明胶对氯化物体系电镀镉及镀层性能的影响

Effect of gelatin on cadmium electroplating in chloride-based bath and coating properties

摘要

[目的]针对氯化物镀镉体系镀液稳定性差、镀层易粗糙等问题，研究明胶作为添加剂对该体系镀液性能及镉镀层综合性能的影响，为高耐蚀 Cd 镀层制备提供理论依据。[方法]在由 45 g/L CdCl ₂·2.5H ₂O、240 g/L NH ₄Cl 和 35 g/L NaCl 组成的镀镉基础液中添加不同质量浓度明胶，在 1.0 A/dm 2 下电镀 20 min 制备 Cd 镀层。通过线性扫描伏安法(LSV)研究明胶对 Cd 电沉积阴极极化的影响；通过霍尔槽试验测定镀液分散能力；利用扫描电镜(SEM)、激光共聚焦显微镜(CLSM)及接触角测试仪表征 Cd 镀层的微观形貌、表面粗糙度和润湿性；通过动电位极化曲线测试和电化学阻抗谱(EIS)检测 Cd 镀层在 3.5% NaCl 溶液中的耐蚀性；并借助 COMSOL Multiphysics 仿真模拟亲水/疏水镀层的点腐蚀过程。[结果]明胶能显著抑制 Cd 电沉积，进而改善镀层微观形貌、降低表面粗糙度，并提高镀层疏水性与耐蚀性。明胶质量浓度为 1.0 ~ 2.0 g/L 时，镀液分散能力较好，Cd 镀层综合性能更佳，尤其是质量浓度为 1.0 g/L 时具有最佳耐蚀性。仿真模拟显示，疏水镀层腐蚀电流密度显著低于亲水镀层，且其分布更均匀，腐蚀坑深度更浅。[结论]在氯化物镀镉体系中添加适量明胶可有效改善镀液分散能力，显著提升 Cd 镀层疏水性与耐蚀性。本研究为氯化物镀镉添加剂的筛选及高性能镀层制备提供了实验与理论支持。

Abstract

[Objective] To address the poor bath stability and rough coating surface commonly encountered in chloride cadmium plating, the effect of gelatin as an additive on the bath performance and the overall properties of cadmium coatings were studied, aiming to provide a theoretical basis for preparing highly corrosion resistant Cd coatings. [Method] Cd coatings were obtained by electroplating at 1.0 A/dm ² for 20 min from a basic plating bath composed of 45 g/L CdCl ₂·2.5H ₂O, 240 g/L NH ₄Cl, 35 g/L NaCl, and various mass concentrations of gelatin. The effect of gelatin on the cathodic polarization of Cd coating was studied by linear sweep voltammetry (LSV). The throwing power of the bath was studied by Hull cell electroplating test. The microstructure, surface roughness, and wettability of Cd coating were characterized by scanning electron microscopy (SEM), laser confocal microscopy (CLSM), and contact angle measurements. The corrosion resistance of Cd coating in 3.5% NaCl solution was examined by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). In addition, the pitting corrosion process of hydrophilic and hydrophobic coatings was simulated using COMSOL Multiphysics. [Result] Gelatin significantly inhibited cadmium electrodeposition, thereby improving the coating microstructure, reducing surface roughness, and enhancing both hydrophobicity and corrosion resistance. When the gelatin concentration was in the range of 1.0-2.0 g/L, the bath showed good throwing power and the Cd coating achieved superior overall performance; in particular, the best corrosion resistance was obtained at 1.0 g/L. Simulation results revealed that the corrosion current density of hydrophobic coating was significantly lower and more uniformly distributed than that of hydrophilic coatings, resulting in shallower corrosion pits. [Conclusion] The addition of an appropriate amount of gelatin to the chloride cadmium plating bath effectively improves the throwing power and significantly enhances the hydrophobicity and corrosion resistance of Cd coatings. This study provides experimental and theoretical support for the selection of additives and the preparation of high-performance coatings in chloride cadmium plating bath.

关键词

氯化物 / 电镀镉 / 明胶 / 表面形貌 / 疏水性 / 耐蚀性 / 仿真模拟

Key words

chloride / cadmium electroplating / gelatin / surface morphology / hydrophobicity / corrosion resistance / simulation

参考文献

[1] 李博. 无氰镀镉替代氰化镀镉工艺研究[J]. 电镀与精饰, 2016, 38(4): 32-35.

