首页   |   期刊介绍   |   编 委 会   |   投稿指南   |   出版法规   |   出版伦理   |   期刊订阅   |   联系我们   |   留言板   |   广告合作   |   ENGLISH

粉末冶金材料科学与工程 >

2026 , Vol. 31 >Issue 3: 310 - 320

DOI: https://doi.org/10.19976/j.cnki.43-1448/TF.2026021

工艺技术

钛合金表面富锆微弧氧化涂层的原位形成及摩擦学行为

  • 魏剑磊 ,
  • 李思雨 ,
  • 赵庆杰 ,
  • 黄千里
展开
  • 中南大学 粉末冶金研究院,长沙 410083

收稿日期: 2026-02-10

  修回日期: 2026-04-15

  网络出版日期: 2026-07-03

基金资助

中南大学研究生科研创新项目(自主探索类)(1053320231737)

收起

In situ formation and tribological behavior of Zr-rich micro-arc oxidation coatings on titanium alloy

  • WEI Jianlei ,
  • LI Siyu ,
  • ZHAO Qingjie ,
  • HUANG Qianli
Expand
  • Powder Metallurgy Research Institute, Central South University, Changsha 410083, China

Received date: 2026-02-10

  Revised date: 2026-04-15

  Online published: 2026-07-03

Fold

摘要

在传统的磷酸盐、硅酸盐或铝酸盐电解液中制备的微弧氧化涂层,因本征脆性导致耐磨性能较差。针对此问题,本研究采用由氟锆酸钾(K2ZrF6)和六偏磷酸钠((NaPO3)6)组成的稳定电解液,在TC4钛合金表面制备具有多种含Zr物相的微弧氧化耐磨涂层。通过调控微弧氧化处理时间,系统研究TC4钛合金在处理过程中的等离子体放电行为以及涂层的微观结构演变、结合强度及摩擦学性能。结果表明：随微弧氧化处理时间由2 min延长至60 min,TC4钛合金表面等离子体放电密度逐步降低,而放电强度持续增强,阳极电流最终趋近于零。当微弧氧化处理时间由2 min延长至60 min时,涂层厚度由(14.35±3.11) μm增加至(65.72±6.68) μm,划痕试验中的临界载荷力由11.00 N提升至40.69 N。涂层主要由ZrP2O7、K2Zr(PO4)2、ZrTiO4、m-ZrO2、t-ZrO2等相组成,形成了多相协同增强结构。经过48 h干滑动摩擦试验后,涂层表面形成致密转移膜,其磨损率低至(5.44±0.27)×10-6 mm3/(N·m),相较金属基体降低约99.0%,表现出优异的耐磨性。

关键词： 表面改性; 微弧氧化; 氧化涂层; 耐磨涂层; 原位形成; 氧化锆; 长寿命

本文引用格式

魏剑磊 , 李思雨 , 赵庆杰 , 黄千里 . 钛合金表面富锆微弧氧化涂层的原位形成及摩擦学行为[J]. 粉末冶金材料科学与工程, 2026 , 31(3) : 310 -320 . DOI: 10.19976/j.cnki.43-1448/TF.2026021

Abstract

In conventional phosphate-, silicate-, or aluminate-based electrolytes, micro-arc oxidation coatings often suffer from insufficient wear resistance due to their intrinsic brittleness. To address this limitation, a stable electrolyte composed of K2ZrF6 and (NaPO3)6 was employed in this study to fabricate wear-resistant micro-arc oxidation coatings containing multiple Zr-bearing phases on TC4 titanium alloy. By varying the micro-arc oxidation treatment time, the plasma discharge behavior of TC4 titanium alloy during processing, as well as the evolution of coating microstructure, adhesion strength, and tribological performance, were systematically investigated. The results show that, as the micro-arc oxidation treatment time increases form 2 min to 60 min, the plasma discharge density on the TC4 surface gradually decreases, while the discharge intensity continuously increases, and the anodic current eventually approaches zero. When the micro-arc oxidation duration increases from 2 min to 60 min, the coating thickness rises from (14.35±3.11) μm to (65.72±6.68) μm, and critical load force in scratch testing improves from 11.00 N to 40.69 N. The coating is mainly composed of ZrP2O7, K2Zr(PO4)2, ZrTiO4, m-ZrO2 and t-ZrO2, forming a multiphase synergistically reinforced structure. After 48 h of dry sliding tests, a dense transfer film is formed on the coating surface, and the wear rate reduces to (5.44±0.27)×10-6 mm3/(N·m), an approximately 99.0% decrease compared with the metallic substrate, demonstrating excellent wear resistance.

