Effects of Silane Concentration on Structure and Wear-corrosion Resistance of Alkali-treated Biomedical Magnesium Alloy Coatings

DING Cong, DANG Lijun, FU Ruize, SONG Enxiang, LI Xu, QIAO Yang

Surface Technology ›› 2026, Vol. 55 ›› Issue (10) : 291-305.

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Surface Technology ›› 2026, Vol. 55 ›› Issue (10) : 291-305. DOI: 10.16490/j.cnki.issn.1001-3660.2026.10.024
Functional Surfaces and Technology

Effects of Silane Concentration on Structure and Wear-corrosion Resistance of Alkali-treated Biomedical Magnesium Alloy Coatings

  • DING Cong1, DANG Lijun2, FU Ruize1, SONG Enxiang1, LI Xu1, QIAO Yang1,*
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Abstract

Magnesium alloys have attracted considerable interest in the field of orthopedic implants due to their elastic modulus being comparable to that of natural bone, their excellent biodegradability, and their ability to avoid secondary removal surgery. However, their high chemical reactivity leads to rapid corrosion in physiological environments. During service, simultaneous mechanical friction further accelerates the detachment of corrosion products and induces wear-corrosion coupling failures, ultimately causing premature loss of mechanical support and severely limiting their clinical applicability. Silane modification, as an environmentally friendly and cost-effective surface treatment method, can form an organic-inorganic hybrid coating through hydrolysis and condensation reactions of silane molecules on metal surfaces, providing both biocompatibility and protective functionality. Nevertheless, the coating density, crosslinking degree, and interfacial bonding quality are highly dependent on processing parameters, particularly the silane concentration. Therefore, this study investigates Mg-1.6Ca-2.0Zn medical magnesium alloys and systematically elucidates how silane concentration regulates the microstructure of the alkali-treated coating, the interfacial chemical bonding mechanism, and the resulting wear and corrosion resistance, so as to provide theoretical support and technological guidance for surface functionalization and clinical translation of magnesium-based implant materials. In this work, self-fabricated Mg-1.6Ca-2.0Zn alloys are wire-cut, mechanically polished, and subsequently alkali-treated using a NaOH solution to generate a porous Mg(OH)2-rich precursor layer. Samples are then immersed in hydrolyzed BTSPS silane solutions of different concentrations (0.5%, 1%, 3%, and 5%) to form surface coatings, and are labeled as AR, Si-0.5, Si-1.0, Si-3.0, and Si-5.0, respectively. Coating morphology and interfacial chemical composition are characterized by SEM, FTIR, and XPS. Reciprocating wear tests are conducted under dry and simulated body fluid (SBF) conditions, while the electrochemical behavior is evaluated through potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results demonstrate that silane concentration exerts a significant influence on coating structure and interfacial bonding. FTIR spectra reveals characteristic Si—O—Si and Si—O—Mg peaks in the 1 000-1 150 cm-1 range, while XPS analysis at the Mg 1s region confirms the presence of Mg—O—Si covalent bonds, indicating that the silane layer is chemically grafted to the substrate. SEM observations show that the Si-0.5 coating is thin, porous, and locally delaminated; the Si-5.0 coating exhibits agglomeration and cracking due to excessive self-condensation; in contrast, the Si-3.0 coating presents uniform thickness, compact structure, and no visible defects, representing the best overall quality. Wear tests reveal that Si-3.0 exhibits superior performance in both dry and wet conditions: the dry wear rate is 0.55×10-5 mm/(N·m) (95% lower than AR), while the wet wear rate is 1.86×10-5 mm/(N·m) (94% lower than AR). The friction coefficient of Si-3.0 remains stable without sudden increases indicating coating failures. Electrochemical measurements further confirm its excellent corrosion resistance, with a corrosion current density of only 1.87×10-5 A/cm2 and a corrosion rate of 0.413 mm/year. EIS analysis reveals a charge-transfer resistance of 1 260.1 Ω·cm2 and a two-time-constant spectrum, indicating significantly enhanced barrier capability against corrosive ions compared with the single-time-constant response of the AR sample. In contrast, Si-0.5 suffers from easy wear-through due to its loose structure, while Si-5.0 degrades due to coating cracks, and both exhibit inferior performance compared with Si-3.0. Overall, a 3% silane concentration achieves the optimal balance among coating thickness, crosslinking density, and interfacial bonding strength. The dense silane layer, reinforced by Mg—O—Si bonding, effectively distributes frictional loads and prevents the permeation of SBF media, thereby fundamentally mitigating corrosion and wear of magnesium implants. This study proposes an efficient and controllable silane-based surface modification strategy and provides a reliable technological pathway for the clinical application of medical magnesium alloys.

