Photothermal self-healing and corrosion resistance of graphene oxide-shape memory epoxy resin/perfluorodecyltrimethoxysilane-polydimethylsiloxane@SiO2 superhydrophobic coatings
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摘要: 针对物理损伤修复时间较长、修复率较低及极端条件下不锈钢易被腐蚀等实际问题，本文以具有光热效应的自修复涂层氧化石墨烯-形状记忆环氧树脂(GO-SMEP)为底层，以多级粗糙微纳米结构的超疏水涂层全氟癸基三甲氧基硅烷-聚二甲基硅氧烷@二氧化硅(PFDT-PDMS@SiO2)为表层，基于双层设计获得了一种快速修复物理损伤的光热自修复超疏水涂层GO-SMEP/PFDT-PDMS@SiO2 (GO-SMEP/PPS)，并对该涂层的制备优化及其润湿性、光热效应、耐蚀性、自修复等性能进行研究。结果表明，当质量比PDMS∶μ-SiO2∶n-SiO2=1.5∶1∶1，PFDT含量为30wt%时，GO-SMEP/PPS涂层在304不锈钢基底上的超疏水性最佳，并表现出明显的镜面现象及对液滴高度排斥。GO-SMEP/PPS涂层的光热效应随着光热转化剂GO含量的增加而增强，GO含量为0.5wt%的GO-SMEP/PPS涂层经3周期的近红外光循环辐射，其光热效应保持稳定。将GO-SMEP/PPS受损涂层置于808 nm近红外光下，经3 min短时间的辐射，其物理划痕由40 μm修复至1 μm左右，基于修复前后涂层的低频阻抗模量(|Z|0.01 Hz)进一步计算其修复率高达97.5%。交流阻抗谱(EIS)分析表明，GO-SMEP/PPS(0.5wt% GO)涂层的耐蚀性由GO-SMEP底层和PPS表层共同决定，其容抗弧半径大，低频阻抗模量|Z|0.01 Hz高达3.2×105 Ω·cm2，对腐蚀性介质的阻隔性强，表现出良好的耐蚀性。在304不锈钢基底上涂覆该涂层后，所测点蚀电位(Eb=0.263 V)和维钝电流密度(Ip=4.80×10−8 A/cm2)表明对不锈钢防腐效果良好。Abstract:
In this paper, based on the two-layer design, a photothermal self-healing superhydrophobic coating graphene oxide-shape memory epoxy resin (GO-SMEP)/perfluorodecyltrimethoxysilane-polydimethylsiloxane (PFDT-PDMS)@SiO2 (GO-SMEP/PPS) that could quickly repair physical damages was prepared. Aiming to solve the practical problems of the physical damage repair time is long, the repair rate is low, and stainless steel is susceptible to corrosion under extreme conditions for a long time. The double-layer coating was designed by combination of self-healing coating with photothermal effect GO-SMEP and the superhydrophobic coating with multi-level rough micro-nano structure PPS. Furthermore, the preparation optimization of the coating and its wettability, photothermal effect, corrosion resistance, self-healing and other properties were studied.The results show that when mass ratio of PDMS∶μ-SiO2∶n-SiO2=1.5∶1∶1 and the PFDT content is 30wt%, the superhydrophobicity of the GO-SMEP/PPS coating on the 304 stainless steel substrate is the best, and exhibits apparent specularity and high repulsion to droplets. The photothermal effect of the GO-SMEP/PPS coating is enhanced with the increase of the photothermal conversion agent GO content, and the GO-SMEP/PPS coating with a GO content of 0.5wt% is subjected to 3 cycles of near-infrared light cycling radiation, its photothermal effect remains highly stable.The damaged GO-SMEP/PPS coating was placed under 808 nm near-infrared light, and the physical scratches were repaired from 40 μm to about 1 μm after a short period of irradiation for 3 min. Based on the low-frequency impedance modulus of the coating before and after repair (|Z|0.01 Hz) further calculates the restoration rate as high as 97.5%. The AC impedance spectroscopy (EIS) analysis shows that the corrosion resistance of the GO-SMEP/PPS (0.5wt% GO) coating is jointly determined by the GO-SMEP bottom layer and the PPS surface layer, with the largest capacitive arc radius and the low-frequency impedance modulus |Z|0.01 Hz is as high as 3.2×105 Ω·cm2, which has the strongest barrier to corrosive media and shows good corrosion resistance. After applying the coating on 304 stainless steel substrate, the measured pitting corrosion potential (Eb=0.263 V) and passive current density (Ip=4.80×10-8 A/cm2) shows good corrosion resistance to stainless steel. -
图 1 氧化石墨烯-形状记忆环氧树脂(GO-SMEP)/全氟癸基三甲氧基硅烷-聚二甲基硅氧烷(PFDT-PDMS)@SiO2 (PPS)涂层的制备过程示意图
Figure 1. Schematic diagram of the preparation process of graphene oxide-shape memory epoxy resin (GO-SMEP)/perfluorodecyltrimethoxysilane-polydimethylsiloxane (PFDT-PDMS)@SiO2 (PPS) coating
