Study on anticorrosive properties of epoxy soybean oil resin coating

doi:10.11949/0438-1157.20200842

Abstract

Abstract:

Using epoxy soybean oil (ESO) as the main raw material and tetraethylenepentamine as the curing agent, epoxy soybean oil resin (ESOR) coatings were prepared on the surface of carbon steel. Field emission scanning electron microscope, Fourier infrared change spectrometer, nano-indenter, thermogravimetric analyzer, contact angle measuring instrument, electrochemical impedance spectroscopy and other techniques were used to characterize the performance of the ESOR coatings. It was found that the content of ESO in the raw materials helps to improve the water resistance of the ESOR coating. When the content of ESO in the raw material gradually increases, the hardness, elastic modulus and corrosion resistance of the ESOR coating will also increase. According to the fitted equivalent circuit, the coating resistance R_c of ESOR coating with a molar ratio of epoxy soybean oil to tetraethylenepentamine equal to 2 can reach 8.22×10¹¹ Ω·cm², and the charge transfer resistance R_ct can reach 1.32×10¹⁰ Ω·cm², which shows excellent anti-corrosion performance.

Key words: carbon steel, epoxidized soybean oil, coating, electrochemical impedance spectroscopy, corrosion

摘要：

以环氧大豆油（ESO）为主要原料，四亚乙基五胺为固化剂，在碳钢基底表面制备了环氧豆油树脂（ESOR）涂层。利用场发射扫描电镜、傅里叶红外变化光谱仪、纳米压痕仪、热重分析仪、接触角测量仪、电化学阻抗谱等技术对ESOR涂层的性能进行了表征。结果发现，原料中ESO的含量有助于提高ESOR涂层的耐水性；而当原料中ESO的含量逐渐增加时，ESOR涂层的硬度、弹性模量和耐蚀性都会随之增强；根据拟合的等效电路，ESO与四亚乙基五胺的摩尔比为2的ESOR涂层的涂层电阻R_c能达到8.22×10¹¹ Ω·cm²，电荷转移电阻R_ct能达到1.32 $×$ 10¹⁰ Ω·cm²，表现出了优异的防腐性能。

关键词: 碳钢, 环氧大豆油, 涂层, 电化学阻抗谱, 腐蚀

CLC Number:

TQ 050.9

HE Jizhe, LIU Mingyan, XU Yangshuhan. Study on anticorrosive properties of epoxy soybean oil resin coating[J]. CIESC Journal, 2021, 72(2): 1067-1077.

何吉喆, 刘明言, 徐杨书函. 环氧豆油树脂涂层的防腐性能研究[J]. 化工学报, 2021, 72(2): 1067-1077.

