目的 解决深海环境中铝合金牺牲阳极钝化问题,提高其表面活性。方法 在商用Al-Zn-In阳极基础上,结合文献优选出Ga、Mg、Ca、Mn、Ti 5种合金化元素,采用正交试验法设计出梯度成分的八元铝合金。结果 通过金相和扫描电镜（SEM）证实多种合金化元素的添加细化了铝阳极显微组织,但过高的Mg添加会导致缺陷增加;电子衍射仪（EDS）表明Mg、Zn、Ga、Mn等元素固溶于铝合金基体中,Ca、Ti、In则以直径小于2 μm的析出相在晶内均匀析出;扫描Kelvin探针（SKP）证明高含量的合金化元素导致表面电位分布不均,电位差增加,电偶腐蚀倾向增加;极化曲线结果证明低温、低氧环境导致阳极钝化电位区间增加,高压导致阳极自腐蚀电流密度增加,适当合金化元素的添加会减小阳极钝化电位区间,降低钝化电流和自腐蚀电流密度;电化学性能试验得出Mg、Ti、Ca、Mn最佳元素成分（质量分数）区间分别为0.9%~1%、0.018%~0.02%、0.05%~0.06%、0.09%~0.1%,八元铝阳极最大电流效率超过92%。X射线光电子能谱仪（XPS）证实八元铝阳极表面腐蚀层由Al2O3、Al(OH)3、ZnO、Mg(OH)2、Ga、In构成,表明腐蚀层中以Al2O3主导的钝化作用被破坏。结论 适量添加Ga、Mg、Ca、Mn、Ti合金化元素可显著提高铝阳极在高压、低温以及低氧海水环境中的电化学活性,为未来深海环境铝阳极开发提供了数据支撑。
Abstract
The deep sea represents a largely untapped strategic resource reservoir that has yet to be fully explored or exploited by both scientific and industrial sectors. In contrast to shallow marine environments, the deep-sea harbors abundant mineral deposits, natural gas hydrates, coal, petroleum, and other critical resources, as evidenced by available geological surveys. The sustainable extraction and utilization of these resources can significantly mitigate the global resource scarcity crisis. The harsh deep-sea environment characterized by high pressure, low temperature, and low dissolved oxygen accelerates the corrosion rate of deep-sea equipment primarily made of high-strength steel and titanium alloys, leading to reduced mechanical stability and service life. However, existing sacrificial anode materials are unsuitable for deep-sea applications, highlighting the urgent need for research on deep-sea sacrificial anodes. In this paper, to enhance the surface activity of aluminum (Al) alloy sacrificial anodes for deep-sea applications, five alloying elements (Ga, Mg, Ca, Mn, Ti) were selected on the basis of the commercial Al-Zn-In anode in combination with literature. An orthogonal experimental design was employed to develop octonary Al alloy anodes with gradient compositions. Metallographic and scanning electron microscopy (SEM) analyses confirmed that multi-element alloying refined the microstructure of the Al anode, but excessive Mg addition introduced defects. X-ray diffraction (XRD) and energy-dispersive spectroscopy (EDS) revealed that Mg, Zn, Ga, and Mn were solid-solved in the Al matrix, while Ca, Ti, and In precipitated uniformly within grains as phases smaller than 2 μm in diameter. Scanning Kelvin probe (SKP) measurements demonstrated that high alloying content led to uneven surface potential distribution and increased potential difference, resulting in high galvanic corrosion susceptibility. Potentiodynamic polarization curves indicated that low temperature and low oxygen in the deep-sea environment expanded the passivation potential range of the anodes, while high pressure increased their self-corrosion current density. Proper alloying reduced the passivation range while decreasing both passivation and self-corrosion current densities. Electrochemical performance tests and the range analysis determined the optimal composition ranges for Mg, Ti, Ca, and Mn to be 0.9%-1%, 0.018%-0.02%, 0.05%-0.06% and 0.09%-0.1%, respectively, achieving a maximum current efficiency exceeding 92% for the octonary Al anode. Moreover, the factor range difference (Rj) indicated that the order of influence of different alloying elements on current efficiency of anodes was Mg > Ca = Mn > Ti. Therefore, the Mg content had a more significant effect on the octonary Al anode. X-ray photoelectron spectroscopy (XPS) confirmed that the corrosion layer on the octonary anode surface comprised Al2O3, Al(OH)3, ZnO, Mg(OH)2, Ga, and In, suggesting disruption of the Al2O3-dominated passivation effect. In simulated deep-sea conditions, micron-scale precipitates of Ca, In, and Ti formed micro-galvanic couples uniformly distributed across the anode surface, enhancing surface activity while mitigating self-corrosion. Activators like Zn, In, and Ga facilitated the "activation-redeposition" mechanism to reactivate the Al2O3-rich corrosion product layer, while Mg(OH)2 from Mg increased defect density via volumetric effects, further activating the anode surface. These findings provide a theoretical and experimental foundation for optimizing the activation behavior and performance of Al alloy anodes in deep sea.
