纳米聚多巴胺六方氮化硼–二氧化硅/环氧树脂涂层对水泥砂浆抗碳化能力的影响

刘嘉源; 张宏亮; 左晓宝; 邹欲晓

doi:10.13801/j.cnki.fhclxb.20221213.004

纳米聚多巴胺六方氮化硼–二氧化硅/环氧树脂涂层对水泥砂浆抗碳化能力的影响

doi: 10.13801/j.cnki.fhclxb.20221213.004

南京理工大学　理学院，南京 210094

基金项目: 国家自然科学基金(52078252；51778297)

详细信息

通讯作者:
左晓宝，博士，教授，研究方向为混凝土材料与结构　E-mail：xbzuo@sina.com

中图分类号: TU593；TB332
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出版历程
- 收稿日期: 2022-10-05
- 修回日期: 2022-11-13
- 录用日期: 2022-12-02
- 网络出版日期: 2022-12-14
- 刊出日期: 2023-09-15

Effect of nano polydopamine hexagonal boron nitride-functionalised silicon dioxide/epoxy coating for resistance carbonation ability of cement mortar

School of Science, Nanjing University of Science and Technology, Nanjing 210094, China

Funds: National Natural Science Foundation of China (52078252; 51778297)

摘要

摘要: 为了获得具有良好分散性、填充性和阻隔性的纳米材料，同时将其作为填料以提升环氧树脂涂层对水泥砂浆试件的防护能力，本文制备了纳米聚多巴胺六方氮化硼–二氧化硅(PDABN-fSiO₂)/环氧树脂涂层，涂覆于水泥砂浆试件表面，研究涂层对试件的防护效果。首先，利用盐酸多巴胺(DA)自聚合形成的聚多巴胺(PDA)与偶联剂(KH550)，分别修饰纳米六方氮化硼(hBN)与纳米二氧化硅(SiO₂)，获得纳米聚多巴胺六方氮化硼(PDABN)与功能化的SiO₂(fSiO₂)；其次，经聚合以制备纳米PDABN-fSiO₂；最后，将其作为填料改性环氧树脂，并涂覆于水泥砂浆表面。通过FTIR、SEM-EDS和XPS等微观表征，观察并研究了纳米材料的微观特征；开展了碳化试验和涂层透气性试验，分析了纳米PDABN-fSiO₂对环氧树脂涂层的改性效果。结果表明：制备的纳米PDABN-fSiO₂具有“片层+颗粒”特殊结构，且在涂层中具有良好的分散性，可有效减缓其涂层中CO₂的渗透；同无填料涂层相比，涂覆有纳米PDABN-fSiO₂/环氧树脂涂层的水泥砂浆试件，在碳化7天、14天和28天时的碳化深度分别下降了68.7%、72.9%和64.8%，其涂层在48 h的透气性降低了34.7%。因此，纳米PDABN-fSiO₂掺入环氧树脂涂层后，明显地提高了涂层水泥砂浆试件的抗碳化能力，并降低了环氧树脂涂层的透气性。
- 纳米聚多巴胺六方氮化硼(PDABN)-功能化的SiO₂(fSiO₂) /
- 环氧树脂涂层 /
- 微观表征 /
- 碳化 /
- 透气性
Abstract: In order to obtain nanomaterials with better dispersal, filling and barrier properties, which were used as fillers to enhance the protection of the epoxy coatings for cement mortar, the polydopamine (PDA), which was prepared by self-polymerization of dopamine hydrochloride (DA) and silane coupling agent (KH550), was utilized to modify nano hexagonal boron nitride (hBN) and nano silicon dioxide (SiO₂), respectively, to obtain two nanomaterials polydopamine hexagonal boron nitride (PDABN) and functionalised SiO₂(fSiO₂) by polymerization reactions. A new nanomaterial, polydopamine hexagonal boron nitride-functionalised silicon dioxide (PDABN-fSiO₂), was synthesized, and it was mixed with epoxy to prepare a modified coating. The coating was covered on the surface of cement mortar to enhance its carbonation resistance. The microscopic characteristics of nano materials were observed by FTIR, SEM-EDS and XPS. The modified effect of epoxy coating by nano PDABN-fSiO₂ was analyzed by carbonation experiments and permeability tests. Results indicate that the prepared nano PDABN-fSiO₂ has a layer-particle structure and better dispersion in coating, which can effectively slow down the penetration of CO₂ in the coating. Compared with the blank coating, the carbonation depth of the cement mortar coated with nano PDABN-fSiO₂/epoxy coating is decreased by 68.7%, 72.9% and 64.8% at 7, 14 and 28 days of carbonation, respectively, and the permeability of its coating is decreased by 34.7% at 48 hours. Thus, the epoxy coating with nano PDABN-fSiO₂ can significantly improve the carbonation resistance of cement mortar and reduce its permeability.
- nano polydopamine hexagonal boron nitride (PDABN)-functionalised silicon dioxide (fSiO₂) /
- epoxy coating /
- microscopic test /
- carbonation /
- permeability