Figures/Tables 15

Fig.1 Thickness of ESOR coatings

Fig.2 DSC curves of ESOR coatings

Fig.3 Curing degree α of ESOR coatings

Fig.4 Load-displacement curves of ESOR coatings

Fig.5 Static mechanical properties of ESOR coatings

Fig.6 TG-DTG curves of ESOR coatings

Fig.7 FTIR of ESO and ESOR coatings

Fig.8 Microscopic of 20# carbon steel and ESOR coatings

Fig.9 Microscopic of ESOR coating soaking in 3.5% NaCl solution for 30 d

Fig.10 Wetting behaviors of pure water on samples surface

Fig.11 Contact angle of ESOR coatings

Fig.12 Bode diagram of ESOR coatings

Fig.13 Nyquist diagram of ESOR coatings

Fig.14 Equivalent circuits model for EIS fitting

Table 1 Simulation data of equivalent circuits of ESOR coatings

涂层	Q_c/ (s^-ⁿ/(cm²·Ω))	R_c/ (Ω·cm²)	Q_dl/ (s^-ⁿ/(cm²·Ω))	R_ct/ (Ω·cm²)
E0.5-0d	2.18 $×$ 10^-11	5.60 $×$ 10⁹	—	—
E0.5-1d	3.34 $×$ 10^-11	9.87 $×$ 10⁸	—	1.31 $×$ 10⁹
E0.5-15d	1.21 $×$ 10^-10	1.12 $×$ 10⁸	7.43 $×$ 10^-11	4.11 $×$ 10⁸
E0.5-30d	7.76 $×$ 10^-9	1.67 $×$ 10⁷	4.88 $×$ 10^-10	1.88 $×$ 10⁷
E1.0-0d	2.03 $×$ 10^-11	4.81 $×$ 10¹¹	—	—
E1.0-1d	2.80 $×$ 10^-11	1.34 $×$ 10¹¹	—	—
E1.0-15d	9.61 $×$ 10^-11	2.11 $×$ 10⁹	3.15 $×$ 10^-11	1.57 $×$ 10⁹
E1.0-30d	3.21 $×$ 10^-10	5.13 $×$ 10⁸	4.33 $×$ 10^-11	4.57 $×$ 10⁸
E1.5-0d	2.07 $×$ 10^-11	5.43 $×$ 10¹¹	—	—
E1.5-1d	2.41 $×$ 10^-11	1.78 $×$ 10¹¹	—	—
E1.5-15d	8.14 $×$ 10^-11	2.86 $×$ 10¹⁰	3.09 $×$ 10^-11	7.66 $×$ 10⁹
E1.5-30d	4.65 $×$ 10^-10	1.23 $×$ 10⁹	4.09 $×$ 10^-11	1.36 $×$ 10⁹
E2.0-0d	1.77 $×$ 10^-11	8.22 $×$ 10¹¹	—	—
E2.0-1d	1.76 $×$ 10^-11	5.57 $×$ 10¹¹	—	—
E2.0-15d	5.13 $×$ 10^-11	3.09 $×$ 10¹⁰	1.43 $×$ 10^-11	1.32 $×$ 10¹⁰
E2.0-30d	1.46 $×$ 10^-10	2.57 $×$ 10⁹	2.11 $×$ 10^-11	3.17 $×$ 10⁹

Table 1 Simulation data of equivalent circuits of ESOR coatings

涂层	Q_c/ (s^-ⁿ/(cm²·Ω))	R_c/ (Ω·cm²)	Q_dl/ (s^-ⁿ/(cm²·Ω))	R_ct/ (Ω·cm²)
E0.5-0d	2.18 $×$ 10^-11	5.60 $×$ 10⁹	—	—
E0.5-1d	3.34 $×$ 10^-11	9.87 $×$ 10⁸	—	1.31 $×$ 10⁹
E0.5-15d	1.21 $×$ 10^-10	1.12 $×$ 10⁸	7.43 $×$ 10^-11	4.11 $×$ 10⁸
E0.5-30d	7.76 $×$ 10^-9	1.67 $×$ 10⁷	4.88 $×$ 10^-10	1.88 $×$ 10⁷
E1.0-0d	2.03 $×$ 10^-11	4.81 $×$ 10¹¹	—	—
E1.0-1d	2.80 $×$ 10^-11	1.34 $×$ 10¹¹	—	—
E1.0-15d	9.61 $×$ 10^-11	2.11 $×$ 10⁹	3.15 $×$ 10^-11	1.57 $×$ 10⁹
E1.0-30d	3.21 $×$ 10^-10	5.13 $×$ 10⁸	4.33 $×$ 10^-11	4.57 $×$ 10⁸
E1.5-0d	2.07 $×$ 10^-11	5.43 $×$ 10¹¹	—	—
E1.5-1d	2.41 $×$ 10^-11	1.78 $×$ 10¹¹	—	—
E1.5-15d	8.14 $×$ 10^-11	2.86 $×$ 10¹⁰	3.09 $×$ 10^-11	7.66 $×$ 10⁹
E1.5-30d	4.65 $×$ 10^-10	1.23 $×$ 10⁹	4.09 $×$ 10^-11	1.36 $×$ 10⁹
E2.0-0d	1.77 $×$ 10^-11	8.22 $×$ 10¹¹	—	—
E2.0-1d	1.76 $×$ 10^-11	5.57 $×$ 10¹¹	—	—
E2.0-15d	5.13 $×$ 10^-11	3.09 $×$ 10¹⁰	1.43 $×$ 10^-11	1.32 $×$ 10¹⁰
E2.0-30d	1.46 $×$ 10^-10	2.57 $×$ 10⁹	2.11 $×$ 10^-11	3.17 $×$ 10⁹

