| 引用本文: | 方秀梅,连利仙,刘颖,李三雁.腐蚀添加剂对Cu-Mn合金制备孔径可控纳米多孔铜的影响[J].材料科学与工艺,2022,30(5):27-33.DOI:10.11951/j.issn.1005-0299.20220006. |
| FANG Xiumei,LIAN Lixian,LIU Ying,LI Sanyan.Effect of corrosion additives on preparation of nanoporous copper with tunable pore size by Cu-Mn alloy[J].Materials Science and Technology,2022,30(5):27-33.DOI:10.11951/j.issn.1005-0299.20220006. |
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| 摘要: |
| 以铜锰单相固溶体为前躯体合金,利用去合金化法,在盐酸腐蚀液中添加适量不同的络合剂、金属盐可制备出成分纯净、孔形貌可控的三维连通纳米多孔铜(NPC)。采用X射线衍射仪(XRD)、扫描电镜能谱(SEM-EDS)、图像分析软件(Image-Pro Plus)对样品的物相、组分、微观形貌和平均孔径尺寸进行表征。结果表明:腐蚀添加剂的种类和浓度对孔结构形成过程和孔形貌具有重要影响。与未添加络合剂相比,添加硫脲、柠檬酸等络合剂后,腐蚀后的样品的孔径和韧带尺寸都发生不同程度的细化,络合常数越大,铜原子表面扩散系数越小,细化效果越明显；添加硫脲后能显著细化多孔结构,NPC平均韧带尺寸可在18~90 nm之间调控,且其浓度越高,孔径、韧带尺寸越小；添加适量金属盐Fe2(SO4)3、CuSO4、ZnSO4后腐蚀液中出现副反应,反应速率大幅度提高,孔结构发生粗化,出现韧带尺寸分布呈纳米级和微米级共存的多孔结构,当CuSO4添加浓度超过20 mmol/L时,多孔样品断裂截面失去初始晶粒特征,孔结构从纳米级逐步过渡为微米级。 |
| 关键词: 去合金化 纳米多孔铜 腐蚀添加剂 孔径可控 细化 |
| DOI：10.11951/j.issn.1005-0299.20220006 |
| 分类号:TG146.1 |
| 文献标识码:A |
| 基金项目:成都锦城学院教研科研项目(2020jcky0044). |
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| Effect of corrosion additives on preparation of nanoporous copper with tunable pore size by Cu-Mn alloy |
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FANG Xiumei1, LIAN Lixian2, LIU Ying2, LI Sanyan1
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(1.Chengdu Jincheng College, Chengdu 611731, China; 2.College of Materials Science and Engineering, Sichuan University, Chengdu 610065, China)
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| Abstract: |
| Three-dimensional interconnected nanoporous copper (NPC) with tunable pore structure was fabricated by dealloying Cu-Mn single-phase precursor in HCl solution with different amounts of complexing agents and metal salts. The phase, components, micromorphology, and average pore size of the samples were characterized by X-ray diffractometer (XRD), scanning electron microscopy and energy dispersive spectrum (SEM-EDS), and image analysis software (Image-Pro Plus). Results show that the types and concentrations of corrosion additives had important effects on the formation of pore structure and the morphology of pore. With the addition of complexing agents such as thiourea and citric acid, the ligaments and pores of samples were refined to different degrees after corrosion. With the increase in the stability constants of complexing agents, the surface diffusion coefficient of copper atoms decreased, and the refinement was more obvious. Thiourea could significantly refine the porous structure, and the average ligament size of NPC could be tuned between 18 nm and 90 nm; the higher the concentration was, the smaller the pore/ligament size was. After adding an appropriate amount of metal salts (Fe2(SO4)3, CuSO4, ZnSO4) in the HCl solution, side reactions occurred, and reaction rate increased significantly. Pore structures were coarsened, and NPC with nanoscale and micron scale ligaments coexisted. When the concentration of CuSO4 added exceeded 20 mmol/L, the fracture cross-section of the porous samples lost the initial grain characteristics, and the porous structure gradually changed from nanoscale to micron scale. |
| Key words: dealloying nanoporous copper corrosion additives tunable pore structure refinement |
