共价功能化碳化硅-磺化聚苯胺/环氧树脂防腐复合涂层的制备及防腐性能

段俊; 欧宝立; 周龙平; 郭艳; 支倩

doi:10.13801/j.cnki.fhclxb.20210805.003

共价功能化碳化硅-磺化聚苯胺/环氧树脂防腐复合涂层的制备及防腐性能

doi: 10.13801/j.cnki.fhclxb.20210805.003

段俊¹,
欧宝立^{1, 2, ,},
周龙平¹,
郭艳¹,
支倩¹

1.
湖南科技大学　材料科学与工程学院，湘潭 411201
2.
清华大学　摩擦学国家重点实验室，北京 100084

基金项目: 国家自然科学基金项目(51775183；51905167)；湖南省自然科学基金项目(2021JJ30259；2020JJ5197)；清华大学摩擦学国家重点实验室开放基金项目(SKLTKF21B17)；湖南省普通高等学校教学改革研究项目(湘教通[2019]291号)

详细信息

通讯作者:
欧宝立，博士，教授，博士生导师，研究方向为自修复、防腐、超疏水复合材料　E-mail：B.Ou@hnust.edu.cn

中图分类号: TQ174.75
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出版历程
- 收稿日期: 2021-05-10
- 修回日期: 2021-06-23
- 录用日期: 2021-07-09
- 网络出版日期: 2021-08-05
- 刊出日期: 2022-03-23

Preparation and anticorrosive performance of covalently functionalized silicon carbide-sulfonated polyaniline/epoxy resin anticorrosive composite coating

DUAN Jun¹,
OU Baoli^{1, 2
, ,},
ZHOU Longping¹,
GUO Yan¹,
ZHI Qian¹

1.
School of Materials Science and Engineering, Hunan University of Science and Technology, Xiangtan 411201, China
2.
State Key Laboratory of Tribology, Tsinghua University, Beijing 100084, China

摘要

摘要: 聚合物/无机物纳米复合材料由于其独特的性能成为目前材料研究的热点之一。为得到疏水性能及防腐性能俱优的碳化硅 (SiC) 防腐复合涂层材料，利用硅烷偶联剂 (KH-550) 对碳化硅 (SiC) 纳米粒子进行氨基化处理，然后以苯胺、氨基苯磺酸和氨基化SiC纳米粒子为原料，通过一步法氧化聚合反应合成共价功能化碳化硅-磺化聚苯胺 (SiC-NH₂-SPANI) 复合材料，采用FT-IR、UV-vis、XRD 和SEM对复合材料的微观结构和形貌进行表征分析。最后通过喷涂法将SiC-NH₂-SPANI复合涂层材料涂覆于基材上并对其进行性能测试，主要研究涂层的疏水性能和防腐性能；并探讨了不同SiC纳米粒子和过硫酸铵(APS)的反应量以及复合材料加入量对共价功能化碳化硅-磺化聚苯胺/环氧树脂 (SiC-NH₂-SPANI/EP) 防腐复合涂层的影响。研究结果表明，加入质量分数为3wt%SiC-NH₂-SPANI的复合涂层具备较优的疏水性能，接触角(CA)值达到99.87°。SiC纳米粒子和过硫酸铵反应量对涂层防腐性能研究结果表明，当SiC-NH₂用量为15wt%时，采用过硫酸铵与含氨基单体(苯胺和氨基苯磺酸)摩尔比为1∶1时所制备的SiC-NH₂-SPANI/EP涂层的防腐性能最好。掺杂不同材料的复合涂层 (SiC/EP、SiC-NH₂/EP和SiC-NH₂-SPANI/EP) 中，SiC-NH₂/EP涂层的接触角最大，疏水性能最好，防腐性能表现最好。由此也说明涂层疏水性能与防腐性能存在关系，疏水性能越好，防腐性能越好。随浸泡时间增加，质量分数为3wt%SiC-NH₂-SPANI/EP复合涂层展现出更优异的长期稳定性和防腐性能。
- 碳化硅纳米粒子 /
- 功能化 /
- 磺化聚苯胺 /
- 复合涂层 /
- 防腐蚀
Abstract: Polymer/inorganic nanocomposites have attracted extensive research interests due to their unique properties. In order to obtain SiC composite coating material with excellent hydrophobic and anticorrosive performance, silicon carbide (SiC) nanoparticles were ammoniated by silane coupling agent (KH-550), and then the covalently functionalized SiC-sulfonated polyaniline (SiC-NH₂-SPANI) composites were synthesized by one-step oxidative polymerization of aniline, aminobenzenesulfonic acid and aminated SiC nanoparticles, the microstructure and morphology of the composites were characterizated by FT-IR, UV-vis, XRD and SEM. Finally, the SiC-NH₂-SPANI epoxy coating was coated on the substrate by spraying method and the hydrophobic and anticorrosion performance of the prepared coating was studied. The effects of the amount of different SiC nanoparticle, ammonium persulfate and the amount of the composite materials on the covalently functionalized silicon carbide-sulfonated polyaniline/epoxy resin anticorrosive composite coating (SiC-NH₂-SPANI/EP) was investigated. The results of hydrophobic property show that the contact angle value of the composite coating with 3wt%SiC-NH₂-SPANI reaches 99.87°, which is higher than that of the composite coating that used the pristine SiC substituted for SiC-NH₂. With regard to the influence of different reaction amount of SiC and ammonium persulfate, the anticorrosion performance of SiC-NH₂-SPANI/EP is the best when the mass ratio of 15wt%SiC-NH₂ to ammonium persulfate (APS) is 1 : 1. Among the composite coatings doped with different materials (SiC/EP, SiC-NH₂/EP and SiC-NH₂-SPANI/EP), the SiC-NH₂/EP coating has the largest contact angle, the best hydrophobic performance and anticorrosion performance. It also shows that there is a relationship between hydrophobic property and anticorrosion pro-perty and the hydrophobic performance is directly proportional to anticorrosive performance. With regard to the influence of the content of composite coatings, the long-term stability and corrosion resistance are more excellent when the addition of SiC-NH₂-SPANI/EP is 3wt%.
- silicon carbide nanoparticle /
- functionalization /
- sulfonated polyaniline /
- composite coating /
- anticorrosion

