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金属学报  2019, Vol. 55 Issue (5): 647-656    DOI: 10.11900/0412.1961.2018.00285
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电弧复合磁控溅射结合热退火制备Ti2AlC涂层
李文涛1,2,王振玉2,张栋2,潘建国1,柯培玲2(),汪爱英2
1. 宁波大学材料科学与化学工程学院 宁波 315201
2. 中国科学院宁波材料技术与工程研究所中国科学院海洋新材料与应用技术重点实验室 宁波 315201
Preparation of Ti2AlC Coating by the Combination of a Hybrid Cathode Arc/Magnetron Sputtering with Post-Annealing
Wentao LI1,2,Zhenyu WANG2,Dong ZHANG2,Jianguo PAN1,Peiling KE2(),Aiying WANG2
1. Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315201, China
2. Key Laboratory of Marine Materials and Related Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
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摘要: 

利用电弧复合磁控溅射技术制备不同Ti/Al比的Ti-Al-C涂层,结合后续的退火处理制备Ti2AlC相涂层。利用SEM、EDS、XRD、Raman光谱仪和TEM等研究了Ti/Al比及退火温度对退火后Ti-Al-C涂层的相和微观结构的影响。结果表明,Ti-Al-C沉积态涂层为富Al层和TiCx层交替堆垛的多层结构,涂层表面大颗粒较少且结构致密。Ti/Al比对退火后涂层中的相结构有重要的影响:当Ti/Al比为2.04时,退火后涂层中Ti2AlC的纯度和结晶度最高;Ti/Al比过高(3.06)时,退火后涂层中形成TiC和Ti3AlC杂质相,而低Ti/Al比(0.54)则大幅度降低Ti2AlC相的纯度和结晶度。同时,退火温度很大程度影响Ti2AlC相的形成,当沉积态涂层中Ti/Al比为2.38时,Ti2AlC相涂层形成的最佳退火温度为750 ℃,偏低的退火温度(600 ℃)下,原子不能充分扩散,难以形成211结构的Ti2AlC相,而退火温度过高时(900 ℃)涂层中存在较多的TiC、TiAlx等杂质相。

关键词 电磁复合磁控溅射Ti2AlCTi-Al-C涂层Ti/Al比退火温度    
Abstract

Nuclear power generation provides a reliable and economic supply of electricity, due to low carbon emissions and relatively few waste. However, the reaction between zirconium and steam at high temperature is accompanied by the release of large amounts of hydrogen gas, which will bring serious consequences. After the Fukushima nuclear accident, the concept of accident-tolerant fuels (ATF) has been proposed and widely investigated. In terms of nuclear claddings, one key requirement is reduced oxidation kinetics with high-temperature steam and hence significantly reduced heat and hydrogen generation. An economical and simple method could be the preparation of protective coatings on the surface of zirconium alloys to improve the oxidation resistance. The MAX phase has been considered to be one of the most promising coating materials for nuclear cladding coatings. In this work, Ti-Al-C coatings with different Ti/Al ratios have been deposited on Zirlo alloy using a hybrid arc/magnetron sputtering method, and the Ti2AlC coatings were obtained by post-annealing. The effects of Ti/Al ratios and annealing temperatures on the phase and microstructure of Ti-Al-C coatings after annealing were studied by SEM, EDS, XRD, Raman spectrometer and TEM. It is found that Ti-Al-C coatings with different Ti/Al ratios deposited by the hybrid cathode arc/magnetron sputtering are a multi-layer structure of an alternative Al-rich layer and TiCx layer. The as-deposited coatings are compact with a small amount of large particles. The Ti/Al ratio has an important influence on the phase structure of the annealed coating. When the Ti/Al ratio is 2.04, the highest purity and crystallinity of Ti2AlC are obtained. TiC and Ti3AlC impurities will form within the coating at a higher Ti/Al ratio (3.06), while the purity and crystallinity of Ti2AlC will decrease at a lower Ti/Al ratio (0.54). In addition, the annealing temperature affects the formation of Ti2AlC to a great extent. When the Ti/Al ratio is 2.38, the optimum temperature for Ti-Al-C coatings to Ti2AlC coatings is at 750 ℃. The atom cannot diffuse fully at a lower annealing temperature (600 ℃), which is difficult to form the Ti2AlC phase, while a higher annealing temperature (900 ℃) will enable the formation of Ti2AlC coatings with more TiC, TiAlx and other impurities.

Key wordshybrid cathode arc/magnetron sputtering    Ti2AlC    Ti-Al-C coating    Ti/Al ratio    annealing temperature
收稿日期: 2018-06-29     
ZTFLH:  TB37  
基金资助:国家重大科技专项项目(2015ZX06004-001);中国博士后基金项目(2018M632513);浙江省自然科学基金项目(LQ19E01002);宁波市工业重点攻关项目(2017B10042)
通讯作者: 柯培玲     E-mail: kepl@nimte.ac.cn
Corresponding author: Peiling KE     E-mail: kepl@nimte.ac.cn
作者简介: 李文涛,男,1988年生,硕士生

引用本文:

李文涛,王振玉,张栋,潘建国,柯培玲,汪爱英. 电弧复合磁控溅射结合热退火制备Ti2AlC涂层[J]. 金属学报, 2019, 55(5): 647-656.
Wentao LI, Zhenyu WANG, Dong ZHANG, Jianguo PAN, Peiling KE, Aiying WANG. Preparation of Ti2AlC Coating by the Combination of a Hybrid Cathode Arc/Magnetron Sputtering with Post-Annealing. Acta Metall Sin, 2019, 55(5): 647-656.

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2018.00285      或      https://www.ams.org.cn/CN/Y2019/V55/I5/647

图1  电弧复合磁控溅射示意图

Procedure

Ar flow

mL·min-1

CH4 flow

mL·min-1

Presure

Pa

Bias voltage

V

Current / A
Ion gunArcSputter
Etching40---3000.2--
TiC layer200503.99-100-70-
Ti-Al-C layer200153.99-200-608.0
表1  Ti-Al-C涂层沉积参数
SampleNo.1No.2No.3No.4No.5
As-deposited2.382.041.640.660.42
As-annealed3.061.751.090.990.54
表2  No.1~No.5样品中涂层在沉积态和退火态时的Ti/Al比
图2  No.1~No.5沉积态涂层表面形貌的SEM像
图3  No.1~No.5退火态涂层表面形貌的SEM像
图4  No.1~No.5退火态涂层截面形貌的SEM像
图5  No.2和No.4样品经800 ℃退火1 h后截面的线扫描图及面分布图
图6  No.1~No.5样品经800 ℃退火1 h后的XRD谱
图7  No.1样品退火前后的Raman光谱
图8  No.1样品中涂层在沉积态及800 ℃退火1 h后的HRTEM分析
图9  No.1样品沉积态及经不同温度退火1 h后表面形貌的SEM像
图10  No.1样品沉积态及经不同温度退火1 h后的截面形貌及线扫描图
图11  No.1样品经600~900 ℃退火1 h后的XRD谱
图12  No.1样品经600~900 ℃退火1 h后的Raman光谱
图13  No.1样品(0002)和(10$\bar{1}$3)晶面处晶粒尺寸随退火温度的变化
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