非晶包裹纳米晶核壳结构Ni-W涂层及其磨损行为研究

朱丽霞; 罗金恒; 龙岩; 王楠; 宋成立; 武刚; 李丽锋

doi:10.16490/j.cnki.issn.1001-3660.2026.17.005

PDF(12168 KB)

表面技术 ›› 2026, Vol. 55 ›› Issue (17) : 56-67. DOI: 10.16490/j.cnki.issn.1001-3660.2026.17.005

摩擦磨损与润滑

非晶包裹纳米晶核壳结构Ni-W涂层及其磨损行为研究

朱丽霞^1,*, 罗金恒¹, 龙岩¹, 王楠², 宋成立¹, 武刚¹, 李丽锋¹

作者信息 +

Ni-W Coatings with Amorphous-wrapped Nanocrystalline Core-shell Structure and Their Wear Performance

ZHU Lixia^1,*, LUO Jinheng¹, LONG Yan¹, WANG Nan², SONG Chengli¹, WU Gang¹, LI Lifeng¹

Author information +

文章历史 +

摘要

目的揭示电流密度调控下Ni-W涂层由晶态向非晶态的结构转变,阐明非晶包裹纳米晶核壳结构的形成机制及其对涂层耐磨性的增强机理。方法采用电沉积技术在10~30 A/dm²电流密度范围内制备Ni-W涂层。利用SEM、EDS、XRD、TEM表征涂层的微观形貌、元素组成、物相结构及微观组织;通过往复摩擦磨损试验测试涂层的摩擦系数与磨损率,结合白光干涉仪分析磨损轨迹,采用划痕测试仪评价涂层结合力;并借助分子动力学模拟揭示原子尺度的磨损行为。结果随着电流密度由10 A/dm²增至30 A/dm²,涂层中的W质量分数由24.6%提高至44.8%,结构由晶态转变为非晶态。W质量分数为44.8%的非晶涂层中形成了Ni₄W纳米析出相（8~10 nm）被非晶所包裹的核壳结构。该非晶涂层与基体结合力达103.6 N,平均摩擦系数为0.42,较晶态涂层综合性能明显提升;其磨损轨迹浅而窄,磨损机制以磨粒磨损为主。分子动力学模拟结果显示,滑动距离为18 nm时,晶态与非晶涂层的磨损原子数分别为7 619个与6 872个,验证了非晶涂层优异的耐磨性。结论通过调控电流密度可实现Ni-W涂层由晶态向非晶态的结构转变,并在高W含量非晶涂层中形成非晶包裹Ni₄W纳米晶的核壳结构。该结构通过表层非晶的高硬度与抗塑性变形能力、亚表面核壳结构对应力集中的协调缓解以及Ni₄W相的析出强化,协同提升强度与耐磨性。

Abstract

The work aims to propose and construct a novel amorphous-wrapped nanocrystalline core-shell structure to reveal the current density-controlled structural transition of Ni-W coatings from crystalline to amorphous, to elucidate the formation mechanism of the core-shell structure and its synergistic enhancement mechanism on the wear resistance of the coating, and to provide new insights into the structural design of high-performance wear-resistant protective coatings. Ni-W coatings were prepared by electrodeposition within a current density range of 10 to 30 A/dm². The microstructure, elemental composition, phase constituents, and morphology of the coatings were systematically characterized by SEM, EDS, XRD, and TEM. The friction coefficient and wear rate were evaluated through reciprocating sliding wear tests, and the three-dimensional morphology of the wear tracks was analyzed with a white light interferometer. The adhesion strength of the coatings was assessed with a scratch tester. In addition, molecular dynamics simulations were employed to investigate the intrinsic wear behavior of the coatings at the atomic scale. The results showed that as the current density increased from 10 A/dm² to 30 A/dm², the tungsten content in the coatings increased from 24.6wt.% to 44.8wt.%, accompanied by a structural transition from crystalline to amorphous. TEM analysis confirmed that in the amorphous coating with a tungsten content of 44.8wt.% and a core-shell structure was formed, consisting of Ni₄W nanoprecipitates (8-10 nm) uniformly distributed within and encapsulated by the amorphous matrix. The formation of this structure was attributed to the preferential segregation of W atoms at grain boundaries, which induced lattice distortion and subsequently promoted a local transition from crystalline to amorphous. Wear performance tests revealed that the amorphous coating with the core-shell structure exhibited an adhesion strength of 103.6 N and an average friction coefficient of 0.42. The wear track of the amorphous coating was shallow and narrow, and the dominant wear mechanism was identified as abrasive wear, in sharp contrast to the typical adhesive wear observed in the crystalline coating. Molecular dynamics simulations further verified the superior wear resistance of the amorphous coating at the atomic scale: at a sliding distance of 18 nm, the number of worn atoms in the amorphous coating (6 872) was significantly lower than that in the crystalline coating (7 619). In this study, a core-shell structure consisting of Ni₄W nanocrystals wrapped by an amorphous phase was constructed, and its wear resistance enhancement mechanism was elucidated through three synergistic effects: the high hardness and plastic deformation resistance of the surface amorphous layer, the mitigation of stress concentration through coordinated deformation in the subsurface core-shell structure, and the precipitation strengthening effect of the Ni₄W phase. This structural design enabled a synergistic enhancement of strength and wear resistance. This study provides a new theoretical basis for the performance optimization of Ni-W coatings and offers a novel technical approach for the development of other metal-based wear-resistant coatings.