References 45

1	Choi M S, Rehman S U, Kim H, et al. Migration of epoxidized soybean oil from polyvinyl chloride/polyvinylidene chloride food packaging wraps into food simulants[J]. Environmental Science and Pollution Research, 2018, 25(5): 5033-5039.
2	Kong X, Narine S S. Physical properties of sequential interpenetrating polymer networks produced from canola oil-based polyurethane and poly (methyl methacrylate)[J]. Biomacromolecules, 2008, 9(5): 1424-1433.
3	Vu C M, Nguyen V H, Baćh Q H. Phosphorous-jointed epoxidized soybean oil and rice husk-based silica as the novel additives for improvement mechanical and flame retardant of epoxy resin[J]. Journal of Fire Sciences, 2020, 38(1): 3-27.
4	何飞强, 傅和青, 周威. 环氧大豆油和硅氧烷改性水性聚氨酯胶黏剂[J]. 化工学报, 2014, 65(11): 4599-4606.
	He F Q, Fu H Q, Zhou W. Waterborne polyurethane adhesive modifieel by epoxy oil soybean and 3-aminopropyltriethoxysilane [J]. CIESC Journal, 2014, 65(11): 4599-4606.
5	Heinen M, Gerbase A E, Petzhold C L. Vegetable oil-based rigid polyurethanes and phosphorylated flame- retardants derived from epoxydized soybean oil[J]. Polymer Degradation and Stability, 2014, 108: 76-86.
6	Li X, Nie X, Chen J, et al. Synthesis and application of a novel epoxidized plasticizer based on cardanol for poly (vinyl chloride) [J]. Journal of Renewable Materials, 2017, 5(2): 154-164.
7	张继昌, 张艳维, 朱心奇, 等. 绿色增塑剂环氧大豆油的合成与表征[J]. 塑料科技, 2012, 40(8): 93-95.
	Zhang J C, Zhang Y W, Zhu X Q, et al. Study on synthesis and characterization of green plasticizer epoxidized soybean oil[J]. Plastics Science and Technology, 2012, 40(8): 93-95.
8	龚新怀, 辛梅华, 李明春, 等. 环氧大豆油增塑聚乳酸/茶渣生物质复合材料的制备与性能研究[J]. 塑料科技, 2019, 47(4): 54-58
	Gong X H, Xin M H, Li M C, et al. Study on preparation and properties of PLA/TW biocomposites plasticized with ESO[J]. Plastics Science and Technology, 2019, 47(4): 54-58.
9	Karmalm P, Hjertberg T, Jansson A, et al. Network formation by epoxidised soybean oil in plastisol poly(vinyl chloride) [J]. Polymer Degradation and Stability, 2009, 94(11): 1986-1990.
10	Hutzler B W, Machado Lugão A B L D B, et al. Properties of irradiated PVC plasticized with non-endocrine disruptor[J]. Radiation Physics and Chemistry, 2000, 57(3/4/5/6): 381-384.
11	Özşeker A, Karadeniz K, Ylmaz R F. Intrinsically flame retardant polyurethane prepared with epoxidized soybean oil and vinylphosphonic acid[J]. Croatica Chemica Acta, 2018, 91(4): 589-597.
12	Meng X, Bocharova V, Tekinalp H, et al. Toughening of nanocelluose/PLA composites via bio-epoxy interaction: mechanistic study[J]. Materials & Design, 2018, 139(5): 188-197.
13	Qi M, Xu Y, Rao W H, et al. Epoxidized soybean oil cured with tannic acid for fully bio-based epoxy resin[J]. RSC Advances, 2018, 8(47): 26948-26958.
14	Zhao S J, Wang Z, Kang H J, et al. Fully bio-based soybean adhesive in situ cross-linked by interactive network skeleton from plant oil-anchored fiber[J]. Industrial Crops and Products, 2018, 122: 366-374.