DGEBA—Bisphenol A diglycidyl ether; D-230—Polyetheramine D-230; DMF—Dimethylformamide
图 2 PDMS (a)、PFDT (b) 含量对PPS涂层水接触角(CA)和滚动角(SA)的影响
Figure 2. PDMS (a), PFDT (b) content on water contact angle (CA) and sliding angle (SA) of PPS coating
图 3 (a) SMEP、GO、GO-SMEP和GO-SMEP/PPS的FTIR图谱；(b) SMEP、GO、GO-SMEP和GO-SMEP/PPS的XPS图谱；((c)~(e)) SMEP、GO、GO-SMEP的C1s图谱
Figure 3. (a) FTIR spectra of SMEP, GO, GO-SMEP and GO-SMEP/PPS; (b) XPS spectra of SMEP, GO, GO-SMEP and GO-SMEP/PPS; ((c)-(e)) C1s spectra of SMEP, GO, GO-SMEP
图 4 GO-SMEP和GO-SMEP/PPS样品：((a), (b)) 在近红外光(NIR)照射下的温度变化；((c), (d)) 循环辐照曲线(0.5wt%GO)
Figure 4. GO-SMEP and GO-SMEP/PPS samples: ((a), (b)) Temperature changes of the samples under near infrared (NIR) irradiation; ((c), (d)) Cyclic irradiation curves (0.5wt%GO)
图 5 GO-SMEP (a)、PPS (b)、GO-SMEP/PPS (c) 的SEM图像；水滴滴于GO-SMEP (d)、PPS (f)、GO-SMEP/PPS (h) 涂层表面的照片；GO-SMEP (e)、PPS (g)、GO-SMEP/PPS (i) 浸泡在去离子水中的照片；GO-SMEP (j)、PPS (l)、GO-SMEP/PPS (n) 的水接触角；水流射在GO-SMEP (k)、PPS (m)、GO-SMEP/PPS (o) 涂层表面的光学照片
Figure 5. SEM images of GO-SMEP (a), PPS (b), GO-SMEP/PPS (c); Photographs of the GO-SMEP (d), PPS (f), GO-SMEP/PPS (h) coatings with water droplet; Photographs of GO-SMEP (e), PPS (g), GO-SMEP/PPS (i) soaked in deionized in water; Water contact angles of GO-SMEP (j), PPS (l), GO-SMEP/PPS (n) coating; Optical photograph of the surface of GO-SMEP (k), PPS (m), GO-SMEP/PPS (o) coatings with blue drops
图 6 不同涂层的Nyquist图 (a)、阻抗模量曲线 (b)、相位角曲线 (c) 和GO-SMEP/PPS涂层的阻抗模量曲线 (d)
Figure 6. Nyquist plot (a), impedance modulus curves (b), phase angle (c) and impedance modulus curves (d) of GO-SMEP/PPS coating
Z', Z"—Nyquist diagram represent the real and imaginary parts of the impedance
图 8 不同GO含量的GO-SMEP/PPS涂层近红外光辐射前后的阻抗模量曲线 ((a)~(d)) 和相位角图 ((e)~(h))
Figure 8. Impedance modulus ((a)-(d)) and phase angle ((e)-(h)) of GO-SMEP/PPS coatings with different contents of GO before and after near-infrared irradiation
图 9 GO-SMEP/PPS(0.5wt%GO)涂层在近红外光下辐射3 min修复前后的表面形貌：(a) 修复前；(b) 修复后；在近红外光下辐射不同时间对应的红外热成像图片：(c) 0 min；(d) 1 min；(e) 2 min；(f) 3 min
Figure 9. Surface morphologies of GO-SMEP/PPS (0.5wt%GO) coatings before and after healing under near-infrared light for 3 min: (a) Before repair; (b) After repair; Corresponding to different time of irradiation under near-infrared light infrared thermal imaging: (c) 0 min; (d) 1 min; (e) 2 min; (f) 3 min
表 1 裸不锈钢、涂覆PPS、SMEP、GO-SMEP及GO-SMEP/PPS涂层的不锈钢基底防腐评价相关参数
Table 1. Corrosion-resistant evaluation parameters of bare stainless steel, stainless steel substrate coated with PPS, SMEP, GO-SMEP and GO-SMEP/PPS coating
Coating Ecorr/V Icorr/A Eb/V Ip/A 304 stainless steel −0.741 6.21×10−5 −0.0137 8.19×10−5 PPS −0.439 1.42×10−5 −0.0103 1.47×10−5 SMEP −0.356 1.922×10−6 −0.0700 3.01×10−7 GO-SMEP −0.240 8.582×10−7 0.1800 2.40×10−7 GO-SMEP/PPS −0.106 2.612×10−8 0.2630 4.80×10−8 Notes: Ecorr—Self-corrosion potential; Icorr—Self-corrosion current density; Eb—Pitting potential; Ip—Passive current density. 
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表 2 修复前后GO-SMEP/PPS涂层的接触角及滚动角
Table 2. Contact angle and rolling angle of GO-SMEP/PPS coatings before and after healing
CA/(°) SA/(°) 0.1wt%GO 0.5wt%GO 1.0wt%GO 2.0wt%GO 0.1wt%GO 0.5wt%GO 1.0wt%GO 2.0wt%GO Original 154.3° 154.6° 154.8° 154.9° 5.3° 4.9° 4.6° 4.3° Scratched 147.0° 145.4° 146.4° 146.0° 16.6° 17.8° 16.1° 17.0° Healed 152.8° 153.6° 152.9° 152.4° 6.2° 5.2° 5.5° 6.5°
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