Ta含量对CrTaN涂层微观结构与耐腐蚀性能的影响

丁明理; 张凤玲; 张武; 高峰; 于鑫枫; 卢旭东; 郭策安

doi:10.16490/j.cnki.issn.1001-3660.2025.20.009

PDF(15345 KB)

表面技术 ›› 2025, Vol. 54 ›› Issue (20) : 124-134. DOI: 10.16490/j.cnki.issn.1001-3660.2025.20.009

腐蚀与防护

Ta含量对CrTaN涂层微观结构与耐腐蚀性能的影响

丁明理, 张凤玲, 张武, 高峰, 于鑫枫, 卢旭东, 郭策安^*

作者信息 +

Effect of Ta Content on Microstructure and Corrosion Resistance of CrTaN Coating

DING Mingli, ZHANG Fengling, ZHANG Wu, GAO Feng, YU Xinfeng, LU Xudong, GUO Cean^*

Author information +

文章历史 +

摘要

目的研究Ta含量对CrTaN涂层微观结构和耐腐蚀性能的影响。方法通过磁控溅射技术,采用不同组分的CrTa靶材在炮钢表面制备了不同Ta含量的CrTaN涂层。利用X射线衍射仪、扫描电子显微镜及电化学工作站对涂层的微观结构和耐腐蚀性能进行分析。结果当Ta含量为1.12%（原子数分数）时,CrTaN涂层呈现出菜花状表面形貌;随着Ta含量增加,涂层表面形貌逐渐转变为三棱锥形貌。CrTaN涂层始终保持CrN（111）晶面择优取向,且随着Ta含量的增加,（111）、（200）、（220）和（311）晶面的衍射峰逐渐向低角度偏移,Cr₈₈Ta₁₂N涂层中出现Ta（111）和Ta（222）晶面。加入少量Ta后,CrTaN涂层的腐蚀电流密度呈单调递减趋势。其中,Cr₉₆Ta₄N涂层的腐蚀电流密度最低（5.8×10^-6A/cm²）,耐腐蚀性能最佳。随着Ta含量进一步增加,CrTaN涂层表面缝隙变多,腐蚀电流密度增加,耐腐蚀性能下降。恒电位极化测试表明,Cr₉₆Ta₄N涂层未出现明显的钝化膜破裂或局部腐蚀,而纯CrN涂层则发生多次钝化膜破裂并伴随局部腐蚀现象。结论 CrTaN涂层表面致密连续无明显缺陷,截面呈现明显的柱状晶结构;随着Ta含量的增加,涂层的表面及截面形貌发生显著变化;CrTaN涂层与CrN涂层相比,耐腐蚀性均得到提升。

