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笼形聚倍半硅氧烷-六方氮化硼-苯胺三聚体共掺杂的改性环氧树脂防腐涂层

叶建宇 郑祥宏 祝奥奇 曾碧榕 许一婷 袁丛辉 罗伟昂 陈国荣 戴李宗

叶建宇, 郑祥宏, 祝奥奇, 等. 笼形聚倍半硅氧烷-六方氮化硼-苯胺三聚体共掺杂的改性环氧树脂防腐涂层[J]. 复合材料学报, 2022, 39(0): 1-13
引用本文: 叶建宇, 郑祥宏, 祝奥奇, 等. 笼形聚倍半硅氧烷-六方氮化硼-苯胺三聚体共掺杂的改性环氧树脂防腐涂层[J]. 复合材料学报, 2022, 39(0): 1-13
Jianyu YE, Xianghong ZHENG, Aoqi ZHU, Birong ZENG, Yiting XU, Conghui YUAN, Weiang LUO, Guorong CHEN, Lizong DAI. Epoxy resin anticorrosive coating modified by the co-doping of polyhedral silsesquioxane/hexagonal boron nitride/aniline trimer[J]. Acta Materiae Compositae Sinica.
Citation: Jianyu YE, Xianghong ZHENG, Aoqi ZHU, Birong ZENG, Yiting XU, Conghui YUAN, Weiang LUO, Guorong CHEN, Lizong DAI. Epoxy resin anticorrosive coating modified by the co-doping of polyhedral silsesquioxane/hexagonal boron nitride/aniline trimer[J]. Acta Materiae Compositae Sinica.

笼形聚倍半硅氧烷-六方氮化硼-苯胺三聚体共掺杂的改性环氧树脂防腐涂层

基金项目: 阻燃环氧树脂基Vitrimer复合材料构筑与性能研究,国家自然科学基金(52173081);高分子材料检测公共服务平台,2019市公共技术服务平台定向项目(YDZX20193502000004)
详细信息
    通讯作者:

    曾碧榕,博士,副教授,硕士生导师,研究方向:聚合物基复合材料 E-mail:brzeng@xmu.edu.cn

    戴李宗,博士,教授,硕士/博士生导师,研究方向:高分子材料 E-mail:lzdai@xmu.edu.cn

  • 中图分类号: TB332

Epoxy resin anticorrosive coating modified by the co-doping of polyhedral silsesquioxane/hexagonal boron nitride/aniline trimer

  • 摘要: 为了改善环氧树脂(EP)涂层防腐性能,采用笼形聚倍半硅氧烷(POSS)修饰的六方氮化硼(h-BN)和苯胺三聚体(AT)作为填料加入环氧固化体系中进行共掺杂,研究两种POSS分子、两种添加方式以及不同添加量对复合涂层的性能影响。首先通过高温剥离六方氮化硼得到羟基化氮化硼(OH-BN),而后采用硅烷偶联剂KH-560对其表面进行乙氧基功能化修饰,再分别将氨丙基七异丁基POSS(APS)和八氨苯基POSS(OAPPS)与之接枝,经反应合成出两种新型的POSS杂化氮化硼功能助剂APS-BN和OAPPS-BN;进一步将它们和AT通过π-π相互作用共混,以不同的添加比例分散到环氧树脂中制备有机无机杂化的环氧复合防腐涂层材料,最后表征涂层的交流阻抗谱、塔菲尔曲线、盐雾试验、接触角、热性能和机械性能等。结果表明,与纯环氧涂层相比,掺杂0.5% OAPPS-BN-AT的环氧复合涂层性能提升幅度最大,阻抗值为1.27×1011 Ω·cm2;腐蚀电位提高了0.35 V,达到−0.052 V;耐盐雾性能也有明显提高,30天未出现点蚀和起泡。此外,基于POSS杂化氮化硼功能助剂中POSS表面迁移作用和h-BN屏障作用,复合涂层铅笔硬度提高到3H级别;表面疏水性有所提升,接触角从纯环氧涂层的67.1°增大到93.2°,并且还显示出优良的附着力、耐冲击性、柔韧性和耐热性能,说明OAPPS-BN-AT/EP防腐涂层在金属腐蚀与防护领域将具有一定的潜在应用前景。

     

  • 图  1  两种POSS杂化氮化硼功能助剂( APS-BN和OAPPS-BN)的合成路线图

    Figure  1.  Schematic illustration of APS-BN and OAPPS-BN

    图  2  h-BN、OH-BN、KH-560-BN、APS-BN、OAPPS-BN的红外光谱图

    Figure  2.  Infrared spectra of h-BN, OH-BN, KH-560-BN, APS-BN, OAPPS-BN

    图  3  (a) h-BN、OH-BN、KH-560-BN、APS-BN、OAPPS-BN的XRD谱图全谱;(b) OAPPS-BN的XRD局部放大图

    Figure  3.  (a) Full XRD patterns of h-BN, OH-BN, KH-560-BN, APS-BN, OAPPS-BN; (b) Partial enlarged view of XRD spectrum of OAPPS-BN

    图  4  h-BN (a)、OH-BN (b)、KH-560-BN (c)、APS-BN (d)和OAPPS-BN (e)的扫描电镜图

    Figure  4.  SEM images of h-BN (a), OH-BN (b), KH-560-BN (c), APS-BN (d) and OAPPS-BN (e)

    图  5  EP、0.5%OH-BN-AT/EP、0.5%APS-BN-AT/EP、0.5%BN-OPPS-AT/EP、0.25%、0.5%、0.75%OAPPS-BN-AT/EP浸泡1天的Bode-Phase图(a)、1天的Nyquist图(b)、15天的Bode-Phase图(c)、15天的Nyquist图(d)、30天的Bode-Phase图(e)和30天的Nyquist图 (f)