[2] LI B. New process research for the replacement of cyanide cadmium plating by cyanide free cadmium plating[J]. Plating & Finishing, 2016, 38(4): 32-35.

[3] 万冰华, 杨军, 王福新, 等. 无氰镀镉工艺开发研究与应用[J]. 电镀与精饰, 2014, 36(3): 22-25, 46.

[4] WAN B H, YANG J, WANG F X, et al. Investigation and application on cyanide-free cadmium electroplating technology[J]. Plating & Finishing, 2014, 36(3): 22-25, 46.

[5] 李成龙, 李成银, 林强. 环保退镀和除锈工艺在航空零部件中应用的可行性[J]. 电镀与涂饰, 2024, 43(10): 41-48.

[6] LI C L, LI C Y, LIN Q. Feasibility of applying environmentally friendly coating stripping and derusting process to aviation parts[J]. Electroplating & Finishing, 2024, 43(10): 41-48.

[7] CIHANGIR S. Greening industrially applied toxic cadmium plating with γ‐Ni₂Zn₁₁ alloy in deep eutectic solvents: promising electroplating efficiency and chemical corrosion resistance [J]. Advanced Engineering Materials, 2023, 25(20): 2300731.

[8] SMIRNOV K N, ARKHIPOV E A, VAGRAMYAN T A, et al. The influence of cadmium plating of 60S2A steel in cyanide-free electrolytes on its strength characteristics and some properties of cadmium coatings[J]. Steel in Translation, 2023, 53(10): 842-845.

[9] VARMA R, HOELLER T, ROSS L, et al. Reduced hydrogen cadmium plating[J]. Journal of the Electrochemical Society, 1991, 138(1): 162.

[10] SABELKIN V, MALL S, MISAK H. Corrosion fatigue of coated AISI 4340 high strength steel with dent damage[J]. Fatigue & Fracture of Engineering Materials & Structures, 2018, 41(3): 653-662.

[11] MAZZA M T C, CICCO L D, ROSA G D, et al. Preparation and activity of complexes of transition metals and thiolic heterocyclic ligands[J]. Bollettino Della Società Italiana Di Biologia Sperimentale, 1996, 72(3/4): 79-86.

[12] BYRTUS H, PAWLOWSKI M, CHARAKCHIEVA-MINOL S, et al. 3‐(ω‐aminoalkyl)-5,5-dialkyl(or spirocycloalkyl-1′,5-)hydantoins as new 5‐HT1A and 5‐HT2A receptor ligands[J]. Archiv der Pharmazie, 1996, 329(6): 283-290.

[13] 徐雷, 鲍其鹏, 王亚齐, 等. 渗透剂 JFC 对高强度钢氨羧配位体系无氰镀镉−钛合金的影响[J]. 电镀与涂饰, 2024, 43(5): 1-7.

[14] XU L, BAO Q P, WANG Y Q, et al. Effect of penetrant JFC on cyanide-free cadmium-titanium alloy electroplating with amino carboxylic acid as complexing agent[J]. Electroplating & Finishing, 2024, 43(5): 1-7.

[15] 严鹏飞, 罗迎禧, 刘春秘, 等. 循环伏安法测定氯化铵镀镉溶液中镉离子质量浓度[J]. 电镀与精饰, 2024, 46(5): 99-104.

[16] YAN P F, LUO Y X, LIU C M, et al. Determination of cadmium ion in ammonium chloride cadmium plating solution by cyclic voltammetry method[J]. Plating & Finishing, 2024, 46(5): 99-104.

[17] 宋宜强, 皮志超, 张泽齐, 等. 钢铁表面无氰镀镉及其性能研究进展[J]. 机械制造与自动化, 2022, 51(5): 48-53, 73.

[18] SONG Y Q, PI Z C, ZHANG Z Q, et al. Progress in cyanide-free cadmium plating on steel surface and its properties[J]. Machine Building & Automation, 2022, 51(5): 48-53, 73.

[19] 郑玉, 张骐, 詹中伟, 等. 麦芽糖对氨羧配位体系无氰镀镉的影响[J]. 电镀与涂饰, 2022, 41(17): 1203-1207.