Key words： surface modification; micro-arc oxidation; oxide coating; wear-resistant coating; in situ formation; zirconia; long service life

参考文献

[1] ALIOFKHAZRAEI M, MACDONALD D D, MATYKINA E, et al.Review of plasma electrolytic oxidation of titanium substrates: mechanism, properties, applications and limitations[J]. Applied Surface Science Advances, 2021, 5: 100121.
[2] KANG S H, TU W B, HAN J X, et al.A significant improvement of the wear resistance of Ti6Al4V alloy by a combined method of magnetron sputtering and plasma electrolytic oxidation (PEO)[J]. Surface and Coatings Technology, 2019, 358: 879-890.
[3] 陈奏君, 林泽华, 段中元, 等. TiH2粉末制备钛合金的组织与力学性能[J]. 粉末冶金材料科学与工程, 2021, 26(3): 243-249.
CHEN Zoujun, LIN Zehua, DUAN Zhongyuan, et al.Microstructure and mechanical properties of titanium alloys prepared with TiH2[J]. Materials Science and Engineering of Powder Metallurgy, 2021, 26(3): 243-249.
[4] CHI Y M, GU G C, YU H J, et al.Laser surface alloying on aluminum and its alloys: a review[J]. Optics and Lasers in Engineering, 2018, 100: 23-37.
[5] 张凯, 陈小明, 张磊, 等. 激光熔覆制备耐磨耐蚀涂层技术研究进展[J]. 粉末冶金材料科学与工程, 2019, 24(4): 308-314.
ZHANG Kai, CHEN Xiaoming, ZHANG Lei, et al.Research progress of wear-resistant and corrosion-resistant coatings prepared by laser cladding[J]. Materials Science and Engineering of Powder Metallurgy, 2019, 24(4): 308-314.
[6] MO J L, ZHU M H, LEI B, et al.Comparison of tribological behaviours of AlCrN and TiAlN coatings: deposited by physical vapor deposition[J]. Wear, 2007, 263(7/8/9/10/11/12): 1423-1429.
[7] 孙沛, 古一, 李雅琪, 等. 钛及钛合金多弧离子镀Ta-10W涂层的腐蚀性能[J]. 粉末冶金材料科学与工程, 2019, 24(5): 413-421.
SUN Pei, GU Yi, LI Yaqi, et al.Corrosion performance of Ta-10W coating on titanium and its alloy by multi-arc ion plating[J]. Materials Science and Engineering of Powder Metallurgy, 2019, 24(5): 413-421.
[8] HAUBNER R.The history of hard CVD coatings for tool applications at the University of Technology Vienna[J]. International Journal of Refractory Metals and Hard Materials, 2013, 41: 22-34.
[9] CAI Z B, ZHANG G G, ZHU Y K, et al.Torsional fretting wear of a biomedical Ti6Al7Nb alloy for nitrogen ion implantation in bovine serum[J]. Tribology International, 2013, 59: 312-320.
[10] KASEEM M, FATIMAH S, NASHRAH N, et al.Recent progress in surface modification of metals coated by plasma electrolytic oxidation: principle, structure, and performance[J]. Progress in Materials Science, 2021, 117: 100735.
[11] HUSSEIN R O, NORTHWOOD D O, NIE X.The effect of processing parameters and substrate composition on the corrosion resistance of plasma electrolytic oxidation (PEO) coated magnesium alloys[J]. Surface and Coatings Technology, 2013, 237: 357-368.
[12] HUSSEIN R O, NIE X, NORTHWOOD D O.A spectroscopic and microstructural study of oxide coatings produced on a Ti-6Al-4V alloy by plasma electrolytic oxidation[J]. Materials Chemistry and Physics, 2012, 134(1): 484-492.
[13] 黄山, 谭鹏飞, 黄千里. 软火花微弧氧化技术突破: TiNbZr中熵合金超厚耐蚀涂层生长行为研究[J]. 金属世界, 2025(3): 1-8.
HUANG Shan, TAN Pengfei, HUANG Qianli.Breakthrough of soft spark micro-arc oxidation technology: growth behavior of TiNbZr medium entropy alloy ultra-thick corrosion resistant coatings[J]. Metal World, 2025(3): 1-8.
[14] 方雷, 马运柱, 刘文胜, 等. 氧化时间对铝合金微弧氧化膜层结构及耐腐蚀性能的影响[J]. 粉末冶金材料科学与工程, 2018, 23(5): 503-510.
FANG Lei, MA Yunzhu, LIU Wensheng, et al.Effects of oxidation time on microstructure and corrosion resistance of micro-arc oxidation film on aluminum alloy[J]. Materials Science and Engineering of Powder Metallurgy, 2018, 23(5): 503-510.
[15] YANG C P, MENG X Z, LI X R, et al.Effect of electrolyte composition on corrosion behavior and tribological performance of plasma electrolytic oxidized TC4 alloy[J]. Transactions of Nonferrous Metals Society of China, 2023, 33(1): 141-156.
