高熵十二硼化物增强相对镁合金性能影响

褚振华; 陈景昆; 李斯勇; 许竞翔; 郑兴伟

高熵十二硼化物增强相对镁合金性能影响

1.
上海海洋大学, 工程学院, 上海 201306
2.
神州创为科技有限公司, 苏州 215434
3.
东华大学, 物理学院, 上海 201620

基金项目: 国家自然科学基金 (51872072)

详细信息

中图分类号: TB333
计量
- 文章访问数: 27
- HTML全文浏览量: 26
- 被引次数: 0
出版历程
- 收稿日期: 2024-07-31
- 修回日期: 2024-09-11
- 录用日期: 2024-09-22
- 网络出版日期: 2024-10-19

Effect of High-Entropy Dodecaboride Reinforcements on the Properties of Magnesium Alloys

1.
Shanghai Ocean University, College of Engineering, Shanghai, 201306, China
2.
Shenzhou Chuangwei Technology Co., Ltd., 215434, China
3.
Donghua University, College of Physics, Shanghai, 201620

Funds: National Natural Science Foundation of China (No.51872072)

摘要

摘要: 海洋装备科技的飞速发展促使海洋装备轻量化需求不断增加。镁合金因比重小、比强度高和铸造性佳，在交通运输、航空航天等领域广泛应用，是极具潜力的材料。然而，其较低的硬度和较差的耐蚀性严重制约了在海洋环境中的应用。本研究以超硬的十二硼化物高熵陶瓷作为AZ31镁合金的增强相，制备了一系列不同增强相含量的复合材料，系统探讨高熵陶瓷相对AZ31镁合金组织和性能的影响。研究发现，经氢氟酸表面活化处理后，增强相与基体的结合性能得到改善。其中，2%经活化的高熵陶瓷增强相镁合金综合性能最佳，其自腐蚀电位提升至−1.398V，自腐蚀电流密度降至 49.58 μA/cm²，硬度提高到83.42 HV，屈服强度提升至52.17 MPa。
- 镁合金 /
- 高熵陶瓷 /
- 增强相 /
- 耐蚀性 /
- 力学性能
Abstract: As the demand for lightweight marine equipment continues to grow, lightweight and high-strength magnesium alloy materials have shown broad application prospects in the field of marine equipment. However, magnesium alloys have relatively low hardness and poor corrosion resistance, which severely limits their application in marine environments. In this study, ultra-hard material high-entropy ceramics (high-entropy dodecaboride REB12, RE = Dy, Ho, Er, Tm, Lu) were used as reinforcement phases for AZ31 magnesium alloy to prepare composite materials with different mass percentage contents of high-entropy ceramic reinforcement phases. The influence of high-entropy ceramics on the microstructure and properties of AZ31 magnesium alloy was investigated. The results showed that the high-entropy ceramics did not react with the AZ31 magnesium alloy, and the combination performance between the reinforcement phase and the matrix was improved after hydrofluoric acid surface activation treatment of the high-entropy ceramics. After 2% activation treatment, the self-corrosion potential of the high-entropy ceramic reinforced magnesium alloy was increased to −1.398 V, the self-corrosion current density was reduced to 49.58 μA/cm², the hardness was increased to 83.4 HV, and the yield strength was increased to 62.7 MPa, showing the best comprehensive performance.
- Magnesium Alloy /
- High-Entropy Ceramics /
- Reinforcement Phase /
- Corrosion Resistance /
- Mechanical Properties

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图 1 拉伸试样参数图单位：mm

Figure 1. Tensile specimen parameter diagram. Unit:mm

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图 2 高熵陶瓷活化前后形貌图：(a)活化前高熵陶瓷形貌图；(b)活化后高熵陶瓷形貌图

Figure 2. Morphology of High-Entropy Ceramics Before and After Activation: (a) Morphology of high-entropy ceramics before activation; (b) Morphology of high-entropy ceramics after activation

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图 3 xHECBs /AZ31 镁合金 XRD 图

Figure 3. XRD pattern of xHECBs /AZ31 magnesium alloy

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图 4 xHECBs /AZ31镁合金抛光态光学显微组织图与晶界图；

(a) 2%HECBs/AZ31(活)抛光态光学显微组织图(b) 0%HECBs/AZ31(未)金相图(c) 2%HECBs/AZ31(活)金相图

Figure 4. The optical microstructure and grain boundary images of the xHECBs/AZ31 magnesium alloy in the polished state;

(a) Optical microstructure of 2%HECBs/AZ31 (activated) in the polished state (b) Metallographic image of 0%HECBs/AZ31 (unactivated) (c) Metallographic image of 2%HECBs/AZ31 (activated).

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图 5 xHECBs/AZ31镁合金SEM和部分EDS能谱图(a) xHECBs/AZ31镁合金SEM扫描图(b) EDS的Er能谱(c) EDS的Dy能谱(d) EDS 的 Ho 能谱

Figure 5. SEM images and partial EDS spectra of xHEDBs/AZ31 magnesium alloy; (a) Enlarged SEM image (b) EDS spectrum for Er (c) EDS spectrum for Dy (d) EDS spectrum for Ho

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图 6 xHECBs/AZ31 极化图

Figure 6. Polarization plot of xHECBs/AZ31 magnesium alloy.

