基于纳米容器BTA@MSNs-PAA的智能防腐涂层的制备及性能

doi:10.16085/j.issn.1000-6613.2020-1087

摘要/Abstract

摘要：

碳钢被广泛应用于工农业生产中，智能涂层的研究和应用为碳钢的腐蚀防护提供了新的途径。本文以正硅酸乙酯（TEOS）为原料，通过加入扩孔剂1,3,5-三甲苯（TMB）合成了大孔径的介孔SiO₂纳米容器（MSNs），采用聚丙烯酸（PAA）对MSNs进行化学修饰制备了一种装载缓蚀剂苯并三氮唑（BTA）的pH敏感性智能纳米容器BTA@MSNs-PAA。通过扫描电子显微镜（SEM）、动态光散射粒径分析（DLS）、X射线衍射分析（XRD）、傅里叶红外光谱（FTIR）、热重/差热分析（TGA/DTA）和紫外可见光谱（UV-vis）对BTA@MSNs-PAA的结构和性能进行了表征。通过将BTA@MSNs-PAA掺杂到环氧树脂涂层中，在碳钢表面制备了一种智能防腐涂层，采用电化学阻抗谱（EIS）和盐雾加速腐蚀试验对智能涂层的防腐性能进行了评价。结果表明，BTA@MSNs-PAA近似呈球形且表面光滑，平均粒径为320nm。BTA@MSNs-PAA可通过PAA与BTA之间的静电相互作用装载BTA分子，其装载量可达16.49%，BTA@MSNs-PAA可响应酸性刺激而加速释放BTA分子。基于BTA@MSNs-PAA的智能防腐涂层对碳钢表现出显著的腐蚀防护性能，这可能是因为当碳钢基体发生腐蚀时，其腐蚀点位下降的pH触发纳米容器快速释放BTA分子，从而有效抑制了基体的进一步腐蚀。

关键词: pH敏感性, 纳米容器, 智能涂层, 碳钢, 腐蚀防护, 电化学阻抗谱

Abstract:

Carbon steel is widely utilized in industrial and agricultural processes. The study and application of the smart coating provide a new approach for the corrosion protection of carbon steel. In this work, mesoporous silica nanocontainers (MSNs) with large pore size were synthesized by using tetraethyl orthosilicate (TEOS) as the reactant through the addition of the pore-expanding agent of 1,3,5-trimethylbenzene (TMB). The prepared MSNs were modified by poly(acrylic acid) (PAA) to obtain the intelligent nanocontainers of BTA@MSNs-PAA with pH-sensitivity. The structure and performance of BTA@MSNs-PAA were characterized by scanning electron microscopy (SEM), dynamic light scattering analysis (DLS), X-ray diffraction analysis, infrared spectroscopy (FTIR), thermogravimetry/differential thermal analysis (TGA/DTA), and ultraviolet-visible spectroscopy (UV-vis). Meanwhile, the smart coating was fabricated on carbon steel through the dispersion of BTA@MSNs-PAA into epoxy resin. The protective properties of the smart coatings were evaluated by electrochemical impedance spectroscopy and salt spray accelerated experiments. The results showed that BTA@MSNs-PAA presented a near-spherical and smooth surface with an average diameter of 320nm. BTA@MSNs-PAA could load BTA by electrostatic interaction between PAA and BTA molecules. The amount of BTA loaded in BTA@MSNs-PAA is up to 16.49%. The releasing rate of BTA from BTA@MSNs-PAA can be accelerated under acidic conditions. The prepared coating presents remarkable anti-corrosion performance for carbon steel in NaCl corrosion medium, which may be because the releasing of BTA from BTA@MSNs-PAA is triggered by corrosion-induced pH decrease. Therefore, it can prevent the further corrosion of carbon steel substrate.

Key words: pH-sensitivity, nanocontainers, smart coating, carbon steel, corrosion protection, electrochemical impedance spectroscopy

中图分类号:

TG174.42

文家新, 张欣, 刘云霞, 和志强, 屈琦超. 基于纳米容器BTA@MSNs-PAA的智能防腐涂层的制备及性能[J]. 化工进展, 2021, 40(5): 2685-2694.

WEN Jiaxin, ZHANG Xin, LIU Yunxia, HE Zhiqiang, QU Qichao. Preparation and performance of smart anti-corrosion coating based on nanocontainers of BTA@MSNs-PAA[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2685-2694.

