blends were investigated using dynamic mechanical thermal analysis. The storage modulus of the blends was less than that of the unmodified resin, whereas the loss modulus of the blends was higher than that of the neat epoxy. The tensile strength of the blends improved slightly, whereas flexural strength remained the same as that of the unmodified resin. Fracture toughness was found to increase with an increase in PENT content in the blends. Toughening mechanisms like local plastic deformation of the matrix, crack path deflection, crack pinning, ductile tearing of thermoplastic, and particle bridging were evident from the scanning electron micrographs of failed specimens from the fracture toughness measurements. The thermal stability of the blends were comparable to that of the neat resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3536–3544, 2006 相似文献
95.
Dense blend membranes were prepared by blending hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(ethyleneimine) (PEI), which were then crosslinked by glutaraldehyde (GA) in a mixture of solvents under the catalysis of hydrochloric acid (HCl) for the dehydration of tetrahydrofuran (THF) by pervaporation. The effect of experimental parameters such as feed water concentration, permeate pressure, and membrane thicknesses on permeate parameters, i.e., flux and selectivity were determined with feed water concentration less than 40 wt %. The membranes were found to have good potential for breaking the azeotrope of 94 wt % THF with a flux of 1.072 and 0.376 kg/m2 h for plane PVA/PEI and crosslinked PVA/PEI blend membrane, which exhibited high selectivity of 156 and 579 respectively. Selectivity was found to improve with decreasing feed water concentration and increasing membrane thickness, whereas flux decreased correspondingly. High permeate pressure causes a reduction in both flux and selectivity. These effects were clearly elucidated with the aid of the known relationship among plasticization effect, degree of swelling, permeate pressure, and feed water concentration. These blend membranes were also subjected to sorption studies to evaluate the extent of interaction and degree of swelling in pure as well as binary feed mixtures. Further ion exchange capacity studies were carried out for all the crosslinked and uncrosslinked membranes to determine the total number of interacting groups present in the membranes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1152–1161, 2006 相似文献
96.
U. Sridevi Narayan C. Pradhan B.K.B. Rao C.V. Satyanarayana B.S. Rao 《Catalysis Letters》2002,79(1-4):69-73
The alkylation of benzene with isopropyl alcohol was studied in an integral pressure reactor over silicon substituted aluminophosphate molecular sieves, SAPO-5. The influence of various process parameters such as temperature, pressure, time on stream, weight hourly space velocity, and mole ratio of reactants on cumene yield and selectivity were investigated. The activity of SAPO-5 was compared with that of Hbeta for this reaction under similar conditions and in the same reactor. At pressures higher than atmospheric, almost the theoretical maximum yields of cumene were achieved on this SAPO-5. Among the diisopropyl benzenes formed by the alkylation of cumene, the meta-isomer was found to form in a significant amount followed by the para-isomer. The ortho-isomer with relatively high strain energy of 4.26 kcal/mol was almost negligible. The cumene yield goes through a maximum in the temperature range 498-543 K studied. Cumene selectivity was found to decrease at higher temperatures, higher pressures and lower benzene to isopropanol mole ratios. 相似文献
97.
98.
Summary Inside a microporous polyethylene film, 2-acrylamido-2-methylpropane sulfonic acid was graft polymerized by ultraviolet irradiation. A humidity sensor was fabricated by depositing gold electrodes on both sides of the grafted film. The impedance was measured as a function of humidity for the acid and alkali salts of sulfonate. The sensor has long term stability and is resistant to water. 相似文献
99.
100.
Several investigations have been carried out on Cu/ZnO catalysts by employing extended Xray absorption fine structure (EXAFS) and Xray photoelectron spectroscopy (XPS). EXAFS investigations of Cu/ZnO catalysts subjected to hydrogen reduction show the presence of Cu1+ species and Cu microclusters. The proportion of Cu1+ depends on the rate of increase of the reduction temperature and on the amount of alumina added. An XPS study of the interaction of CO with model Cu/ZnO catalysts prepared in situ in the electron spectrometer shows the formation of CO2
-, CO3
2- and C2O4
2- species, their proportion relative to CO increasing with the Cu1+/Cu0 ratio. A study of the interaction of CH3OH with Cu clusters deposited on ZnO films reveals reversible molecular adsorption and the formation of CH3O on clean Cu clusters. If the Cu clusters are pretreated with oxygen, however, both CH3O and HCOO- species are produced. Model Cu/ZnO catalyst surfaces containing both Cu1+ and Cu0 species show interesting oxidation properties. On a Cu0-rich catalyst surface, only the CH3O species is formed on interaction with CH3OH. On a Cu1+rich surface, the HCOO- ion is the predominant species. 相似文献