Surface modification between nickel titanium and rubber and Research on the Mechanism of Adhesive Bonding Enhancement

ZHANG Yuehong; GAO Delong; ZHANG Yang; SUI Jinjie; LI Rongguang

doi:10.16490/j.cnki.issn.1001-3660.2026.14.018

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Surface Technology ›› 2026, Vol. 55 ›› Issue (14) : 205-213. DOI: 10.16490/j.cnki.issn.1001-3660.2026.14.018

Functional Surfaces and Technology

Surface modification between nickel titanium and rubber and Research on the Mechanism of Adhesive Bonding Enhancement

ZHANG Yuehong^a,*, GAO Delong^b, ZHANG Yang^c, SUI Jinjie^d, LI Rongguang^c

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Abstract

This study investigates the effects of fluoridation film pretreatment process parameters on the adhesion and surface morphology of cyanide-plated brass coatings on nickel-titanium alloy wires, and the influence of cyanide-plating process parameters on the surface structure and elemental composition of such coatings. It also examines the rubber adhesion properties of the plated layer under different cyanide brass plating process parameters and identifies the optimal process parameters based on the rubber adhesion performance of the plated layer. Nickel-titanium alloy wire is use as the substrate and high-purity graphite is used as the anode, the substrate is polished with 1 200-2 000 grit sandpaper until a smooth surface is obtained. It is then degreased using anhydrous alcohol, air-dried with cold airflow, and subsequently transferred to a desiccator for later use. As titanium is an active metal prone to oxidation and the formation of oxide films in air, substrate pretreatment prior to electrodeposition is required to create a clean, transitional surface that promotes coating adhesion, thereby providing a foundation for subsequent plating processe. The microstructure, composition, and thickness of the coating surface are examined using a scanning electron microscope (JEOL-IT800). Elemental composition analysis is performed with an energy dispersive X-ray spectrometer (EDS). Phase identification and analysis of the X-ray diffraction patterns (Bruker D8) are conducted using MDI Jade software. Finally, rubber adhesion performance testing is conducted on the plating layer. The rubber adhesion performance is determined using the extraction method specified in GB/T 3513-2018 "Determination of Adhesion between Vulcanized Rubber and Single Steel Wire." By analyzing the variation in rubber adhesion performance of brass coatings electroplated on nickel-titanium alloy wires, the optimal process parameters for the electroplating of brass on nickel-titanium alloy wires are identified. The process parameters of fluoridation film pretreatment have a significant influence on cyanide brass plating on nickel-titanium alloy wires. As the number of fluoridation membrane treatments and the duration of each treatment increase, the adhesion of the cyanide brass plating on nickel-titanium alloy wires progressively improves. Furthermore, this process does not have a significant effect on the elemental peak intensity of the plating layer. When the fluoridation film pretreatment is performed twice, each lasting 60 seconds, a dense and well-formed fluoridation film is formed between the layers, which exhibits excellent performance. Current density and plating time jointly govern the surface morphology, elemental ratio, and coating thickness of the cyanide-plated brass coating on nickel-titanium alloy wires. At a current density of 7 A/dm² and a plating time of 20 minutes, the coating surface exhibits a dense, bright morphology with elemental ratios of 72.43∶27.57 and 73.15∶26.85, respectively, and coating thicknesses of 15.38 µm and 16.69 µm, respectively. The corrosion potentials relative to the standard electrode are -0.226 V and -0.226 V, respectively, and the minimum corrosion currents are 2.991 mA/cm² and 1.105 mA/cm², respectively.Elemental composition and coating thickness have a significantly influence on the rubber adhesion properties of coating. When the copper-to-zinc ratio is within the range of 7∶3 to 8∶2, sulfur bond density reaches an optimal value,resulting in the highest rubber adhesion strength. Optimal performance and adhesion are achieved when coating thickness is within the range of 5-20 µm, which demonstrates excellent rubber bonding characteristics. Consequently, under conditions of a current density of 7 A/dm² and a plating time of 20 minutes , coating exhibits maximum rubber adhesion strength, with the cyanide-plated brass coating on nickel-titanium alloy wires achieving a rubber bonding strength of 140 N/mm². fluoridation film pretreatment has a significant impact on coating adhesion but has little effect on elemental content. Process parameters for cyanide brass plating have a substantial influence on coating morphology, elemental composition, and thickness. Both elemental content and coating thickness have a significant effect on rubber adhesion strength.