关键词
铝合金牺牲阳极 /
深海环境条件 /
合金化元素 /
表面活化 /
电化学性能
Key words
Al alloy sacrificial anode /
deep-sea environmental conditions /
alloying elements /
surface activation /
electrochemical performance
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参考文献
[1] HALLWOOD P. Deep Sea Mining, Developing Legal Regime, Bonus Bidding and the Sharing of Economic Rents[J]. Resources Policy, 2025, 105: 105602.
[2] FU Y, LI Z K, CHEW D, et al.Deep-Sea Rare Earth Element-Rich Sediments: A Review of Distribution, Carriers and Petrogenesis[J]. Global and Planetary Change, 2025, 252: 104870.
[3] MILLER K A, THOMPSON K F, JOHNSTON P, et al.An Overview of Seabed Mining Including the Current State of Development, Environmental Impacts, and Knowledge Gaps[J]. Frontiers in Marine Science, 2018, 4: 418.
[4] LI Z, FAN L, MA L, et al.Perspective Review on Factors that Influence the Stress Corrosion of Ti Alloys for Deep-Sea Applications[J]. Journal of Materials Science & Technology, 2025, 222: 228-249.
[5] YANG X W, LIN B, ZHANG H L, et al.Influence of Stress on the Corrosion Behavior of Ti Alloys: A Review[J]. Journal of Alloys and Compounds, 2024, 985: 173346.
[6] WU Y M, ZHAO W J, WANG L P.State of the Art and Current Trends on the Metal Corrosion and Protection Strategies in Deep Sea[J]. Journal of Materials Science & Technology, 2025, 215: 192-213.
[7] 李成杰, 杜敏. 深海钢铁材料的阴极保护技术研究及发展[J]. 中国腐蚀与防护学报, 2013, 33(1): 10-16.
LI C J, DU M.Research and Development of Cathodic Protection for Steels in Deep Seawater[J]. Journal of Chinese Society for Corrosion and Protection, 2013, 33(1): 10-16.
[8] 张海兵, 马力, 李威力, 等. 深海牺牲阳极模拟环境电化学性能研究[J]. 材料开发与应用, 2015, 30(5): 63-67.
ZHANG H B, MA L, LI W L, et al.Electrochemical Performance of Deep-Sea Sacrificial Anode in Simulated Environment[J]. Development and Application of Materials, 2015, 30(5): 63-67.
[9] LIU R, CUI Y, ZHANG B, et al.Unveiling the Effect of Hydrostatic Pressure on the Passive Films of the Deformed Titanium Alloy[J]. Corrosion Science, 2021, 190: 109705.
[10] 曲本文, 马力, 闫永贵, 等. 海水温度对Al-Zn-Ga-Si低电位牺牲阳极性能的影响[J]. 腐蚀科学与防护技术, 2015, 27(3): 259-263.
QU B W, MA L, YAN Y G, et al.Influence of Temperature on Electrochemical Performance of Low Driving Voltage Al-Zn-Ga-Si Anode in Seawater[J]. Corrosion Science and Protection Technology, 2015, 27(3): 259-263.
[11] 李威力, 闫永贵, 陈光, 等. Al-Zn-In系牺牲阳极低温电化学性能研究[J]. 腐蚀科学与防护技术, 2009, 21(2): 122-124.
LI W L, YAN Y G, CHEN G, et al.ELECTROCHEMICAL BEHAVIOR OF Al-Zn-Ln SACRIFICIAL ANODE IN LOW TEMPERATURE ENVIRONMENT[J]. Corrosion Science and Protection Technology, 2009, 21(2): 122-124.
[12] 胡胜楠. 模拟深海环境下Al-Zn-In牺牲阳极性能研究[D]. 哈尔滨: 哈尔滨工程大学, 2012.
HU S N.Study on Properties of Al-Zn-In Sacrificial Anode in Simulated Deep Sea Environment[D]. Harbin: Harbin Engineering University, 2012.
