Preparation of GO/epoxy acrylic coating and application in corrosion resistance of concrete to deicing salt
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摘要: 以环氧树脂E-44和3种丙烯酸类单体为原料，采用原位聚合法引入不同掺量的改性氧化石墨烯(GO) (KH560-GO (KGO)和A151-GO (AGO))，得到GO改性环氧丙烯酸(WEP)乳液，加入适量填料及助剂制得KGO/WEP和AGO/WEP防腐涂料并制成复合涂层。结果表明：加入KGO或AGO均可提高WEP涂层的热稳定性；其中0.05wt%KGO/WEP的综合性能较优，该复合涂层的铅笔硬度为5H，冲击强度≥50 cm，粘结强度1.79 MPa，吸水率1.06%，接触角78.05°；紫外老化1000 h后，色差变化较小为0.75，光泽度保持较好为9.7；液体化学介质腐蚀240 h后，涂层形貌仍保持良好；涂层氯离子渗透量为0.34×10−3 mg/(cm2·d)。将GO/WEP涂层涂装于混凝土砂浆试块表面，进行耐除冰盐冻融循环40次后，涂层和混凝土试块的测试结果表明：0.05wt%KGO/WEP涂层综合性能较好，腐蚀后的涂层粘结强度最大为1.91 MPa；砂浆试块的质量增长率为1.46%，6 h氯离子电通量为532 C，抗压强度损失率为18.2%。该复合涂层可有效提高混凝土基材表面的耐除冰盐腐蚀性，对道路养护水平的提升具有重要的研究意义。Abstract: AGO/WEP and KGO/WEP anti-corrosion coating was prepared, using epoxy resin E-44 and three acrylic monomers as raw materials, modified by different dosages of graphene oxide (KH560/GO (KGO), A151/GO (AGO)) under in-situ polymerization method. The results show that the addition of KGO or AGO can both improve the thermal performance of the composite coating. The comprehensive performance of 0.05wt%KGO/WEP is better, the pencil hardness of the composite coating is 5H, the impact strength is more than 50 cm, the bonding strength is 1.79 MPa, the water absorption rate is 1.06%, the contact angle is 78.05°, the color difference after 1000 h UV aging is 0.75, the gloss is maintained well at 9.7, the coating morphology is maintained well after 240 h of chemical resistance, and the chloride ion permeability of the coating is 0.34×10−3 mg/(cm2·d). The results show that the 0.05wt%KGO/WEP coating has good comprehensive performance and a maximum bond strength is 1.91 MPa after 40 salt freeze cycles. The mass growth rate is 1.46%, the chloride ion flux at 6 h is 532 C, the compressive strength loss is 18.2%. The composite coating can effectively improve the corrosion resistance of snow melting salt on the surface of concrete substrate, and has important research significance for improving the maintenance level of roads.
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Key words:
- concrete /
- salt freezing corrosion /
- graphene oxide /
- water-based acrylic paint /
- anticorrosion coating
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图 1 硅烷改性氧化石墨烯(GO)的制备
Figure 1. Preparation of silane-modified graphene oxide (GO)
T—Temperature
图 2 原位聚合GO/环氧丙烯酸(WEP)乳液的制备
Figure 2. Preparation of in-situ polymerization GO/epoxy acrylic (WEP) emulsion
SDBS—Sodium dodecyl benzene sulfonate; OP-10—Octyl phenol polyoxyethylene ether-10; MMA—Methyl methacrylate; MAA—Methacrylic acid; BA—Butyl acrylate; E-44—E-44 epoxy resin; APS—Ammonium persulfate
图 3 混凝土单面法盐冻测试装置图
Figure 3. Concrete single-sided method salt freezing test device drawing
图 4 GO改性前后的红外图谱
Figure 4. Infrared spectra of GO before and after modification
KGO—KH560-GO; AGO—A151-GO
图 6 GO、KGO和AGO的TG (a)和DTG (b)曲线
Figure 6. TG (a) and DTG (b) curves of GO, KGO and AGO
图 7 GO (a)、KGO (b)、AGO (c)的SEM图像和EDS图谱
Figure 7. SEM images and EDS spectra of GO (a), KGO (b) and AGO (c)
