镁合金AZ31辉光等离子表面耐蚀合金层的研究
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摘要
镁是结构材料中最轻的金属材料,镁合金具有高的比强度和比刚度、弹性模量低、减震性好、加工性能优良、尺寸稳定性好、磁屏蔽、原料丰富以及可回收等诸多优点,被认为是21世纪最具开发和应用前景的“绿色工程材料”,在汽车、计算机、航空、通讯、运动器械、手动工具和家用电器等领域具有十分广阔的应用前景。但由于镁及镁合金耐蚀性较差,严重阻碍了其优势的发挥。因此,运用现代表面工程技术对镁合金材料进行表面处理以提高其耐蚀性,对发挥镁及镁合金的性能优势有着重要的现实意义。
本文利用辉光等离子表面合金化技术在镁合金AZ31表面制备Al-Mg、Al-Cr-Fe、Ni-Cr-Mo-Cu耐蚀合金层。采用透射电镜、X射线衍射和扫描电镜分析方法对合金层的显微组织、化学成分及相组成进行了综合分析,结果表明:合金层具有特殊的微观结构,即由最外层表面的非晶层及次外层表面的纳米晶层组成。采用电化学方法对表面改性层在3.5%NaCl溶液中的耐蚀性能进行测定,三种非晶/纳米晶耐蚀合金层的自腐蚀电位低于镁合金AZ31,维钝电流密度则相反,随着电位的变化,电流密度保持在1μA/cm2以下。
采用辉光离子合金化技术单阴极放电(自溅射)模式,在纯Fe表面制备非晶/纳米晶薄膜,以研究其形成非晶的机制。在Ar+轰击作用下,大量纳米尺寸的非晶相从表面溅射出来,在随后的驰豫过程中等效冷却速率高达1014℃/s,薄膜或固体物质从远离平衡态到达某个平衡态或亚稳态从而使薄膜或材料表面发生结构或组织的变化,形成非晶。这不符合Inoue提出的制备大块非晶态合金的经验规律。证明辉光离子合金化技术是一种制备大块非晶态合金层的新方法。
Magnesium is the lightest metal used in engineering. Magnesium alloys have advantageous properties including high specific strength, high specific toughness, low elastic module, excellent damping characteristics, good machinability and dimensional stability, electromagnetic shielding, abundant in resource as well as easy to be recycled. So magnesium alloys have found a wide applications in such area as automobile, computer, electronics, aeronautics and astronautics, sporting goods, handhold tools and household equipment, et al., and been regarded as“green engineering material”with greet potential development in 21st century. However, magnesium and its alloys have several drawbacks including poor resistance to corrosion and wear, poor creep resistance and high chemical reactivity, which restrict their extensive application in many industry fields.
In this dissertation, Al-Mg, Al-Cr-Fe, Ni-Cr-Mo-Cu film is prepared by double glow plasmas technique, and there microstructure and corrosion behavior are investigated. The film consists of two different regions, i.e., an amorphous layer on outmost surface and an underlying lamellar nanocrystalline layer with a grain size of less than 10 nm. The corrosion behavior of amorphous/nanocrystalline film in 3.5% NaCl solution is investigated using an electrochemical polarization measurement. Compared with the AZ31 magnesium alloy, the amorphous/nanocrystalline film exhibits more positive corrosion potentials and lower corrosion current densities than that of AZ31 magnesium alloy.
In present study, we have found that the novel technique—glow discharge used for making amorphous and nanocrystal film, which break through empirical rules for the achievement of large glass-forming. In the double cathode mode, both target cathode and substrate cathodes are subject to Ar ion sputter by glow discharge. As a result, a large number of nano particles escapes from the surface of one cathode materials and deposit on the surface of the other cathode materials surface. In the mono-cathode mode, due to a stronger ion sputter effect at a higher electrode voltage, the crystalline order on the surface of the electrode was destroyed by the Ar ion attack, leading to atomic displacement and the transformation from a crystalline state to an amorphous state. Meanwhile, a large amount of nanosize amorphous particles by glow discharge sputtering are redeposited on the workpiece surface. Likely, the two mechanisms can be proposed to explain the unique structure of the film formed on the pure iron by mono-cathode glow discharge.
本文利用辉光等离子表面合金化技术在镁合金AZ31表面制备Al-Mg、Al-Cr-Fe、Ni-Cr-Mo-Cu耐蚀合金层。采用透射电镜、X射线衍射和扫描电镜分析方法对合金层的显微组织、化学成分及相组成进行了综合分析,结果表明:合金层具有特殊的微观结构,即由最外层表面的非晶层及次外层表面的纳米晶层组成。采用电化学方法对表面改性层在3.5%NaCl溶液中的耐蚀性能进行测定,三种非晶/纳米晶耐蚀合金层的自腐蚀电位低于镁合金AZ31,维钝电流密度则相反,随着电位的变化,电流密度保持在1μA/cm2以下。
采用辉光离子合金化技术单阴极放电(自溅射)模式,在纯Fe表面制备非晶/纳米晶薄膜,以研究其形成非晶的机制。在Ar+轰击作用下,大量纳米尺寸的非晶相从表面溅射出来,在随后的驰豫过程中等效冷却速率高达1014℃/s,薄膜或固体物质从远离平衡态到达某个平衡态或亚稳态从而使薄膜或材料表面发生结构或组织的变化,形成非晶。这不符合Inoue提出的制备大块非晶态合金的经验规律。证明辉光离子合金化技术是一种制备大块非晶态合金层的新方法。
Magnesium is the lightest metal used in engineering. Magnesium alloys have advantageous properties including high specific strength, high specific toughness, low elastic module, excellent damping characteristics, good machinability and dimensional stability, electromagnetic shielding, abundant in resource as well as easy to be recycled. So magnesium alloys have found a wide applications in such area as automobile, computer, electronics, aeronautics and astronautics, sporting goods, handhold tools and household equipment, et al., and been regarded as“green engineering material”with greet potential development in 21st century. However, magnesium and its alloys have several drawbacks including poor resistance to corrosion and wear, poor creep resistance and high chemical reactivity, which restrict their extensive application in many industry fields.
In this dissertation, Al-Mg, Al-Cr-Fe, Ni-Cr-Mo-Cu film is prepared by double glow plasmas technique, and there microstructure and corrosion behavior are investigated. The film consists of two different regions, i.e., an amorphous layer on outmost surface and an underlying lamellar nanocrystalline layer with a grain size of less than 10 nm. The corrosion behavior of amorphous/nanocrystalline film in 3.5% NaCl solution is investigated using an electrochemical polarization measurement. Compared with the AZ31 magnesium alloy, the amorphous/nanocrystalline film exhibits more positive corrosion potentials and lower corrosion current densities than that of AZ31 magnesium alloy.
In present study, we have found that the novel technique—glow discharge used for making amorphous and nanocrystal film, which break through empirical rules for the achievement of large glass-forming. In the double cathode mode, both target cathode and substrate cathodes are subject to Ar ion sputter by glow discharge. As a result, a large number of nano particles escapes from the surface of one cathode materials and deposit on the surface of the other cathode materials surface. In the mono-cathode mode, due to a stronger ion sputter effect at a higher electrode voltage, the crystalline order on the surface of the electrode was destroyed by the Ar ion attack, leading to atomic displacement and the transformation from a crystalline state to an amorphous state. Meanwhile, a large amount of nanosize amorphous particles by glow discharge sputtering are redeposited on the workpiece surface. Likely, the two mechanisms can be proposed to explain the unique structure of the film formed on the pure iron by mono-cathode glow discharge.
引文
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