选区激光熔化成形含<strong>Cu</strong>中熵合金的微观组织及耐腐蚀性能

doi:10.11902/1005.4537.2024.064

中国腐蚀与防护学报

2024, Vol. 44

Issue (6): 1589-1600 CSTR: 32134.14.1005.4537.2024.064 DOI: 10.11902/1005.4537.2024.064

研究报告

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选区激光熔化成形含Cu中熵合金的微观组织及耐腐蚀性能

易铄¹, 周生璇¹, 叶鹏¹, 杜晓洁¹, 徐震霖¹^,², 何宜柱¹^,²(

)

1.安徽工业大学材料科学与工程学院马鞍山 243032
2.安徽工业大学材料与加工安徽省重点实验室马鞍山 243032

Microstructure and Corrosion Resistance of Cu-containing Fe-Mn-Cr-Ni Medium-entropy Alloy Prepared by Selective Laser Melting

YI Shuo¹, ZHOU Shengxuan¹, YE Peng¹, DU Xiaojie¹, XU Zhenlin¹^,², HE Yizhu¹^,²(

)

1. School of Materials Science and Engineering, Anhui University of Technology, Ma'anshan 243032, China
2. Anhui Key Laboratory of Materials and Processing, Anhui University of Technology, Ma'anshan 243032, China

引用本文:

易铄, 周生璇, 叶鹏, 杜晓洁, 徐震霖, 何宜柱. 选区激光熔化成形含Cu中熵合金的微观组织及耐腐蚀性能[J]. 中国腐蚀与防护学报, 2024, 44(6): 1589-1600.
Shuo YI, Shengxuan ZHOU, Peng YE, Xiaojie DU, Zhenlin XU, Yizhu HE. Microstructure and Corrosion Resistance of Cu-containing Fe-Mn-Cr-Ni Medium-entropy Alloy Prepared by Selective Laser Melting[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(6): 1589-1600.

全文: PDF(13146 KB) HTML

摘要:

以选区激光熔化(SLM)制备的Fe-Mn-Cr-Ni中熵合金(MEA)为对象，重点研究了打印态和经不同时效温度处理的MEA在1 mol/L NaOH溶液中的耐腐蚀性能，分析了微观组织对腐蚀行为的影响。结果表明，SLM-MEA经过300℃时效后，晶界处的富Cu相优先被溶解，从而抑制了活性部位溶解，提高了耐腐蚀性能。对比打印态，300℃时效态的腐蚀电流下降了37.37%，极化电阻提高了2倍。随着时效温度升高，富Cu析出相的位置沿晶界处向胞状亚晶内部转移。富Cr碳化物随着温度升高发生粗化，削弱了钝化膜的保护能力。此外，300℃时效态中富Cu析出相的溶解，提高了钝化膜中Cr + Ni/Fe + Mn阳离子比，其值为打印态的1.2倍，促进更致密连续的钝化膜形成。

关键词 ：中熵合金, 选区激光熔化, 时效处理, 微观组织, 腐蚀性能

Abstract：

The Cu-containing Fe-Mn-Cr-Ni medium entropy alloy (MEA) was prepared by selective laser melting (SLM) and followed by post aging treatment, and then its microstructure and corrosion performance in 1 mol/L NaOH solution were studied. The results show that the Cu-rich phase at grain boundaries of SLM-MEA is preferentially dissolved after aging at 300^oC, which inhibits the dissolution of the active site and improves the corrosion resistance. Compared with the SLM alloy, the corrosion current of the alloy after being aged at 300^oC decreased by 37.37% and the polarization resistance increased by 2 times. As the aging temperature increased, the Cu-rich precipitates migrate from grain boundaries to the interior of the cellular sub-crystal. Cr-rich carbides coarsened with the increasing temperature, which weakened the protective ability of the passivation film. In addition, the dissolution of Cu-rich precipitates in the alloy aged at 300^oC increased the cation ratio of Cr + Ni to Fe + Mn in the passivation film, which was 1.2 times that of the as prepared SLM alloy, and promoted the formation of a denser and continuous passivation film.

