三基色镍基自敏复合涂层的制备及其性能研究

doi:10.15541/jim20160243

摘要/Abstract

摘要：

检测耐腐蚀涂层在腐蚀环境下的完整性, 对预测涂层工作寿命至关重要。通过电化学沉积法成功地将三基色无机荧光颗粒: BaMgAl₁₁O₁₇: Eu²⁺(蓝粉), Y₂O₃: Eu³⁺(红粉), CeMgAl₁₁O₁₉: Tb³⁺(绿粉)与金属镍复合, 在瓦特光亮镀镍浴中沉积出具有三基色指示功能的镍基自敏复合涂层。采用X射线衍射(XRD)、扫描电镜(SEM)、表面轮廓仪、维氏硬度计、荧光发射光谱和电化学测试手段分别对涂层组织形貌结构、润湿性、沉积率、硬度、发光性能及自敏性能进行了检测, 结果表明, 阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)和非离子表面活性剂聚乙二醇(PEG)可以有效提高三基色荧光粒子沉积率。三种荧光粒子与金属镍之间表现出不同的润湿性和匹配性, 使得其在镍基复合涂层中具有不同的作用: Y₂O₃: Eu³⁺荧光粒子改变了涂层结晶取向, 且使晶粒细化, BaMgAl₁₁O₁₇: Eu²⁺使涂层组织呈现节瘤状, Y₂O₃: Eu³⁺和CeMgAl₁₁O₁₉: Tb³⁺粒子明显提高了涂层硬度。三基色荧光粒子在腐蚀前后表现出不同的发光特性, 可以有效指示出涂层工作周期内的完整性, 起到良好的自敏检测作用。

关键词: 荧光颗粒, 电化学沉积, 自敏检测, 镍基复合涂层

Abstract:

It is very important for coating to detect integrity and working life in corrosive environment. The self-sensitization luminescent coating were fabricated by electroplating technique from a modified Watts bath combined with blue-emitting (BaMgAl₁₁O₁₇: Eu²⁺), red-emitting (Y₂O₃: Eu³⁺), and green-emtting (CeMgAl₁₁O₁₉: Tb³⁺) rare-earth fluorescent particles. The surface morphology, microstructure, wettability, deposition rate, hardness, and self-sensitization luminescent property of the obtained composite coatings were characterized by using fluorescence spectrophotometer, surface profile measuring instrument, vickers, scanning electronmicroscope (SEM), X-ray diffraction (XRD), and electrochemical test techniques. The results show that surfactants of non-ionic PEG (polyethylene glycol) and cationic CTAB (cetyltrimethylammonium bromide) effectively improve the particles deposition rate. The fluorescent particles shows different wettability and matching with nickel, which have different effects on microstructure of the composite coatings. Y₂O₃: Eu³⁺fluorescent particles change the coating crystal orientation and grain refinement, BaMgAl₁₁O₁₇: Eu²⁺ fluorescent particles make the coating morphology presents knot. The coating hardness is increased obviously in composite coatings containing Y₂O₃: Eu³⁺ and CeMgAl₁₁O₁₉: Tb³⁺ particles. The fluorescent particles show different luminescent characteristics after corrosion, indicating good self-sensitization and effective monitor on the integrity of the composite coatings.

Key words: fluorescent particles, electrodeposition, self-sensitization monitor, Ni-base composite coatings

中图分类号:

TQ153

何玲, 李乾坤, 李文生, 崔帅. 三基色镍基自敏复合涂层的制备及其性能研究[J]. 无机材料学报, 2017, 32(1): 56-62.

HE Ling, LI Qian-Kun, LI Weng-Sheng, CUI Shuai. Synthesis and Properties of Self-sensitization Luminescent Composite Coatings[J]. Journal of Inorganic Materials, 2017, 32(1): 56-62.

图/表 11

表1 电解液成份

Table1 Chemical composition of the electrodeposition bath

Composition	NiSO₄·6H₂O	NiCl₂·6H₂O	H₃BO₃	Saccharin	1, 4-butynediolcoumarin	Coumarin	CTAB	PEG
Concentration/ (g·L^-1)	250	45	40	1	0.3	0.1	0.1/0.2	0.04

图1 不同浓度镀液中三基色荧光颗粒在复合涂层的沉积率

Fig. 1 Deposition rate of fluorescence particles on the composite coatings in the plating bath with different concentrations

图2 表面活性剂(CTAB)浓度对粒子沉积率的影响

Fig. 2 Effect of surfactant (CTAB) concentration on deposition rate of fluorescence particles

图3 不同复合涂层线性伏安曲线

Fig. 3 Curves of linear sweep voltammetry of different composite coatings

图4 三基色发光复合涂层的表面SEM照片

Fig. 4 Surface morphologies of composite coatings(a) Ni-BaMgAl11O17: Eu2+; (b) Ni-CeMgAl11O19: Tb3+; (c) Ni-Y2O3: Eu3+

图5 三基色发光复合涂层的断面形貌照片

Fig. 5 Cross-sectional optical micrographs of composite coatings(a) Ni-BaMgAl11O17: Eu2+; (b) Ni-CeMgAl11O19: Tb3+; (c) Ni-Y2O3: Eu3+

图6 三基色发光复合涂层的XRD图谱

Fig. 6 XRD patterns of composite coatings

图7 荧光粒子添加浓度对复合涂层硬度的影响

Fig. 7 Effect of concentration of fluorescence particles on the hardness of coatings

表2 复合涂层相关参数

Table 2 Properties of the coatings studied

Coating	Grain size/nm	Microhardness, HV	Roughness parameters, R_a /µm	Roughness parameters, R_max/µm
Ni-BaMgAl₁₁O₁₇: Eu²⁺	23.5	530	1.389	7.50
Ni-CeMgAl₁₁O₁₉: Tb³⁺	17.1	745	0.847	3.96
Ni-Y₂O₃: Eu³⁺	11.1	756	1.296	7.60

图8 三基色发光复合涂层的发射光谱图

Fig. 8 Emission spectra of composite coatings(a) Ni-BaMgAl11O17: Eu2+; (b) Ni-CeMgAl11O19: Tb3+; (c) Ni-Y2O3: Eu3+

图9 腐蚀前后三基色发光复合涂层的发光强度

Fig. 9 Emission spectra of composite coatings before and after corrode in the 3.5wt% NaCl solution(a) Ni-BaMgAl11O17: Eu2+; (b) Ni-CeMgAl11O19: Tb3+; (c) Ni-Y2O3: Eu3+

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