15	Pradhan S, Mohanty S, Nayak S K. In-situ aerobic biodegradation study of epoxy-acrylate film in compost soil environment[J]. Journal of Polymers and the Environment, 2018, 26(3): 1133-1144.
16	Wu B, Wang Y, Chen S, et al. Bis-uracil based high efficient heat stabilizers used in super transparent soft poly (vinyl chloride) [J]. Polymer Degradation and Stability, 2018, 149: 143-151.
17	Jin H, Zhang Y, Wang C, et al. Thermal, mechanical, and morphological properties of soybean oil-based polyurethane/epoxy resin interpenetrating polymer networks (IPNs)[J]. Journal of Thermal Analysis and Calorimetry, 2014, 117(2): 773-781.
18	鲍俊翔, 谢晖, 黄莉, 等. UV固化生物基改性柔性环氧丙烯酸酯的合成及性能[J]. 涂料工业, 2020, 50(2): 7-13.
	Bao J X, Xie H, Huang L, et al. Synthesis and performance of UV-curing bio-based modified flexible epoxy acrylates[J]. Paint & Coating industry, 2020, 50(2): 7-13.
19	Yadav S K, Hu F, la Scala J, et al. Toughening anhydride-cured epoxy resins using fatty alkyl-anhydride-grafted epoxidized soybean oil[J]. ACS omega, 2018, 3(3): 2641-2651.
20	Hwang H S, Erhan S Z. Synthetic lubricant basestocks from epoxidized soybean oil and Guerbet alcohols[J]. Industrial Crops and Products, 2006, 23(3): 311-317.
21	Wang W, Xue L, Zhang T, et al. The influence of MgO/ZrO₂/Al₂O₃ refractories on the refining process of Ti-containing steel based on kinetic study[J]. Ceramics International, 2020, 46(11): 17561-17568
22	Song G L, Atrens A. Corrosion mechanisms of magnesium alloys [J]. Advanced Engineering Materials, 1999, 1(1): 11-33.
23	Song G. Recent progress in corrosion and protection of magnesium alloys[J]. Advanced Engineering Materials, 2005, 7(7): 563-586.
24	Popoola L T, Grema A S, Latinwo G K, et al. Corrosion problems during oil and gas production and its mitigation[J]. International Journal of Industrial Chemistry, 2013, 4(1): 1-15.
25	Minhaj A, Saini P A, Quraishi M A, et al. A study of natural compounds as corrosion inhibitors for industrial cooling systems[J]. Corrosion Prevention and Control, 1999, 46(2): 32-38.
26	Chen X H, Chen C S, Xiao H N, et al. Corrosion behavior of carbon nanotubes-Ni composite coating[J]. Surface and Coatings Technology, 2005, 191(2/3): 351-356.
27	Sato Y. Corrosion protection by organic coatings[J]. Corrosion Engineering, 1978, 27(7): 356-366.
28	Liu Y, Zhao Q. Study of electroless Ni-Cu-P coatings and their anti-corrosion properties[J]. Applied Surface Science, 2004, 228(1/2/3/4): 57-62.
29	Jagielski J, Khanna A S, Kucinski J, et al. Effect of chromium nitride coating on the corrosion and wear resistance of stainless steel[J]. Applied Surface Science, 2000, 156(1/2/3/4): 47-64.
30	Wang Z, Liu L M. Corrosion resistant performances of Al-rich epoxy resin based paint on arc-sprayed Al coating[J]. Materials and Corrosion, 2010, 61(2): 152-156.
