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1.
The energy interaction curves of a number of diatomic and polyatomic dication systems were calculated in order to study their energy-trapping properties. Generally, the ab initio complete active space multiconfiguration self-consistent field method was used in an extended valence + polarization basis set, with compact effective potentials replacing the core electrons. The diatomic dications include all ten possible binary combinations of oxygen, sulphur, selenium, and tellurium. O22+ shows the largest exothermicity, measured from equilibrium to the monocation combination asymptote, and highest barrier to dissociation. The calculated equilibrium bond length and harmonic vibrational frequency agree very well with experiment. The O22+, SO2+, SeO2+, and TeO2+ series show progressively decreasing exothermicities but similar barrier heights. The non-oxides, in contrast, show similar exothermicities but decreasing barriers with increasing size of the atom constituents. These trends are interpreted in terms of both valence bond curve-crossing and molecular orbital bonding models. The ozone dication, O32+, is found to have a number of low-lying singlet and triplet stationary state structures spanning near-linear to D3h2+ symmetries. Although the calculated exothermicity is even larger than for O22+, the barrier to O2+ + O+ dissociation is predicted to be low in each case. O22+ surrounded by six argon atoms to model an isolating environment shows increased equilibrium O–O bond length, decreased exothermicity, and increased barrier to dissociation, relative to the bare dication. O22+ flanked at each end by a perpendicularly oriented H2 molecule in a staggered conformation is obstructed from direct conversion to the water dimer dication by a high barrier. However, [(H2O)2]2+ dissociates smoothly from equilibrium to two water monocations with a large exothermicity but a small barrier. 相似文献
2.
In CFD simulation of diesel combustion, the predictive capabilities of the spray model play the most important role. Consequently, under the strict guidelines of the V&V, a method to adjust parameters of diesel spray model WAVE to accompany with the in-cylinder physical progress has been investigated in this paper. Moreover, the simulation of the spray has been validated by high-speed photography experiments and verified by the equation proposed by Hiroyasu. Finally, a modified setup for the WAVE spray model has been proposed and applied in the spray and combustion simulation for Deutz1013 diesel in different engine speed. 相似文献
3.
Whereas cooperative effect in catalysis, in which multiple chemical interactions participate cooperatively to achieve significant enhancement in catalytic activity and/or selectivity, is common in enzymatic reactions, it has been sparingly employed in heterogeneous catalytic systems. Here, some recent literature examples of abiotic catalysis, with emphasis on heterogeneous systems, that employ cooperation between acid and base and two metal centers are briefly described to demonstrate the principles involved. Since effective cooperation places strict demand on the positions of the different functional groups, new synthetic methods and strategies are needed to design and construct structures useful for cooperative catalysis. Recent progress in our laboratory in synthesizing new nanocage structures that possess molecular-size cavities, atomic layer thick, porous shells with internal functional groups is described. These recent developments suggest possibilities of new catalytic transformations that have not been attempted before. This is illustrated with two speculative examples utilizing cooperative catalysis: oxidative hydrolytic desulfurization and terminal carbon activation of hydrocarbon molecules. 相似文献
4.
5.
Aliphatic polybenzoxazoles, polybenzothiazoles, and polybenzimidazoles have been prepared by three methods: in poly(phosphoric acid), by the polyamide precursor, and by melt polymerization. The melt polymerization method was found to be the most satisfactory. All of the aliphatic heterocyclic polymers had excellent thermal stability, resistance to alkaline hydrolysis, high glass transition temperatures, and a high degree of flexibility. The only class of polymer found having any degree of solubility, however, was the polybenzimidazoles. Aliphatic polybenzimidazole films were prepared by solution casting. These films were found to be extremely flexible at ambient and cryogenic temperatures. The films were unaffected by alkaline hydrolysis, even in an oxidizing medium. A molding prepared from the aliphatic polybenzimidazole had excellent physical properties at both cryogenic and room temperature. 相似文献
6.
Semih Eser Robert G. Jenkins Guangquan Wei Harold H. Schobert Joseph T. Joseph 《Fuel》1991,70(12):1445-1455
High pressure microdilatometer experiments were performed on a subbituminous (Wyodak) and a bituminous (Illinois no. 6) coal in helium and hydrogen atmospheres with and without added tetralin. Wyodak coal samples showed no swelling but contractions ranging between 24 and 40 vol% upon heating at 20 and 100 °C min− 1 under helium or hydrogen pressures between 150 and 1000 psig (˜1.0–6.9 MPa). Under the same conditions, Illinois no. 6 coals displayed contractions (25–60 vol%) prior to swelling up to 117 vol%. Upon tetralin addition (at 35–190 wt% of the coal), Wyodak coal samples did not swell but showed an increasing contraction with increasing helium or hydrogen pressure due to a slight softening and fusion of the coal particles. In contrast, addition of tetralin at much lower concentrations (5–35 wt%) had a marked effect on the contraction and swelling behaviour of Illinois no. 6. A maximum swelling of 200 vol% was obtained at a tetralin addition of 30 wt%. The increased swelling results from more extensive softening and fusion of coal particles in the presence of tetralin. Both coals showed a decreasing char yield with increasing tetralin concentration. The substantially lower extent of interaction observed between Wyodak coal samples and tetralin compared to Illinois no. 6 coal can be attributed to the differences in pore structure and/or chemical constitution of the two coal samples. Examination of the resultant solids by optical microscopy revealed the microstructural changes produced by thermal treatment in dilatometer experiments. 相似文献
7.