Abstract

The growing demand for durable and corrosion-resistant materials in defense system applications has driven the development of advanced coating technologies. Among these, CrTaN coatings have emerged as promising candidates due to their superior mechanical properties and corrosion resistance. This study focuses on investigating the influence of tantalum (Ta) content on the microstructural evolution and corrosion behaviors of CrTaN coatings deposited on gun steel substrates, with the aim of optimizing their performance in challenging environments. The CrTaN coatings were deposited by magnetron sputtering with precisely controlled Ta composition ranging from 1.12at.% to 6.1at.%. The microstructural morphology and corrosion resistance assessment of the coatings were characterized through X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and electrochemical workstation analysis. The surface morphological analysis revealed that all coatings exhibited compact, uniform, and defect-free surfaces, with distinct evolutionary patterns observed as Ta content increased. The CrN coating showed a typical cauliflower-like structure, which retained in the CrTaN coatings with 1.12at.% Ta content. With the increase of Ta content, the surface morphology gradually evolved a triangular pyramidal shape at 6.1at.% Ta content. The cross-sectional characterization revealed excellent coating uniformity and good adhesion, with a continuous columnar crystal structure throughout the coating thickness. At lower Ta content (1.12at.%), the columnar crystals exhibited dense packing and uniform orientation. However, increasing Ta content led to increased columnar crystal width, irregular crystal structure arrangement, and the formation of inter-columnar gaps. The XRD analysis identified four primary diffraction peaks corresponding to CrN (111), (200), (220) and (311) planes, with peak positions at 37.9°, 43.9°, 64.3° and 76.8°, respectively. Compared with the CrN coatings, the incorporation of Ta introduced additional diffraction peaks corresponding to Cr (110), (200) and (211) crystal planes, suggesting incomplete nitridation of Cr during the deposition process, which was potentially due to suboptimal reaction conditions or excessive target current. The CrTaN coatings maintained a preferred CrN (111) orientation, with diffraction peaks gradually shifted to lower angles indicating lattice distortion effects induced by Ta incorporation. Notably, the emergence of Ta (111) and Ta (222) diffraction peaks in the Cr₈₈Ta₁₂N coatings confirmed the presence of metallic Ta in the coatings. Electrochemical evaluation demonstrated significant improvements in corrosion resistance with Ta incorporation. The CrTaN coatings exhibited lower corrosion current densities and increased charge transfer resistance compared with the CrN coatings. The enhanced corrosion resistance at lower Ta content was attributed to the formation of dense and continuous coatings with well-defined columnar structures, effectively inhibiting electrolyte penetration. However, further increase in Ta content beyond the optimal concentration led to structural modifications, including irregular columnar growth and gap formation, which facilitated electrolyte penetration and consequently increased corrosion rates of the coatings. Among all compositions, the Cr₉₆Ta₄N coatings exhibited superior corrosion resistance, with minimal corrosion current density (5.8×10^-6 A/cm²) and maximum charge transfer resistance (2 218 Ω/cm²). The potentiostatic polarization test showed that no obvious passivation film rupture or local corrosion occurred in the Cr₉₆Ta₄N coatings, while the pure CrN coatings experienced multiple passivation film ruptures accompanied by local corrosion. These findings provide valuable insights into the structure-property relationships in CrTaN coatings and establish optimal Ta content for enhanced corrosion protection in demanding applications.

导出引用

丁明理, 张凤玲, 张武, 高峰, 于鑫枫, 卢旭东, 郭策安. Ta含量对CrTaN涂层微观结构与耐腐蚀性能的影响[J]. 表面技术. 2025, 54(20): 124-134 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.20.009

DING Mingli, ZHANG Fengling, ZHANG Wu, GAO Feng, YU Xinfeng, LU Xudong, GUO Cean. Effect of Ta Content on Microstructure and Corrosion Resistance of CrTaN Coating[J]. Surface Technology. 2025, 54(20): 124-134 https://doi.org/10.16490/j.cnki.issn.1001-3660.2025.20.009

