Next Article in Journal
Microstructure and Corrosion Resistance of Quartz Sand-Modified Enamel-Coated Steel Plates
Next Article in Special Issue
Investigation of Microstructure, Mechanics, and Corrosion Properties of Ti6Al4V Alloy in Different Solutions
Previous Article in Journal
Study on Microstructure and Mechanical Properties of A100-Y2O3 Coatings on Low-Carbon Steel by Laser Cladding
Previous Article in Special Issue
Comparison of the Mechanical Properties and Corrosion Resistance of the Cr-CrN, Ti-TiN, Zr-ZrN, and Mo-MoN Coatings
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Coatings
Volume 13
Issue 10
10.3390/coatings13101703
coatings-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Research on Nano-Titanium Modified Phenolic Resin Coating and Corrosion Resistance

by
Chengwu Zheng
1,
Xingdong Yuan
1,*,
Xiaojing Li
2,
Xuegang Wang
1,
Fadong Cui
1 and
Xiaoliang Wang
1
1
School of Material Science and Engineering, Shandong Jianzhu University, Jinan 250101, China
2
Shandong Institute for Product Quality Inspection, Jinan 250101, China
*
Author to whom correspondence should be addressed.
Coatings 2023, 13(10), 1703; https://doi.org/10.3390/coatings13101703
Submission received: 28 August 2023 / Revised: 20 September 2023 / Accepted: 26 September 2023 / Published: 28 September 2023
(This article belongs to the Special Issue Corrosion Effects and Smart Coatings of Corrosion Protection)
Browse Figures
Review Reports Versions Notes

Abstract

:
Nano-titanium can be used in the field of anticorrosive coatings due to its excellent corrosion resistance. In this paper, phenolic resin was modified by nano-titanium using a physicochemical method. The nano-titanium-modified phenolic resin was used as a matrix to prepare the anticorrosive coating. The microstructures of the coatings were analyzed by Scanning Electron Microscope (SEM), X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR). Raman and UV spectrum adhesion of the coating was tested by a scratching method. The corrosion behavior was studied by electrochemical workstation and salt spray test. The results showed that the corrosion resistance of pure phenolic resin coating was significantly improved by the nano-titanium-modified phenolic resin. The coating containing 4% titanium nanoparticles exhibited the best corrosion resistance, with the highest impedance and the smallest corrosion current. The coating remained intact after 480 h of salt spray, showing the best salt spray resistance performance.

1. Introduction

Corrosion is one of the most prevalent hazardous problems in all types of industries, with economic losses of USD 2.5 trillion annually [1]. Corrosion of materials can be effectively reduced through appropriate corrosion control techniques. Currently, one of the most effective corrosion control techniques is to spray anti-corrosion coatings on metal surfaces [2,3].
The most widely used anti-corrosion coatings are organic coatings [4,5,6,7]. However, some corrosive mediums can reach the substrate along the pores in organic polymers, causing localized corrosion [8,9]. In the last decade or so, nanomaterials have often been filled into organic polymers to improve their corrosion resistance [10,11,12], such as graphene [13], silicon dioxide (SiO2) [14], titanium (Ti) [15] and TiO2 [16]. Nanomaterials can form a “labyrinth effect” in the coating with their lamellar structure and large specific surface area. The pores in the coating can be filled largely, and then the path for corrosive mediums to reach the substrate can be lengthened [17,18].
The latest research of nano-titanium-modified polymers focused on the relationship between coating formulations, organizational structure, properties such as corrosion resistance and weathering resistance, and the development of high-performance nano-titanium titanium coatings. Chen et al. [19] have found that a titanium enamel phenol polymer (UTP) can alter the interlayer spacing of montmorillonite (OMMT), which enhanced the compatibility of UTPOMMT with epoxy resin (EP). Meanwhile, UTPOMMT possessed a zigzagging and complex pathway, which resulted in a coating with excellent densification and corrosion resistance. Guo et al. [20] used the in situ growth method to prepare KGO@LM fillers with good dispersion and compatibility in EP coatings so that EP coatings have excellent long-term corrosion resistance.
Phenolic resin (PF) is the first synthetic polymer material, which is formed by the polycondensation of phenols and aldehydes in the presence of a catalyst [21,22]. Due to its excellent corrosion resistance and mechanical properties, it is widely used in the field of anti-corrosion coatings [23,24]. Phenolic resin has become an important polymer material in the fields of aviation, shipping, power generation and construction. With the demand of science and technology and social development, high anti-corrosion performance phenolic resin has become a new development direction. In recent years, researchers have grafted various metals or metal oxides into phenolic resins to improve their corrosion resistance, such as magnesium, zinc and aluminum oxide [25,26].
Titanium has good corrosion resistance because it can easily form a dense titanium dioxide film in the air [27,28]. The study aims to develop a novel waterborne anti-corrosion coating using nano-titanium and phenolic resin. In doing so, a nano-titanium-modified phenolic resin was prepared by a physicochemical method. The corrosion resistance of the coating with nano-titanium-modified phenolic resin was studied using an electrochemical workstation and salt spray test. The microstructures of the coating were analyzed by SEM, EDS, FTIR, and Raman and UV spectrum.

