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111.
112.
An anomalous rate enhancement with increasing conversion has been observed during the liquid phase hydrogenation of nitrobenzene and crotonaldehyde over Ge/Pd/C catalysts at ambient temperature and atmospheric pressure. Inductive coupled plasma atomic emission spectroscopy and electrochemical measurement of the oxidation state of catalysts during reaction revealed that the bimetallic particles were partially oxidized by the reactants, which resulted in Ge-dissolution and increased exposure of Pd on the surface. It is proposed that the surface and bulk composition of Ge/Pd catalysts are a function of their oxidation state. This behaviour is due to the unusually high mobility of Ge in the Pd lattice and to the good solubility of GeO2 in polar solvents. The influence of hydrogen transport on the corrosion process and the stability of other X/Pd type bimetallic catalysts during liquid phase hydrogenation are also discussed. 相似文献
113.
114.
甲基偶氮四唑热稳定性和热分解机理的量子化学研究 总被引:2,自引:0,他引:2
采用量子化学方法全优化计算了1—甲基—5—偶氮四唑(1—MAT)和2—甲基—5—偶氮四唑(2—MAT)热分解反应位能曲线,探讨了热稳定性和分解机理。热分解活化能计算值分别为245.9,183.2k/mo1,静态分子结构和动态分解性质都显示出1—MAT比2—MAT有更好的热稳定性。裂解优先以开环方式发生。 相似文献
115.
Boon-Seang Chu Sosaku Ichikawa Sumiyo Kanafusa Mitsutoshi Nakajima 《Journal of the American Oil Chemists' Society》2007,84(11):1053-1062
This work was initiated to prepare protein-stabilized β-carotene nanodispersions using emulsification–evaporation. A pre-mix
of the aqueous phase composed of a protein and hexane containing β-carotene was subjected to high-pressure homogenization
using a microfluidizer. Hexane in the resulting emulsion was evaporated under reduced pressures, causing crystallization and
precipitation of β-carotene inside the droplets and formation of β-carotene nanoparticles. Sodium caseinate (SC) was the most
effective emulsifier among selected proteins in preparing the nanodispersion, with a monomodal β-carotene particle-size distribution
and a 17-nm mean particle size. The results were confirmed by transmission-electron microscopy analysis. SC-stabilized nanodispersion
also had considerably high ζ-potential (−27 mV at pH 7), suggesting that the nanodispersion was stable against particle aggregation.
Increasing the SC concentration decreased the mean particle size and improved the polydispersity of the nanodispersions. Nanodispersions
prepared with higher β-carotene concentrations and higher organic-phase ratios resulted in larger β-carotene particles. Although
increased microfluidization pressure did not decrease particle size, it did improve the polydispersity of the nanodispersions.
Repeating the microfluidization process at 140 MPa caused the nanodispersions to become polydisperse, indicating the loss
of emulsifying capacity of SC due to protein denaturation. 相似文献
116.
Influence of the composition of the binder and the carbonation on the zeta potential values of hardened cementitious materials 总被引:1,自引:0,他引:1
Electroosmotic experiments have been carried out on eight different mixes of hardened cementitious matrixes including concrete, mortar and pastes, different types of binders, carbonated and non-carbonated specimens and different test conditions. From these trials, the zeta potential values have been determined and the optimum experimental parameters and devices have been established. In addition, the influence of the composition of the binder on the zeta potential has been quantified indicating that higher amounts of Al2O3 in the binder lead to higher positive values of zeta potential, while the SiO2 acts just on the opposite side. This has been explained in terms of the different i.e.p. (isoelectric point) for both oxides. Concerning the influence of carbonation, it increases the absolute value of the zeta potential toward more negative values; this behaviour has been attributed to the influence of the specifically adsorbed Ca2+ in the negative sites of the surface in the non-carbonated samples. 相似文献
117.
基于理想流体,将进水塔简化成水中悬臂梁体系,推导了其受迫振动时的动力响应方程,给出了进水塔内外表面动水压力的解析表达式。与有限元法、水工抗震规范公式计算结果进行了对比,分析验证了该方法在进水塔结构上的适用性及准确性。结果表明:动水压力表达式与结构振型密切相关。该方法的动水压力曲线趋势与有限元方法相似,均在水面以下某深度处迅速变大及达到最大值后曲线值减小弯回,两者最终在塔体底部收于相近的值;最大值大于有限元法,其最大值处曲线折回明显,幅度较大。弹性模量和进水塔高度对动水压力的曲线形态和数值有重要影响。同时,输入激励荷载的频率对动水压力影响巨大,尤其频率与进水塔某阶频率相近时会导致动水压力的异常增大。该方法对分析进水塔动水压力具有参考价值。 相似文献
118.
