铈离子对高强铝合金应力腐蚀开裂的缓蚀作用

doi:10.11868/j.issn.1001-4381.2016.000220

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摘要

基于慢应变速率拉伸实验（SSRT），采用恒电流极化、电化学噪声（ECN）与电化学阻抗（EIS）等方法，研究7A04铝合金在3.5%（质量分数）NaCl水溶液中的应力腐蚀开裂（SCC）行为以及Ce³⁺对其SCC的缓蚀作用，探讨Ce³⁺对裂纹孕育与发展过程的抑制机理。结果表明：无论是阳极还是阴极极化，均会促进7A04的SCC倾向，前者增加了裂尖的阳极溶解，后者则加速了裂尖的氢脆效应。Ce³⁺的加入能延缓7A04的SCC断裂时间，但其有效性仅限于裂纹的萌生阶段。由于Ce³⁺能够抑制铝合金表面的亚稳态点蚀发育和长大，因而使裂纹的孕育时间显著延长，降低了SCC的敏感性。不过一旦裂纹进入扩展阶段或者试样表面有预裂纹，则由于Ce³⁺很难迁移到裂纹尖端或在裂尖区难以成膜，不能对裂纹的生长起到有效抑制作用，因而无法降低7A04的SCC发展速率。SEM分析表明7A04铝合金光滑试样SCC主要源于亚稳态或稳态点蚀的诱导作用。

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关键词 ：铝合金, 应力腐蚀, 电化学噪声, 点蚀, 缓蚀剂

Abstract：

The stress corrosion cracking (SCC) susceptibility of 7A04 high strength aluminum alloy in 3.5% (mass fraction) NaCl solution and the Ce³⁺ inhibition of SCC were investigated by slow stress rate test(SSRT), using constant current polarization, electrochemical noise (ECN) and electrochemical impedance spectroscopy (EIS) techniques. The inhibition mechanism of Ce³⁺ ions on the initiation and propagation of cracking was also analyzed. The results indicate that both anodic and cathodic galvanostatic polarizations can accelerate the SCC of 7A04, the former increases anodic dissolution but the latter accelerates hydrogen embrittlement of crack tip. SCC susceptibility of 7A04 can be reduced effectively by the addition of cerium ions, the fracture time is delayed and slowed down, but only during the initiation other than the propagation stage of cracking. Ce³⁺ ions can restrain the initiation of metastable pitting on the surface of 7A04 specimen, which therefore increase the induction time of the cracking since that the micro pits are usually the source of cracking.However, once the crack begins to propagate or the specimen is notched, the addition of cerium ions can rarely inhibit the cracking process. This is possibly attributed to that the radius of Ce³⁺ ion is too large to diffuse into the crack tip or it is hard to form protective CeO₂ layer, Ce³⁺ ion therefore fails to rehabilitate the active alloy at the crack tip and further reduce the SCC developing rate of 7A04. SEM also indicates that the crack initiation of smooth 7A04 specimens is mainly induced by metastable or stable pits.

Key words： aluminium alloy SCC electrochemical noise pitting corrosion inhibitor

收稿日期: 2016-03-02 出版日期: 2017-05-17

中图分类号:

O69

基金资助:国家自然科学基金资助项目(51371087)

通讯作者: 董泽华 E-mail: zehua.dong@gmail.com

作者简介: 董泽华(1968-), 男, 博士, 教授, 主要从事金属腐蚀与防护、腐蚀电化学、电化学科学仪器以及工业腐蚀监测方法等领域的研究, 联系地址:湖北省武汉市洪山区珞喻路华中科技大学化学与化工学院(430074), E-mail:zehua.dong@gmail.com

引用本文:

李文婷, 王浩伟, 余军, 董泽华, 郭兴蓬. 铈离子对高强铝合金应力腐蚀开裂的缓蚀作用[J]. 材料工程, 2017, 45(5): 20-30.
Wen-ting LI, Hao-wei WANG, Jun YU, Ze-hua DONG, Xing-peng GUO. Inhibition of Ce³⁺ on Stress Corrosion Crack of High Strength Aluminum Alloy. Journal of Materials Engineering, 2017, 45(5): 20-30.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2016.000220 或 http://jme.biam.ac.cn/CN/Y2017/V45/I5/20

Table 1 7A04铝合金化学成分(质量分数/%)

Fig.1 慢拉伸试样的尺寸 (a)光滑试样；(b)缺口试样

Fig.2 7A04铝合金在恒电流阳极极化作用下的SSRT曲线(a)及SCC敏感因子比较(b)

Fig.3 阳极恒电流极化作用下7A04铝合金拉伸试样断口SEM形貌 (a)自然腐蚀状态；(b)16μA·cm^-2；(c)32μA·cm^-2；(d)160μA·cm^-2

Fig.4 7A04铝合金在阴极恒电流极化作用下的SSRT曲线(a)及SCC敏感性比较(b)

Fig.5 阴极恒电流极化作用下7A04拉伸试样断口SEM形貌 (a)自然腐蚀状态；(b)-8μA·cm^-2；(c)-15μA·cm^-2；(d)-42μA·cm^-2

Fig.6 7A04铝合金在空气、3.5%NaCl以及添加Ce³⁺介质中的SSRT曲线 (a)光滑试样；(b)缺口试样

Fig.7 7A04铝合金在不同溶液SSRT过程中的应力-时间与电化学噪声曲线 (a)3.5%NaCl；(b)8mmol/L CeCl₃+3.5%NaCl

Fig.8 7A04铝合金裂纹萌生阶段的ECN统计分析 (a)形核速率；(b)噪声电阻；(c)平均积分电量；(d)平均峰幅值

Fig.9 7A04试样裂纹扩展过程中的ECN曲线 (a)3.5%NaCl；(b)8mmol/L CeCl₃+3.5%NaCl；(1) 弹性变形阶段；(2) 塑性变形阶段

Fig.10 7A04拉伸试样的SEM形貌 (a)断口垂直方向；(b)截面方向；(1)3.5%NaCl；(2)8mmol/L CeCl₃+3.5%NaCl

Fig.11 SSRT过程中7A04拉伸试样在不同溶液中的阻抗随时间变化曲线 (a)3.5%NaCl；(b)8mmol/L CeCl₃+3.5%NaCl

Fig.12 SSRT过程中7A04铝合金在不同溶液中R_p与应力随时间的变化 (a)3.5%NaCl；(b)8mmol/L CeCl₃+3.5%NaCl

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