Key words

Nickel titanium alloy / Pre-processing / Cyanide plated brass / Electrochemistry / Adhesion force

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ZHANG Yuehong, GAO Delong, ZHANG Yang, SUI Jinjie, LI Rongguang. Surface modification between nickel titanium and rubber and Research on the Mechanism of Adhesive Bonding Enhancement[J]. Surface Technology. 2026, 55(14): 205-213

References

[1] 北京化工大学, 杭州海潮橡胶有限公司,南京绿金人橡塑高科有限公司. 一种高效节能的橡胶轮胎部件的制备方法及所得轮胎部件和应用: 202510402735.5[P].2025-06-10.
BUCT Hangzhou Haichao Rubber Co., Ltd Nanjing Lvjinjin Rubber High tech Co., Ltd Preparation Method and Application of an Efficient and Energy-saving Rubber Tire Component[P].2025-06-10.
[2] 刘湘慧. 橡胶轮胎和软管用高强度钢帘线盘条的研发[J]. 橡塑技术与装备, 2021, 47(1): 51-57.
LIU X H.Research and Development of High-strength Steel Cord Reel for Rubber Tires and Hoses[J]. Rubber and Plastic Technology and Equipment, 2021, 47(1): 51-57.
[3] CHOWDHURY S G, CHANDA J, GHOSH S, et al.Impact of Adhesive Ingredients on Adhesion between Rubber and Brass-Plated Steel Wire in Tire[J]. Polymer Engineering & Science, 2020, 60(8): 1973-1983.
[4] 肖健, 王博文, 沈少凡, 等. 钛合金表面激光原位制备CaTiO₃/CaSiO₃复合涂层及其组织性能研究[J]. 表面技术, 2025, 54(16): 182-191
XIAO J, WANG B W, SHEN S F, et al.Laser In-situ Preparation of CaTiO₃/CaSiO₃ Composite Coating on Titanium Alloy Surface and Study on Its Microstructure and Properties[J]. Surface Technology, 2025, 54(16): 182-191.
[5] HOURMAND M, SARHAN A A D, SAYUTI M, et al. A Comprehensive Review on Machining of Titanium Alloys[J]. Arabian Journal for Science and Engineering, 2021, 46(8): 7087-7123.
[6] 师文海, 海几哲, 单春龙, 等. Na₂B₄O₇对钛合金微弧氧化涂层耐磨和耐腐蚀性能的影响[J]. 表面技术, 2024, 53(24): 88-98.
SHI W H, HAI J Z, SHAN C L, et al.Effect of Na₂B₄O₇ on Wear and Corrosion Resistance of Micro-Arc Oxidation Coating on Titanium Alloy[J]. Surface Technology, 2024, 53(24): 88-98.
[7] 贾六军, 岳广新, 贺婷, 等. 非均质镍钛合金超弹性三尖瓣成型环的长期动物实验研究[J]. 中国生物医学工程学报, 2025, 44(4): 457-464.
JIA L J, YUE G X, HE T, et al.Long Term Animal Experimental Study on a Heterogeneous Tricuspid Annuloplasty Ring Made of a Hyperelastic Nitinol[J]. Chinese Journal of Biomedical Engineering, 2025, 44(4): 457-464.
[8] 严淼宁, 周磊, 梁佳楠, 等. 纳秒光纤激光精密切割超弹镍钛合金薄板工艺技术的研究[J]. 机电工程技术, 2023, 52(1): 85-88.
YAN M N, ZHOU L, LIANG J N, et al.Research on Nanosecond Fiber Laser Precision Cutting Process Technology of Superelastic Nitinol Sheets[J]. Mechanical & Electrical Engineering Technology, 2023, 52(1): 85-88.
