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张羊换 《武汉理工大学学报(材料科学英文版)》2013,28(3):604-611
The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1?x Co x (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo2 and Mg instead of altering the major phase Mg2Ni. No amorphous phase is detected in the as-quenched Cofree alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient (D) along with the limiting current density (I L ) and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible. 相似文献
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张羊换 《武汉理工大学学报(材料科学英文版)》2018,33(4):812-822
The La-Mg-Ni-Mn-based AB2-type La1-xCexMgNi3.5Mn0.5 (x = 0, 0.1, 0.2, 0.3, and 0.4) alloys were fabricated by melt spinning technology. The effects of Ce content on the structures and electrochemical hydrogen storage performances of the alloys were studied systematically. The XRD and SEM analyses proved that the experimental alloys consist of a major phase LaMgNi4 and a secondary phase LaNi5. The variation of Ce content causes an obvious change in the phase abundance of the alloys without changing the phase composition. Namely, with the increase of Ce content, the LaMgNi4 phase augments and the LaNi5 phase declines. The lattice constants and cell volumes of the alloys clearly shrink with increasing Ce content. Moreover, the Ce substitution for La results in the grains of the alloys clearly refined. The electrochemical tests showed that the substitution of Ce for La obviously improves the cycle stability of the as-spun alloys. The analyses on the capacity degradation mechanism demonstrate that the improvement can be attributed to the ameliorated anti-corrosion and anti-oxidation ability originating from substituting partial La with Ce. The as-spun alloys exhibit excellent activation capability, reaching the maximum discharge capacities just at the first cycling without any activation treatment. The substitution of Ce for La evidently improves the discharge potential characteristics of the as-spun alloys. The discharge capacity of the alloys first increases and then decreases with growing Ce content. Furthermore, a similar trend also exists in the electrochemical kinetics of the alloys, including the high rate discharge ability (HRD), hydrogen diffusion coefficient (D), limiting current density (IL) and charge transfer rate. 相似文献
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Nanocrystalline and amorphous LaMg_(12)-type LaMg_(11)Ni + x wt% Ni(x = 100, 200) alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter(DSC) connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability(HRD) and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time. 相似文献
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采用不同球磨时间(10,20,30,40 h)制备了Mg_(22)Y_2Ni_(10)Cu_2+x%Ni(x=0,50,100,150;质量分数)复合材料,并对材料的结构、形貌、电化学及动力学储氢性能进行了系统的研究。分析了球磨时间和镍添加量对Mg_(22)Y_2Ni_(10)Cu_2合金储氢性能的影响。结果表明,球磨可以改善合金的显微结构,促进合金中非晶、纳米晶的形成,而镍的加入显著促进了该过程的进行,使复合材料中非晶、纳米晶的含量大幅度升高;随球磨时间和镍复合量的增加,合金放电比容量显著增加,当复合镍为x=100、球磨时间为40 h时,其值已达到最大的669.7 mAh·g~(-1)。循环稳定性的改善也较为明显,复合镍x=150、球磨20 h试样的S_(20)已经达到了80%。此外,球磨和镍的添加还可以明显优化合金的高倍率放电、交流阻抗和动电位极化等动力学性能。此外,包覆于合金表面的镍不但对合金性能起到催化作用,提高了合金的表面活性,还有效地提高了合金的综合储氢性能。 相似文献