缓蚀型聚邻甲苯胺-氧化石墨烯基防腐材料的制备与性能

王海花; 叶梦玉; 费贵强; 李焱宇; 王丹丹

doi:10.13801/j.cnki.fhclxb.20230817.006

缓蚀型聚邻甲苯胺-氧化石墨烯基防腐材料的制备与性能

doi: 10.13801/j.cnki.fhclxb.20230817.006

陕西科技大学　化学与化工学院，西安 710021

基金项目: 国家自然科学基金面上项目(21978164；22078189)

详细信息

通讯作者:
王海花，博士，教授，博士生导师，研究方向为高性能及功能复合材料等　E-mail: 13679286323@163.com

中图分类号: TQ630；TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2023-06-09
- 修回日期: 2023-07-30
- 录用日期: 2023-08-03
- 网络出版日期: 2023-08-18
- 刊出日期: 2024-04-01

Preparation and properties of corrosion inhibited poly(o-toluidine)-graphene oxide-based anticorrosive materials

College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology, Xi'an 710021, China

Funds: National Natural Science Foundation of China (21978164; 22078189)

摘要

摘要: 为开发缓蚀剂高效利用的新途径，选取氧化石墨烯为基材、聚邻甲苯胺微胶囊为壁材、缓蚀剂2-巯基苯并噻唑为芯材，制备了缓蚀型聚邻甲苯胺-氧化石墨烯基防腐材料，并将其作为填料用于水性环氧树脂涂层(WEP)的改性。通过FTIR、XRD、XPS和SEM等对材料进行了结构和形貌的表征，采用紫外可见光谱对缓蚀剂的释放行为进行分析，采用万能试验机、电化学测试和盐雾实验对涂层的拉伸性能和防腐性能进行了评价。结果表明：缓蚀剂成功包覆于聚邻甲苯胺微胶囊内部，并通过共价键方式将微胶囊连接在改性氧化石墨烯表面，使缓蚀剂得到了充分利用，提高了涂层的拉伸性能、自修复性能及对腐蚀介质的屏蔽性能。紫外可见光谱测试结果表明，微胶囊在人工破损96 h后，内部缓蚀剂的释放量达78%；拉伸性能测试结果表明，与纯WEP相比，当填料加入量为0.3wt%时，涂层应力从14.281 MPa增加到24.25 MPa；SEM结果表明，被划伤的涂层在常温下放置10 h后自修复；电化学测试和盐雾实验结果表明，涂层腐蚀电位从−0.6216 V提高到−0.1554 V，腐蚀电流密度从4.271×10⁻⁷ A·cm⁻²减小到1.016×10⁻¹¹ A·cm⁻²，阻抗模量可达到1.5757×10⁹ Ω·cm²，在盐雾500 h后仍表现出较好的防腐性能。
- 氧化石墨烯 /
- 聚邻甲苯胺 /
- 微胶囊 /
- 水性环氧树脂 /
- 防腐涂层
Abstract: In order to develop a new way of efficient utilization of corrosion inhibitors, a corrosion inhibited poly(o-toluidine)-graphene oxide-based anticorrosive materials was prepared by using graphene oxide as the substrate, poly(o-toluidine) microcapsules as the wall material and 2-mercaptobenzothiazole as the corrosion inhibitor as the core material, and it was used as the filler for the modification of waterborne epoxy resin coating (WEP). The structure and morphology of the coating were characterized by FTIR, XRD, XPS and SEM. The release behavior of the corrosion inhibitor was analyzed by UV-Vis spectroscopy. The tensile property and anti-corrosion properties of the coating were evaluated by universal testing machine, electrochemical test and salt spray test. The results show that the corrosion inhibitor is successfully coated inside poly(o-toluidine) microcapsules, and the microcapsules are connected to the surface of the modified graphene oxide by covalent bond, so that the corrosion inhibitor is fully utilized, and the tensile property, self-healing properties and shielding properties of the coating against corrosive media are improved. UV-vis spectrum test results show that the release of corrosion inhibitor in microcapsules reaches 78% after 96 h of artificial damage. The tensile property test results show that, compared with pure WEP, the coating stress increases from 14.281 MPa to 24.25 MPa when the filler content is 0.3wt%. SEM results show that the scratched coating self-healing after 10 h at room temperature. The electrochemical test and salt spray test results show that the corrosion potential of the coating increases from −0.6216 V to −0.1554 V, the corrosion current density decreases from 4.271×10⁻⁷ A·cm⁻² to 1.016×10⁻¹¹ A·cm⁻², and the impedance modulus can reach 1.5757×10⁹ Ω·cm². After 500 h of salt spray, the corrosion resistance is still good.
- graphene oxide /
- poly(o-toluidine) /
- microcapsule /
- water-based epoxy resin /
- anticorrosive coating