[9] DONG J W, ZHANG Z, WANG D G, et al. Research on Erosion Wear Behavior of NiTi Alloy Coating Fabricated via High-Frequency Induction Heating Technology[J]. Wear, 2024, 556/557: 205506.
[10] 张中平, 董秀萍, 黄明吉. 金属橡胶研究进展与展望[J]. 材料导报, 2026, 40(3): 183-194.
ZHANG Z P, DONG X P, HUANG M J.Research Progress and Prospects of Metal Rubber[J]. Materials Review, 2026, 40(3): 183-194.
[11] 梁睿君, 郝文龙, 陈蔚芳. 金属橡胶力学性能及应用研究进展[J]. 中南大学学报(自然科学版), 2023, 54(1): 36-52.
LIANG R J, HAO W L, CHEN W F.Review on Mechanical Properties and Applications of Metal Rubber[J]. Journal of Central South University (Science and Technology), 2023, 54(1): 36-52.
[12] 马福秋. 镍钛合金表面银基复合镀层的制备与性能研究[D]. 哈尔滨: 哈尔滨工程大学, 2012.
MA F Q.Studies on the Preparation and Properties of Silver-based Composite Plating on then Ickel-titanium Allo[D]. Harbin: Harbin Engineering University, 2012.
[13] 商业帅, 邓涛. 胎圈钢丝表面形态对橡胶黏合性能的影响[J]. 橡塑技术与装备, 2021, 47(15): 42-45.
SHANG Y S, DENG T.Influence of Bead Wire Surface Morphology on Rubber Adhesive Performance[J]. China Rubber/Plastics Technology and Equipment, 2021, 47(15): 42-45.
[14] 范军富, 王秀兰, 潘之珩, 等. 改性煤系高岭土对丁苯橡胶性能补强研究[J]. 非金属矿, 2021, 44(2): 95-98.
FAN J F, WANG X L, PAN Z H, et al.Properties of Styrene Butadiene Rubber Composites Filled with Modified Coal Series Kaolin[J]. Non-Metallic Mines, 2021, 44(2): 95-98.
[15] 樊国福. 钛合金镀前处理技术[J]. 电镀与精饰, 1990, 12(3): 17-19.
FAN G F.Pretreatment Technology of Titanium Alloy Plating[J]. Plating & Finishing, 1990, 12(3): 17-19.
[16] 李博. 提高TC6钛合金零件镀铬层结合力的方法[J]. 电镀与精饰, 2014, 36(3): 26-28.
LI B.Methods for Improving the Coating Adhesion of Chrome Plating on TC6 Titanium Parts[J]. Plating & Finishing, 2014, 36(3): 26-28.
[17] DOMÍNGUEZ-RÍOS C, GARDEA-HERNÁNDEZ G, TORRES-SÁNCHEZ R, et al. Influence of the Conditions of Zincate on the Electroless Brass Plating of Steel[J]. Industrial & Engineering Chemistry Research, 2009, 48(8): 3837-3843.
[18] 孙志华. 钛及钛合金的电镀工艺述评[J]. 腐蚀与防护, 2005, 26(11): : 493-496.
SUN Z H.A Review of Electroplating Technology on Titanium and Titanium Alloys[J]. Corrosion & Protection, 2005, 26(11): : 493-496.
[19] 邵龙, 吴惠舒, 张留艳, 等. 冷喷涂铜锌合金复合涂层的腐蚀行为研究[J]. 热加工工艺, 2022, 51(14): 99-102.
SHAO L, WU H S, ZHANG L Y, et al.Study on Corrosion Behavior of Copper Zinc Alloy Composite Coating Prepared by Cold Spraying[J]. Hot Working Technology, 2022, 51(14): 99-102.
