纳米ZrB2 增强CoNiCrAlY复合粉末的机械合金化制备及其涂层的组织与性能

doi:10.11900/0412.1961.2023.00177

金属学报

2025, Vol. 61

Issue (4): 619-631 DOI: 10.11900/0412.1961.2023.00177

研究论文

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纳米ZrB₂ 增强CoNiCrAlY复合粉末的机械合金化制备及其涂层的组织与性能

杨康, 辛越, 姜自滔, 刘侠, 薛召露, 张世宏(

)

安徽工业大学先进金属材料绿色制备与表面技术教育部重点实验室马鞍山 243002

Mechanical Alloying Fabrication of Nano-ZrB₂-Reinforced CoNiCrAlY Composite Powders and Microstructure-Property Characterization of the Resultant Coatings

YANG Kang, XIN Yue, JIANG Zitao, LIU Xia, XUE Zhaolu, ZHANG Shihong(

)

Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials, Ministry of Education, Anhui University of Technology, Ma'anshan 243002, China

引用本文:

杨康, 辛越, 姜自滔, 刘侠, 薛召露, 张世宏. 纳米ZrB₂ 增强CoNiCrAlY复合粉末的机械合金化制备及其涂层的组织与性能[J]. 金属学报, 2025, 61(4): 619-631.
Kang YANG, Yue XIN, Zitao JIANG, Xia LIU, Zhaolu XUE, Shihong ZHANG. Mechanical Alloying Fabrication of Nano-ZrB₂-Reinforced CoNiCrAlY Composite Powders and Microstructure-Property Characterization of the Resultant Coatings[J]. Acta Metall Sin, 2025, 61(4): 619-631.

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摘要:

针对高温炉辊在高温重载环境下的氧化、磨损等失效问题，采用一步式和分步式机械合金化(MA)工艺分别合成了2种CoNiCrAlY-20%ZrB₂ (质量分数)复合粉末并制备成涂层，对其组织和性能进行了研究。结果表明，用分步式MA成功合成了纳米ZrB₂增强的CoNiCrAlY复合粉末，较一步式球磨，分步式球磨的ZrB₂颗粒更加均匀地分布在金属基体相中。分步式MA球磨35 h复合粉末的平均粒径符合超音速火焰喷涂(HVOF)要求。采用HVOF制备复合涂层，发现分步式MA粉末制备的涂层熔化状态较一步式MA粉末制备的涂层更好，且分步式涂层孔隙率更低、硬度更高、韧性更强。2种涂层在750 ℃以上均具有良好的自润滑能力，且在950 ℃时涂层表面形成了连续完整的“上釉层”。950 ℃时分步式涂层磨损率比一步式涂层低了60%，说明在高温环境下分步式涂层具有更好的耐磨性能。此外，与纯CoNiCrAlY涂层相比，纳米ZrB₂颗粒加入可以显著提升涂层的高温摩擦磨损性能。