[13] PIÑOL S, MORALES M, ESPIELL F. Low Temperature Anode-Supported Solid Oxide Fuel Cells Based on Gadolinium Doped Ceria Electrolytes[J]. Journal of Power Sources, 2007, 169(1): 2-8.
[14] 李妍, 熊睿, 张国庆. 海洋深水铝合金牺牲阳极的性能[J]. 腐蚀与防护, 2023, 44(10): 95-97.
LI Y, XIONG R, ZHANG G Q.Performance of Aluminum Alloy Sacrificial Anode in Deep Water[J]. Corrosion & Protection, 2023, 44(10): 95-97.
[15] 张炬焕, 刘静, 彭晶晶, 等. Al-Zn-In系牺牲阳极在模拟海洋环境下的电化学性能研究[J]. 中国腐蚀与防护学报, 2024, 44(5): 1223-1233.
ZHANG J H, LIU J, PENG J J, et al.Electrochemical Performance of a Novel Al-Zn-in-Sn-La Sacrificial Anode Alloy in Simulated Marine Environments[J]. Journal of Chinese Society for Corrosion and Protection, 2024, 44(5): 1223-1233.
[16] 张一晗, 张海兵, 辛永磊, 等. Al-Zn-In-Mg-Ti-Ga-Mn牺牲阳极在极地低温环境中的电化学性能[J]. 中国有色金属学报, 2023, 33(4): 1209-1219.
ZHANG Y H, ZHANG H B, XIN Y L, et al.Electrochemical Performance of Al-Zn-in-Mg-Ti-Ga-Mn Sacrificial Anode in Polar Low Temperature Environment[J]. The Chinese Journal of Nonferrous Metals, 2023, 33(4): 1209-1219.
[17] LIANG R, SU Y, SUI X L, et al.Effect of Mg Content on Discharge Behavior of Al-0.05Ga-0.05Sn-0.05Pb-xMg Alloy Anode for Aluminum-Air Battery[J]. Journal of Solid State Electrochemistry, 2019, 23(1): 53-62.
[18] ZHOU S G, TIAN C, ALZOABI S, et al.Performance of an Al-0.08Sn-0.08Ga-XMg Alloy as an Anode for Al-Air Batteries in Alkaline Electrolytes[J]. Journal of Materials Science, 2020, 55(25): 11477-11488.
[19] 余波, 孙明先, 闫永贵, 等. 镁含量对Al-Zn-In-Mg-Ti-Ga-Mn合金牺牲阳极组织和性能的影响[J]. 材料开发与应用, 2012, 27(3): 56-59.
YU B, SUN M X, YAN Y G, et al.Effect of Mg Content on Microstructure and Electrochemical Performance of Al-Zn-in-Mg-Ti-Ga-Mn Sacrificial Anode[J]. Development and Application of Materials, 2012, 27(3): 56-59.
[20] WU Z B, ZHANG H T, GUO C, et al.Effects of Indium, Gallium, or Bismuth Additions on the Discharge Behavior of Al-Mg-Sn-Based Alloy for Al-Air Battery Anodes in NaOH Electrolytes[J]. Journal of Solid State Electrochemistry, 2019, 23(8): 2483-2491.
[21] SUN Z G, LU H M.Performance of Al-0.5In as Anode for Al-Air Battery in Inhibited Alkaline Solutions[J]. Journal of the Electrochemical Society, 2015, 162(8): A1617-A1623.
[22] ZHUANG Z H, FENG Y, PENG C Q, et al.Effect of Ga on Microstructure and Electrochemical Performance of Al-0.4Mg-0.05Sn-0.03Hg Alloy as Anode for Al-Air Batteries[J]. Transactions of Nonferrous Metals Society of China, 2021, 31(9): 2558-2569.
[23] PARK I J, CHOI S R, KIM J G.Aluminum Anode for Aluminum-Air Battery - Part II: Influence of in Addition on the Electrochemical Characteristics of Al-Zn Alloy in Alkaline Solution[J]. Journal of Power Sources, 2017, 357: 47-55.
[24] ZHANG H T, DONG X, WU Z B, et al.Revealing the Role of Ca on the Electrochemical Properties of Al-Mg-Sn-Ga-Ca Alloy as Anodes for Al-Air Batteries[J]. Journal of Materials Research and Technology, 2022, 21: 2053-2060.
[25] WAN H X, HUANGFU W Z, LIU Z Y, et al.Influence of Sea Mud State on the Anodic Behavior of Al-Zn-in-Mg-Ti Sacrificial Anode[J]. Ocean Engineering, 2017, 136: 11-17.