Key words： medium entropy alloy selective laser melting aging treatment microstructure corrosion resistance

收稿日期: 2024-03-01 32134.14.1005.4537.2024.064

ZTFLH:

TG174

基金资助:国家自然科学基金(51971001);安徽省科技重大专项(2022a05020017)

通讯作者: 何宜柱，E-mail：heyizhu@ahut.edu.cn，研究方向为金属材料加工

Corresponding author: HE Yizhu, E-mail: heyizhu@ahut.edu.cn

作者简介: 易铄，男，1998年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2024.064 或 https://www.jcscp.org/CN/Y2024/V44/I6/1589

图1 中熵合金粉末的微观形貌和粒径分布图

图2 试样扫描策略和切割位置示意图

图3 时效处理后SLM-MEA的XRD谱和(200)放大图

图4 不同时效处理后的SLM-MEA微观结构

表1 图 4中标记点的化学成分 (mass fraction / %)

图5 不同时效态样品在1 mol/L NaOH溶液中的开路电位

图6 不同时效态样品的动电势极化曲线及Ecorr，Ip和Icorr

图7 不同时效态样品在1 mol/L NaOH溶液中电化学阻抗谱和拟合电路

表2 等效电路中参数的拟合值

图8 不同时效态样品在1 mol/L NaOH溶液中电化学腐蚀形貌

图9 不同时效态样品的电化学腐蚀形貌3D图和腐蚀深度图

图10 UT和AT-300在1 mol/L NaOH 溶液中浸泡7 d后钝化膜的XPS谱

图11 UT和AT-300在1 mol/L NaOH 溶液中浸泡7 d钝化膜中的阳离子含量

图12 UT，AT-300和AT-700样品在1 mol/L NaOH溶液中的腐蚀行为示意图

1	Hou S, Sun M Y, Bai M J, et al. A hybrid prediction frame for HEAs based on empirical knowledge and machine learning [J]. Acta Mater., 2022, 228: 117742
2	George E P, Curtin W A, Tasan C C. High entropy alloys: A focused review of mechanical properties and deformation mechanisms [J]. Acta Mater., 2020, 188: 435 doi: 10.1016/j.actamat.2019.12.015
3	Zhang L S, Ma G L, Fu L C, et al. Recent progress in high-entropy alloys [J]. Adv. Mat. Res., 2013, 631-632: 227
4	Chang X T, Song J Q, Wang B, et al. Effect of micro-alloying with Cr, N and Al on corrosion resistance of high manganese austenitic steel in acidic salt spray environment [J]. J. Chin. Soc. Corros. Prot., 2024, 44: 47
4	(常雪婷, 宋嘉琪, 王冰等. 微合金化对高锰奥氏体钢在酸性盐雾环境下的耐蚀性能影响研究 [J]. 中国腐蚀与防护学报, 2024, 44: 47)
5	Han B L, Zhang C C, Feng K, et al. Additively manufactured high strength and ductility CrCoNi medium entropy alloy with hierarchical microstructure [J]. Mater. Sci. Eng., 2021, 820A: 141545
6	Jiang H, Nai Q L, Xu C, et al. Sensitive temperature and reason of rapid fatigue crack propagation in nickel-based superalloy [J]. Acta Metall. Sin., 2023, 59: 1190 doi: 10.11900/0412.1961.2023.00151
6	(江河, 佴启亮, 徐超等. 镍基高温合金疲劳裂纹急速扩展敏感温度及成因 [J]. 金属学报, 2023, 59: 1190)
7	Shang J, Gu Y, Zhao J, et al. Corrosion behavior in molten salts at 850 ℃ and its effect on mechanical properties of Hastelloy X alloy fabricated by additive manufacturing [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 671
7	(尚进, 古岩, 赵京等. 增材制造Hastelloy X合金在850℃混合硫酸盐中热腐蚀行为及其对力学性能的影响 [J]. 中国腐蚀与防护学报, 2023, 43: 671)
8	Wang Y Q, Liu B, Yan K, et al. Probing deformation mechanisms of a FeCoCrNi high-entropy alloy at 293 and 77 K using in situ neutron diffraction [J]. Acta Mater., 2018, 154: 79
9	Gu D D, Wang H Q, Chang F, et al. Selective laser melting additive manufacturing of TiC/AlSi₁₀Mg bulk-form nanocomposites with tailored microstructures and properties [J]. Phys. Procedia, 2014, 56: 108
10	Xia X J, Wan X Y, Chen Y X, et al. Effect of heat treatments on corrosion behavior of 3Cr low carbon steel [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 656
10	(夏晓健, 万芯媛, 陈云翔等. 两种热处理工艺对3Cr钢腐蚀行为影响及机理研究 [J]. 中国腐蚀与防护学报, 2023, 43: 656) doi: 10.11902/1005.4537.2022.195
11	Zhu Z G, Ma K H, Yang X, et al. Annealing effect on the phase stability and mechanical properties of (FeNiCrMn)_(100- _x₎ Cox high entropy alloys [J]. J. Alloy. Compd., 2017, 695: 2945
