基于团簇模型设计的Cu-Cu_(12)-[M_(x/(12+x))Ni_(12/(12+x))]_5(M=Si,Cr,Cr+Fe)合金抗高温氧化研究

High temperature oxidation resistance of cluster model designed alloys Cu-Cu_(12)-[M_(x/(12+x))Ni_(12/(12+x))]_5(M=Si,Cr,Cr+Fe)

文章在稳定固溶体团簇模型的指导下,对白铜合金进行微合金化,将Cu元素在合金中的含量固定为72.22 at.%,改变Ni与M(M为Si,Cr,Cr+Fe)的比例,设计了系列合金成分,并对其抗高温氧化性能及其机制进行了研究.同时加入基体中的Ni-Si元素可以从两方面提高合金的抗氧化性能:以团簇形式加入,形成稳定固溶体结构,可以降低Cu-Ni-Si合金的化学反应活性;Si/Ni比增大后,合金在少量固溶的基础上能析出抗氧化性能优于基体的析出相,且析出越多,抗高温氧化性能越好.所以其抗氧化能力的来源并不是形成致密Si氧化物薄膜.Ni-Cr的同时加入可以明显抑制Cu合金在800?C以下的中温氧化,但其抗高温氧化能力主要与外氧化层中是否形成连续的Cr氧化层有关,因而该系列合金的抗高温氧化能力与Cr/Ni比有密切联系,合理选择团簇内Cr/Ni比例,才能够提高Cu合金的抗高温氧化能力.第四组元Fe和第三组元Cr相比较,不能够起到优先氧化、生成保护性氧化皮的作用,所以Cr,Fe同时添加只能抑制Cu在800?C以下的中温氧化,却不能够提高Cu合金的抗高温氧化能力.

Based on the stable solid solution cluster model, cupronickel is microalloylized in this paper. Alloys with different Ni-M （M = Si, Cr, Cr＋Fe） ratios are designed at constant atomic ration of Cu （72.22 at.%）. The high temperature oxidation resistance and mechanism of alloy are also investigated. In the Cu-Ni-Si system, the addition of Ni-Si can enhance the oxidation resistance of the alloy from two aspects： firstly, the Ni-Si is in solid solution state when being added as a cluster, it can inhibit the chemical reactivity of Cu-Ni-Si alloy;secondly, anti-oxidation precipitation can be obtained with the increase of Si/Ni ratio. Therefore, the oxidation resistance of the alloy is not because of the formation of the compact silicon oxide film. In the Cu-Ni-Cr system, the oxidation is obviously inhibited at medium temperatures （lower than 800 ？C）. But at higher temperatures, the oxidation resistance is relevant to the integrality of chrome oxide layer. The high temperature oxidation resistance is closely related to Cr/Ni ratio, hence an appropriate Cr/Ni ratio is necessary for the good high temperature oxidation resistance. Compared with the third element Cr, the forth element Fe cannot be oxidized first. Therefore, combined addition of Cr and Fe can only inhibit the medium temperature oxidation, but not high temperature oxidation.