The phase transformation activation energy of the Cu61.13Zn33.94A14.93 alloys, which were treated at 4 GPa and 700 ℃ for 15 minutes, was calculated by means of differential scanning calorimetry curves obtained at var...The phase transformation activation energy of the Cu61.13Zn33.94A14.93 alloys, which were treated at 4 GPa and 700 ℃ for 15 minutes, was calculated by means of differential scanning calorimetry curves obtained at various heating and cooling rates. Then, the effects of high-pressure heat treatments on the solid-state phase transformation and the microstructures of Cu61.13Zn33.94A14.93 alloys were investigated. The results show that high-pressure heat treatments can refine the grains and can change the preferred orientation from （111） to （200） of α phase. Compared with the as-cast alloy, the sample with high-pressure heat treatment has finer grains, lower β＇→β and/β→β＇ transformation temperature and activation energy. Furthermore, we found that high cooling rate favours the formation of fine needle-like α phase in the range of 5-20℃/min.展开更多
Methanol synthesis from CO_(2)hydrogenation catalyzed by Zn/Cu alloy has been widely studied,but there is still debate on its catalytic active phase and whether the Zn can be oxidized during the reaction process.What ...Methanol synthesis from CO_(2)hydrogenation catalyzed by Zn/Cu alloy has been widely studied,but there is still debate on its catalytic active phase and whether the Zn can be oxidized during the reaction process.What is more,as Zn atoms could locate on Zn/Cu alloy surface in forms of both single atom and cluster,how Zn surface distribution affects catalytic activity is still not clear.In this work,we performed a systematic theoretical study to compare the mechanistic natures and catalytic pathways between Zn single atom and small cluster on catalyst surface,where the surface oxidation was shown to play the critical role.Before surface oxidation,the Zn single atom/Cu is more active than the Zn small cluster/Cu,but its surface oxidation is difficult to take place.Instead,after the easy surface oxidation by CO_(2)decomposition,the oxidized Zn small cluster/Cu becomes much more active,which even exceeds the hardlyoxidized Zn single atom/Cu to become the active phase.Further analyses show this dramatic promotion of surface oxidation can be ascribed to the following factors:i)The O from surface oxidation could preferably occupy the strongest binding sites on the center of Zn cluster.That makes the O intermediates bind at the Zn/Cu interface,preventing their too tight binding for further hydrogenation;ii)The higher positive charge and work function on the oxidized surface could also promote the hydrogenation of O intermediates.This work provided one more example that under certain condition,the metal cluster can be more active than the single atom in heterogeneous catalysis.展开更多
This paper reports on laser surface remelting experiments performed on a Zn-2wt.%Cu hypoperitectic alloy by employing a 5kW CW CO2 laser at scanning velocities between 6 and 1207mm/s. The growth velocities of the mi- ...This paper reports on laser surface remelting experiments performed on a Zn-2wt.%Cu hypoperitectic alloy by employing a 5kW CW CO2 laser at scanning velocities between 6 and 1207mm/s. The growth velocities of the mi- crostructures in the laser molten pool were accurately measured. The planar interface structure caused by the high velocity absolute stability was achieved at a growth velocity of 210 mm/s. An implicit expression of the critical solidification velocity for the cellular-planar transition was carried out by nonlinear stability analyses of the planar interface. The results showed a better agreement with the measured critical velocity than that predicted by M-S theory. Cell-free structures were observed throughout the whole molten pool at a scanning velocity of 652 mm/s and the calculated minimum temperature gradient in this molten pool was very close to the critical temperature gradient for high gradient absolute stability （HGAS） of the η phase. This indicates that HGAS was successfully achieved in the present experiments.展开更多
文摘The phase transformation activation energy of the Cu61.13Zn33.94A14.93 alloys, which were treated at 4 GPa and 700 ℃ for 15 minutes, was calculated by means of differential scanning calorimetry curves obtained at various heating and cooling rates. Then, the effects of high-pressure heat treatments on the solid-state phase transformation and the microstructures of Cu61.13Zn33.94A14.93 alloys were investigated. The results show that high-pressure heat treatments can refine the grains and can change the preferred orientation from （111） to （200） of α phase. Compared with the as-cast alloy, the sample with high-pressure heat treatment has finer grains, lower β＇→β and/β→β＇ transformation temperature and activation energy. Furthermore, we found that high cooling rate favours the formation of fine needle-like α phase in the range of 5-20℃/min.
基金financially supported by the NSFC,China(No.22022504)the Guangdong“Pearl River”Talent Plan,China(No.2019QN01L353)+3 种基金the Higher Education Innovation Strong School Project of Guangdong Province of China,China(2020KTSCX122)the Guangdong Provincial Key Laboratory of Catalysis,China(No.2020B121201002)support from the Center for Computational Science and Engineering at SUSTechfinancial support by the National Key Research and Development Program of China,China(No.2017YFC0210905)。
文摘Methanol synthesis from CO_(2)hydrogenation catalyzed by Zn/Cu alloy has been widely studied,but there is still debate on its catalytic active phase and whether the Zn can be oxidized during the reaction process.What is more,as Zn atoms could locate on Zn/Cu alloy surface in forms of both single atom and cluster,how Zn surface distribution affects catalytic activity is still not clear.In this work,we performed a systematic theoretical study to compare the mechanistic natures and catalytic pathways between Zn single atom and small cluster on catalyst surface,where the surface oxidation was shown to play the critical role.Before surface oxidation,the Zn single atom/Cu is more active than the Zn small cluster/Cu,but its surface oxidation is difficult to take place.Instead,after the easy surface oxidation by CO_(2)decomposition,the oxidized Zn small cluster/Cu becomes much more active,which even exceeds the hardlyoxidized Zn single atom/Cu to become the active phase.Further analyses show this dramatic promotion of surface oxidation can be ascribed to the following factors:i)The O from surface oxidation could preferably occupy the strongest binding sites on the center of Zn cluster.That makes the O intermediates bind at the Zn/Cu interface,preventing their too tight binding for further hydrogenation;ii)The higher positive charge and work function on the oxidized surface could also promote the hydrogenation of O intermediates.This work provided one more example that under certain condition,the metal cluster can be more active than the single atom in heterogeneous catalysis.
基金Project supported by the National Natural Science Foundation of China （Grant Nos 50201012 and 50471065）.
文摘This paper reports on laser surface remelting experiments performed on a Zn-2wt.%Cu hypoperitectic alloy by employing a 5kW CW CO2 laser at scanning velocities between 6 and 1207mm/s. The growth velocities of the mi- crostructures in the laser molten pool were accurately measured. The planar interface structure caused by the high velocity absolute stability was achieved at a growth velocity of 210 mm/s. An implicit expression of the critical solidification velocity for the cellular-planar transition was carried out by nonlinear stability analyses of the planar interface. The results showed a better agreement with the measured critical velocity than that predicted by M-S theory. Cell-free structures were observed throughout the whole molten pool at a scanning velocity of 652 mm/s and the calculated minimum temperature gradient in this molten pool was very close to the critical temperature gradient for high gradient absolute stability （HGAS） of the η phase. This indicates that HGAS was successfully achieved in the present experiments.