Ten samples of mineral-matter residue were obtained by the radio-frequency low-temperature ashing of subbituminous and bituminous coals. The low-temperature ash samples were then heated progressively from 400 °C to 1400 °C at 100 °C intervals. Mineral phases present at each temperature interval were determined by X-ray diffraction analyses. The minerals originally present in the coals (quartz, kaolinite, illite, pyrite, calcite, gypsum, dolomite, and sphalerite) were all altered to higher temperature phases. Several of these phases, including kaolinite, metakaolinite, mullite, anhydrite, and anorthite, were found only in limited temperature ranges. Therefore the temperature of formation of the ashes in which they occur may be determined. Mineralogical differences were observed between coal samples from the Rocky Mountain Province, the Illinois Basin, and the Appalachians; and as a result of these mineralogical differences, different high-temperature phases resulted as the samples were heated. However, regional generalizations cannot be made until a greater number of samples have been studied. 相似文献
8.
J. Harold Falls 《Nutrient Cycling in Agroecosystems》1991,28(2):239-249
The AOAC indirect, AOAC direct and EEC direct available P2O5 methods are compared by two different collaborative studies on DAP and GTSP. The collaborative studies found the AOAC direct and EEC direct available P2O5 methods to be lower than the AOAC indirect P2O5 method when the citrate insoluble P2O5 was greater than 0.3% P2O5. Results found in the Association of Florida Phosphate Chemist Check Sample Program confirmed the lower analysis.Until 1950 the primary method of analysis for available P2O5 was the AOAC indirect method. A faster method for available P2O5 was developed and adopted in the 50's by the AOAC. Diammonium phosphate from phosphate rock was not manufactured until 1959. The current fertilizer of today was not evaluated by the AOAC direct available P2O5 method because the fertilizer had not been manufactured.The current practice to use the empirical method for determining available P2O5 for plants was evaluated in the 30's, but it is still being applied to fertilizer materials of today. Several agronomic studies with current fertilizers have shown the so-called citrate insoluble P2O5 to be available to plants, which implies a new agronomic study should be evaluated for today's fertilizer to determine its availability.Based on the high cost of P2O5 production, available P2O5 methods must be equal when applied to the same fertilizer. Manufacturers of P2O5 in fertilizers cannot tolerate a 1.0% P2O5 difference between different available P2O5 methods. No one manufacturer or buyer should have an advantage over another because of the analytical method used to determine the available P2O5. If the so-called citrate insoluble P2O5 can be proved as available P2O5, the manufacturer should be able to sell that product as total available P2O5. If every regulatory agency developed their own available P2O5 method, the result would be confusion in determining the available P2O5 and inequities in the marketing of the product. The AOAC should establish methods that are equal in value for available P2O5.Quick, unofficial available P2O5 methods used to determine large volumes of fertilizer samples can be used by regulatory agencies to speed up the analyses. When deficient fertilizer samples are found by the unofficial method, the official methods should be used to determine true availability. The quick methods of questionable accuracy should be used for screening only. Regulatory agencies should operate in a posture of being fair to the consumer and manufacturer. 相似文献
9.
Grain coarsening tests were carried out on Al-4.5 pct Cu and Al-4.5 pct Si alloys. The effects of three variables, melt composition, pour temperature, and mold temperature, were determined. It was found that the macrostructure generally coarsened with increased pour and mold temperatures. Coarsening was extreme in the unrefined alloys but was retarded by the active grain refiners like titanium and columbium. The effect of boron was spectacular in suppressing coarsening tendencies. The results of the investigation support the carbide theory of nucleation as opposed to the peritectic theory. 相似文献
10.
Srinath Viswanathan Ph.D. Vinod K. Sikka Ph.D. Harold D. Brody Sc.D. 《JOM Journal of the Minerals, Metals and Materials Society》1992,44(9):37-40
Quality criteria used in the computer-aided design and analysis of casting processes typically relate geometric, thermal, or solidification parameters to structural features such as centerline shrinkage and microporosity. Quality criteria for the prediction of porosity in castings have been used successfully in steel, but the application of criteria functions to nonferrous alloys has been less successful. Recent work suggests that the dominating mechanism that determines the amount and distribution of porosity in castings is strongly dependent on the solidification mode of the alloy and the solidification conditions. Accordingly, casting processes and alloy types are divided into four groups, and a different set of criteria functions are obtained for each group. 相似文献