中图分类号： TG174.4

参考文献

[1] HU M, TANG Y Y, ZHAO Y, et al.Analysis of Marine Service Environment and Corrosion Mechanism of Naval Gun Barrel[J]. Materials Protection, 2022, 55(6): 164-172.
[2] DECRESCENTE M A, BORNSTEIN N S.Formation and Reactivity Thermodynamics of Sodium Sulfate with Gas Turbine Alloys[J]. Corrosion, 1968, 24(5): 127-133.
[3] MAO B, ZHAO Q, BAI X, et al.Review and Prospect of Life Extension Technology for Gun Barrels[J]. Acta Armamentarii, 2023, 44(3): 638.
[4] CHANG Z K, WAN X S, PEI Z L, et al.Microstructure and Mechanical Properties of CrN Coating Deposited by Arc Ion Plating on Ti₆Al₄V Substrate[J]. Surface and Coatings Technology, 2011, 205(19): 4690-4696.
[5] PRIYADARSHINI B, ANWAR S, CHOUDHARY B, et al.Influence of Annealing Temperature on Microstructural, Mechanical and Chemical Properties of CrAlN Coatings[J]. Physica B: Condensed Matter, 2023, 669: 415304.
[6] SU Y L, KAO W H, HORNG J H, et al.Corrosion Resistance and Conductivity Behavior of Cr-Al-N MAX Phase Coatings Prepared by Magnetron Sputtering Technology[J]. Thin Solid Films, 2024, 793: 140274.
[7] JIN J, ZHENG D C, HAN S W, et al.Effect of Ni Content on the Electrical and Corrosion Properties of CrNiN Coating in Simulated Proton Exchange Membrane Fuel Cell[J]. International Journal of Hydrogen Energy, 2017, 42(2): 1142-1153.
[8] WANG H X, YE Y W, WANG Y X. Structure, Corrosion,Tribological Properties of CrSiN Coatings with Various Si Contents in 3.5% NaCl Solution[J]. Surface and Interface Analysis, 2018, 50(4): 471-479.
[9] JAHODOVA V, DING X Z, SENG D H L, et al. Mechanical, Tribological and Corrosion Properties of CrBN Films Deposited by Combined Direct Current and Radio Frequency Magnetron Sputtering[J]. Thin Solid Films, 2013, 544: 335-340.
[10] DING X Z, TAN A L K, ZENG X T, et al. Corrosion Resistance of CrAlN and TiAlN Coatings Deposited by Lateral Rotating Cathode Arc[J]. Thin Solid Films, 2008, 516(16): 5716-5720.
[11] SHAN L, ZHANG Y R, WANG Y X, et al.Corrosion and Wear Behaviors of PVD CrN and CrSiN Coatings in Seawater[J]. Transactions of Nonferrous Metals Society of China, 2016, 26(1): 175-184.
[12] 汪汝佳, 王振玉, 刘应瑞, 等. Ni含量对CrNiN涂层结构与性能的影响[J]. 表面技术, 2022, 51(5): 158-165.
WANG R J, WANG Z Y, LIU Y R, et al.Influence of the Ni Content on Structure and Properties of CrNiN Coatings[J]. Surface Technology, 2022, 51(5): 158-165.
[13] KONG J Z, HOU T J, WANG Q Z, et al.Influence of Titanium or Aluminum Doping on the Electrochemical Properties of CrN Coatings in Artificial Seawater[J]. Surface and Coatings Technology, 2016, 307: 118-124.
[14] CHEN Y I, LIN Y T, CHANG L C, et al.Preparation and Annealing Study of CrTaN Coatings on WC-Co[J]. Surface and Coatings Technology, 2011, 206(7): 1640-1647.
[15] CHEN Y I, LIN K Y, WANG H H, et al.Thermal Stability of TaN, CrTaN, TaSiN, and CrTaSiN Hard Coatings in Oxygen-Containing Atmospheres[J]. Surface and Coatings Technology, 2014, 259: 159-166.
[16] ČEKADA M, PANJAN P, NAVINŠEK B, et al. Characterization of (Cr, Ta) N Hard Coatings Reactively Sputtered at Low Temperature[J]. Vacuum, 1999, 52(4): 461-467.
[17] SCHALK N, POHLER M, HIRN S, et al.Microstructure, Mechanical Properties and Cutting Performance of Cr_1-_yTa_yN Single Layer and Ti_1-_xAl_xN/Cr_1-_yTa_yN Multilayer Coatings[J]. International Journal of Refractory Metals and Hard Materials, 2018, 71: 211-216.