12	Zhou C S, Wu F Y, Tang D, et al. Effect of subcritical-temperature heat treatment on corrosion of SLM SS316L with different process parameters [J]. Corros. Sci., 2023, 218: 111214
13	Sarkar S, Mukherjee S, Kumar C S, et al. Effects of heat treatment on microstructure, mechanical and corrosion properties of 15-5 PH stainless steel parts built by selective laser melting process [J]. J Manuf. Process., 2020, 50: 279 doi: 10.1016/j.jmapro.2019.12.048
14	Xi T, Shahzad M B, Xu D K, et al. Effect of copper addition on mechanical properties, corrosion resistance and antibacterial property of 316L stainless steel [J]. Mater. Sci. Eng., 2017, 71C: 1079
15	Wu W, Dai Z Y, Liu Z Y, et al. Synergy of Cu and Sb to enhance the resistance of 3%Ni weathering steel to marine atmospheric corrosion [J]. Corros. Sci., 2021, 183: 109353
16	Xu Q F, Gao K W, Lv W T, et al. Effects of alloyed Cr and Cu on the corrosion behavior of low-alloy steel in a simulated groundwater solution [J]. Corros. Sci., 2016, 102: 114
17	Elangeswaran C, Cutolo A, Muralidharan G K, et al. Effect of post-treatments on the fatigue behaviour of 316L stainless steel manufactured by laser powder bed fusion [J]. Int. J. Fatigue, 2019, 123: 31
18	Prashanth K G, Eckert J. Formation of metastable cellular microstructures in selective laser melted alloys [J]. J. Alloy. Compd., 2017, 707: 27
19	Wang P J, Zhao J B, Ma L W, et al. Effect of grain ultra-refinement on microstructure, tensile property, and corrosion behavior of low alloy steel [J]. Mater. Charact., 2021, 179: 111385
20	Li W J, Che X Y, Tang Y C, et al. Effect of plastic deformation processing on corrosion behavior of pure zinc in a leaching solution of soil at Tianjin [J]. J. Chin. Soc. Corros. Prot., 2024, 44: 497
20	(李文杰, 车晓钰, 唐永存等. 塑性变形加工对纯锌在天津土壤浸出液中腐蚀行为的影响 [J]. 中国腐蚀与防护学报, 2024, 44: 497) doi: 10.11902/1005.4537.2023.108
21	Zhao J L, Zhai Z F, Sun D, et al. Antibacterial durability and biocompatibility of antibacterial-passivated 316L stainless steel in simulated physiological environment [J]. Mater. Sci. Eng., 2019, 100C: 396
22	Wang J Y, Li W H, Yang H L, et al. Corrosion behavior of CoCrNi medium-entropy alloy compared with 304 stainless steel in H₂SO₄ and NaOH solutions [J]. Corros. Sci., 2020, 177: 108973
23	Della Rovere C A, Alano J H, Silva R, et al. Characterization of passive films on shape memory stainless steels [J]. Corros. Sci., 2012, 57: 154
24	Lu Z, Zhang C C, Fang R R, et al. Microstructure evolution and corrosion behavior of the novel maraging stainless steel manufactured by selective laser melting [J]. Mater. Charact., 2022, 190: 112078
25	Wang Y, Qiu Y B, Chen Z Y, et al. Corrosion of polypyrrole: kinetics of chemical and electrochemical processes in NaOH solutions [J]. Corros. Sci., 2017, 118: 96
26	Luo H, Zou S W, Chen Y H, et al. Influence of carbon on the corrosion behaviour of interstitial equiatomic CoCrFeMnNi high-entropy alloys in a chlorinated concrete solution [J]. Corros. Sci., 2020, 163: 108287
27	Xu Z L, Zhang H, Du X J, et al. Corrosion resistance enhancement of CoCrFeMnNi high-entropy alloy fabricated by additive manufacturing [J]. Corros. Sci., 2020, 177: 108954