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图 8 2%HECBs /AZ31腐蚀产物截面膜图

Figure 8. 2%HECBs /AZ31 Cross-sectional Image of Corrosion Products

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图 7 xHECBs /AZ31 阻抗 Bode 和Nyquist (a)阻抗 Nyquist 图；(b) Bode 图阻抗和频率图；(c) Bode 图相位角和频率关图

Figure 7. Impedance Bode and Nyquist plots of xHECBs /AZ31 magnesium alloy; (a) Impedance Nyquist plot; (b) Bode plot of impedance versus frequency; (c) Bode plot of phase angle versus frequency

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图 9 x%HECBs /AZ31模拟电路示意图：(a)拟合等效电路；(b)拟合等效电路物理模型

Figure 9. Schematic diagram of x%HECBs/AZ31 analog circuit: (a) Fitting the equivalent circuit; (b)Fitting the physical model of the equivalent circuit

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图 10 xHECBs/AZ31镁合金常温下维氏硬度规律图(10 N, 15 s)

Figure 10. Vickers hardness pattern of xHECBs/AZ31 magnesium alloy at room temperature (10 N, 15 s).

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图 11 xHECBs /AZ31镁合金拉伸性应力应变图

Figure 11. Tensile stress - strain diagram of xHECBs/AZ31 magnesium alloy

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图 12 拉伸后断面 SEM 图(a)无添加高熵陶瓷相拉伸断面图；(b)活化前高熵陶瓷相拉伸断面图；(c)活化后高熵陶瓷相拉伸断面图

Figure 12. SEM image of the tensile fracture surface:(a) Fracture surface SEM image without high-entropy ceramic phase addition; (b) Fracture surface SEM image before activation of the high-entropy ceramic phase; (c) Fracture surface SEM image after activation of the high-entropy ceramic phase.

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图 13 (a)活化前高熵陶瓷与基体截面状态图(b)活化后高熵陶瓷与基体截面状态图

Figure 13. (a) Pre-activation state of high-entropy ceramic and matrix cross-section (b) Post-activation state of high-entropy ceramic and matrix cross-section

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表 1 高熵陶瓷粉末与AZ31镁合金熔炼质量

Table 1. Melting Mass of High-Entropy Ceramic Powders and AZ31 Magnesium Alloy

Alloys	Quality of AZ31/g	Quality of High-entropy ceramic powder/g
0%HECBs/AZ31(Unactivated)	1000	0 (Unactivated)
1%HECBs/AZ31(Unactivated)	1000	10 (Unactivated)
2%HECBs/AZ31(Unactivated)	1000	20.4 (Unactivated)
1%HECBs/AZ31(Activated)	1000	10 (Activated)
2%HECBs/AZ31(Activated)	1000	20.4 (Activated)
5%HECBs/AZ31(Unactivated)	1000	52.6 (Unactivated)
Note: HECB—High-entropy Bodecaboride

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表 2 添加高熵陶瓷前后 AZ31 镁合金极化曲线的拟合结果

Table 2. Fitting Results of Polarization Curves for AZ31 Magnesium Alloy Before and After the Addition of High-Entropy Ceramics.

Alloys	E_corr/V	I_corr/(μA·cm⁻²)	Corrosion Rate (mm·a⁻¹)
0%HECBs/AZ31 (Unactivated)	−1.792	6.103×10³	1.969×10
1%HECBs/AZ31 (Unactivated)	−1.715	9.516×10³	3.071×10
2%HECBs/AZ31 (Unactivated)	−1.426	3.552×10²	1.146×10⁻¹
1%HECBs/AZ31 (Activated)	−1.553	1.672×10²	5.395×10⁻²
2%HECBs/AZ31 (Activated)	−1.398	4.958×10	1.959×10⁻²
5%HECBs/AZ31 (Unactivated)	−1.516	4.686×10²	1.512×10⁻¹
Notes E_corr represents self - corrosion voltage; I_corr represents self - corrosion curren

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表 3 xHECBs/AZ31电化学阻抗谱的拟合结果

Table 3. Fitting Results of Electrochemical Impedance Spectroscopy for xHECBs/AZ31.

Alloys	R_s/(Ω·cm²)	R_f/(Ω·cm²)	CPE_f/(F·cm⁻²)	R_ct/(Ω·cm²)	CPE_dl/(F·cm⁻²)	L/(H·cm²)	Fitting Percentage/%
0%HECBs/AZ31(Unactivated)	16.19	8.68	9.5787 e⁻⁶	48.19	8.3309 e⁻⁶	11.25	95.6
1%HECBs/AZ31(Unactivated)	10.66	33.63	1.8457 e⁻⁵	95.58	2.1758 e⁻⁵	30	94.2
2%HECBs/AZ31(Unactivated)	14.54	110.2	1.1564 e⁻⁵	298.9	1.6486 e⁻⁵	35.6	96.8
1%HECBs/AZ31(Activated)	16.65	48.39	3.5798 e⁻⁵	169.6	5.0000 e⁻⁵	35.25	96.5
2%HECBs/AZ31 (Activated)	30.41	113.2	6.4743 e⁻⁶	288.4	1.0842 e⁻⁵	44.68	97.6
5%HECBs/AZ31(Unactivated)	10.27	55.5	7.6560 e⁻⁶	134.6	9.0412 e⁻⁶	60.34	98.4
Notes R_s represents the solution resistance; R_f represents the film resistance; R_ct represents the charge - transfer resistance; CPE_f represents the capacitive effect formed by the NaCl solution and the corrosion product film on the alloy surface; CPE_dl represents the capacitive effect formed between the area below the corrosion product film and the metal substrate;L represents the inductance generated after the magnesium alloy is corroded.

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