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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

王海花, 叶梦玉, 费贵强, 等. 缓蚀型聚邻甲苯胺-氧化石墨烯基防腐材料的制备与性能[J]. 复合材料学报, 2024, 41(4): 1900-1913. doi: 10.13801/j.cnki.fhclxb.20230817.006
引用本文: 王海花, 叶梦玉, 费贵强, 等. 缓蚀型聚邻甲苯胺-氧化石墨烯基防腐材料的制备与性能[J]. 复合材料学报, 2024, 41(4): 1900-1913. doi: 10.13801/j.cnki.fhclxb.20230817.006
WANG Haihua, YE Mengyu, FEI Guiqiang, et al. Preparation and properties of corrosion inhibited poly(o-toluidine)-graphene oxide-based anticorrosive materials[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1900-1913. doi: 10.13801/j.cnki.fhclxb.20230817.006
Citation: WANG Haihua, YE Mengyu, FEI Guiqiang, et al. Preparation and properties of corrosion inhibited poly(o-toluidine)-graphene oxide-based anticorrosive materials[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1900-1913. 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
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

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

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

     

  • 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

    图  2  GO和GAP的红外图谱

    Figure  2.  Fourier infrared spectra of GO and GAP

    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

    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)

    图  5  GAP和MBT@GAP的TEM图像

    Figure  5.  TEM images of GAP and MBT@GAP

    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

    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

    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%

    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

    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

    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

    Rcoat—Coating resistance; CPEcoat—Coating non-ideal capacitance; CPEdl—Double layer non-ideal capacitor; RCT—Charge transfer resistance; Rs—Solution resistance

    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)

    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

    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

    Ecorr/VIcorr/(A·cm−2)βa/(V·dec−1)βc/(V·dec−1)Rp/(Ω·cm2)
    WEP−0.62164.271×10−70.17810.21129.823×104
    MBT@GAP/WEP-0.1wt%−0.43803.150×10−100.19620.18771.322×108
    MBT@GAP/WEP-0.2wt%−0.28281.937×10−100.13970.2002 1.845×108
    MBT@GAP/WEP-0.3wt%−0.15541.016×10−110.12120.06441.797×109
    MBT@GAP/WEP-0.4wt%−0.32042.262×10−100.14530.22121.683×108
    MBT@GAP/WEP-0.5wt%−0.54816.507×10−100.19570.15795.832×107
    Notes: Ecorr—Corrosion potential; Icorr—Corrosion current density; βa—Anode slope; βc—Cathode slope; Rp—Polarization resistance.
    下载: 导出CSV

    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

    SampleRcoat/(Ω·cm2)CPEcoatγ/(Ω−1·cm−2·sn)n
    WEP4.967×1069.129×10−100.8288
    MBT@GAP/WEP-0.1wt%8.643×1072.816×10−100.8915
    MBT@GAP/WEP-0.2wt%2.781×1081.107×10−100.9185
    MBT@GAP/WEP-0.3wt%2.837×1099.922×10−110.9388
    MBT@GAP/WEP-0.4wt%1.234×1082.015×10−100.9101
    MBT@GAP/WEP-0.5wt%2.132×1073.313×10−100.8667
    Notes: n—Empirical index of CPEcoat; γ—Proportional factor.
    下载: 导出CSV

    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/hRcoat/(Ω·cm2)CPEcoatγ/(Ω−1·cm−2·sn)nRCT/(Ω·cm2)CPEdlγ/(Ω−1·cm−2·sn')n'
    02.837×1099.922×10−110.9388
    1007.760×1083.725×10−100.9225
    2002.454×1084.339×10−100.9981
    3001.243×1081.024×10−100.9662
    4004.885×1075.424×10−100.8778
    5008.169×1065.606×10−100.84013.111×1068.138×10−80.4673
    Note: n'—Empirical index of CPEdl.
    下载: 导出CSV
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  • 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:  2024-04-15

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