HTML全文

图 1 掺入纳米聚多巴胺六方氮化硼-二氧化硅(PDABN-fSiO₂)的环氧树脂涂层制备流程

Figure 1. Preparation process of nano polydopamine hexagonal boron nitride-functionalised silicon dioxide (PDABN-fSiO₂) epoxy coating

下载: 全尺寸图片幻灯片

图 2 环氧树脂中纳米填料的分散过程

Figure 2. Dispersion process of nano fillers in epoxy resins

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图 3 涂层透气性试验装置示意图

Figure 3. Experimental diagram of the gas permeability of coatings

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图 4 各种纳米材料的FTIR图谱

Figure 4. FTIR spectra of various nano materials

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图 5 各种纳米填料的SEM图像及纳米PDABN-fSiO₂不同测试区域的EDS图谱

Figure 5. SEM images of various nano fillers and EDS spectra of nano PDABN-fSiO₂ about different areas

D—Diameter of nano fSiO₂ particles; T—Thickness of nano PDABN layers

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图 6 各种环氧树脂涂层断面处SEM图像及其Mapping分析结果

Figure 6. SEM images and mapping analysis results of cross sectional about various epoxy coatings

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图 7 纳米PDABN-fSiO₂的XPS图谱与纳米PDABN-fSiO₂的XPS高分辨图谱

Figure 7. XPS spectra of nano PDABN-fSiO₂ and its high-resolution XPS spectra

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图 8 水泥砂浆表面涂覆掺入不同填料的环氧树脂涂层在7、14和28天时酚酞显色结果

Figure 8. Results of phenolphthalein color test on cement mortar coated with epoxy coatings with different fillers at 7, 14 and 28 days

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图 9 水泥砂浆表面涂覆掺入不同填料的环氧树脂涂层在7、14和28天时水泥砂浆试件碳化深度

Figure 9. Carbonization depth of cement mortar coated with epoxy coatings with different fillers at 7, 14 and 28 days

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图 10 干燥剂吸水量随时间变化曲线

Figure 10. Curves of water absorption of desiccant with time

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表 1 水泥的氧化物组成

Table 1. Oxide composition of cement wt%

Cement	CaO	SiO₂	Al₂O₃	Fe₂O₃	SO₃	MgO	K₂O	Na₂O	TiO₂
P.II 52.5	66.92	19.28	4.20	3.78	2.07	1.84	0.74	0.30	0.26

下载: 导出CSV

表 2 制备各种含有填料的环氧树脂涂层所需材料与用量

Table 2. Materials and quantities required for the preparation of various epoxy coatings with fillers