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图 1 共价功能化碳化硅-磺化聚苯胺/环氧树脂 (SiC-NH₂-SPANI/EP) 防腐复合涂层制备过程示意图

Figure 1. Schematic illustrating process for the preparation of covalently functionalized silicon carbide-sulfonated polyaniline/epoxy resin (SiC-NH₂-SPANI/EP) anticorrosive composite coating

APS—Ammonium persulfate; KH550—3-Aminopropyltriethoxysilane

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图 2 SiC-NH₂-SPANI的FT-IR图谱(a)、紫外光谱图 (b) 和X射线衍射图 (c)

Figure 2. FT-IR (a), UV-vis spectra (b) and XRD patterns (c) of SiC-NH₂-SPANI

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图 3 SiC-NH₂-SPANI的SEM图像

Figure 3. SEM images of SiC-NH₂-SPANI

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图 4 原始SiC (a)、 SiC-NH₂ (b)、1wt%SiC-NH₂-SPANI (c)、3wt%SiC-NH₂-SPANI(d)和5wt%SiC-NH₂-SPANI(e) 复合涂层的水接触角(CA)对比

Figure 4. Comparison of water contact angles (CA) of pristine SiC (a), SiC-NH₂ (b), 1wt%SiC-NH₂-SPANI (c), 3wt%SiC-NH₂-SPANI (d) and 5wt%SiC-NH₂-SPANI (e) composite coating

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图 5 SiC用量(a)和APS用量(b)对SiC-NH₂-SPANI/EP复合材料涂层的Nyquist图影响

Figure 5. Influence of SiC dosage (a) and APS dosage (b) on the Nyquist plot of SiC-NH₂-SPANI/EP composite coating

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图 6 SiC用量(a)和APS用量(b)对SiC-NH₂-SPANI/EP复合材料涂层的Bode图影响

Figure 6. Influence of SiC dosage (a) and APS dosage (b) on the Bode plot of SiC-NH₂-SPANI/EP composite coating

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图 8 不同材料复合涂层的Nyquist图 (a)、Bode图 (b) 和塔菲尔曲线图 (c)

Figure 8. Nyquist plot (a), Bode plot (b) and Tafel curve plot (c) of different composite coating

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图 7 SiC用量(a)和APS用量(b)对SiC-NH₂-SPANI/EP涂层的塔菲尔曲线的影响

Figure 7. Influence of SiC dosage (a) and APS dosage (b) on the Tafel curve of SiC-NH₂-SPANI/EP composite coating