HTML全文

图 1 缓蚀型聚邻甲苯胺-氧化石墨烯基(MBT@GAP)复合材料的制备过程

Figure 1. Preparation process of corrosion inhibited poly(o-toluidine)-graphene oxide-based (MBT@GAP) composite materials

C—Graphite; GO—Graphene oxide; ASA—3-aminobenzenesulfonic acid; APS—Ammonium persulphate; POT—Poly(o-toluidine); MBT—2-mercaptobenzothiazole; GAP—POT-GO

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图 2 GO和GAP的红外图谱

Figure 2. Fourier infrared spectra of GO and GAP

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图 3 (a) GO的XPS全谱图；(b) GAP的XPS全谱图；(c) GAP的C1s谱图；(d) GAP的N1s谱图

Figure 3. (a) XPS spectrum of GO; (b) XPS spectrum of GAP; (c) C1s spectrum of GAP; (d) N1s spectrum of GAP

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图 4 GAP (a)和放大倍率下单个聚邻甲苯胺(POT)微胶囊及人工破损后(b)的SEM图像

Figure 4. SEM images of GAP (a) and a single poly o-toluidine (POT) microcapsule at magnification and after artificial damage (b)

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图 5 GAP和MBT@GAP的TEM图像

Figure 5. TEM images of GAP and MBT@GAP

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图 6 (a) 微球破损后MBT浓度的紫外光谱图；(b) MBT吸光度随浓度变化的标准曲线图；(c) 胶囊的释放量随时间的变化图

Figure 6. (a) Ultraviolet-visible spectra of MBT concentration in damaged microspheres; (b) Standard plot of MBT absorbance as a function of concentration; (c) Plot of capsule release over time

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图 7 不同MBT@GAP添加量时胶膜的应力-应变曲线

WEP—Waterborne epoxy resin coating

Figure 7. Stress-strain curves of film with different contents of MBT@GAP

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图 8 不同MBT@GAP添加量时胶膜断面SEM图像：(a) 0wt%；(b) 0.1wt%；(c) 0.2wt%；(d) 0.3%, (e) 0.4wt%；(f) 0.5wt%

Figure 8. Cross-sectional SEM images of film with different contents of MBT@GAP: (a) 0wt%; (b) 0.1wt%; (c) 0.2wt%; (d) 0.3wt%; (e) 0.4wt%; (f) 0.5wt%

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图 9 不同MBT@GAP添加量时复合涂层盐雾前后的附着力变化

Figure 9. Adhesion changes of composite coating before and after salt spray at different adding amounts of MBT@GAP

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图 10 不同MBT@GAP添加量时复合涂层的极化曲线(a)、阻抗模量曲线 (b)、相位角曲线 (c)、Nyquist图 (d)

Figure 10. Polarization curves (a), impedance modulus curves (b), phase angle curves (c), Nyquist diagram (d) of composite coatingwith different contents of MBT@GAP

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图 11 MBT@GAP/WEP-0.3wt%涂层不同盐雾时间下的阻抗模量曲线(a)、相位角曲线(b)、Nyquist图(c)、等效电路模型(d)

Figure 11. Impedance modulus curves (a), phase angle curves (b), Nyquist diagram (c), electrical equivalent circuit models (d) of MBT@GAP/WEP-0.3wt% coating under different salt spray time

R_coat—Coating resistance; CPE_coat—Coating non-ideal capacitance; CPE_dl—Double layer non-ideal capacitor; R_CT—Charge transfer resistance; R_s—Solution resistance

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图 12 (a) 裸马口铁、WEP及MBT@GAP/WEP-0.3wt%涂层盐雾500 h前后的照片；WEP (b)和MBT@GAP/WEP-0.3wt%涂层(c)的耐腐蚀机制图

Figure 12. (a) Photos of bare tinplate, WEP and MBT@GAP/WEP-0.3wt% coating salt spray before and after 500 h; Corrosion resistance mechanism diagram of WEP (b) and MBT@GAP/WEP-0.3wt% coatings (c)

