重防腐涂层/TA2在模拟万米超深海环境防护行为研究

doi:10.11949/0438-1157.20251241

摘要/Abstract

摘要：

为探究重防腐涂层在万米超深海环境下的防护行为，以TA2钛材为基体，系统研究了粉末与无溶剂液体2种防腐涂层2个典型涂层厚度在实验室100 MPa静态及交变压力自然海水环境中的防护性能演变规律。采用电化学阻抗谱、局部电化学阻抗谱、热重分析、差示扫描量热法、激光共聚焦显微镜和扫描电子显微镜等表征手段对比分析了2种涂层在不同压力、不同厚度条件下的电化学行为、吸水特性与形貌等。结果表明：粉末涂层在整个试验周期内表现出优异的耐海水渗透性能，更低的吸水率和更好的防护性能；交变压力因压缩-膨胀疲劳效应加速了涂层内部微观缺陷的萌生、扩展，导致其防护性能下降高于静态压力。

关键词: 超深海, 防腐涂层, 腐蚀, 环境, 电化学

Abstract:

To investigate the protective behavior of heavy-duty anti-corrosive coatings in ultra-deep sea environments, this study systematically examined two coating systems epoxy powder and solvent-free liquid epoxy applied on TA2 titanium substrate. The protective performance was evaluated under laboratory simulated conditions, including 100 MPa static pressure and 0.1~100 MPa alternating pressure in natural seawater. The characterization techniques such as electrochemical impedance spectroscopy(EIS), local electrochemical impedance spectroscopy(LEIS), thermogravimetric(TG) ,differential scanning calorimetry(DSC), laser confocal microscopy(CLSM) and scanning electron microscopy(SEM) were employed to compare the electrochemical behavior, water absorption characteristics and micromorphology of the two coating systems under different pressure regimes. Results demonstrate that the epoxy powder coating exhibited superior resistance to seawater penetration and lower water absorption throughout the testing period. Alternating pressure due to tensile-compressive fatigue effects, accelerated the propagation of micro-defects within the coating, leading to a significantly higher degradation of protective performance compared to static pressure.

Key words: ultra deep-sea, anti-corrosive coating, corrosion, environment, electrochemistry

中图分类号:

TG 174

张贺琦, 陆卫中, 李国华, 王红飞, 陈颖. 重防腐涂层/TA2在模拟万米超深海环境防护行为研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251241.

Heqi ZHANG, Weizhong LU, Guohua LI, Hongfei WANG, Ying CHEN. Study on the protective behavior of heavy-duty anti-corrosive coatings/TA2 in simulated ultra deep-sea 10,000 meters environment[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251241.

图/表 17

表1 环氧粉末涂料成分组成

Table 1 Material composites of powder coating

材料名称	质量分数/%
合计	100.0
高玻璃化温度、高韧性固体改性环氧树脂	48.6
活性纳米和片状填料	36.9
改性多官能羟氨类固化剂	10.2
颜料	1.5
助剂	2.8

表2 无溶剂环氧液体涂料成分组成

Table 2 Material composites of solvent-free liquid coating

材料名称	质量分数/%
合计	100
高韧性液体改性环氧树脂	48.6
活性纳米和片状填料	36.9
颜料	1.5
腰果壳液、乙二胺和甲醛合成聚合物	6.0
环氧-胺加成物	2.2
羟基化酚聚多胺	2.0
助剂	2.8

图1 涂层力学性能与截面形貌

Fig. 1 Mechanical properties and cross section characterization of coatings

图2 150 μm粉末涂层在0.1~100 MPa交变压力下EIS

Fig.2 EIS results of 150 μm powder coating under 0.1~100 MPa alternating pressure

图3 150 μm液体涂层在0.1~100 MPa交变压力下EIS

Fig.3 EIS results of 150 μm liquid coating under 0.1~100 MPa alternating pressure

图4 300 μm粉末涂层在0.1~100 MPa交变压力下EIS

Fig.4 EIS results of 300 μm powder coating under 0.1~100 MPa alternating pressure

图5 300 μm液体涂层在0.1~100 MPa交变压力下EIS

Fig.5 EIS results of 300 μm liquid coating under 0.1~100 MPa alternating pressure

图6 300 μm粉末涂层在100 MPa静态压力下的EIS

Fig.6 EIS results of 300 μm powder coating under 100 MPa static pressure

图7 300 μm液体涂层在100 MPa静态压力下的EIS

Fig.7 EIS results of 300 μm liquid coating under 100 MPa static pressure

图8 EIS电路元件参数拟合与数据分析

Fig.8 EIS parameter fitting and data analysis

表3 不同试验条件下的RC + Rct比值

Table 3 Coating resistance （RC + Rct） ratio under different conditions

实验对象	实验条件	时间
实验对象	实验条件	1 d	11 d	15 d	18 d	20 d	22 d
体系（粉末/液体涂层）	0.1~100 MPa， 150 μm粉末/150 μm液体	1.0	1.5	4.3	20.0	15.0	8.3
	0.1~100 MPa， 300 μm粉末/300 μm液体	1.0	7.2	10.0	2.2	2.9	2.8
	100 MPa条件下 300 μm粉末/300 μm液体	1.0	9.0	7.5	7.0	7.3	10.0
厚度（300 μm/150 μm）	0.1~100 MPa， 300 μm粉末150 μm粉末	2.0	11.0	7.6	3.2	2.9	2.0
厚度（300 μm/150 μm）	0.1~100 MPa， 300 μm液体/150 μm液体	2.0	2.5	3.3	29.0	7.7	2.5
环境（静态压力/交变压力）	100 MPa/0.1~100 MPa 300 μm粉末涂层	1.0	2.6	3.0	6.3	6.0	3.0
环境（静态压力/交变压力）	100 MPa/0.1~100 MPa 300 μm液体涂层	1.0	2.0	4.0	2.1	2.1	2.0

图9 2种涂层在不同压力环境下LEIS分析

Fig.9 LEIS analysis of two kinds coatings under different pressure environment

图10 不同时间和压力环境下涂层吸水率

Fig.10 Water absorption of coating under different time and pressure

图11 浸泡前后涂层TG-DTG曲线

Fig.11 Analysis of coating weight loss curves before and after immersion

图12 浸泡前后涂层DSC曲线

Fig.12 DSC curves analysis of coating before and after immersion

图13 300 μm涂层表面CLSM形貌

Fig.13 CLSM surface morphologies analysis of 300 μm coatings

图14 涂层截面 SEM形貌

Fig.14 SEM cross section micromorphologies of coatings

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