Key words

magnesium alloy / silane modification / coating / wear resistance / corrosion resistance

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DING Cong, DANG Lijun, FU Ruize, SONG Enxiang, LI Xu, QIAO Yang. Effects of Silane Concentration on Structure and Wear-corrosion Resistance of Alkali-treated Biomedical Magnesium Alloy Coatings[J]. Surface Technology. 2026, 55(10): 291-305

References

[1] BANDYOPADHYAY A, MITRA I, GOODMAN S B, et al.Improving Biocompatibility for Next Generation of Metallic Implants[J]. Progress in Materials Science, 2023, 133: 101053.
[2] SONG M S, ZENG R C, DING Y F, et al.Recent Advances in Biodegradation Controls over Mg Alloys for Bone Fracture Management: A Review[J]. Journal of Materials Science & Technology, 2019, 35(4): 535-544.
[3] WANG T X, XU Y C, LIU Z Q, et al.A Chitosan/ Polylactic Acid Composite Coating Enhancing the Corrosion Resistance of the Bio-Degradable Magnesium Alloy[J]. Progress in Organic Coatings, 2023, 178: 107469.
[4] ESEN Z, DIKICI B, DUYGULU O, et al.Titanium- Magnesium Based Composites: Mechanical Properties and In-Vitro Corrosion Response in Ringer's Solution[J]. Materials Science and Engineering: A, 2013, 573: 119-126.
[5] STAIGER M P, PIETAK A M, HUADMAI J, et al.Magnesium and Its Alloys as Orthopedic Biomaterials: A Review[J]. Biomaterials, 2006, 27(9): 1728-1734.
[6] KAMRANI S, FLECK C.Biodegradable Magnesium Alloys as Temporary Orthopaedic Implants: A Review[J]. BioMetals, 2019, 32(2): 185-193.
[7] WANG J L, XU J K, HOPKINS C, et al.Biodegradable Magnesium-Based Implants in Orthopedics—A General Review and Perspectives[J]. Advanced Science, 2020, 7(8): 1902443.
[8] BEXIGA N M, ALVES M M, TARYBA M G, et al.Early Biomimetic Degradation of Mg-2Ca Alloy Reveals the Impact of Β-Phases at the Interface of this Biomaterial on a Micro-Scale Level[J]. Corrosion Science, 2022, 207: 110526.
[9] BAI J Y, YANG Y, WEN C, et al.Applications of Magnesium Alloys for Aerospace: A Review[J]. Journal of Magnesium and Alloys, 2023, 11(10): 3609-3619.
[10] CHEN B, LIN Z J, SAIDING Q, et al.Enhancement of Critical-Sized Bone Defect Regeneration by Magnesium Oxide-Reinforced 3D Scaffold with Improved Osteogenic and Angiogenic Properties[J]. Journal of Materials Science & Technology, 2023, 135: 186-198.
[11] ATALLAH M S, KHLIFI A, KHLIFI K, et al.Biodegradation and Mechanical Performance of Silane-Chitosan- Graphene Oxide Composite Coating on AZ31 Magnesium Alloys for Biomedical Applications[J]. International Journal of Biological Macromolecules, 2025, 287: 138568.
[12] 王松, 廖振华, 冯平法, 等. 骨科植入物金属材料生物摩擦腐蚀研究进展[J]. 摩擦学学报, 2017, 37(1): 130-138.
WANG S, LIAO Z H, FENG P F, et al.Research Progress on Biotribocorrosion of Metal Material in Orthopedic Implants[J]. Tribology, 2017, 37(1): 130-138.
[13] LI L X, XIE Z H, FERNANDEZ C, et al.Development of a Thiophene Derivative Modified LDH Coating for Mg Alloy Corrosion Protection[J]. Electrochimica Acta, 2020, 330: 135186.
[14] SUEGAMA P H, DE MELO H G, RECCO A A C, et al. Corrosion Behavior of Carbon Steel Protected with Single and Bi-Layer of Silane Films Filled with Silica Nanoparticles[J]. Surface and Coatings Technology, 2008, 202(13): 2850-2858.