31	Mo M, Zhao W, Chen Z, et al. Corrosion inhibition of functional graphene reinforced polyurethane nanocomposite coatings with regular textures[J]. RSC Advances, 2016, 6(10): 7780-7790.
32	Rossi S, Chini F, Straffelini G, et al. Corrosion protection properties of electroless Nickel/PTFE, Phosphate/MoS₂ and Bronze/PTFE coatings applied to improve the wear resistance of carbon steel[J]. Surface and Coatings Technology, 2003, 173(2/3): 235-242.
33	Prakash A, Ravindra G, Hyeon J, et al. Controlled hydroxyl functionality of soybean oil-based polyols for polyurethane coatings with improved anticorrosion properties[J]. Macromolecular Research, 2018, 26(8): 696-703.
34	Ammar S, Iling A, Ramesh K, et al. Development of fully organic coating system modified with epoxidized soybean oil with superior corrosion protection performance[J]. Progress in Organic Coatings, 2020, 140: 105523.
35	Lingner M, Heinen M, Silva R C, et al. Reinforcing anticorrosive properties of biobased organic coatings through chemical functionalization with amino and aromatic groups[J]. Progress in Organic Coatings, 2018, 125: 372-383.
36	Ibrahim M S, Mohamed H A, Kandile N G, et al. Electron beam processed plasticized epoxy coatings for surface protection[J]. Materials Chemistry and Physics, 2011, 130(1/2): 237-242
37	徐杨书函, 董强, 刘求安, 等. 一种用于金属表面防腐蚀的环氧豆油树脂涂层的制备方法: 201910476127. 3 [P]. 2019-08-16.
	Xu Y S H, Dong Q, Liu Q A, et al. A preparation method of epoxy soybean oil resin coating for anticorrosion of metal surface: 201910476127. 3 [P]. 2019-08-16.
38	谢存毅. 纳米压痕技术在材料科学中的应用[J]. 物理, 2001, (7): 47-50.
	Xie C Y. Application of nano-indentation technology in materials science[J]. Physics, 2001, (7): 47-50.
39	路富有. 聚苯胺/丙烯酸聚氨酯树脂涂层的制备及性能研究[D]. 天津: 天津大学, 2017.
	Lu F Y. Preparation and properties of polyaniline/acrylic polyurethane resin coating[D]. Tianjin: Tianjin University, 2017.
40	曹楚南, 张鉴清. 电化学阻抗谱导论[M]. 北京: 科学出版社, 2004: 156-160.
	Cao C N, Zhang J Q. An Introduction to Electrochemical Impedance Spectroscopy[M]. Beijing: Science Press, 2004: 156-160.
41	Darowicki K, Szociński M, Zieliński A. Assessment of organic coating degradation via local impedance imaging[J]. Electrochimica Acta, 2010, 55(11): 3741-3748.
42	Olivier M G, Poelman M, Demuynck M, et al. EIS evaluation of the filiform corrosion of aluminium coated by a cataphoretic paint[J]. Progress in Organic Coatings, 2005, 52(4): 263-270.
43	Lu F, Song B, He P, et al. Electrochemical impedance spectroscopy (EIS) study on the degradation of acrylic polyurethane coatings[J]. RSC Advances, 2017, 7(23): 13742-13748.
44	Walter G. The application of impedance spectroscopy to study the uptake of sodium chloride solution in painted metals [J]. Corrosion Science, 1991, 32(10): 1041-1058.
45	Wei H, Ding D, Wei S, et al. Anticorrosive conductive polyurethane multiwalled carbon nanotube nanocomposites[J]. Journal of Materials Chemistry A, 2013, 1(36): 10805-10813.

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