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金属学报  2018, Vol. 54 Issue (8): 1193-1203    DOI: 10.11900/0412.1961.2017.00491
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铝基非晶纳米晶复合涂层显微组织与腐蚀性能研究
梁秀兵1,2(), 范建文1, 张志彬1, 陈永雄1,2
1 陆军装甲兵学院机械产品再制造国家工程研究中心 北京 100072
2 军事科学院国防科技创新研究院 北京 100071
Microstructure and Corrosion Properties of Aluminum Base Amorphous and Nanocrystalline Composite Coating
Xiubing LIANG1,2(), Jianwen FAN1, Zhibin ZHANG1, Yongxiong CHEN1,2
1 National Engineering Research Center for Mechanical Product Remanufacturing, Academy of Armored Army Forces, Beijing 100072, China
2 Innovation Research Institute of National Defense Science and Technology, Academy of Military Sciences, Beijing 100071, China
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摘要: 

针对钢结构材料易腐蚀问题,采用高速电弧喷涂技术在45钢表面制备了含有高非晶含量的Al-Ni-Zr非晶纳米晶复合涂层,研究了复合涂层的显微组织、宏观腐蚀性能和微区腐蚀性能。利用XRD、SEM、EDS和TEM等技术手段,确定了复合涂层微观结构中灰色组织区为非晶富集区;采用扫描Kelvin探针显微镜技术(SKPM),发现复合涂层各相腐蚀的先后顺序依次为:富Al相、氧化物相、非晶相。复合涂层显微硬度高于45钢,约为364 HV0.1。EIS拟合结果显示,复合涂层电荷转移电阻为纯Al涂层和45钢的2~4倍,具有2个时间常数,低频区受扩散过程控制,主要与腐蚀产物的堆积和扩散有关;动电位极化曲线拟合结果显示,复合涂层的自腐蚀电位正于纯Al涂层和45钢,自腐蚀电流密度为1.08 μA/cm2,分别是纯Al涂层和45钢的7/100和1/3。复合涂层的腐蚀形貌显示,涂层表面无明显点蚀,富Al相区表面附着大量的NaCl晶体,为优先腐蚀区,而非晶富集区表面光滑平整;同时,涂层出现了腐蚀坑、微裂纹和点蚀富集等,主要与Cl-的侵蚀作用和涂层受到溶胀作用有关。

关键词 铝基非晶纳米晶复合涂层微区腐蚀耐蚀性钢结构表面防护    
Abstract

It is easy to corrode the steel structural materials. In view of this problem, the Al-Ni-Zr amorphous and nanocrystalline composite coating with high amorphous volume was prepared by high velocity arc spraying on the 45 steel. The microstructure, macroscopic corrosion performance and microzone corrosion performance of the composite coating was investigated. XRD, SEM with EDS and TEM were applied to confirm that the gray zone of the composite coating microstructure was the amorphous enrichment zone. It was found by the scanning Kelvin probe microscopy (SKPM) that the corrosion failure order of each phase of the composite coating was arranged in order of the aluminum rich phases, the oxidation phases and the amorphous phase. The microhardness of the composite coating was about 364 HV0.1 which was greater than that of 45 steel. The EIS fitting results showed that the charge transfer resistance of the composite coating is 2~4 times of the aluminum coating and 45 steel. It has two time constants in the spectrum. The corrosion failure behavior of the composite coating in the low frequency was controlled by the diffusion process, which was related to the accumulation and diffusion of the corrosion products. The potentiodynamic polarization curves fitting results indicated that the self-corrosion potential of the composite coating was higher than those of the aluminum coating and 45 steel. And the self-corrosion current density of the composite coating was about 1.08 μA/cm2, which was 7/100 and 1/3 of that of the aluminum coating and 45 steel, respectively. According to the corrosion morphology of the composite coating, there was no obvious pitting. A large number of NaCl crystals were attached to the surface of the aluminum rich phase region as the preferred corrosion zone. But the surface of the amorphous enrichment zone was smooth. At the same time, the corrosion pits, micro-cracks and pitting enrichment occurred on the surface of the composite coating, which was mainly related to the effects of Cl- erosion and swelling.

Key wordsaluminum base amorphous and nanocrystalline composite coating    microzone corrosion    corrosion resistance    surface protection for steel structure
收稿日期: 2017-11-27     
ZTFLH:  TG174.4  
基金资助:国家自然科学基金项目Nos.51505500和51375492
作者简介:

作者简介 梁秀兵,男,1974年生,研究员,博士

引用本文:

梁秀兵, 范建文, 张志彬, 陈永雄. 铝基非晶纳米晶复合涂层显微组织与腐蚀性能研究[J]. 金属学报, 2018, 54(8): 1193-1203.
Xiubing LIANG, Jianwen FAN, Zhibin ZHANG, Yongxiong CHEN. Microstructure and Corrosion Properties of Aluminum Base Amorphous and Nanocrystalline Composite Coating. Acta Metall Sin, 2018, 54(8): 1193-1203.

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2017.00491      或      https://www.ams.org.cn/CN/Y2018/V54/I8/1193

图1  铝基非晶纳米晶Al-Ni-Zr复合涂层和纯Al涂层的XRD谱
图2  Al-Ni-Zr复合涂层和纯Al涂层横截面的SEM像
图3  Al-Ni-Zr复合涂层横截面形貌的高倍SEM像
Zone Al Ni Zr O
I 16.28 21.75 25.84 36.13
II 68.60 19.55 6.01 5.84
III 74.67 15.76 5.81 3.76
IV 86.47 7.17 2.25 4.11
表1  图3中Al-Ni-Zr复合涂层的SEM-EDS分析
图4  Al-Ni-Zr复合涂层TEM明场像及选区电子衍射(SAED)花样
Zone Al Ni Zr
I 74.30 18.58 7.12
II 88.79 8.48 2.73
III 100.00 - -
表2  图4中Al-Ni-Zr复合涂层的TEM-EDS分析
图5  Al-Ni-Zr复合涂层截面方向显微硬度
图6  Al-Ni-Zr复合涂层、纯Al涂层和45钢在3.5%NaCl溶液中的动电位极化曲线
Sample Ecorr / V icorr / (μAcm-2) Rp / (kΩcm-2) βA / mV βC / mV
Al-Ni-Zr coating -0.645 1.08 24.51 108.0 140
Al coating -1.297 15.46 3.99 1167.5 162
45 steel -0.712 3.72 7.62 76.1 458
表3  动电位极化曲线拟合结果
图7  Al-Ni-Zr复合涂层、纯Al涂层和45钢在3.5%NaCl溶液中的Nyquist曲线
图8  45钢、纯Al涂层、Al-Ni-Zr复合涂层和Al-Ni-Zr复合涂层超声清洗后的腐蚀形貌
图9  Al-Ni-Zr复合涂层背散射电子像及元素分布图
图10  Al-Ni-Zr复合涂层表面电势分布图
图11  Al-Ni-Zr复合涂层腐蚀形貌
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