导出引用

朱丽霞, 罗金恒, 龙岩, 王楠, 宋成立, 武刚, 李丽锋. 非晶包裹纳米晶核壳结构Ni-W涂层及其磨损行为研究[J]. 表面技术. 2026, 55(17): 56-67

ZHU Lixia, LUO Jinheng, LONG Yan, WANG Nan, SONG Chengli, WU Gang, LI Lifeng. Ni-W Coatings with Amorphous-wrapped Nanocrystalline Core-shell Structure and Their Wear Performance[J]. Surface Technology. 2026, 55(17): 56-67

中图分类号： TH117

参考文献

[1] HASEEB A S M A, ALBERS U, BADE K. Friction and Wear Characteristics of Electrodeposited Nanocrystalline Nickel-Tungsten Alloy Films[J]. Wear, 2008, 264(1/2): 106-112.
[2] SHACHAM-DIAMAND Y, SVERDLOV Y.Electrochemically Deposited Thin Film Alloys for ULSI and MEMS Applications[J]. Microelectronic Engineering, 2000, 50(1/2/3/4): 525-531.
[3] SRIRAMAN K R, GANESH SUNDARA RAMAN S, SESHADRI S K. Synthesis and Evaluation of Hardness and Sliding Wear Resistance of Electrodeposited Nanocrystalline Ni-W Alloys[J]. Materials Science and Engineering: A, 2006, 418(1/2): 303-311.
[4] ZHONG Z M, CLOUSER S J.Nickel-Tungsten Alloy Brush Plating for Engineering Applications[J]. Surface and Coatings Technology, 2014, 240: 380-386.
[5] ELIAZ N, SRIDHAR T M, GILEADI E.Synthesis and Characterization of Nickel Tungsten Alloys by Electrodeposition[J]. Electrochimica Acta, 2005, 50(14): 2893-2904.
[6] ALIMADADI H, AHMADI M, ALIOFKHAZRAEI M, et al.Corrosion Properties of Electrodeposited Nanocrystalline and Amorphous Patterned Ni-W Alloy[J]. Materials & Design, 2009, 30(4): 1356-1361.
[7] KIRIHARA S, UMEDA Y, TASHIRO K, et al.Development of Ni-W Alloy Plating as a Substitution of Hard Chromium Plating[J]. Transactions of the Materials Research Society of Japan, 2016, 41(1): 35-39.
[8] WU Y Y, CHANG D, KIM D, et al.Influence of Boric Acid on the Electrodepositing Process and Structures of Ni-W Alloy Coating[J]. Surface and Coatings Technology, 2003, 173(2/3): 259-264.
[9] KRÓLIKOWSKI A, PŁOŃSKA E, OSTROWSKI A, et al. Effects of Compositional and Structural Features on Corrosion Behavior of Nickel-Tungsten Alloys[J]. Journal of Solid State Electrochemistry, 2009, 13(2): 263-275.
[10] HE F J, YANG J, LEI T X, et al.Structure and Properties of Electrodeposited Fe-Ni-W Alloys with Different Levels of Tungsten Content: A Comparative Study[J]. Applied Surface Science, 2007, 253(18): 7591-7598.
[11] LIU B, YAN S M, HE Y, et al.Study on Wear Resistance and Corrosion Resistance of Zirconium Phenylphosphonate Reinforced Ni-W Composite Coating[J]. Applied Surface Science, 2022, 603: 154483.
[12] AMADEH A A, SANI M H, MORADI H.Wear Behavior of Carbon Steel Electrodeposited by Nanocrystalline Ni-W Coating[J]. International Journal of Iron & Steel Society of Iran, 2009, 6(2): 14-19.
[13] KUPTSOV K A, ANTONYUK M N, BONDAREV A V, et al.Electrospark Deposition of Wear and Corrosion Resistant Ta(Zr)C-(Fe, Mo, Ni) Coatings to Protect Stainless Steel from Tribocorrosion in Seawater[J]. Wear, 2021, 486: 204094.
[14] GUO B S, NI S, SHEN R J, et al.Fabrication of Ti-Al₃Ti Core-Shell Structured Particle Reinforced Al Based Composite with Promising Mechanical Properties[J]. Materials Science and Engineering: A, 2015, 639: 269-273.
[15] CHEN T J, GENG L B, QIN H, et al.Core-Shell- Structured Particle Reinforced A356 Matrix Composite Prepared by Powder-Thixoforming: Effect of Reheating Temperature[J]. Materials, 2018, 11(9): 1718.