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图 13 WEP涂层划伤后0 h (a₁)、5 h (a₂)、10 h (a₃)和MBT@GAP/WEP-0.3wt%涂层划伤后0 h (b₁)、5 h (b₂)、10 h (b₃)的SEM图像；(c) MBT@GAP/WEP-0.3wt%复合涂层划痕自修复后的EDS谱图

Figure 13. SEM images of 0 h (a₁), 5 h (a₂), 10 h (a₃) after scratch of WEP coating and 0 h (b₁), 5 h (b₂), 10 h (b₃) after scratch of MBT@GAP/WEP-0.3wt% coating; (c) EDS spectrum of MBT@GAP/WEP-0.3wt% composite coating scratches after self-healing

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表 1 不同MBT@GAP添加量时复合涂层极化曲线参数

Table 1. Polarization curve parameters of composite coating with different contents of MBT@GAP

	E_corr/V	I_corr/(A·cm⁻²)	β_a/(V·dec⁻¹)	β_c/(V·dec⁻¹)	R_p/(Ω·cm²)
WEP	−0.6216	4.271×10⁻⁷	0.1781	0.2112	9.823×10⁴
MBT@GAP/WEP-0.1wt%	−0.4380	3.150×10⁻¹⁰	0.1962	0.1877	1.322×10⁸
MBT@GAP/WEP-0.2wt%	−0.2828	1.937×10⁻¹⁰	0.1397	0.2002	1.845×10⁸
MBT@GAP/WEP-0.3wt%	−0.1554	1.016×10⁻¹¹	0.1212	0.0644	1.797×10⁹
MBT@GAP/WEP-0.4wt%	−0.3204	2.262×10⁻¹⁰	0.1453	0.2212	1.683×10⁸
MBT@GAP/WEP-0.5wt%	−0.5481	6.507×10⁻¹⁰	0.1957	0.1579	5.832×10⁷
Notes: E_corr—Corrosion potential; I_corr—Corrosion current density; β_a—Anode slope; β_c—Cathode slope; R_p—Polarization resistance.

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表 2 不同MBT@GAP添加量时复合涂层交流阻抗谱图拟合参数

Table 2. Fitting parameters of alternating current impedance spectra of composite coating with different contents of MBT@GAP

Sample	R_coat/(Ω·cm²)	CPE_coatγ/(Ω⁻¹·cm⁻²·sⁿ)	n
WEP	4.967×10⁶	9.129×10⁻¹⁰	0.8288
MBT@GAP/WEP-0.1wt%	8.643×10⁷	2.816×10⁻¹⁰	0.8915
MBT@GAP/WEP-0.2wt%	2.781×10⁸	1.107×10⁻¹⁰	0.9185
MBT@GAP/WEP-0.3wt%	2.837×10⁹	9.922×10⁻¹¹	0.9388
MBT@GAP/WEP-0.4wt%	1.234×10⁸	2.015×10⁻¹⁰	0.9101
MBT@GAP/WEP-0.5wt%	2.132×10⁷	3.313×10⁻¹⁰	0.8667
Notes: n—Empirical index of CPE_coat; γ—Proportional factor.

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表 3 MBT@GAP/WEP-0.3wt%复合涂层随盐雾时间变化的电化学阻抗拟合参数

Table 3. Electrochemical impedance fitting parameters for MBT@GAP/WEP-0.3wt% composite coatings with salt spray time

Salt spray time/h	R_coat/(Ω·cm²)	CPE_coatγ/(Ω⁻¹·cm⁻²·sⁿ)	n	R_CT/(Ω·cm²)	CPE_dlγ/(Ω⁻¹·cm⁻²·s^n')	n'
0	2.837×10⁹	9.922×10⁻¹¹	0.9388	—	—	—
100	7.760×10⁸	3.725×10⁻¹⁰	0.9225	—	—	—
200	2.454×10⁸	4.339×10⁻¹⁰	0.9981	—	—	—
300	1.243×10⁸	1.024×10⁻¹⁰	0.9662	—	—	—
400	4.885×10⁷	5.424×10⁻¹⁰	0.8778	—	—	—
500	8.169×10⁶	5.606×10⁻¹⁰	0.8401	3.111×10⁶	8.138×10⁻⁸	0.4673
Note: n'—Empirical index of CPE_dl.

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