[20] EKEN T Y, SARıOĞLU C, KÜÇÜK İ. Comparison of Tafel Extrapolation and Linear Polarization Resistance Readings for TRC 8006 Aluminium Alloys in 3.5 WT.% NaCI Aqueous Solution[J]. Journal of Innovative Science and Engineering (JISE), 2018, 2: 19-24.
[21] 田忠良, 郭春, 赵泽军, 等. Bi含量对锌负极Bi2O3@ZnO材料结构与电化学性能的影响[J]. 中国有色金属学报, 2021, 31(12): 3583-3591.
TIAN Z L, GUO C, ZHAO Z J, et al.Effects of Bi content on structure and electrochemical performance of Bi2O3@ZnO composite for zinc anode[J]. The Chinese Journal of Nonferrous Metals, 2021, 31(12): 3583-3591.
[22] 吴学昆, 罗兵辉, 柏振海, 等. Cu/Mg含量对2024铝合金耐蚀性能的影响[J]. 有色金属材料与工程, 2022, 43(6): 1-7.
WU X K, LUO B H, BAI Z H, et al.Effect of Cu/Mg Content on Corrosion Resistance of 2024 Aluminum Alloy[J]. Nonferrous Meaterials and Engineering, 2022, 43(6): 1-7.
[23] 张振宇, 王守仁, 王高琦, 等. 铜合金表面激光制备Ni60-WC-Cu涂层的显微组织与摩擦磨损性能[J]. 中国有色金属学报, 2024, 34(4): 1252-1267.
ZHANG Z Y, WANG S R, WANG G Q, et al.Microstructure and Friction and Wear Properties of Ni60-WC-Cu Coating Prepared by Laser on Copper Alloy Surface[J]. The Chinese Journal of Nonferrous Metals, 2024, 34(4): 1252-1267.
[24] OZAWA K, KAKUBO T, AMINO N, et al.Angle- Resolved HAXPES Investigation on the Chemical Origin of Adhesion between Natural Rubber and Brass[J]. Langmuir, 2017, 33(38): 9582-9589.
[25] JEON G S, HAN M H, SEO G.Effect of ZnO Contents at the Surface of Brass-Plated Steel Cord on the Adhesion Property to Rubber Compound[J]. Korean Journal of Chemical Engineering, 1999, 16(2): 248-252.
[26] Song Seong-Hun, Deok Young B, Kil Won C, 等. 胎圈钢丝锡含量和胶料类型对橡胶界面形态的影响[J]. 轮胎工业, 2010, 30(10): 633-635.
SEONG H S, DEOK Y B, KIL W C, et al.Effect of Tin Content in Bead Wire and Rubber Compound Type on Rubber Interface Morphology[J]. Tire Industry, 2010, 30(10): 633-635.
[27] BANERJEE A, DUTTA M, BHOWMICK A K, et al.Effect of Sn on the Adhesion between Cu-Sn Alloy Coated Steel and Styrene Butadiene Based Rubber[J]. ISIJ International, 2014, 54(3): 671-676.
[28] 李呐, 周志嵩, 寇首鹏, 等. 电镀镀层对帘线黏合剥离性能影响[J]. 电镀与精饰, 2024, 46(2): 30-36.
LI N, ZHOU Z S, KOU S P, et al.Effect of Electroplating Coating on Adhesion and Peeling Property of Steel Cord[J]. Plating & Finishing, 2024, 46(2): 30-36.
[29] 李龙腾, 吴宇坤, 郗雨林, 等. 物理气相沉积黄铜镀层对钛丝绳和橡胶黏合性能的影响研究[J]. 材料开发与应用, 2021, 36(1): 39-44.
LI L T, WU Y K, CHI Y L, et al.Study on Adhesion of Brass Layer by Physical Vapor Deposition to Titanium Rope and Rubber[J]. Development and Application of Materials, 2021, 36(1): 39-44.