Microstructure and Properties of In-situ Laser-fabricated CaTiO3/CaSiO3 Composite Coatings on Titanium Alloy Surfaces

XIAO Jian; WANG Bowen; SHEN Shaofan; PAN Cunliang; QIU Changjun; ZHU Hongmei

doi:10.16490/j.cnki.issn.1001-3660.2025.16.015

PDF(6342 KB)

Surface Technology ›› 2025, Vol. 54 ›› Issue (16) : 182-191. DOI: 10.16490/j.cnki.issn.1001-3660.2025.16.015

Surface Functionalization

Microstructure and Properties of In-situ Laser-fabricated CaTiO₃/CaSiO₃ Composite Coatings on Titanium Alloy Surfaces

XIAO Jian, WANG Bowen, SHEN Shaofan, PAN Cunliang, QIU Changjun, ZHU Hongmei^*

Author information +

History +

Abstract

Ti-6Al-4V (TC4) alloy is widely utilized as an implantable material for human bone tissue repair due to its excellent biocompatibility, mechanical properties and processing characteristics. However, TC4 alloy is susceptible to corrosion in the physiological environment, leading to the release of harmful ions that degrades its long-term stability and safety. Wollastonite (CaSiO₃) has been applied as a coating to enhance the bioactivity of TC4 alloy, owing to its superior chemical stability, corrosion resistance and bioactivity. In this study, CaTiO₃/CaSiO₃ composite coatings have been in-situ fabricated on the surface of TC4 alloy with a commercially available mixture of CaO, TiO₂ and SiO₂ powders (2∶1∶1, mol%) with particle sizes ranging from 53 µm to 105 µm as the laser cladding material. This work aims to provide a theoretical reference and experimental basis for the laser preparation of low-cost and high-performance composite coatings on titanium alloy surfaces.
The cladding powder was mixed with a 5 wt.% polyvinyl alcohol (PVA) binder solution to create a paste, which was uniformly preplaced to the TC4 substrate surface. The coated substrate was air-dried at room temperature for 24 h, and then placed in a vacuum drying oven at 40 ℃ for 2 h. Laser cladding was conducted with an XL-F500 fiber laser. The microstructure, surface morphology and micro-area composition of the specimens was examined by a MERLIN scanning electron microscope (SEM) equipped with energy-dispersive spectroscopy (EDS). The phase constituent of the coating was analyzed with an X-D6 X-ray diffractometer (XRD). Corrosion resistance testing was performed with a CS2350H electrochemical workstation, and in vitro bioactivity was assessed by immersing the specimens in simulated body fluid (SBF) at 36.5 ℃.
The in-situ laser-fabricated CaTiO₃/CaSiO₃ composite coating exhibited an excellent metallurgical bonding with the TC4 substrate, free from cracks and other defects. The coating primarily consisted of 50.4% CaTiO₃ and 35.7% β-CaSiO₃ without the presence of the substate phases, which reasonably inhibited the release of harmful elements such as Al and V from the substrate. The corrosion rate of the composite coating was measured at 0.0816 µm/a, which was approximately half that of the substrate (0.162 3 µm/a). Additionally, the composite coating exhibited significantly larger capacitive arc radius and phase angles compared to the substrate, with the coating resistance (R_t) reaching 1 021 Ω·cm², nearly double that of the substrate (646 Ω·cm²). After 14 days of immersion in simulated body fluid (SBF), the composite coating surface developed spherical aggregates with a Ca/P ratio of 1.69, and the relative content of hydroxyapatite (HA) reached 48.41%, demonstrating outstanding bioactivity.
The CaTiO₃/CaSiO₃ composite coatings, prepared in-situ by laser cladding technique, are defect-free and exhibit a metallurgical bond with the TC4 substrate. This bond can significantly inhibit the release of hazardous elements from the substrate while simultaneously exhibiting excellent corrosion resistance, with a corrosion rate decrease of approximately twice compared to the substrate. After immersion in SBF, the specimen surface exhibits small spherical aggregates with a Ca/P ratio of 1.69 and a high hydroxyapatite (HA) content, indicating excellent bioactivity. The CaTiO₃/CaSiO₃ composite coating, fabricated in situ via laser cladding in this study, demonstrates high hardness, superior corrosion resistance, and excellent bioactivity. This combination of properties offers promising potential for enhancing the long-term safety and efficacy of titanium alloy implants that contain harmful ions.