Sample	Coating filler component	Epoxy dosage/g	Total amount of filler/g
Epoxy coating	Blank	5	−
Nano SiO₂/epoxy coating	Nano SiO₂	5	0.05
Nano PDABN/epoxy coating	Nano PDABN	5	0.05
Nano PDABN-SiO₂/epoxy coating	Nano PDABN-fSiO₂	5	0.05

下载: 导出CSV

参考文献(32)

[1]	孙伟. 荷载与环境因素耦合作用下结构混凝土的耐久性与服役寿命[J]. 东南大学学报(自然科学版), 2006, 36(S2):7-14. SUN Wei. Durability and service life of structure concrete under load and environment coupling effects[J]. Journal of Southeast University (Natural Science Edition),2006,36(S2):7-14(in Chinese).
[2]	李士彬, 孙伟. 疲劳、碳化和氯盐作用下混凝土劣化的研究进展[J]. 硅酸盐学报, 2013, 41(11):1459-1464. LI Shibin, SUN Wei. Review on deterioration of concrete subjected to coupling effect of fatigue load, carbonation and chlorides[J]. Journal of the Chinese Ceramic Society,2013,41(11):1459-1464(in Chinese).
[3]	柏朱安. 有机成膜涂层混凝土抗碳化性能的时变退化[D]. 徐州: 中国矿业大学, 2017. BO Zhu'an. Time-varying degradation of carbonation re-sistance of organic film-forming coated concrete[D]. Xuzhou: China University of Mining and Technology, 2017(in Chinese).
[4]	马骏, 孙冬, 张明爽, 等. 氧化石墨烯改性环氧树脂涂料的制备及防腐性能[J]. 化工进展, 2021, 40(8):4456-4462. doi: 10.16085/j.issn.1000-6613.2020-1790 MA Jun, SUN Dong, ZHANG Mingshuang, et al. Preparation of graphene oxide modified epoxy resin coating and research on its anti-corrosive performance[J]. Chemical Industry and Engineering Progress,2021,40(8):4456-4462(in Chinese). doi: 10.16085/j.issn.1000-6613.2020-1790
[5]	汪雨微, 欧宝立, 鲁忆, 等. 功能化纳米TiO₂/环氧树脂超疏水防腐复合涂层的制备与性能[J]. 复合材料学报, 2021, 38(12):3971-3985. WANG Yuwei, OU Baoli, LU Yi, et al. Preparation and pro-perties of functionalized nano-TiO₂/epoxy resin superhydrophobic anticorrosive composite coating[J]. Acta Materiae Compositae Sinica,2021,38(12):3971-3985(in Chinese).
[6]	LI G, HU W J, CUI H Y, et al. Long-term effectiveness of carbonation resistance of concrete treated with nano-SiO₂ modified polymer coatings[J]. Construction and Building Materials,2019,201:623-630. doi: 10.1016/j.conbuildmat.2019.01.004
[7]	范春华. 氧化石墨烯改性环氧树脂涂层提升混凝土抗碳化性能的研究[D]. 徐州: 中国矿业大学, 2021. FAN Chunhua. Research on graphene oxide modified epoxy resin coating to enhance the anti-carbonation performance of concrete[D]. Xuzhou: China University of Mining and Technology, 2021(in Chinese).
[8]	郑昌佶, 王博, 杨佳明, 等. 纳米SiO₂分散性对SiO₂/LDPE纳米复合材料直流介电性能的影响[J]. 复合材料学报, 2023, 40(3):1417-1429. ZHENG Changji, WANG Bo, YANG Jiaming, et al. Influence of nano-SiO₂ dispersion on the direct current dielectric properties of SiO₂/LDPE nanocomposite[J]. Acta Materiae Compositae Sinica,2023,40(3):1417-1429(in Chinese).
[9]	YU Z X, DI H H, MA Y, et al. Fabrication of graphene oxide-alumina hybrids to reinforce the anti-corrosion performance of composite epoxy coatings[J]. Applied Surface Science,2015,351:986-996. doi: 10.1016/j.apsusc.2015.06.026
[10]	徐凡, 刘雨薇, 高梦幻, 等. 碳掺杂六方氮化硼通过增强静电相互作用高效去除水中的Cu²⁺[J]. 离子交换与吸附, 2021, 37(6):481-493. XU Fan, LIU Yuwei, GAO Menghuan, et al. Carbon doped h-boron nitride for effective removal of Cu²⁺ from water via enhanced electrostatic interaction[J]. Ion Exchange and Adsorption,2021,37(6):481-493(in Chinese).