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图 9 不同含量SiC-NH₂-SPANI复合涂层的Nyquist图(a)、Bode图(b)和塔菲尔曲线图(c)

Figure 9. Nyquist plot (a), Bode plot (b) and Tafel curve plot (c) of SiC-NH₂-SPANI composite coatings with different contents

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图 10 不同浸泡时间下不同含量SiC-NH₂-SPANI/EP的Nyquist图 ((a), (c), (e)) 和Bode图 ((b), (d), (f))

Figure 10. Nyquist plot ((a), (c), (e)) and Bode plot ((b), (d), (f)) of different contents for SiC-NH₂-SPANI/EP with different soak time

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图 11 不同浸泡时间下3wt%SiC-NH₂-SPANI/EP的Nyquist图 (a) 和Bode图 (b)

Figure 11. Nyquist plot (a) and Bode plot (b) of 3wt%SiC-NH₂-SPANI/EP with different soak time

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图 12 腐蚀过程下第一阶段(a)和第二阶段(b)的等效电路

Figure 12. Equivalent circuit of the first stage (a) and the second stage (b) under the corrosion process

R_s—Solution resistance; R_c—Coating resistance; C_c—Coated capacitance; R_ct—Diffusion layer resistance; C_dl—Diffusion layer capacitance

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表 1 Q235钢涂覆涂层电极在3.5wt%NaCl溶液中的电化学参数

Table 1. Electrochemical parameters of Q235 steel coated electrode in 3.5wt% NaCl solution

Coating	β_c/(mV·dec⁻¹)	β_a/(mV·dec⁻¹)	lgi_c	lgi_a	i_corr/A	E_corr/V	lgi_corr	R_p/Ω
5wt%SiC	6.505	4.575	−7.386	−7.450	5.023×10⁻⁸	−0.869	−7.415	781163
10wt%SiC	4.058	6.501	−7.326	−7.337	6.136×10⁻⁵	−0.575	−7.335	671055
15wt%SiC	5.993	4.544	−7.509	−7.548	3.976×10⁻⁸	−0.800	−7.531	103779
n(APS) : n(SPANI)=0.8 : 1	6.554	4.432	−7.151	−7.228	9.340×10⁻⁸	−0.856	−7.193	423726
n(APS) : n(SPANI)=1 : 1	5.994	8.231	−7.557	−7.700	3.027×10⁻⁸	−0.708	−7.598	100981
n(APS) : n(SPANI)=1.2 : 1	9.244	2.803	−7.225	−7.193	7.668×10⁻⁸	−0.932	−7.208	470681
Notes: E_corr—Corrosion potential; i_corr—Corrosion current density; β_a—Anode slope; β_c—Cathode slope; R_p—Polarization resistance; i_{c ,}i_a—Current density；n : n—Mole ratio.

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表 2 三种复合涂层电极在3.5wt%NaCl溶液中的电化学参数

Table 2. Electrochemical parameters of three epoxy-coated electrodes in 3.5wt%NaCl solution

Coating	β_c/(mV·dec⁻¹)	β_a/(mV·dec⁻¹)	lgi_c	lgi_a	i_corr/A	E_corr/V	lgi	R_p/Ω
SiC	6.777	5.852	−7.272	−7.251	6.956×10⁻⁸	−0.792	−7.262	494930
SiC-NH₂-SPANI	4.058	6.501	−7.326	−7.337	6.136×10⁻⁸	−0.575	−7.335	671055
SiC-NH₂	5.963	6.663	−7.098	−7.025	1.087×10⁻⁷	−0.716	−7.047	319574

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表 3 不同含量SiC-NH₂-SPANI复合涂层电极在3.5wt%NaCl溶液中的电化学参数

Table 3. Electrochemical parameters of SiC-NH₂-SPANI epoxy coated electrodes with different contents in 3.5wt%NaCl solution

Coating	β_c/(mV·dec⁻¹)	β_a/(mV·dec⁻¹)	lgi_c	lgi_a	i_corr/A	E_corr/V	lgi	R_p/Ω
1wt%SiC-NH₂-SPANI	3.170	9.283	−6.656	−6.664	2.780×10⁻⁷	−0.634	−6.661	125590
3wt%SiC-NH₂-SPANI	5.994	8.231	−7.557	−7.700	3.027×10⁻⁸	−0.708	−7.598	100981
5wt%SiC-NH₂-SPANI	4.058	6.501	−7.326	−7.337	6.136×10⁻⁸	−0.575	−7.335	671055

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