[26] SUN H J, LIU L, LI Y, et al.The Performance of Al-Zn-In-Mg-Ti Sacrificial Anode in Simulated Deep Water Environment[J]. Corrosion Science, 2013, 77: 77-87.
[27] 丁枫林, 李祯, 张一晗, 等. 牺牲阳极材料在深海中的研究进展[J]. 装备环境工程, 2024, 21(11): 100-109.
DING F L, LI Z, ZHANG Y H, et al.Research Progress of Sacrificial Anode Materials in Deep Sea[J]. Equipment Environmental Engineering, 2024, 21(11): 100-109.
[28] YANG M, LIU X B, XING L Y, et al.Corrosion and Mechanical Behavior of the As-Cast and Solid-Solution- Treated AM50 Magnesium Alloy in Different Media[J]. Materials, 2023, 16(6): 2406.
[29] GAO S C, LI Z, FAN L, et al.Mechanism of the Element Microsegregation Induced Corrosion Difference of Ti6321 Weldment[J]. Corrosion Science, 2023, 219: 111194.
[30] 郭为民, 孙明先, 邱日, 等. 材料深海自然环境腐蚀实验研究进展[J]. 腐蚀科学与防护技术, 2017, 29(3): 313-317.
GUO W M, SUN M X, QIU R, et al.Research Progress on Corrosion and Aging of Materials in Deep-Sea Environment[J]. Corrosion Science and Protection Technology, 2017, 29(3): 313-317.
[31] MORETO J A, MARINO C E B, BOSE FILHO W W, et al. SVET, SKP and EIS Study of the Corrosion Behaviour of High Strength Al and Al-Li Alloys Used in Aircraft Fabrication[J]. Corrosion Science, 2014, 84: 30-41.
[32] NYLUND A, OLEFJORD I.Surface Analysis of Oxidized Aluminium. 1. Hydration of Al2O3 and Decomposition of Al(OH)3 in a Vacuum as Studied by ESCA[J]. Surface and Interface Analysis, 1994, 21(5): 283-289.
[33] IWAKURO H, TATSUYAMA C, ICHIMURA S.XPS and AES Studies on the Oxidation of Layered Semiconductor GaSe[J]. Japanese Journal of Applied Physics, 1982, 21(1R): 94.
[34] PROCOP M.XPS Data for Sputter-Cleaned In0.53Ga0.47As, GaAs, and InAs Surfaces[J]. Journal of Electron Spectroscopy and Related Phenomena, 1992, 59(2): R1-R10.
[35] WEHNER P S, MERCER P N, APAI G.Interaction of H2 and CO with Rh4(CO)12 Supported on ZnO[J]. Journal of Catalysis, 1983, 84(1): 244-247.
[36] HAYCOCK D E, KASRAI M, NICHOLLS C J, et al.The Electronic Structure of Magnesium Hydroxide (Brucite) Using X-Ray Emission, X-Ray Photoelectron, and Auger Spectroscopy[J]. Journal of the Chemical Society, Dalton Transactions, 1978(12): 1791-1796.
[37] SHI H L, LIU D X, JIA T Y, et al.Effect of the Ultrasonic Surface Rolling Process and Plasma Electrolytic Oxidation on the Hot Salt Corrosion Fatigue Behavior of TC11 Alloy[J]. International Journal of Fatigue, 2023, 168: 107443.
[38] 曲本文, 马力, 李威力, 等. 合金元素Ga在铝合金牺牲阳极中的应用[J]. 全面腐蚀控制, 2015, 29(7): 52-54.
QU B W, MA L, LI W L, et al.The Application of Alloy Elements Ga in Al Alloy Sacrificial Anode[J]. Total Corrosion Control, 2015, 29(7): 52-54.
[39] LI L, LIU H, YAN Y, et al.Effects of Alloying Elements on the Electrochemical Behaviors of Al-Mg-Ga-in Based Anode Alloys[J]. International Journal of Hydrogen Energy, 2019, 44(23): 12073-12084.
[40] 魏然, 王浩, 秦立高, 等. 海上某油田油管腐蚀失效原因分析[J]. 全面腐蚀控制, 2020, 34(11): 7-12.
WEI R, WANG H, QIN L G, et al.Failure Analysis of Corrosion Perforation of Tubing in Offshore Oilfield[J]. Total Corrosion Control, 2020, 34(11): 7-12.
基金
国家自然科学基金（52201090）; 国家重点研发计划（2022YFB3808800）
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