[16] RÍOS J M, QUINTERO D, CASTAÑO J G, et al. Comparison among the lubricated and unlubricated tribological behavior of coatings obtained by PEO on the Ti6Al4V alloy in alkaline solutions[J]. Tribology International, 2018, 128: 1-8.
[17] HABAZAKI H, ONODERA T, FUSHIMI K, et al.Spark anodizing of β-Ti alloy for wear-resistant coating[J]. Surface and Coatings Technology, 2007, 201(21): 8730-8737.
[18] DURDU S, USTA M.The tribological properties of bioceramic coatings produced on Ti6Al4V alloy by plasma electrolytic oxidation[J]. Ceramics International, 2014, 40(2): 3627-3635.
[19] 王雪, 于秀涛. SiC含量对内燃机用Ti-6Al-4V合金复合膜组织和摩擦性能的影响[J]. 粉末冶金材料科学与工程, 2020, 25(6): 458-464.
WANG Xue, YU Xiutao.Effects of SiC content on the composite membrane structure and friction properties of Ti-6Al-4V alloy for internal combustion engine[J]. Materials Science and Engineering of Powder Metallurgy, 2020, 25(6): 458-464.
[20] YAO Z P, JIANG Y L, JIA F Z, et al.Growth characteristics of plasma electrolytic oxidation ceramic coatings on Ti-6Al-4V alloy[J]. Applied Surface Science, 2008, 254(13): 4084-4091.
[21] YANG C, CUI S H, WU Z C, et al.High efficient co-doping in plasma electrolytic oxidation to obtain long-term self-lubrication on Ti6Al4V[J]. Tribology International, 2021, 160: 107018.
[22] HUANG P, WANG F, XU K W, et al.Mechanical properties of titania prepared by plasma electrolytic oxidation at different voltages[J]. Surface and Coatings Technology, 2007, 201(9/10/11): 5168-5171.
[23] SHIN K R, KIM Y S, YANG H W, et al.In vitro biological response to the oxide layer in pure titanium formed at different current densities by plasma electrolytic oxidation[J]. Applied Surface Science, 2014, 314: 221-227.
[24] CHENG Y L, PENG Z M, WU X Q, et al.A comparison of plasma electrolytic oxidation of Ti-6Al-4V and Zircaloy-2 alloys in a silicate-hexametaphosphate electrolyte[J]. Electrochimica Acta, 2015, 165: 301-313.
[25] WANG L L, WANG G W, DONG H, et al.Plasma electrolytic oxidation coatings on additively manufactured aluminum-silicon alloys with superior tribological performance[J]. Surface and Coatings Technology, 2022, 435: 128246.
[26] LI Q B, YANG W B, LIU C C, et al.Correlations between the growth mechanism and properties of micro-arc oxidation coatings on titanium alloy: effects of electrolytes[J]. Surface and Coatings Technology, 2017, 316: 162-170.
[27] ZHANG G, CHEN Y S, CAO Y K, et al.Superior self-lubricating coatings with heterogeneous nanocomposite structures on Ti-Nb-Zr-Ta-Hf refractory multi-principal element alloy[J]. Advanced Functional Materials, 2024, 34(44): 2405657.
[28] BARATI N, MELETIS E I, FARD F G, et al.Al2O3-ZrO2 nanostructured coatings using DC plasma electrolytic oxidation to improve tribological properties of Al substrates[J]. Applied Surface Science, 2015, 356: 927-934.
[29] TANG M Q, LI W P, LIU H C, et al.Preparation Al2O3/ZrO2 composite coating in an alkaline phosphate electrolyte containing K2ZrF6 on aluminum alloy by microarc oxidation[J]. Applied Surface Science, 2012, 258(15): 5869-5875.
[30] BARTOLOMÉ J F, PECHARROMÁN C, MOYA J S, et al. Percolative mechanism of sliding wear in alumina/zirconia composites[J]. Journal of the European Ceramic Society, 2006, 26(13): 2619-2625.
[31] 单科, 郭兴敏. 氧化镁稳定氧化锆纳米粉末的制备与物相分析[J]. 粉末冶金材料科学与工程, 2013, 18(3): 429-433.
SHAN Ke, GUO Xingmin.Preparation and characterization of nano-powder zirconia stabilized by magnesia[J]. Materials Science and Engineering of Powder Metallurgy, 2013, 18(3): 429-433.
[32] MUHAFFEL F, KABA M, CEMPURA G, et al.Influence of alumina and zirconia incorporations on the structure and wear resistance of titania-based MAO coatings[J]. Surface and Coatings Technology, 2019, 377: 124900.
[33] LI H, SUN Y Z, ZHANG J.Effect of ZrO2 particle on the performance of micro-arc oxidation coatings on Ti6Al4V[J]. Applied Surface Science, 2015, 342: 183-190.
