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金属玻璃的原子团簇堆积模型及镍基非晶合金涂层
其他题名An atomic cluster packing model for metallic glasses and Ni-based amorphous metallic coatings
王爱萍
学位类型博士
导师卢柯
2007-05-10
学位授予单位中国科学院金属研究所
学位授予地点金属研究所
学位专业材料学
关键词金属玻璃 结构模型 非晶合金涂层 腐蚀性能
摘要金属玻璃的结构特性和相关应用一直是人们关心的两个主题。基于有效填充空间这一概念,并结合有关金属玻璃中程有序模拟研究的最新进展,本论文发展了一种金属玻璃的原子团簇堆积模型以进行块体金属玻璃的合金成分的预测。另一方面,考虑到金属玻璃具有良好的耐蚀、耐磨性能,而其块体样品塑性较差,本论文更多地关注其作为表面涂层的潜在应用,即利用超音速热喷涂(High Velocity Air Fuel,HVAF)和动力金属喷涂(Kinetic Metallization,KM)技术制备镍基非晶合金涂层,并研究涂层的结构特性及腐蚀行为。主要结论如下: 1、基于有效填充空间这一概念,发展了一种金属玻璃的原子团簇堆积模型以计算具有高玻璃形成能力的合金成分:考虑了化学因素对原子团簇堆积的影响;计算了原子填充过程中产生的应变,当应变达到临界值时,这些团簇的结构发生“崩塌”,从而形成无序的非晶态结构。该模型可解释绝大部分已经被发现的块体金属玻璃的合金成分,并成功预测出新的块体金属玻璃,如Fe-B-Nb 和Hf-Al-Cu合金体系。 2、将Miracle的ECP(Efficient Cluster Packing,ECP)结构模型和多组元合金的拓扑不稳定性准则相结合,提出了一种设计镍基块体金属玻璃的经验方法。基于此方法,制备出最佳玻璃形成能力为2 mm的简单三元Ni-Nb-Zr块体金属玻璃体系,该体系在1M HCl水溶液中具有优异的耐蚀性能。 3、利用超音速热喷涂(HVAF)技术,制备出结构致密的Ni-Zr-Ti-Si-Sn及Ni-Nb-Ti-Zr-Co-Cu部分非晶合金涂层,涂层中的孔隙率及非晶相含量与工艺参数密切相关。Ni-Zr-Ti-Si-Sn非晶合金及其涂层在0.05M H2SO4 + 0.05M Na2SO4水溶液中展示出良好的耐蚀性,而Ni-Nb-Ti-Zr-Co-Cu非晶合金及其涂层在强腐蚀性介质1 M HCl 水溶液中具有优异的耐蚀性能。 4、利用动力金属喷涂(KM)新技术,制备出高耐蚀性的Ni-Nb-Ti-Zr-Co-Cu完全非晶合金涂层。随喷涂温度的增加,涂层结构趋于致密;随涂层厚度的增加,贯穿孔隙难于形成,涂层表现出较高的耐蚀性能。 5、基于动电位极化曲线及XPS(X-ray Photoelectron Spectroscopy)表面分析,比较了Ni-Zr-Ti-Si-Sn和Ni-Nb-Ti-Zr-Co-Cu两种非晶合金及其晶化样品在1M HCl水溶液中的腐蚀行为。研究结果表明,非晶合金的腐蚀性能敏感于成分,而其结构均匀性仅起到有益的辅助作用。
其他摘要The structural feature and industrial application of metallic glasses have long been challenging topics. In this thesis, an atomic cluster packing model was proposed to predict alloy compositions of bulk metallic glasses (BMGs) based on the concept of efficient filling and the recent progress on medium range order in metallic glasses. On the other hand, due to the intrinsic nature of low plasticity in BMGs, much attention was focused on their good corrosion resistance and wear resistance, which make them more attractive to use as coatings than as bulk materials. Ni-based amorphous metallic coatings were fabricated by High Velocity Air Fuel (HVAF) thermal spraying and Kinetic Metallization (KM), and the effect of spraying parameters on the structure and corrosion behavior of coatings was investigated. The conclusions were summarized as follows: 1. An atomic clusters packing model was proposed for calculating alloy compositions with high glass forming ability (GFA) based on the concept of efficient filling. The chemical effect on atomic clusters packing was considered and the strain was calculated during the atomic filling. When the critical strain is reached, the dense packing of clusters is “collapsed” to amorphous state. This model provides an explanation to many BMGs found so far, and new Fe-B-Nb and Hf-Al-Cu BMGs are successfully predicted. 2. Miracle’s efficient cluster packing (ECP) model for metallic glasses and the topological instability criterion for multi-component alloy systems have been combined to formulate a design protocol for BMGs. A simple ternary Ni-Nb-Zr BMG with best GFA of 2 mm was successfully designed and fabricated. The new BMG exhibits excellent corrosion resistance in 1M HCl aqueous solution. 3. Ni-Zr-Ti-Si-Sn and Ni-Nb-Ti-Zr-Co-Cu partial amorphous metallic coatings with dense structure were prepared by HVAF thermal spraying. It was found that the porosity and amorphous phase fraction in coatings are sensitive to spraying parameters. The Ni-Zr-Ti-Si-Sn amorphous alloy and its coating present good corrosion resistance in 0.05M H2SO4 + 0.05M Na2SO4 aqueous solution, while the Ni-Nb-Ti-Zr-Co-Cu amorphous alloy and its coating exhibit high corrosion resistance in severely corrosive environment of 1 M HCl aqueous solution. 4. Ni-Nb-Ti-Zr-Co-Cu fully amorphous metallic coating with high corrosion resistance was fabricated by KM. The coating becomes much denser with increasing spraying temperature, and it exhibits higher corrosion resistance with increasing thickness due to the difficulty to form through-pores. 5. The corrosion behaviors of Ni-Zr-Ti-Si-Sn and Ni-Nb-Ti-Zr-Co-Cu amorphous alloy and their crystalline counterparts in 1M HCl aqueous solution were compared by potentiodynamic polarization curves and X-ray Photoelectron Spectroscopy (XPS) analysis. It was found that the corrosion resistance of Ni-based amorphous alloys is very sensitive to the compositions and the structural homogeneity only has a beneficial effect on the corrosion resistance.
页数114
语种中文
文献类型学位论文
条目标识符http://ir.imr.ac.cn/handle/321006/16865
专题中国科学院金属研究所
推荐引用方式
GB/T 7714
王爱萍. 金属玻璃的原子团簇堆积模型及镍基非晶合金涂层[D]. 金属研究所. 中国科学院金属研究所,2007.
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