关键词 ：机械合金化, HVOF, CoNiCrAlY-ZrB₂复合涂层, 高温摩擦磨损

Abstract：

High-temperature furnace rolls are subjected to extreme conditions, including high temperatures and heavy loads, rendering them susceptible to oxidation, wear, and other forms of failure. To address these issues, this study investigates the preparation and properties of CoNiCrAlY-ZrB₂ composite powders and coatings. CoNiCrAlY serves as the metal matrix, and ZrB₂ acts as the ceramic reinforcement phase. Two variants of CoNiCrAlY-20%ZrB₂ (mass fraction) composite powders were fabricated using one-step and step-fashion mechanical alloying (MA) techniques (marked by MA-1 and MA-2, respectively). The microstructure and phase composition of the coatings were studied using SEM, XRD, and TEM. Mechanical properties were also investigated. High-temperature friction and wear tests were conducted at 550-950 ^oC. Results indicate that the particle size of the composite powder decreases with increasing MA time. Step-fashion MA successfully produced ZrB₂-reinforced CoNiCrAlY composite powder, with ZrB₂ particles evenly distributed throughout the CoNiCrAlY matrix. When alloyed for 35 h, the average particle size (D₅₀ = 38.6 μm) met the specifications for high-velocity oxygen-fuel (HVOF) spraying. CoNiCrAlY-20%ZrB₂ composite coatings were then prepared via HVOF spraying. Coatings derived from MA-2 powders exhibited higher melting states, denser microstructures, and lower porosity (0.28%) compared to those made with MA-1 powders. These coatings also displayed superior hardness (738 HV_0.3) and fracture toughness (5.21 MPa·m^1/2). High-temperature wear resistance was tested for both MA-1 and MA-2 composite coatings. At 950 ^oC, a protective glazing layer of Al₂O₃, Cr₂O₃, and CoCr₂O₄ was formed on the surface of the composite coatings. The coatings demonstrated effective self-lubrication at 750 ^oC due to the formation of the “glazing layer”. Above 750 ^oC, the MA-2 composite coating outperformed the one-step coating in wear resistance. Specifically, at 950 ^oC, the wear rate of the MA-2 composite coating was 1.71 × 10^-14 m³·N^-1·m^-1, considerably lower than that of the MA-1 composite coating (4.28 × 10^-14 m³·N^-1·m^-1). In conclusion, the addition of ZrB₂ nanoparticles to the CoNiCrAlY coating considerably enhanced its friction and wear properties at high temperatures. The step-fashion mechanical alloying method demonstrated superior coating density, hardness, and high-temperature wear resistance.

Key words： mechanical alloying HVOF CoNiCrAlY-ZrB₂ composite coating high-temperature friction and wear

收稿日期: 2023-04-21

ZTFLH:

TG174.442

基金资助:国家自然科学基金项目(U22A20110);安徽省杰出青年项目(2108085J22)

通讯作者: 张世宏，shzhang@ahut.edu.cn，主要从事金属表面科学与技术研究

Corresponding author: ZHANG Shihong, professor, Tel: (0555)2315291, E-mail: shzhang@ahut.edu.cn

作者简介: 杨康，男，1994年生，博士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2023.00177 或 https://www.ams.org.cn/CN/Y2025/V61/I4/619

表1 CoNiCrAlY粉末及ZrB2陶瓷粉末化学成分 (mass fraction / %)

图1 球磨不同时间后一步式和分步式机械合金化(MA-1和MA-2)工艺制备的复合粉末筛分前表面形貌SEM像

图2 球磨不同时间后MA-1、MA-2复合粉末的平均粒径(D50)及筛分后质量占比

图3 一步式30 h和分步式35 h复合粉末的截面SEM像和EDS元素分布图

图4 CoNiCrAlY、MA-1及MA-2涂层的XRD谱

图5 不同涂层喷涂态的表面形貌及截面形貌

图6 MA-2涂层的TEM像、HRTEM像及选区电子衍射花样和EDS结果

表2 3种涂层的孔隙率、显微硬度、断裂韧性及结合强度

图7 3种涂层在不同温度下的摩擦系数(COF)曲线

图8 3种涂层在不同温度下的平均COF和磨损率

图9 3种涂层磨痕的2D形貌

图10 不同温度下CoNiCrA1Y涂层的磨损表面形貌SEM像

表3 不同温度下CoNiCrA1Y涂层磨损表面的EDS分析 (mass fraction / %)

表4 不同温度下MA-1涂层磨损表面的EDS分析 (in Fig.11)(mass fraction / %)

表5 不同温度下MA-2涂层磨损表面的EDS分析 (mass fraction / %)

图11 不同温度下MA-1涂层的磨损表面形貌SEM像

图12 不同温度下MA-2涂层的磨损表面形貌SEM像

图13 不同温度下涂层摩擦磨损后磨痕的Raman光谱

表6 本工作与其他文献报道[2,5,19,24,25]的COF和磨损率比较

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