[16] DETOR A J, SCHUH C A.Tailoring and Patterning the Grain Size of Nanocrystalline Alloys[J]. Acta Materialia, 2007, 55(1): 371-379.
[17] SRIRAMAN K R, GANESH SUNDARA RAMAN S, SESHADRI S K. Synthesis and Evaluation of Hardness and Sliding Wear Resistance of Electrodeposited Nanocrystalline Ni-W Alloys[J]. Materials Science and Engineering: A, 2006, 418(1/2): 303-311.
[18] ROFAGHA R, SPLINTER S J, ERB U, et al.XPS Characterization of the Passive Films Formed on Nanocrystalline Nickel in Sulphuric Acid[J]. Nanostructured Materials, 1994, 4(1): 69-78.
[19] DETOR A J, SCHUH C A.Tailoring and Patterning the Grain Size of Nanocrystalline Alloys[J]. Acta Materialia, 2007, 55(1): 371-379.
[20] DETOR A J, SCHUH C A. Grain Boundary Segregation, Chemical Ordering and Stability of Nanocrystalline Alloys: Atomistic Computer Simulations in the Ni-W System[J]. Acta Materialia, 2007, 55(12): 4221-4232.
[21] JUŠKĖNAS R, VALSIŪNAS I, PAKŠTAS V, et al. On the State of W in Electrodeposited Ni-W Alloys[J]. Electrochimica Acta, 2009, 54(9): 2616-2620.
[22] SRIDHAR T M, ELIAZ N, GILEADI E.Electroplating of Ni₄W[J]. Electrochemical and Solid-State Letters, 2005, 8(3): C58.
[23] VAMSI M V N, WASEKAR N P, SUNDARARAJAN G. Influence of Heat Treatment on Microstructure and Mechanical Properties of Pulse Electrodeposited Ni-W Alloy Coatings[J]. Surface and Coatings Technology, 2017, 319: 403-414.
[24] ALLAHYARZADEH M H, ALIOFKHAZRAEI M, REZVANIAN A R, et al.Ni-W Electrodeposited Coatings: Characterization, Properties and Applications[J]. Surface and Coatings Technology, 2016, 307: 978-1010.
[25] BRANDL C, GERMANN T C, MISRA A.Structure and Shear Deformation of Metallic Crystalline-Amorphous Interfaces[J]. Acta Materialia, 2013, 61(10): 3600-3611.
[26] LIU C, LI Z M, LU W J, et al.Reactive Wear Protection through Strong and Deformable Oxide Nanocomposite Surfaces[J]. Nature Communications, 2021, 12: 5518.
[27] MENG A, LIANG F, GU L, et al.An Exceptionally Wear-Resistant CoFeNi₂ Medium Entropy Alloy via Tribo-Induced Nanocrystallites with Amorphous Boundaries[J]. Applied Surface Science, 2023, 614: 156102.
[28] HONG Q, ZHOU R C, GUO X P, et al.A Novel Strategy for Improving the Wear Resistance of Electrodeposited Ni-Diamond Composite Coatings by Diamond Surface Morphology Modification[J]. Diamond and Related Materials, 2023, 137: 110093.
[29] LAVAKUMAR B, PRASAD M J N V, PHANI P S, et al. Influence of Compositional and Microstructural Gradient on the Wear Performance of Nanocrystalline Ni-W Coatings[J]. Wear, 2023, 530/531: 205039.
[30] VAN HAU T, VAN DUONG L, HONG HANH P, et al.Hexagonal Boron Nitride Nanosheets Reinforcing Ni-Mo Alloy Coating for Improved Wear Resistance[J]. Materials Letters, 2023, 352: 135054.
[31] KOUSAR H, UMER M A, SHEHZAD K, et al.Exceptional Mechanical Properties and Wear Behavior of Al₂O₃ Nanoparticle Reinforced Ni-W-P Coatings[J]. Tribology International, 2024, 194: 109533.
[32] SATTAWITCHAYAPIT S, YORDSRI V, WUTIKHUN T, et al.Stress-Induced, Debris-Modulated Friction and Wear Resistance Performance of Nanostructured Ni-Co Coatings[J]. Wear, 2024, 538: 205184.
[33] SHEU H H, WANG Q Y, LEE Y W.Effects of Boron Carbide Particle Content on Corrosion Resistance and Wear Resistance of Ni-B/B₄C Composite Coatings[J]. International Journal of Electrochemical Science, 2022, 17(11): 221166.