[34] CHEN X W, ZHANG M, ZHANG D F, et al.The effect of addition of K2ZrF6 on the structures and properties of AZ31 magnesium alloy MAO coating[J]. Journal of Alloys and Compounds, 2023, 966: 171474.
[35] TU C H, CHEN X Y, LIU C C, et al.Plasma electrolytic oxidation coatings of a 6061 Al alloy in an electrolyte with the addition of K2ZrF6[J]. Materials, 2023, 16(11): 4142.
[36] CHU C L, HAN X, BAI J, et al.Fabrication and degradation behavior of micro-arc oxidized biomedical magnesium alloy wires[J]. Surface and Coatings Technology, 2012, 213: 307-312.
[37] GAO G R, LI Y, HU D, et al.Structure and infrared emissivity properties of the MAO coatings formed on TC4 alloys in K2ZrF6-based solution[J]. Materials, 2018, 11(2): 254.
[38] LUO Q, CAI Q Z, LI X W, et al.Preparation and characterization of ZrO2/TiO2 composite photocatalytic film by micro-arc oxidation[J]. Transactions of Nonferrous Metals Society of China, 2013, 23(10): 2945-2950.
[39] ARRABAL R, MATYKINA E, HASHIMOTO T, et al.Characterization of AC PEO coatings on magnesium alloys[J]. Surface and Coatings Technology, 2009, 203(16): 2207-2220.
[40] CHEN P H, WU Z Z, HUANG Q, et al.A quasi-2D material CePO4 and the self-lubrication in micro-arc oxidized coatings on Al alloy[J]. Tribology International, 2019, 138: 157-165.
[41] MATYKINA E, ARRABAL R, SKELDON P, et al.Incorporation of zirconia nanoparticles into coatings formed on aluminium by AC plasma electrolytic oxidation[J]. Journal of Applied Electrochemistry, 2008, 38(10): 1375-1383.
[42] CLYNE T W, TROUGHTON S C.A review of recent work on discharge characteristics during plasma electrolytic oxidation of various metals[J]. International Materials Reviews, 2019, 64(3): 127-162.
[43] SHAO M Z, WANG W, YANG H B, et al.Preparation of wear-resistant coating on Ti6Al4V alloy by cold spraying and plasma electrolytic oxidation[J]. Coatings, 2021, 11(11): 1288.
[44] SHOKOUHFAR M, ALLAHKARAM S R.Formation mechanism and surface characterization of ceramic composite coatings on pure titanium prepared by micro-arc oxidation in electrolytes containing nanoparticles[J]. Surface and Coatings Technology, 2016, 291: 396-405.
[45] HUSSEIN R O, NIE X, NORTHWOOD D O, et al.Spectroscopic study of electrolytic plasma and discharging behaviour during the plasma electrolytic oxidation (PEO) process[J]. Journal of Physics D: Applied Physics, 2010, 43(10): 105203.
[46] XIANG H M, FENG Z H, ZHOU Y C.Ab initio computations of electronic, mechanical, lattice dynamical and thermal properties of ZrP2O7[J]. Journal of the European Ceramic Society, 2014, 34(7): 1809-1818.
[47] YAO Z P, SU P B, SHEN Q X, et al.Preparation of thermal control coatings on Ti alloy by plasma electrolytic oxidation in K2ZrF6 solution[J]. Surface and Coatings Technology, 2015, 269: 273-278.
[48] EGORKIN V S, GNEDENKOV S V, SINEBRYUKHOV S L, et al.Increasing thickness and protective properties of PEO-coatings on aluminum alloy[J]. Surface and Coatings Technology, 2018, 334: 29-42.
[49] YANG W, DENG Z N, ZHANG D, et al.Microstructure and tribological behavior of self-lubricating (Si:N)-DLC/MAO coatings on AZ80 magnesium substrate[J]. Acta Metallurgica Sinica (English Letters), 2013, 26(6): 693-698.
[50] MU M, ZHOU X J, XIAO Q, et al.Preparation and tribological properties of self-lubricating TiO2/graphite composite coating on Ti6Al4V alloy[J]. Applied Surface Science, 2012, 258(22): 8570-8576.
[51] 王奎. 氮化硅基复合陶瓷材料的海洋腐蚀/磨损行为研究[D]. 西安: 陕西科技大学, 2019.
WANG Kui.Investigation of tribological properties and corrosion behaviors of silicon nitride-based ceramic composites under marine environment[D]. Xi’an: Shaanxi University of Science and Technology, 2019.
Options
文章导航

/

〈 〉

版权所有 © 《粉末冶金材料科学与工程》编辑部
地址：长沙市麓山南路中南大学粉末冶金研究院　邮编：410083　电话：0731-88877163　邮箱：pmbjb@csu.edu.cn
本系统由北京玛格泰克科技发展有限公司设计开发　技术支持：support@magtech.com.cn