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典型二元共晶合金熔体结构研究
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摘要
高温熔体物性和结构的研究是一个有着重要学术和应用意义的课题。实验难度大,数据分析困难。本文以高温X射线衍射技术和电阻测量技术为主要手段,并辅以DSC分析和粘度测量等方法,借助于自主建立的模型,以Al-Ge、Co-Sn和Ni-Si三种典型的二元共晶合金熔体为研究对象,对典型二元共晶合金熔体在凝固过程中的结构演化以及电阻率随温度的变化等方面进行研究,探讨了合金熔体结构与其固态结构的相关性,并初步揭示了合金在凝固过程中容易产生深过冷状态的原因。
     高温X射线衍射实验获得了Al_(71.6)Ge_(28.4)合金熔体在1150℃、950℃、750℃和550℃的衍射强度,通过分析结构因子、径向分布函数和双体分布函数,发现在测量的范围内,有序度在1150℃至950℃间突然变大。在此基础上,通过“液态微观多相模型”及自主建立的“纳米晶粒模型”的计算,指出Al_(71.6)Ge_(28.4)合金熔体是由72.8%α相原子团簇和27.2%β相原子团簇组成。凝固前后,α相原子团簇的液态结构与其固态相同,而β相原子团簇的结构则由液态时的拓扑有序结构转变为固态时的FCC结构,并且原子间的结合方式也由金属键转变为共价键,导致Al_(71.6)Ge_(28.4)合金的液固两相结构存在很大的差异,这使得该合金在凝固容易出现深过冷现象。通过自主研发的电阻率测量设备,测量了不同成分的Al-Ge合金在凝固过程中的电阻率变化趋势。研究表明,熔体电阻率均随温度降低而线性减少,当成分超过50%后,熔体的电阻率温度系数相差无几。熔体的粘度在780℃和600℃两个温度点都存在突变,前者是由于熔体中发生了由BCC短程有序结构到FCC短程有序结构的转变,后者则是在新的结构基础上进行的数量的改变。
     对于Co_(79.5)Sn_(20.5)的高温X射线研究表明:组成该熔体的原子团簇结构稳定,熔体的有序度在1250℃至1150℃时发生突变。通过研究该合金的液固相关性,指出该合金熔体是由βCo_3Sn_2原子团簇和βCo原子团簇等比例组成,其液态结构与固态结构保持一致。但由于组成熔体的两种团簇在熔体中等比例存在,原子团簇周围出现相同种类的原子团簇的几率降到最低,凝固时难以形核,从而该合金凝固时易出现深过冷现象。合金熔体的电阻率与温度在1210℃偏离线性关系;同时DSC分析发现当过热到1260℃时,熔体凝固时所达到的过冷度最小,明确了该熔体中发生了结构的变化。
     Ni_(53)Si_(47)合金熔体高温X射线衍射实验发现,随着温度的降低,Ni_(53)Si_(47)衍射强度曲线上出现了“预峰”,通过液-固态结构相关性分析可知,“预峰”是化合物NiSi液态结构的一种体现,该合金的液态结构和固态结构存在较大的差异,液固态结构不匹配是造成该合金凝固时容易深过冷的原因。对Ni_(53)Si_(47)熔体的电阻率的测量表明,该合金熔体的电阻率温度系数为负值,在1230℃前后电阻率温度系数发生了该改变,这是由于熔体中存在NiSi化合物的形成趋势而造成的,即熔体中的出现的NiSi化合物形成趋势是“预峰”产生和电阻率温度系数改变的原因。
It is an important subject that the properties and the structures of high-temperature melt are analyzed from the point of academic research and practical application. The experiment is very difficult and the data analysis is complicated. In this present paper, the structure evolution and the resistivity with temperature in the solidification process of Al-Ge, Co-Sn and Ni-Si binary alloys were investigated by the primary means of X-ray diffraction and resistivity device, as well as other means were used to analyze the melt, such as DSC, viscosity and self-established model. The melt structures have been discussed, and the correlations between liquid structure and solid structure have been revealed. The reasons of the deep undercooled state during solidification have also been explored.
     With the high temperature X-ray diffraction experiment, the intensity of liquid Al_(71.6)Ge_(28.4) alloy was measured at 1150℃, 950℃, 750℃and 550℃. The correlation radius r_c and the nearest neighbor distance r_l keep stable in the whole temperature range, but the correlation radius r_c has a sudden change at 950℃. It can be concluded that the short order range in the liquid alloy is stable, the sudden change of correlation radius r_c arises abruptly with the forming of the higher degree short range order structured by realignment of construction units. By investigating the structure correlation of Al_(71.6)Ge_(28.4) alloy between liquid and solid states, it is indicated that the liquid Al_(71.6)Ge_(28.4) eutectic alloy consists of 72.8%αclusters and 27.2%βclusters.αclusters structure keeps the FCC structure, butβclusters transform FCC structure into topological structure. The liquid Al_(71.6)Ge_(28.4) structure is different from its solid structure, which is the reason of undercooling of the Al_(71.6)Ge_(28.4) alloy during the solidification. The resistivities of different components of Al-Ge alloys have been measured by the self-developed resistivity equipment during solidification. Studies have shown: The resistivity of Al-Ge melt decreases linearly with temperature decreasing. When the composition is more than 50%, the melt is almost the same temperature coefficient of resistivity. There are two discontinuous points of the viscosity at 780℃and 600℃. The discontinuous viscosity at 780℃in the melt is for the structure change of the clusters form BCC short range to FCC short range, while the latter is the number change based on the new structure.
     The liquid structure of Co_(79.5)Sn_(20.5) eutectic alloy has been investigated by means of X-ray diffraction. From 1350℃to 1150℃, the structure of melt holds quite stable, but the order increases with the temperature decreasing. The short-range order structure of the Co_(79.5)Sn_(20.5_ alloy consists ofβCo3Sn2 clusters andβCo clusters, each which accounts for about 50% in the melt respectively. Therefore the liquid structure is consistent with its solid structure. From the point of the structure correlation between liquid and solid states, reasons of deep undercooling state are discussed further. The liquid alloy consists of two clusters with the same proportion, which adds nucleation difficulty. The Co_(79.5)Sn_(20.5) melt was studied by the measurement of the resistivity and DSC heat. The curves of different physical properties have a discontinuous point at similar temperature during the solidification. The results of experiments indicate that there is microstructure transition in the Co_(79.5)Sn_(20.5) melt during the solidification.
     The liquid structure of Ni_(53)Si_(47) eutectic alloy was studied by the high-temperature X-ray diffractometer. "Pre-peaks" were found in X-ray patterns of Ni_(53)Si_(47) melt, and the intensity of the "pre-peaks" increase with temperature decreasing. For the liquid alloy of Ni_(53)Si_(47), the structure is stable but the order increases. Meanwhile, the correlation between the liquid structure and solid structure has been analyzed by "the Nanocrystal Model". It is shown that the "pre-peaks" are the reflection of liquid structure of NiSi compound. There is a big difference between the liquid structure and solid-state structure, which is the reason of deep undercooling state during solidification. The temperature coefficient of resistivity is negative and changes at about 1230℃. The result explores that there is a trend of the formation of NiSi compounds. In other words, the formation of NiSi compound in the melt lead the "pre-peak" existence and the change of resistivity temperature coefficient.
引文
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