[11]	YANG Y C, SONG Z G, LU G Y, et al. Intrinsic toughening and stable crack propagation in hexagonal boron nitride[J]. Nature,2021,594(7861):57-61. doi: 10.1038/s41586-021-03488-1
[12]	中国国家标准化管理委员会. 水泥胶砂强度检验方法(ISO法): GB/T 17671—2021[S]. 北京: 中国标准出版社, 2021. Standardization Administration of China. Test method of cement mortar strength (ISO method): GB/T 17671—2021[S]. Beijing: Standards Press of China, 2021(in Chinese).
[13]	SONG J, DAI Z D, LI J Y, et al. Polydopamine-decorated boron nitride as nano-reinforcing fillers for epoxy resin with enhanced thermomechanical and tribological properties[J]. Materials Research Express,2018,5(7):075029. doi: 10.1088/2053-1591/aab529
[14]	WAN P Y, ZHAO N, QI F G, et al. Synthesis of PDA-BN@f-Al₂O₃ hybrid for nanocomposite epoxy coating with superior corrosion protective properties[J]. Progress in Organic Coatings,2020,146:105713. doi: 10.1016/j.porgcoat.2020.105713
[15]	中华人民共和国交通运输部. 水运工程混凝土试验检测技术规范: JTS/T 236—2019[S]. 北京: 人民交通出版社, 2019. Ministry of Transport of the People's Republic of China. Testing specifications for concrete in water transport engineering: JTS/T 236—2019[S]. Beijing: China Communications Press, 2019(in Chinese).
[16]	GUO Z Q, SUN L, HOU H, et al. Construction of novel maple leaf-like MnO₂-SiO₂@PDA composites for highly efficient removal of Cu(II), Cd(II) and Ni(II) from aqueous solution[J]. Separation and Purification Technology,2022,291:120943. doi: 10.1016/j.seppur.2022.120943
[17]	MUHAMMAD M, HU S H, MA R N, et al. Enhancing the corrosion resistance of Q235 mild steel by incorporating poly(dopamine) modified h-BN nanosheets on zinc phosphate-silane coating[J]. Surface and Coatings Technology,2020,390:125682. doi: 10.1016/j.surfcoat.2020.125682
[18]	JIN W Q, YUAN L, LIANG G Z, et al. Multifunctional cyclotriphosphazene/hexagonal boron nitride hybrids and their flame retarding bismaleimide resins with high thermal conductivity and thermal stability[J]. ACS Applied Materials & Interfaces,2014,6(17):14931-14944.
[19]	MA G X, XU J X, HAN L, et al. Enhanced inhibition performance of NO₂-intercalated MgAl-LDH modified with nano-SiO₂ on steel corrosion in simulated concrete pore solution[J]. Corrosion Science,2022,204:110387. doi: 10.1016/j.corsci.2022.110387
[20]	WEI N, JIANG Y Y, YING Y, et al. Facile construction of a polydopamine-based hydrophobic surface for protection of metals against corrosion[J]. RSC Advances,2017,7(19):11528-11536. doi: 10.1039/c7ra00267j
[21]	LIU H S, TARIQ N U H, HAN R F, et al. Development of hydrogen-free fully amorphous silicon oxycarbide coating by thermal organometallic chemical vapor deposition technique[J]. Journal of Non-Crystalline Solids,2022,575:121204. doi: 10.1016/j.jnoncrysol.2021.121204