Key words

laser cladding / TC4 alloy / composite coating / microstructure / properties

Cite this article

EndNote

Ris (Procite)

Bibtex

Download Citations

XIAO Jian, WANG Bowen, SHEN Shaofan, PAN Cunliang, QIU Changjun, ZHU Hongmei. Microstructure and Properties of In-situ Laser-fabricated CaTiO₃/CaSiO₃ Composite Coatings on Titanium Alloy Surfaces[J]. Surface Technology. 2025, 54(16): 182-191 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.16.015

References

[1] 马永, 朱红梅, 孙楚光, 等. TC4钛合金表面激光熔覆掺Y₂O₃复合涂层的显微组织和性能[J]. 表面技术, 2017, 46(6): 238-243.
MA Y, ZHU H M, SUN C G, et al.Microstructure and Properties of Y₂O₃-Doped Laser Cladded Composite Coating on TC4 Titanium Alloy[J]. Surface Technology, 2017, 46(6): 238-243.
[2] LIM S G, CHOE H C.Bioactive Apatite Formation on PEO-Treated Ti-6Al-4V Alloy after 3rd Anodic Titanium Oxidation[J]. Applied Surface Science, 2019, 484: 365-373.
[3] 竺俊杰, 王优强, 倪陈兵, 等. 激光增材制造钛合金微观组织和力学性能研究进展[J]. 表面技术, 2024, 53(1): 15-32.
ZHU J J, WANG Y Q, NI C B, et al.Research Progress on Microstructure and Mechanical Properties of Titanium Alloy by Laser Additive Manufacturing[J]. Surface Technology, 2024, 53(1): 15-32.
[4] 崔振铎, 朱家民, 姜辉, 等. Ti及钛合金表面改性在生物医用领域的研究进展[J]. 金属学报, 2022, 58(7): 837-856.
CUI Z D, ZHU J M, JIANG H, et al.Research Progress of the Surface Modification of Titanium and Titanium Alloys for Biomedical Application[J]. Acta Metallurgica Sinica, 2022, 58(7): 837-856.
[5] 孙纯纯, 郭志君, 张金勇, 等. 亚稳β钛合金在生物医学领域的研究进展[J]. 稀有金属材料与工程, 2022, 51(3): 1111-1124.
SUN C C, GUO Z J, ZHANG J Y, et al.Research Progress on Metastable Β-Titanium Alloys for Biomedical Applications[J]. Rare Metal Materials and Engineering, 2022, 51(3): 1111-1124.
[6] DOS SANTOS G G, MEIRELES E C A, MIGUEL F B. Wollastonite/TCP Composites for Bone Regeneration: Systematic Review and Meta-Analysis[J]. Cerâmica, 2020, 66(379): 277-283.
[7] FENG J, WANG J, YANG K L, et al.Microstructure and Performance of YTaO4 Coating Deposited by Atmospheric Plasma Spraying on TC4 Titanium Alloy Surface[J]. Surface and Coatings Technology, 2022, 431: 128004.
[8] KEE C C, NG K, ANG B C, et al.Synthesis, Characterization and In-Vitro Biocompatibility of Electrophoretic Deposited Europium-Doped Calcium Silicate on Titanium Substrate[J]. Journal of the European Ceramic Society, 2023, 43(3): 1189-1204.
[9] LI H C, WANG D G, HU C, et al.Effect of Na₂O and ZnO on the Microstructure and Properties of Laser Cladding Derived CaO-SiO₂ Ceramic Coatings on Titanium Alloys[J]. Journal of Colloid and Interface Science, 2021, 592: 498-508.
[10] WANG Z, LIU C, ZHANG H, et al.Effect of Powder Morphology on the Coating Quality in Laser Cladding of Titanium Alloys[J]. Journal of Materials Processing Technology, 2020, 281: 116637.
[11] SINGH J, CHATHA S S, SINGH H.In Vitro Assessment of Plasma-Sprayed Reinforced Hydroxyapatite Coatings Deposited on Ti₆Al₄V Alloy for Bio-Implant Applications[J]. Journal of Materials Research, 2022, 37(16): 2623-2634.
[12] GALINDO-VALDÉS J S, CORTÉS-HERNÁNDEZ D A, ORTIZ-CUELLAR J C, et al. Laser Deposition of Bioactive Coatings by in Situ Synthesis of Pseudowollastonite on Ti₆Al₄V Alloy[J]. Optics & Laser Technology, 2021, 134: 106586.
[13] SOKOLOVA T S, DOROGOKUPETS P I.Equations of State of Ca-Silicates and Phase Diagram of the CaSiO₃ System under Upper Mantle Conditions[J]. Minerals, 2021, 11(3): 322.
[14] VERMA P C, TIWARI S K, SAURABH A, et al.Recent Advances in High-Entropy Ceramics: Synthesis Methods, Properties, and Emerging Applications[J]. Ceramics, 2024, 7(4): 1365-1389.
[15] VANGOLU Y, YURTCAN M T.Wear and Corrosion Properties of Wollastonite and Boron Nitride Doped, Hydroxyapatite-Based HAp-Wo-BN Composite Coatings Prepared by Pulsed Laser Deposition[J]. Ceramics International, 2021, 47(23): 32969-32978.