We present a simple and fast algorithm to test the thermodynamic stability and determine the necessary chemical environment for the production of a multiternary material, relative to competing phases and compounds formed from the constituent elements. If the material is found to be stable, the region of stability, in terms of the constituent elemental chemical potentials, is determined from the intersection points of hypersurfaces in an (n−1)-dimensional chemical potential space, where n is the number of atomic species in the material. The input required is the free energy of formation of the material itself, and that of all competing phases. Output consists of the result of the test of stability, the intersection points in the chemical potential space and the competing phase to which they relate, and, for two- and three-dimensional spaces, a file which may be used for visualization of the stability region. We specify the use of the program by applying it both to a ternary system and to a quaternary system. The algorithm automates essential analysis of the thermodynamic stability of a material. This analysis consists of a process which is lengthy for ternary materials, and becomes much more complicated when studying materials of four or more constituent elements, which have become of increased interest in recent years for technological applications such as energy harvesting and optoelectronics. The algorithm will therefore be of great benefit to the theoretical and computational study of such materials. 相似文献
119.
Density functional theory is applied to predicting the structures and electrostatic potentials of planar electrochemical surfaces within the framework of the restricted primitive model where small ions are represented by charged hard spheres of equal diameter and the solvent is assumed to be a continuous dielectric medium. The hard-sphere contribution to the excess Helmholtz energy functional is evaluated using the modified fundamentalmeasure theory and the electrostatic contribution is obtained from the quadratic functional Taylor expansion using the second-order direct correlation function from the mean-spherical approximation. Numerical results for the ionic density profiles and the mean electrostatic potentials near a planar surface of various charge densities are in excellent agreement with molecular simulations. In contrast to the modified Gouy-Chapman theory, the present density functional theory correctly predicts the second layer formation and charge inversion of charged surfaces as observed in simulations and in experiments. The theory has also been tested with the zeta potentials of positively charged polystyrene particles in aqueous solutions of KBr. Good agreement is achieved between the calculated and experimental results. 相似文献
120.
N. E. Ermolin 《Combustion, Explosion, and Shock Waves》2007,43(5):549-561
To verify the adequacy of various models of heat release in ammonium dinitramide flame to real processes, chemical processes
in products of thermal decomposition at a pressure of 10 torr and in ammonium dinitramide [ADN; NH4N(NO2)2] flame at a pressure of 0.4 to 60 atm are numerically simulated. The calculations are performed on the basis of a detailed
kinetic mechanism and boundary conditions correlated with experimental data, thermodynamic properties, and chemical composition
of ADN. The kinetic mechanism includes submechanisms that describe high-temperature chemical processes in NH3/N2O/NO/NO2/HNO2/HNO3 and NH3/HN(NO2)2 mixtures, and the global stages of aerosol decomposition. Based on calculated and experimental data, the role of dinitraminic
acid HN(NO2)2, aerosols, and ADN vapor in heat release in the ADN flame zone adjacent to the burning surface is estimated. The calculations
predict that the main source of heat release in the cold flame zone at p ≥ 3 atm is dinitraminic acid incoming through the channel of dissociative evaporation ADNliq → NH3 + HN(NO2)2 from the burning surface. In the high-temperature flame zone, heat release is caused by the reaction that occurs in the NH3/N2O/NO/NO2/HNO2/HNO3 mixture. At moderate pressures, the high-temperature and low-temperature zones are separated by an induction zone. The stage
governing production of the OH radical, which plays an important role in combustion, in the induction zone is the reaction
HNO3 + M → OH + NO2 + M. Because of a high activation energy of the stage, small temperature perturbations in the induction zone at low pressures
lead to a finite change in the stand-off distance between the high-temperature flame zone and the burning surface. Therefore,
small temperature perturbations in the induction zone, which are caused by admixtures in the sample or by heat transfer between
the reacting gas and the ambient medium, may be responsible for disagreement between various experimental data and between
experimental and calculated data on the stand-off distance between the high-temperature flame zone and the burning surface.
In numerical calculations, the position of the high-temperature zone is effectively controlled by varying rate constants of
elementary stages within admissible limits.
__________
Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 5, pp. 64–76, September–October, 2007. 相似文献