图 8 WEP涂层、KGO/WEP复合涂层、AGO/WEP复合涂层的TG (a)和DTG (b)曲线
Figure 8. TG (a) and DTG (b) curves of WEP coating, KGO/WEP and AGO/WEP composite coating
图 9 不同掺量KGO/AGO对GO/WEP涂层粘结强度的影响
Figure 9. Effect of different KGO/AGO dosages on the bonding strength of GO/WEP coating
图 10 不同掺量KGO/AGO对GO/WEP涂层吸水率(a)、疏水性(b)的影响
Figure 10. Effect of different KGO/AGO dosages on water absorption (a) and hydrophobicity (b) of GO/WEP coating
图 11 KGO/WEP复合涂层在紫外老化箱每间隔200 h的色差(a)和光泽度变化(b)
Figure 11. Color difference (a) and gloss change (b) of KGO/WEP composite coating in UV aging chamber every 200 h
ΔE—Color difference; GU—Gloss units
图 12 AGO/WEP复合涂层在紫外老化箱每间隔200 h的色差(a)和光泽度变化(b)
Figure 12. Color difference (a) and gloss change (b) of AGO/WEP composite coating in UV aging chamber every 200 h
图 13 不同掺量KGO/WEP涂层在不同介质中腐蚀后的SEM图像：(a) 0wt%；(b) 0.025wt%；(c) 0.05wt%；(d) 0.075wt%；(e) 0.1wt%
Figure 13. SEM images of the coatings with different dosages the KGO/WEP after corrosion in different media: (a) 0wt%; (b) 0.025wt%; (c) 0.05wt%; (d) 0.075wt%; (e) 0.1wt%
图 14 不同掺量AGO/WEP涂层在不同介质中腐蚀后的SEM图像：(a) 0.025wt%；(b) 0.05wt%；(c) 0.075wt%；(d) 0.1wt%
Figure 14. SEM images of the coatings with different dosages the AGO/WEP after corrosion in different media: (a) 0.025wt%; (b) 0.05wt%; (c) 0.075wt%; (d) 0.1wt%
图 15 不同添加量GO下GO/WEP涂层的氯离子渗透量
Figure 15. Chloride permeability of GO/WEP coatings with different GO addition amounts
图 16 盐冻循环前后混凝土涂层的粘结强度变化
Figure 16. Change of bond strength of concrete coating before and after salt-freeze cycle
图 17 KGO/WEO防腐涂层的防护机制
Figure 17. Protective mechanism of KGO/WEP anti-corrosion coating
表 2 不同掺量的GO对GO/WEP涂层的铅笔硬度与冲击强度的影响
Table 2. Effects of different dosages of GO on pencil hardness and impact strength of GO/WEP coating
Different dosages of GO/wt% Pencil hardness Impact strength/cm KGO/WEP AGO/WEP KGO/WEP AGO/WEP 0 3H 3H 45 45 0.025 4H 3H ≥50 ≥50 0.05 5H 4H ≥50 ≥50 0.075 4H 4H ≥50 ≥50 0.1 4H 4H ≥50 ≥50 
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表 3 混凝土盐冻循环(40次)后的质量增长率
Table 3. Quality growth rate after concrete salting cycles (40 times)
Type of coating Quality growth rate/% Uncoated 5.33 WEP 2.36 0.05wt%KGO/WEP 1.46
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表 4 氯离子渗透电通量评价标准
Table 4. Evaluation criteria for chloride ion permeation flux
6 h electrical flux/C Chloride permeability >4000 High 2000-4000 Medium 1000-2000 Low 100-1000 Very low <100 Ignore
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表 5 混凝土抗氯离子渗透性能
Table 5. Resistance of concrete to chloride ion permeability
Type of coating 6 h electrical
flux/CChloride
permeabilityUncoated 2016 Medium WEP 1387 Low 0.05wt%KGO/WEP 532 Very low
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表 6 混凝土盐冻循环(40次)前后的抗压强度变化
Table 6. Change in compressive strength of concrete before and after the salt-freezing cycle (40 times)
Type of coating Compressive strength before the
salt-freezing cycle/MPaCompressive strength after the
salt-freezing cycle/MPaStrength loss rate/% Uncoated 44 22 50.0 WEP 27 38.6 0.05wt%KGO/WEP 36 18.2
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