[15] AGARWAL S, MORSHED M, LABOUR M N, et al.Enhanced Corrosion Protection and Biocompatibility of a PLGA-Silane Coating on AZ31 Mg Alloy for Orthopaedic Applications[J]. RSC Advances, 2016, 6(115): 113871-113883.
[16] HU J, LIU L, ZHANG J, et al.Studies of Surface Treatment of Aluminum Alloys by BTSE Silane Agent[J]. Acta Metallurgica Sinica-Chinese Edition, 2004, 40: 1189-1194.
[17] MONTEMOR M F, FERREIRA M G S. Electrochemical Study of Modified Bis-[Triethoxysilylpropyl] Tetrasulfide Silane Films Applied on the AZ31 Mg Alloy[J]. Electrochimica Acta, 2007, 52(27): 7486-7495.
[18] NISHITANI Y, KAJIYAMA T, YAMANAKA T.Effect of Silane Coupling Agent on Tribological Properties of Hemp Fiber-Reinforced Plant-Derived Polyamide 1010 Biomass Composites[J]. Materials, 2017, 10(9): 1040.
[19] PENG X X, JING H Y, YU L, et al.Tribological Behavior and Mechanism of Silane-Bridged H-BN/MoS2 Hybrid Filling Epoxy Solid Lubricant Coatings[J]. Nanomaterials, 2025, 15(5): 401.
[20] CONRADI M, KOCIJAN A, KLOBČAR D, et al. Tribological Response of Laser-Textured Ti6Al4V Alloy under Dry Conditions and Lubricated with Hank's Solution[J]. Tribology International, 2021, 160: 107049.
[21] SHABIR S, SHARMA M D.Tribological Behaviour of Laser Textured Ti3AlV 2.5V Alloy under Simulated Body Fluid[J]. Tribology International, 2024, 200: 110076.
[22] 梅斯凯, 晏蕾, 蔡召兵, 等. 深冷处理时间对Al0.5CoCrFeNb0.5Ni高熵合金组织和摩擦学性能的影响[J/OL]. 中国表面工程, (2025-3-12). https://link.cnki.net/urlid/11.3905.tg.20250312.0938.004.
MEI S K, YAN L, CAI Z B, et al. The Effect of Deep Cryogenic Treatment Duration on the Microstructure and Tribological Properties of Al0.5CoCrFeNb0.5Ni High-Entropy Alloy[J/OL]. China Surface Engineering(2025-3-12). https://link.cnki.net/urlid/11.3905.tg.20250312.0938.004.
[23] ZHANG Y, FENG X H, HUANG Q Y, et al.Effect of the Microstructure Parameters on the Corrosion Characteristics of Mg-Zn-Ca Alloy with Columnar Structure[J]. Journal of Magnesium and Alloys, 2023, 11(5): 1709-1720.
[24] INNOCENZI P, BRUSATIN G.A Comparative FTIR Study of Thermal and Photo-Polymerization Processes in Hybrid Sol-Gel Films[J]. Journal of Non-Crystalline Solids, 2004, 333(2): 137-142.
[25] FRANQUET A, TERRYN H, VEREECKEN J.IRSE Study on Effect of Thermal Curing on the Chemistry and Thickness of Organosilane Films Coated on Aluminium[J]. Applied Surface Science, 2003, 211(1/2/3/4): 259-269.
[26] SUZUKI N, ISHIDA H.Acceleration of Silanol Condensation of a Methacryl-Functional Silane in the Model Sizing System[J]. Composite Interfaces, 2005, 12(8/9): 769-785.
[27] GUNJI T, MAKABE Y, TAKAMURA N, et al.Preparation and Characterization of Organic-Inorganic Hybrids and Coating Films from 3-Methacryloxypropylpolysilsesquioxane[J]. Applied Organometallic Chemistry, 2001, 15(8): 683-692.
[28] PANTOJA M, DÍAZ-BENITO B, VELASCO F, et al. Analysis of Hydrolysis Process ofΓ-Methacryloxypropyltrimethoxysilane and Its Influence on the Formation of Silane Coatings on 6063 Aluminum Alloy[J]. Applied Surface Science, 2009, 255(12): 6386-6390.
[29] ZUCCHI F, FRIGNANI A, GRASSI V, et al.Organo- Silane Coatings for AZ31 Magnesium Alloy Corrosion Protection[J]. Materials Chemistry and Physics, 2008, 110(2/3): 263-268.