[18] KAINZ C, SARINGER C, BURTSCHER M, et al.Oxidation Resistance of Cathodic Arc Evaporated Cr_0.74Ta_0.26N Coatings[J]. Scripta Materialia, 2022, 211: 114492.
[19] KAINZ C, POHLER M, GRUBER G C, et al.Influence of Bias Voltage on Microstructure, Mechanical Properties and Thermal Stability of Arc Evaporated Cr_0.74Ta_0.26N Coatings[J]. Surface and Coatings Technology, 2021, 417: 127212.
[20] RAOLE P M, NARSALE A M, KOTHARI D C, et al.Glancing-Angle X-Ray Diffraction and X-Ray Photoelectron Spectroscopy Studies of Nitrogen-Implanted Tantalum[J]. Materials Science and Engineering: A, 1989, 115: 73-77.
[21] LIU W D, JIAO D L, DING H Z, et al.Corrosion Resistance of CrN Film Deposited by High-Power Impulse Magnetron Sputtering on SS304 in a Simulated Environment for Proton Exchange Membrane Fuel Cells[J]. International Journal of Hydrogen Energy, 2023, 48(66): 25901-25917.
[22] DANIEL R, KECKES J, MATKO I, et al.Origins of Microstructure and Stress Gradients in Nanocrystalline Thin Films: The Role of Growth Parameters and Self- Organization[J]. Acta Materialia, 2013, 61(16): 6255-6266.
[23] PELLEG J, ZEVIN L Z, LUNGO S, et al.Reactive- Sputter-Deposited TiN Films on Glass Substrates[J]. Thin Solid Films, 1991, 197(1/2): 117-128.
[24] WANG Z B, LU J, LU K.Wear and Corrosion Properties of a Low Carbon Steel Processed by Means of SMAT Followed by Lower Temperature Chromizing Treatment[J]. Surface and Coatings Technology, 2006, 201(6): 2796-2801.
[25] SHI Z M, LIU M, ATRENS A.Measurement of the Corrosion Rate of Magnesium Alloys Using Tafel Extrapolation[J]. Corrosion Science, 2010, 52(2): 579-588.
[26] KLASSEN R D, ROBERGE P R.Role of solution resistance in measurements from atmospheric corrosivity sensors[C]//Corrosion 2003. Association for Materials Protection and Performance, 2003.
[27] MA C, WANG Z Q, BEHNAMIAN Y, et al.Measuring Atmospheric Corrosion with Electrochemical Noise: A Review of Contemporary Methods[J]. Measurement, 2019, 138: 54-79.
[28] KELLY R G, SCULLY J R, SHOESMITH D, et al.Electrochemical Techniques in Corrosion Science and Engineering[M]. Boca Raton: CRC Press, 2002.
[29] LIU C, BI Q, LEYLAND A, et al.An Electrochemical Impedance Spectroscopy Study of the Corrosion Behaviour of PVD Coated Steels in 0.5 N NaCl Aqueous Solution: Part II. EIS Interpretation of Corrosion Behaviour[J]. Corrosion Science, 2003, 45(6): 1257-1273.
[30] CUI S W, YIN X Y, YU Q L, et al.Polypyrrole Nanowire/TiO₂ Nanotube Nanocomposites as Photoanodes for Photocathodic Protection of Ti Substrate and 304 Stainless Steel under Visible Light[J]. Corrosion Science, 2015, 98: 471-477.
[31] 顾剑锋, 李沛, 钟庆东. 物理气相沉积在耐腐蚀涂层中的应用[J]. 材料导报, 2016, 30(9): 75-80.
GU J F, LI P, ZHONG Q D.Application of Physical Vapor Deposition in Corrosion Resistant Coatings[J]. Materials Review, 2016, 30(9): 75-80.
[32] MATSON D W, MCCLANAHAN E D, LEE S L, et al.Properties of Thick Sputtered Ta Used for Protective Gun Tube Coatings[J]. Surface and Coatings Technology, 2001, 146: 344-350.
[33] KIM J H, AKIYAMA E, HABAZAKI H, et al.The Corrosion Behavior of Sputter-Deposited Amorphous CR—NB and Cr—Ta Alloys in 12 M HCl Solution[J]. Corrosion Science, 1993, 34(12): 1947-1955.
[34] WU J, LU P, DONG L, et al.Combination of Plasma Electrolytic Oxidation and Pulsed Laser Deposition for Preparation of Corrosion-Resisting Composite Film on Zirconium Alloys[J]. Materials Letters, 2020, 262: 127080.