[20] ZHENG Y, ZHANG Q, ZHAN Z W, et al. Effect of maltose on cyanide-free cadmium electroplating with amino carboxylic complexing agent[J]. Electroplating & Finishing, 2022, 41(17): 1203-1207.

[21] 彭雪嵩, 由宏伟, 李兰晨, 等. 钼酸钠−HEC−SPS 复合添加剂对电解铜箔粗化效果的影响[J]. 电镀与涂饰, 2023, 42(17): 56-67.

[22] PENG X S, YOU H W, LI L C, et al. Effect of a composite additive comprising sodium molybdate, HEC, and SPS on roughening of electrolytic copper foil[J]. Electroplating & Finishing, 2023, 42(17): 56-67.

[23] 安茂忠. 电镀理论与技术[M]. 哈尔滨: 哈尔滨工业大学出版社, 2004.

[24] AN M Z. Electroplating Theory and Technology[M]. Harbin: Harbin Institute of Technology Press, 2004.

[25] LI Y Q, LI C Z, LI R P, et al. Experimental and theoretical study of the new leveler basic blue 1 during copper superconformal growth[J]. ACS Applied Materials & Interfaces, 2023, 15(40): 47628-47639.

[26] DESHPANDE K B. Numerical modeling of micro-galvanic corrosion[J]. Electrochimica Acta, 2011, 56(4): 1737-1745.

[27] 彭雪嵩, 江杰, 李铭杰, 等. 基于有限元方法分析加速剂 SPS 对铜柱凸点互连均匀性的影响[J]. 电镀与精饰, 2025, 47(3): 10-17.

[28] PENG X S, JIANG J, LI M J, et al. The influence of accelerator SPS on the bump surface of copper pillar interconnects based on finite element simulation methods[J]. Plating and Finishing, 2025, 47(3): 10-17.

[29] 熊鹏, 董宪姝, 叶贵川, 等. 粗糙度对贫瘦煤表面润湿性的影响[J]. 煤炭工程, 2024, 56(3): 197-204.

[30] XIONG P, DONG X S, YE G C et al. Effect of roughness on the wettability of lean coal surfaces[J]. Coal Engineering, 2024, 56(3): 197-204.

[31] DANG-VU T, HUPKA J, DRZYMALA J. Impact of roughness on hydrophobicity of particles measured by the washburn method[J]. Physicochemical Problems of Mineral Processing, 2006, 40: 45-52.

[32] XIA W, LI Y F. Role of roughness change on wettability of taixi anthracite coal surface before and after the heating process[J]. Energy & Fuels, 2016, 30(1): 281-284.

[33] 尤航, 彭毅, 杨冲, 等. 金属超疏水涂层制备及其耐腐蚀性能研究进展[J]. 中国有色金属学报, 2024, 34(3): 703-724.

[34] YOU H, PENG Y, YANG C, et al. Research progress on preparation of metal superhydrophobic surface coatings and their corrosion resistance[J]. The Chinese Journal of Nonferrous Metals, 2024, 34(3): 703-724.

[35] SCARRATT L R J, STEINER U, NETO C. A review on the mechanical and thermodynamic robustness of superhydrophobic surfaces[J]. Advances in Colloid and Interface Science, 2017: 133.

[36] XU L, YANG X N, FU X, et al. Fluorinated epoxy based superhydrophobic coating with robust self-healing and anticorrosive performances[J]. Progress in Organic Coatings, 2022, 171: 107045.

[37] SABZAVAR S, GHAHARI M, ROSTAMI M, et al. Preparation of active-passive anticorrosion antistatic epoxy nanocomposite coatings loaded with CeO₂, CeO₂@C, and CHS particles [J]. Journal of Coatings Technology and Research, 2024, 21(4): 1263-1279.

[38] 周娟, 彭健, 韦红草, 等. 超疏水涂层在金属防腐蚀领域的研究进展[J]. 复合材料学报, 2025, 42(4): 1739-1762.

[39] ZHOU J, PENG J, WEI H C, et al. Research progress of superhydrophobic coatings in the field of metal corrosion protection[J]. Acta Materiae Compositae Sinica, 2025, 42(4): 1739-1762.

基金资助

国家自然科学基金(22402041)

国家自然科学基金(22502032)

国家自然科学基金(22541202)

福州大学贵重仪器设备开放测试基金(2025T017)