[30] WEI H T, ZHOU J J, ZHENG J, et al.Antioxidation Efficiency and Reinforcement Performance of Precipitated- Silica-Based Immobile Antioxidants Obtained by a Sol Method in Natural Rubber Composites[J]. RSC Advances, 2015, 5(112): 92344-92353.
[31] TALHA M, MA Y C, LIN Y H.Improved In-Vitro Corrosion Performance of Resorbable Magnesium Alloy Using Distinctive Hybrid Silane Coatings with Modified Nano Graphene Oxide[J]. Inorganic Chemistry Communications, 2026, 183: 115746.
[32] SONG Z G, MU Y, XIAO G Y, et al.Preparation and Characterization of Silane Film Modified with Hydroxyapatite Nanoparticles on Magnesium Alloy: Blistering Initiating Film Failure and Inhibitory Effect of Hydroxyapatite Nanoparticles[J]. Nano Materials Science, 2026, 8(1): 107-116.
[33] 吴慧, 王继虎, 温绍国, 等. 镁铝水滑石的制备及其涂层耐腐蚀性能的研究[J]. 表面技术, 2024, 53(12): 126-134.
WU H, WANG J H, WEN S G, et al.Preparation of Magnesium-Aluminium Hydrotalcite and Corrosion Resistance of Its Composite Coatings[J]. Surface Technology, 2024, 53(12): 126-134.
[34] 韩姝慧, 吕慎金, 高冬芳, 等. 基于仿真优化的磁针磁力研磨对镁钙锌合金表面性能影响的研究[J/OL]. 复合材料学报(2025-5-15). https://doi.org/10.13801/j.cnki.fhclxb.20250515.004.
HAN S H, LYU S J, GAO D F, et al. Study on the Effects of Simulation-Optimized Magnetic Needle Abrasive Machining on Surface Properties of Mg-Ca-Zn alloy[J/OL]. Acta Materiae Compositae Sinica(2025-5-15). https://doi.org/10.13801/j.cnki.fhclxb.20250515.004.
[35] AOKI I V, BERNARD M C, CORDOBA DE TORRESI S I, et al. Ac-Impedance and Raman Spectroscopy Study of the Electrochemical Behaviour of Pure Aluminium in Citric Acid Media[J]. Electrochimica Acta, 2001, 46(12): 1871-1878.
[36] 毛兴晨. 生物医用镁合金的表面硅烷化处理及其结构和性能研究[D]. 济南: 山东大学, 2019.
MAO X C.Surface Silanization Treatment of Biomedical Magnesium Alloy and Its Structure and Properties[D]. Jinan: Shandong University, 2019.
[37] AL-SAADI S, BANERJEE P C, ANISUR M R, et al.Hexagonal Boron Nitride Impregnated Silane Composite Coating for Corrosion Resistance of Magnesium Alloys for Temporary Bioimplant Applications[J]. Metals, 2017, 7(12): 518.
[38] QI J, ZHANG W, WANG M Y, et al.In-Depth Analysis of Superhydrophobicity and Corrosion Resistance Enhancing Mechanism by Laser-Textured Brass Surface[J]. Surfaces and Interfaces, 2025, 72: 107025.
[39] ABDRABOH A S, ABDEL-AAL A A, EREIBA K T. Preparation and Characterization of Inorganic Organic Hybrid Material Based on TEOS/MAPTMS for Biomedical Applications[J]. Silicon, 2021, 13(2): 613-622.
[40] LI J, BAI H H, FENG Z Y.Advances in the Modification of Silane-Based Sol-Gel Coating to Improve the Corrosion Resistance of Magnesium Alloys[J]. Molecules, 2023, 28(6): 2563.
[41] ZOMORODIAN A, BRUSCIOTTI F, FERNANDES A, et al.Anti-Corrosion Performance of a New Silane Coating for Corrosion Protection of AZ31 Magnesium Alloy in Hank's Solution[J]. Surface and Coatings Technology, 2012, 206(21): 4368-4375.

Funding

Natural Science Foundation of Shandong Province (ZR2023MC140,ZR2023ME077); The Disciplinary Interdisciplinary Convergence Construction Project of University of Jinan in 2024 (XKJC-202406)
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