[34] HUANG P C, HOU K H, HONG J J, et al.Study of Fabrication and Wear Properties of Ni-SiC Composite Coatings on A356 Aluminum Alloy[J]. Wear, 2021, 477: 203772.
[35] FU X Q, SHI X X, DUAN S L, et al.Studies on the Wear and Corrosion Resistance of Ni-Fe-Co-P-GO Composite Coating Prepared by Scanning Electrodeposition[J]. International Journal of Electrochemical Science, 2020, 15(7): 6448-6463.
[36] ZHANG D Y, PENG Z J, LIU Z L, et al.Study on Wear Protection Performance of HVAF WC-Cr₃C₂-Ni Coatings Deposited on Crystallizer Surface[J]. Surface and Coatings Technology, 2024, 481: 130640.
[37] PURUSHOTHAM N, L P N, SURESH BABU P, et al. High Temperature Sliding Wear Behavior of Detonation Sprayed Ni-5wt.%Al Coating[J]. Wear, 2023, 530/531: 205030.
[38] PURUSHOTHAM N, PARTHASARATHI N L, BABU P S, et al.Effect of Thermal Expansion on the High Temperature Wear Resistance of Ni-20%Cr Detonation Spray Coating on IN718 Substrate[J]. Surface and Coatings Technology, 2023, 462: 129490.
[39] ALIDOKHT S A, CHROMIK R R.Sliding Wear Behavior of Cold-Sprayed Ni-WC Composite Coatings: Influence of WC Content[J]. Wear, 2021, 477: 203792.
[40] ALIDOKHT S A, WU L, BESSETTE S, et al.Microstructure and Tribology of Cold Spray Additively Manufactured Multimodal Ni-WC Metal Matrix Composites[J]. Wear, 2024, 538: 205218.
[41] CUI W Q, LI Y L, LI F Y, et al.Wear and Corrosion Properties of In-Situ TiC-TiB₂ Modified Ni-Based Composite Coatings with Different B/C Ratios Prepared by Laser Cladding[J]. Ceramics International, 2024, 50(1): 2424-2435.
[42] YANG C M, LIU X B, ZHU Z X, et al.Study of Tribological Property of Laser-Cladded FeCoCrNiMn_x High-Entropy Alloy Coatings via Experiment and Molecular Dynamics Simulation[J]. Tribology International, 2024, 191: 109106.
[43] LIANG J, LIU Y, YANG S, et al.Microstructure and Wear Resistance of Laser Cladding Ti-Al-Ni-Si Composite Coatings[J]. Surface and Coatings Technology, 2022, 445: 128727.
[44] YU H, LUO Z A, WANG Y H, et al.Influence of Ni Content on the Microstructure and Reciprocating Wear of Fe-Based/B₄C Composite Coating by Vacuum Cladding[J]. Surface and Coatings Technology, 2021, 423: 127604.
[45] YU T, TANG H Y.Microstructure and High-Temperature Wear Behavior of Laser Clad TaC-Reinforced Ni-Al-Cr Coating[J]. Applied Surface Science, 2022, 592: 153263.
[46] YANG Z R, LIANG H F, ZHANG H H, et al.A Novel Wear-Resistant and Corrosion-Resistant Mo₂NiB₂-Ni Cermet Coating Prepared Using Fast Hot Pressing Sintering[J]. Materials Chemistry and Physics, 2024, 318: 129242.
[47] CHEN X, HAN Z, LI X Y, et al.Friction of Stable Gradient Nano-Grained Metals[J]. Scripta Materialia, 2020, 185: 82-87.
[48] TIAN P Y, KHUN N W, TOR S B, et al.Tribological Behavior of Zr-Based Bulk Metallic Glass Sliding Against Polymer, Ceramic, and Metal Materials[J]. Intermetallics, 2015, 61: 1-8.
[49] LIU J H, LIU Y D, PEI Z L, et al. Influence of Particle Size and Content on the Friction and Wear Behaviors of As-Annealed Ni-Mo/Diamond Composite Coatings[J]. Wear, 2020, 452/453: 203300.
[50] LIU J H, YAN J X, PEI Z L, et al.Effects of Mo Content on the Grain Size, Hardness and Anti-Wear Performance of Electrodeposited Nanocrystalline and Amorphous Ni-Mo Alloys[J]. Surface and Coatings Technology, 2020, 404: 126476.