28	Jabs T, Borthen P, Strehblow H H. X‐ray photoelectron spectroscopic examinations of electrochemically formed passive layers on Ni‐Cr alloys [J]. J. Electrochem. Soc., 1997, 144: 1231
29	Marcus P, Grimal J M. The anodic dissolution and passivation of NiCrFe alloys studied by ESCA [J]. Corros. Sci., 1992, 33: 805
30	Zhao B Z, Zhu M, Yuan Y F, et al. Comparison of corrosion resistance of CoCrFeMnNi high entropy alloys with pipeline steels in an artificial alkaline soil solution [J]. J. Chin. Soc. Corros. Prot., 2022, 42: 425
30	(赵宝珠, 朱敏, 袁永锋等. CoCrFeMnNi高熵合金和管线钢在碱性土壤环境中的耐蚀性对比研究 [J]. 中国腐蚀与防护学报, 2022, 42: 425) doi: 10.11902/1005.4537.2021.161
31	Li Z, Wan H X, Song D D, et al. Corrosion behavior of X80 pipeline steel in the presence of Brevibacterium halotolerans in Beijing soil [J]. Bioelectrochemistry, 2019, 126: 121
32	Li D, Liang Y, Liu X X, et al. Corrosion behavior of Ti₃AlC₂ in NaOH and H₂SO₄ [J]. J. Eur. Ceram. Soc., 2010, 30: 3227
33	Tian D H, Jiao H D, Xiao J S, et al. The corrosion behavior of a Ni_0.91Cr_0.04Cu_0.05 anode for the electroreduction of Fe₂O₃ in molten NaOH [J]. J. Alloy. Compd., 2018, 769: 977
34	Gao Z Y, Jiang B, Fan Z B, et al. Corrosion behavior of typical grounding materials in artificial alkaline soil solution [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 191
34	(高智悦, 姜波, 樊志彬等. 典型接地材料在碱性土壤模拟液中的腐蚀行为研究 [J]. 中国腐蚀与防护学报, 2023, 43: 191) doi: 10.11902/1005.4537.2022.061
35	Wu J F, Zheng X W, Li W P, et al. Copper corrosion inhibition by combined effect of inhibitor and passive film in alkaline solution [J]. Res. Chem. Intermed., 2015, 41: 8557
36	Yin Y Y, Li H X, Pan S H, et al. Electrochemical behaviour of passivation film formed on SLM-fabricated Hastelloy X superalloy surface in 10wt% NaNO₃ solution [J]. Corros. Sci., 2022, 206: 110494
37	Kong D C, Dong C F, Ni X Q, et al. Mechanical properties and corrosion behavior of selective laser melted 316L stainless steel after different heat treatment processes [J]. J. Mater. Sci. Technol., 2019, 35: 1499 doi: 10.1016/j.jmst.2019.03.003
38	Fattah-Alhosseini A, Golozar M A, Saatchi A, et al. Effect of solution concentration on semiconducting properties of passive films formed on austenitic stainless steels [J]. Corros. Sci., 2010, 52: 205
39	Ben Rhouma A, Amadou T, Sidhom H, et al. Correlation between microstructure and intergranular corrosion behavior of low delta-ferrite content AISI 316L aged in the range 550-700^oC [J]. J. Alloy. Compd., 2017, 708: 871
40	Shang Q, Man C, Pang K, et al. Mechanism of post-heat treatment on intergranular corrosion behavior of SLM-316L stainless steel with different carbon content [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 1273
40	(商强, 满成, 逄昆等. 后热处理对不同含碳量SLM-316L不锈钢晶间腐蚀行为的作用机制研究 [J]. 中国腐蚀与防护学报, 2023, 43: 1273)
41	Lewis M H, Hattersley B. Precipitation of M₂₃C₆ in austenitic steels Precipitation de carbures M₂₃C₆, dans les aciers austenitiquesAusscheidung von M₂₃C₆ in austenitischen stählen [J]. Acta Metall., 1965, 13: 1159
42	Kaneko K, Fukunaga T, Yamada K, et al. Formation of M₂₃C₆-type precipitates and chromium-depleted zones in austenite stainless steel [J]. Scr. Mater., 2011, 65: 509

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