[16] XU W, BRANDT M, SUN S, et al.Additive Manufacturing of Strong and Ductile Ti-6Al-4V by Selective Laser Melting via in Situ Martensite Decomposition[J]. Acta Materialia, 2015, 85: 74-84.
[17] DENG Z X, LIU D F, LIU G, et al.Study on the Corrosion Resistance of SiC Particle-Reinforced Hydroxyapatite-Silver Gradient Bioactive Ceramic Coatings Prepared by Laser Cladding[J]. Surface and Coatings Technology, 2023, 467: 129734.
[18] DENG Z X, LIU D F, XIONG Y, et al.Laser Cladding Preparation of HA-Ag Gradient Bioactive Ceramic Coating: A Feasibility Study[J]. Surface and Coatings Technology, 2021, 427: 127848.
[19] BEHERA R R, HASAN A, SANKAR M R, et al.Laser Cladding with HA and Functionally Graded TiO₂-HA Precursors on Ti-6Al-4V Alloy for Enhancing Bioactivity and Cyto-Compatibility[J]. Surface and Coatings Technology, 2018, 352: 420-436.
[20] HUNG G Y, CHEN P Y, WANG C Y, et al.Tailoring Bioactive and Mechanical Properties in Polycrystalline CaO-SiO₂-P₂O₅ Glass-Ceramics[J]. Ceramics International, 2023, 49(5): 7289-7298.
[21] WU Q L, LONG W M, ZHANG L, et al.A Review on Ceramic Coatings Prepared by Laser Cladding Technology[J]. Optics & Laser Technology, 2024, 176: 110993.
[22] LI Z J, WANG S, ZHANG M Q, et al.New Type of High-Power Laser Protection Coatings with both High Reflectivity and Low Thermal Conductivity[J]. Ceramics International, 2025, 51(3): 3176-3184.
[23] 巢文正, 王锐, 孙志林, 等. 放电等离子烧结工艺对制备硅灰石微晶玻璃的影响[J]. 中国陶瓷, 2024, 60(7): 13-19.
CHAO W Z, WANG R, SUN Z L, et al.Effects of Spark Plasma Sintering Process on the Preparation of Wollastonite Glass-Ceramics[J]. China Ceramics, 2024, 60(7): 13-19.
[24] 朱红梅, 胡际鹏, 李柏春, 等. 原位回火对马氏体不锈钢激光熔覆涂层的影响[J]. 表面技术, 2020, 49(11): 303-308.
ZHU H M, HU J P, LI B C, et al.Effects of In-Situ Tempering on the Laser-Cladded Martensitic Stainless Steel Coating[J]. Surface Technology, 2020, 49(11): 303-308.
[25] 张冬冬, 史昆玉, 汤皓晨. TC4钛合金表面沉积TiCN涂层及其耐磨耐腐蚀性能研究[J]. 表面技术, 2020, 49(6): 297-304.
ZHANG D D, SHI K Y, TANG H C.TiCN Coating Deposited on TC4 Titanium Alloy and Its Wear and Corrosion Resistance[J]. Surface Technology, 2020, 49(6): 297-304.
[26] 姜明明, 孙树峰, 王津, 等. 激光熔覆制备高熵合金涂层耐磨性研究进展[J]. 材料工程, 2022, 50(3): 18-32.
JIANG M M, SUN S F, WANG J, et al.Research Progress in Wear Resistance of High Entropy Alloy Coatings Prepared by Laser Cladding[J]. Journal of Materials Engineering, 2022, 50(3): 18-32.
[27] GAO C Z, XU F, SHI X Q, et al.Enhanced Tribo-Corrosion Resistance of Biocompatible TiNbTaZrWC Coating through Intelligent Design Strategy[J]. Chemical Engineering Journal, 2025, 504: 158740.
[28] JIN J B, ZHOU S F, ZHANG W C, et al.Effect of Ceramic Types on the Microstructure and Corrosion Behavior of Titanium Matrix Composites Produced by Selective Laser Melting[J]. Journal of Alloys and Compounds, 2022, 918: 165704.
[29] 廖士铸, 张颂红, 宋振纶, 等. 退火对钛合金钽涂层力学及生物性能的影响[J]. 表面技术, 2024, 53(2): 184-192.
LIAO S Z, ZHANG S H, SONG Z L, et al.Effect of Annealing on Mechanical and Biological Properties of Titanium Alloy Tantalum Coating[J]. Surface Technology, 2024, 53(2): 184-192.
[30] WU G L, ZHANG S, WANG Y, et al.Porous Ceramic Coating Formed on 316L by Laser Cladding Combined Plasma Electrolytic Oxidation for Biomedical Application[J]. Transactions of Nonferrous Metals Society of China, 2022, 32(9): 2993-3004.
[31] ABDEEN D H, EL HACHACH M, KOC M, et al.A Review on the Corrosion Behaviour of Nanocoatings on Metallic Substrates[J]. Materials, 2019, 12(2): 210.
[32] SU Y C, COCKERILL I, ZHENG Y F, et al.Biofunctionalization of Metallic Implants by Calcium Phosphate Coatings[J]. Bioactive Materials, 2019, 4: 196-206.
[33] 邓婉蓉, 杨巍, 李珂珂, 等. 钛合金表面掺Sn微弧氧化层的制备及其在模拟体液环境中的防护性能[J]. 中国表面工程, 2024, 37(5): 288-295.
DENG W R, YANG W, LI K K, et al.Preparation of Sn-Doped Micro-Arc Oxide Coating on Titanium Alloy and Its Protective Properties in Simulated Body Fluid Environment[J]. China Surface Engineering, 2024, 37(5): 288-295.