图/表 10

参考文献 20

1	LI X G, ZHANG D W, LIU Z Y, et al. Materials science: share corrosion data[J]. Nature, 2015, 527(7579): 441-442.
2	王冰, 刘晓娟, 熊哲, 等. 某天然气管道内腐蚀原因及防控措施[J]. 表面技术, 2018, 47(6):89-94.
	WANG Bing, LIU Xiaojuan, XIONG Zhe, et al. Corrosion reasons and control measures of a natural gas pipeline[J]. Surface Technology, 2018, 47(6):89-94.
3	ZHANG F, JU P F, PAN M Q, et al. Self-healing mechanisms in smart protective coatings: a review[J]. Corrosion Science, 2018, 144:74-88.
4	MAYNE J E O. Mechanisms of protection by paints[M]//Shreir’s Corrosion. Amsterdam: Elsevier, 2010: 2666-2677.
5	王万兵, 高晓辉, 李怀阳, 等. 石墨烯/导电聚合物复合防腐蚀材料制备及应用研究进展[J]. 化工进展, 2020, 39(3): 1080-1089.
	WANG Wanbing, GAO Xiaohui, LI Huaiyang, et al. Progress of preparation and application of graphene/conductive polymer composite anticorrosion materials[J]. Chemical Industry and Engineering Progress, 2020, 39(3): 1080-1089.
6	LI Z, QIN B, ZHANG X, et al. Self-healing anti-corrosion coatings based on polymers of intrinsic microporosity for the protection of aluminum alloy[J]. RSC Advances, 2015, 5: 104451-104457.
7	FALCÓN J M, OTUBO L M, AOKI I V. Highly ordered mesoporous silica loaded with dodecylamine for smart anticorrosion coatings[J]. Surface and Coatings Technology, 2016, 303: 319-329.
8	LIANG Y, WANG M D, WANG C, et al. Facile synthesis of smart nanocontainers as key components for construction of self-healing coating with superhydrophobic surfaces[J]. Nanoscale Research Letters, 2016, 11(1): 231-243.
9	陈中华, 梁家妮. 以负载缓蚀剂的二氧化硅微胶囊制备水性智能防腐涂料及其涂层性能研究[J]. 电镀与涂饰, 2018, 37(6): 231-235.
	CHEN Zhonghua, LIANG Jiani. Preparation of waterborne intelligent anticorrosive coating materials with corrosion-inhibitor-loaded silica microcapsules and study on properties of the coatings obtained therefrom[J]. Electroplating & Finishing, 2018, 37(6): 231-235.
10	高朋, 余传柏, 杜琳琳, 等. 中空介孔二氧化硅微球的制备及研究进展[J]. 化工新型材料, 2019, 47(3): 31-34, 38.
	GAO Peng, YU Chuanbai, DU Linlin, et al. Preparation and research progress of hollow mesoporous silica microsphere[J]. New Chemical Materials, 2019, 47(3): 31-34, 38.
11	ZHAO D Y, HUO Q S, FENG J L, et al. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures[J]. Journal of the American Chemical Society, 1998, 120(24):6024-6036.
12	MAILE F J, SCHAUER T, EISENBACH C D. Evaluation of corrosion and protection of coated metals with local ion concentration technique (LICT)[J]. Progress in Organic Coatings, 2000, 38(2): 111-116.
13	KRESGE C T, LEONOWICZ M E, ROTH W J, et al. Ordered mesoporous molecular sieves synthesized by liquid-crystal template mechanism[J]. Nature, 1992, 359(6397): 710-712.
14	余越, 陶春, 杨海跃, 等. 介孔二氧化硅纳米粒的制备及其作为不同功能的药物载体研究进展[J]. 中国新药杂志, 2017, 26(16): 1906-1912.
	YU Yue, TAO Chun, YANG Haiyue, et al. Advances in preparation of mesoporous silica nanoparticles and its use as different functional drug[J]. Chinese Journal of New Drugs, 2017, 26(16):1906-1912.
15	QIAN B, ZHENG Z L, MICHAILIDS M, et al. Mussel-inspired self-healing coatings based on polydopamine-coated nanocontainers for corrosion protection[J]. ACS Applied Materials & Interfaces, 2019, 11(10): 10283-10291.
16	XU J B, CAO Y Q, FANG L, et al. A one-step preparation of inhibitor-loaded silica nanocontainers for self-healing coatings[J]. Corrosion Science, 2018, 140: 349-362.
17	YE X, LI X, SHEN Y Q, et al. Self-healing pH-sensitive cytosine-and guanosine- modified hyaluronic acid hydrogels via hydrogen bonding[J]. Polymer, 2017, 108: 348-360.
18	YUAN L, TANG Q, YANG D, et al. Preparation of pH-responsive mesoporous silica nanoparticles and their application in controlled drug delivery[J]. The Journal of Physical Chemistry C, 2011, 115(20):9926-9932.
19	LYU Z, CHEN H S. A probabilistic method for determining the volume fraction of pre-embedded capsules in self-healing materials[J]. Smart Materials and Structures, 2014, 23 (11): 115009-115021.
20	FENG Y C, CHENG Y F. An intelligent coating doped with inhibitor-encapsulated nanocontainers for corrosion protection of pipeline steel[J]. Chemical Engineering Journal, 2017, 315: 537-551.