[22]	PRASAD V, SEKAR K, JOSEPH M A. Mechanical and water absorption properties of nano TiO₂ coated flax fibre epoxy composites[J]. Construction and Building Materials,2021,284:122803. doi: 10.1016/j.conbuildmat.2021.122803
[23]	XI Z Y, XU Y Y, ZHU L P, et al. A facile method of surface modification for hydrophobic polymer membranes based on the adhesive behavior of poly(DOPA) and poly(dopamine)[J]. Journal of Membrane Science,2009,327:244-253. doi: 10.1016/j.memsci.2008.11.037
[24]	WAN X Y, ZHAN Y Q, LONG Z H, et al. High-performance magnetic poly(arylene ether nitrile) nanocomposites: Co-modification of Fe₃O₄ via mussel inspired poly(dopamine) and amino functionalized silane KH550[J]. Applied Surface Science,2017,425:905-914. doi: 10.1016/j.apsusc.2017.07.136
[25]	WANG D, LIU D, XU J H, et al. Highly thermoconductive yet ultraflexible polymer composites with superior mechanical properties and autonomous self-healing functionality via a binary filler strategy[J]. Materials Horizons,2022,9(2):640-652. doi: 10.1039/D1MH01746B
[26]	张宏亮, 冯礼奎, 宋小宁, 等. 环己胺甲基脲气相缓蚀剂的缓蚀作用研究[J]. 表面技术, 2018, 47(10):45-50. doi: 10.16490/j.cnki.issn.1001-3660.2018.10.006 ZHANG Hongliang, FENG Likui, SONG Xiaoning, et al. Corrosion inhibition of cyclohexyl-aminomethyl-urea as volatile corrosion inhibitor[J]. Surface Technology,2018,47(10):45-50(in Chinese). doi: 10.16490/j.cnki.issn.1001-3660.2018.10.006
[27]	SONG B J, SHI Y C, LIU Q D. An inorganic route to decorate graphene oxide with nanosilica and investigate its effect on anti-corrosion property of waterborne epoxy[J]. Polymers for Advanced Technologies,2020,31(2):309-318. doi: 10.1002/pat.4770
[28]	LIU Y, LIN Q, CHEN J Q, et al. PDMS-OH and nano-SiO₂ modified KH570-TEOS silica-sol coating and protective effect on concrete[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects,2022,648:129279. doi: 10.1016/j.colsurfa.2022.129279
[29]	赵明月, 裴晓园, 王维, 等. 二维纳米填料/环氧树脂复合涂层在腐蚀防护中的应用[J]. 复合材料学报, 2022, 39(5):2049-2059. ZHAO Mingyue, PEI Xiaoyuan, WANG Wei, et al. Application of two-dimensional nanomaterial/epoxy composite coating in corrosion protection[J]. Acta Materiae Compositae Sinica,2022,39(5):2049-2059(in Chinese).
[30]	MA Y, DI H H, YU Z X, et al. Fabrication of silica-decorated graphene oxide nanohybrids and the properties of composite epoxy coatings research[J]. Applied Surface Science,2016,360:936-945. doi: 10.1016/j.apsusc.2015.11.088
[31]	WU Y M, YU J J, ZHAO W J, et al. Investigating the anti-corrosion behaviors of the waterborne epoxy composite coatings with barrier and inhibition roles on mild steel[J]. Progress in Organic Coatings,2019,133:8-18. doi: 10.1016/j.porgcoat.2019.04.028
[32]	随林林, 刘芳, 陈晓蕊, 等. 纳米SiO₂-氧化石墨烯/环氧涂层的制备及其防腐蚀性能[J]. 复合材料学报, 2018, 35(7):1716-1724. SUI Linlin, LIU Fang, CHEN Xiaorui, et al. Preparation and corrosion resistance of nano SiO₂-graphene oxide/epoxy composite coating[J]. Acta Materiae Compositae Sinica,2018,35(7):1716-1724(in Chinese).