葛晨阳,国秀花,李韶林,宋克兴,周延军,刘海涛,张朝民,曹军,曹飞,高岩.稀土Y对铜线材抗氧化行为的影响机理研究[J].表面技术,2024,53(10):144-155.
GE Chenyang,GUO Xiuhua,LI Shaolin,SONG Kexing,ZHOU Yanjun,LIU Haitao,ZHANG Chaomin,CAO Jun,CAO Fei,GAO Yan.Effect Mechanism of Rare Earth Y on Antioxidant Behavior of Copper Wire[J].Surface Technology,2024,53(10):144-155 |
| 稀土Y对铜线材抗氧化行为的影响机理研究 |
| Effect Mechanism of Rare Earth Y on Antioxidant Behavior of Copper Wire |
| 投稿时间：2023-06-05 修订日期：2023-09-12 |
| DOI：10.16490/j.cnki.issn.1001-3660.2024.10.011 |
| 中文关键词: 纯铜线材 稀土元素Y 稀土氧化物 增重率 抗氧化性能 |
| 英文关键词:pure copper wire rare earth element Y rare earth oxides weight gain rate antioxidant properties |
| 基金项目:国家自然科学基金(U21A2051，52173297，52071133);河南省科技研发计划联合基金(222103810037);河南省科学院研发项目(220910009);河南省科技攻关项目(222102230064) |
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| Author | Institution |
| GE Chenyang | Henan Key Laboratory of Non-ferrous Materials Science and Processing Technology, Henan University of Science and Technology, Henan Luoyang 471023, China |
| GUO Xiuhua | Henan Key Laboratory of Non-ferrous Materials Science and Processing Technology, Henan University of Science and Technology, Henan Luoyang 471023, China |
| LI Shaolin | Henan Key Laboratory of Non-ferrous Materials Science and Processing Technology, Henan University of Science and Technology, Henan Luoyang 471023, China |
| SONG Kexing | Henan Key Laboratory of Non-ferrous Materials Science and Processing Technology, Henan University of Science and Technology, Henan Luoyang 471023, China;Henan Academy of Sciences, Zhengzhou 450002, China |
| ZHOU Yanjun | Henan Key Laboratory of Non-ferrous Materials Science and Processing Technology, Henan University of Science and Technology, Henan Luoyang 471023, China |
| LIU Haitao | Henan Key Laboratory of Non-ferrous Materials Science and Processing Technology, Henan University of Science and Technology, Henan Luoyang 471023, China |
| ZHANG Chaomin | Henan Key Laboratory of Non-ferrous Materials Science and Processing Technology, Henan University of Science and Technology, Henan Luoyang 471023, China |
| CAO Jun | School of Mechanical and Power Engineering, Henan Polytechnic University, Henan Jiaozuo 454000, China |
| CAO Fei | Xi'an University of Technology, Xi'an 710000, China |
| GAO Yan | Henan Academy of Sciences, Zhengzhou 450002, China;Henan Institute of Metallurgy Co., Ltd., Zhengzhou 450000, China |
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| 中文摘要: |
| 目的 针对纯铜线材的抗氧化性能不足问题，通过稀土微合金化制备了含微量Y元素的铜线材，研究稀土Y含量对铜线材抗氧化性能的影响。方法 采用扫描电子显微镜(SEM)、EDS能谱仪和X射线衍射仪等表征手段，分析了氧化膜脱落后基体表面形貌以及稀土Y元素在氧化过程中的存在形式与氧化膜的生长过程，揭示了添加稀土元素Y提高纯铜抗氧化性能的作用机理。结果 稀土Y的引入提高了纯铜线材的抗氧化性能，在600 ℃、10 h条件下，Cu-0.03Y线材相对于Cu线材氧化增重率由0.55%降低至0.2%，降幅达63%。稀土元素Y的添加使铜线材的(100)晶面占比减少，(111)晶面占比增多，基体表面易被活化的(100)原子面占比降低，铜线材的抗氧化性能提高。在Cu-0.1Y线材中稀土元素浓度较高时发生偏聚，稀土元素与氧的亲和力大于铜与氧的亲和力，偏聚处形成不连续的稀土氧化物，使氧离子与铜离子的接触反应面积增大，相比Cu-0.03Y线材抗氧化性能降低。结论 氧化过程中稀土离子的扩散速率慢、半径大，对铜离子的向外扩散起到阻碍作用，降低了铜离子的扩散速度，提高了铜线材的抗氧化性能。 |
| 英文摘要: |
| To address the problem of insufficient oxidation resistance of the pure copper wire, a copper wire with trace Y elements was prepared by rare-earth microalloying to study the effect of rare-earth Y content on the oxidation resistance of the copper wire. The oxidation surface morphology of the copper wire and the presence of rare-earth Y elements in the oxidation process, and the growth of oxidation films were analyzed by scanning electron microscopy (SEM), EDS energy spectrometer, and X-ray diffractometer to reveal the mechanism of adding rare-earth element Y to improve the oxidation resistance of pure copper. At different temperature (400, 500, 600 ℃), the introduction of rare earth Y element made the oxidation weight gain rate of the copper wire consistently lower than that of copper wire without the addition of rare earth element, which effectively improved the oxidation resistance of the pure copper wire, and the copper wire had good oxidation resistance when the addition of rare earth Y was 0.03wt.%. Among them, the oxidation weight gain rate of the Cu-0.03Y wire relative to the Cu wire was reduced from 0.55% to 0.2% at 600 ℃ and 10 h, with a reduction of 63%. At 500 and 600 ℃, the particle size of copper wire oxide films with different rare earth contents increased with the temperature increase, and the diameter of surface oxide particles increased, especially at 600 ℃ and 10 h. The average diameter of oxide particles of the copper wire without the addition of rare earth elements was 4.24 μm, which increased about 130% compared with that at 500 ℃. In contrast, the average diameter of oxide particles on the surface of the Cu-0.03Y copper wire was 3.52 μm, and a thick bulk oxide film was formed locally, which was beneficial to improve the oxidation resistance of the copper wire. In the oxidation process, the activation atoms on the surface of the copper substrate were easy to react with oxygen, the activation energy of Cu (100) atomic surface was more significant and easy to become activation atoms. The activation energy of Cu (111) atomic surface was lower and less easy to form activation atoms. The introduction of rare earth elements increased the proportion of Cu (111) atomic surface of the copper wire. It reduced the proportion of Cu (100) atomic surface area on the surface of the copper wire. The more significant the proportion of Cu (111), the larger the atomic surface area of Cu (111), the lower the oxidation weight gain rate of the wire; On the contrary, the more significant the proportion of the atomic surface area of Cu (100), the larger the oxidation weight gain rate of the wire. In addition, because the affinity of rare earth elements with oxygen was greater than the affinity of copper with oxygen, preferential generation of fine, rare earth oxides, rare earth oxides did not react with the substrate, rare earth elements impeded the contact reaction between copper ions and oxygen ions on the surface of the substrate, inhibiting the growth of Cu2O, thus improving the antioxidant performance of the copper wire. In summary, adding rare earth Y elements can effectively improve the oxidation resistance of pure copper wire. This work provides new ideas and methods for studying the surface oxidation resistance of pure copper wires and shows the advantages of rare earth micro alloyed wires for applications in service environments. |
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