    Figure  5.  Bode-Phase diagram soaked for 1 day (a), 15 days (c), 30 days (e) and Nyquist diagram soaked for 1 day (b), 15 days (d), 30 days (f) of EP, 0.5%OH-BN-AT/EP, 0.5%APS-BN-AT/EP, 0.5%BN-OPPS-AT/EP, 0.25%, 0.5%, 0.75%OAPPS-BN-AT/EP

    图  6  EP涂层浸泡30天后的塔菲尔极化曲线

    Figure  6.  Tafel polarization curves of the EP coatings after soaking for 30 days

    图  7  EP复合防腐涂层盐雾箱放置30天后的光学照片

    Figure  7.  Optical photograph of EP coatings put in salt spray tank after 30 days ((a)EP, (b) 0.5%OH-BN-AT/EP, (c) 0.5%APS-BN-AT/EP, (d) 0.5%BN-OPPS-AT/EP, (e,f,g) 0.25%,0.5%,0.75%OAPPS-BN-AT/EP )

    图  8  EP(a,f)、0.5%OH-BN-AT/EP(b,g)、0.5%APS-BN-AT/EP(c,h)、0.5%BN-OPPS-AT/EP(d,i)、0.5%OAPPS-BN-AT/EP(e,j)涂层及其分别放置30天后的表面接触角测试图

    Figure  8.  Contact angle of EP(a,f), 0.5%OH-BN-AT/EP(b,g), 0.5%APS-BN-AT/EP(c,h), 0.5%BN-OPPS-AT/EP(d,i), 0.5%OAPPS-BN-AT/EP(e,j) coatings at initial state and being placed for 30 days

    图  9  EP涂层断面扫描电镜图

    Figure  9.  Sectional SEM images of EP coatings: ((a)EP, (b) 0.5%OH-BN-AT-EP, (c) 0.5%APS-BN-AT-EP, (d) 0.5%BN-OPPS-AT-EP, (e) 0.25%OAPPS-BN-AT/EP, (f) 0.5%OAPPS-BN-AT/EP, and (g) 0.75%OAPPS-BN-AT/EP coating)

    图  10  EP涂层高低温交变实验后的光学照片

    Figure  10.  Optical photograph of EP coatings after high and low temperature alternation experiment ((a)EP, (b) 0.5%OH-BN-AT/EP, (c) 0.5%APS-BN-AT/EP, (d) 0.5%BN-OPPS-AT/EP, (e) 0.5%OAPPS-BN-AT/EP)

    图  11  EP复合涂层的防腐机制

    Figure  11.  Anti-corrosion mechanism of composite EP coating

    表  1  EP,0.5%OH-BN-AT/EP,0.5%APS-BN-AT/EP,0.5%BN-OPPS-AT/EP, 0.25%、0.5%、0.75%OAPPS-BN-AT/EP涂层的塔菲尔曲线拟合值

    Table  1.   Tafel curve fitting value of EP,0.5%OH-BN-AT/EP,0.5%APS-BN-AT/EP,0.5%BN-OPPS-AT/EP,0.25%、0.5%、0.75%OAPPS-BN-AT/EP coatings

    SampleEcorr /VIcorr /(A·cm−2)
    EP−0.409582.971×10−11
    0.5%OH-BN-AT/EP−0.143168.511×10−11
    0.5%APS-BN-AT/EP−0.106026.109×10−14
    0.5%BN-OPPS-AT/EP−0.204803.548×10−13
    0.25%OAPPS-BN-AT/EP−0.100138.551×10−13
    0.5%OAPPS-BN-AT/EP−0.052064.677×10−14
    0.75%OAPPS-BN-AT/EP−0.192339.898×10−11
    Notes: Ecorr is the corrosion potential, Icorr is the corrosion current density.
    下载: 导出CSV

    表  2  环氧复合防腐涂层的物理性能表

    Table  2.   Physical properties of epoxy composite anticorrosive coating

    SampleThickness/μmAdhesionImpact resistanceFlexibilityPencil hardness
    EP35Level 050 cm
    no crack
    2 mm
    no peeling
    2H
    0.25% OH-BN-AT/EP31Level 050 cm
    no crack
    2 mm
    no peeling
    2H
    0.5% OH-BN-
    AT/EP
    30Level 050 cm
    no crack
    2 mm
    no peeling
    2H
    0.75% OH-BN-AT/EP31Level 050 cm
    no crack
    2 mm
    no peeling
    2H
    0.25%APS-BN-AT/EP33Level 050 cm
    no crack
    2 mm
    no peeling
    2H
    0.5% APS-BN-
    AT/EP
    37Level 050 cm
    no crack
    2 mm
    no peeling
    2H
    0.75%APS-BN-AT/EP37Level 050 cm
    no crack
    2 mm
    no peeling
    3H
    0.25%BN-OPPS-AT/EP31Level 050 cm
    no crack
    2 mm
    no peeling
    3H
    0.5%BN-OPPS-AT/EP39Level 050 cm
    no crack
    2 mm
    no peeling
    3H
    0.75%BN-OPPS-AT/EP35Level 050 cm
    no crack
    2 mm
    no peeling
    3H
    0.25%OAPPS-BN-AT/EP39Level 050 cm
    no crack
    2 mm
    no peeling
    3H
    0.5%OAPPS-BN-AT/EP33Level 050 cm
    no crack
    2 mm
    no peeling
    3H
    0.75%OAPPS-BN-AT/EP35Level 050 cm
    no crack
    2 mm
    no peeling
    3H
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-11-03
  • 录用日期:  2021-12-21
  • 修回日期:  2021-12-09
  • 网络出版日期:  2022-01-10

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