样品名称	时间 /h	R_s /Ω·cm^-2	R_c /Ω·cm^-2	CPE_c		CPE_dl		R_ct /Ω·cm^-2
样品名称	时间 /h	R_s /Ω·cm^-2	R_c /Ω·cm^-2	C_C/F·cm^-2	n	C_dl/F·cm^-2	n	R_ct /Ω·cm^-2
未掺杂BTA@MSNs-PAA的环氧涂层	0	28.9	10311	3.31×10^-5	0.6989	―	―	―
	3	25.5	8961	5.17×10^-5	0.6819	―	―	―
	6	24.3	7006	1.03×10^-4	0.6502	2.08×10^-3	0.7007	630
	12	14.0	5616	5.60×10^-4	0.7004	2.52×10^-3	0.6823	552
	24	25.8	4592	8.40×10^-4	0.6883	3.95×10^-3	0.6106	476
	36	22.2	3429	1.23×10^-3	0.6829	5.85×10^-3	0.6183	329
BTA@MSNs-PAA含量为3.0%的智能涂层	0	38.1	11118	9.64×10^-5	0.6530	―	―	―
	3	18.8	7136	2.55×10^-4	0.6970	―	―	―
	6	22.1	8874	6.40×10^-5	0.6925	1.18×10^-3	0.6834	599
	12	53.8	13809	3.69×10^-5	0.6390	9.07×10^-4	0.7011	2070
	24	17.2	15065	2.60×10^-5	0.6721	5.73×10^-4	0.6159	2292
	36	62.0	14834	1.71×10^-5	0.6308	2.82×10^-4	0.6991	2034
BTA@MSNs-PAA含量为6.0%的智能涂层	0	56.9	11878	5.03×10^-5	0.5876	―	―	―
	3	49.3	10361	6.02×10^-5	0.5840	―	―	―
	6	64.0	13285	4.45×10^-5	0.5570	1.38×10^-3	0.6135	781
	12	92.2	16732	3.18×10^-5	0.6022	7.81×10^-4	0.6401	2156
	24	82.8	20932	2.14×10^-5	0.5420	6.43×10^-4	0.6846	2975
	36	103.5	16081	5.10×10^-5	0.5467	1.06×10^-3	0.6085	1991
BTA@MSNs-PAA含量为9.0%的智能涂层	0	57.2	14701	2.80×10^-5	0.6937	―	―	―
	3	40.4	12938	3.53×10^-5	0.6099	―	―	―
	6	67.5	16157	2.75×10^-5	0.6308	1.96×10^-3	0.6365	867
	12	77.9	18974	2.47×10^-5	0.6244	4.75×10^-4	0.6546	2622
	24	119.7	25251	1.29×10^-5	0.5997	1.11×10^-4	0.6056	3513
	36	117.5	24941	2.39×10^-5	0.5841	2.76×10^-4	0.5963	2751

样品名称	时间 /h	R_s /Ω·cm^-2	R_c /Ω·cm^-2	CPE_c		CPE_dl		R_ct /Ω·cm^-2
样品名称	时间 /h	R_s /Ω·cm^-2	R_c /Ω·cm^-2	C_C/F·cm^-2	n	C_dl/F·cm^-2	n	R_ct /Ω·cm^-2
未掺杂BTA@MSNs-PAA的环氧涂层	0	28.9	10311	3.31×10^-5	0.6989	―	―	―
	3	25.5	8961	5.17×10^-5	0.6819	―	―	―
	6	24.3	7006	1.03×10^-4	0.6502	2.08×10^-3	0.7007	630
	12	14.0	5616	5.60×10^-4	0.7004	2.52×10^-3	0.6823	552
	24	25.8	4592	8.40×10^-4	0.6883	3.95×10^-3	0.6106	476
	36	22.2	3429	1.23×10^-3	0.6829	5.85×10^-3	0.6183	329
BTA@MSNs-PAA含量为3.0%的智能涂层	0	38.1	11118	9.64×10^-5	0.6530	―	―	―
	3	18.8	7136	2.55×10^-4	0.6970	―	―	―
	6	22.1	8874	6.40×10^-5	0.6925	1.18×10^-3	0.6834	599
	12	53.8	13809	3.69×10^-5	0.6390	9.07×10^-4	0.7011	2070
	24	17.2	15065	2.60×10^-5	0.6721	5.73×10^-4	0.6159	2292
	36	62.0	14834	1.71×10^-5	0.6308	2.82×10^-4	0.6991	2034
BTA@MSNs-PAA含量为6.0%的智能涂层	0	56.9	11878	5.03×10^-5	0.5876	―	―	―
	3	49.3	10361	6.02×10^-5	0.5840	―	―	―
	6	64.0	13285	4.45×10^-5	0.5570	1.38×10^-3	0.6135	781
	12	92.2	16732	3.18×10^-5	0.6022	7.81×10^-4	0.6401	2156
	24	82.8	20932	2.14×10^-5	0.5420	6.43×10^-4	0.6846	2975
	36	103.5	16081	5.10×10^-5	0.5467	1.06×10^-3	0.6085	1991
BTA@MSNs-PAA含量为9.0%的智能涂层	0	57.2	14701	2.80×10^-5	0.6937	―	―	―
	3	40.4	12938	3.53×10^-5	0.6099	―	―	―
	6	67.5	16157	2.75×10^-5	0.6308	1.96×10^-3	0.6365	867
	12	77.9	18974	2.47×10^-5	0.6244	4.75×10^-4	0.6546	2622
	24	119.7	25251	1.29×10^-5	0.5997	1.11×10^-4	0.6056	3513
	36	117.5	24941	2.39×10^-5	0.5841	2.76×10^-4	0.5963	2751

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