2. Experimental

2.1. Materials

The titanium nanopowder used in the test was purchased from Wuxi Dinglong Mining Co., Ltd. (Wuxi, China). The phenolic resin, NL curing agent and silane coupling agent KH550 were provided by Henan Huanshan Industry Co., Ltd. (Zhengzhou, China). The anhydrous ethanol solution and acetone solution were purchased from Taicang Xintian Alcohol Co. (Taicang, China). The anhydrous ethanol and acetone solution are analytically pure, and the rest of the above materials are industrial grade. Deionized water was used during the test.

2.2. Preparation of Nano-Titanium Modified Phenolic Resin

Nano-titanium-modified phenolic resins with 3 wt.%, 4 wt.% and 5 wt.% titanium nanopowder were prepared according to the following steps.
The nano-titanium-modified phenolic resin was prepared using a cylindrical flask at room temperature. Firstly, deionized water was added to the phenolic resin and magnetic stirred at 500–600 r/min for 5 min. Then, silane coupling agent KH550 and a certain amount of titanium powder were added and stirred at 300 r/min for 10 min to obtain a dark green slurry-like modified product. In this process, the molecular chain of the phenolic resin was broken, and the titanium was grafted onto the phenolic resin based on the principle of mechanochemistry. The formulation of nano-titanium-modified phenolic resin is shown in Table 1.

2.3. Preparation of Coatings

A certain amount of phenolic resin was first dissolved with deionized water. Then, nano-titanium-modified phenolic resin was added and magnetically stirred at 500 r/min to disperse homogeneously. Finally, a certain amount of curing agent was added and dispersed homogeneously with a magnetic stirrer to obtain the nano-titanium-modified phenolic resin anticorrosive coatings. The reference formula is shown in Table 2.
The substrate was Q235 steel panels with dimensions of 30 mm × 20 mm × 0.2 mm. The surface of the steel panels was first polished with 200# sandpaper and then cleaned with acetone solution and ethanol solution to remove the rust or dirt on the surface. Finally, the steel panels were put into the vacuum drying oven for drying. The coating was uniformly applied to the substrate with a special brush and cured at room temperature (25 ± 2 °C) for 168 h to complete the coating production. The Ti-PF coating preparation process is illustrated in Figure 1.

2.4. Structural Characterizations and Performance Testing

The morphology of the nano-titanium-modified phenolic resin coating was analyzed using an SEM equipped with an EDS that scanned a 1 cm × 1 cm surface of the coating after gold spraying.
FTIR was used to characterize the synthesized sample coatings by taking a point in the coating with absorption peaks ranging from 4000 to 500 cm−1 with a resolution of 4.0 cm−1.
A UV-visible spectrophotometer was used to determine the UV absorption of the coating.
Raman spectroscopy tests were conducted using a laser Raman spectrometer (WiTech alpha 300R, Barberà del Vallès, Spain) using a wavelength of 532 nm under the ambient atmosphere. The spectral acquisition times were 5 scans accumulated with 10 s/scan. Each time, 10 spots distributed over the surface of the specimens were tested to ensure representativeness of the results.
The adhesion of coatings was tested using the cross-cut referring to ISO 2409:2020 [29].
The corrosion behavior of the coatings was tested by a natural salt spray test referring to ISO 9227:2017 [30].
Electrochemical measurements of coatings were performed using an electrochemical workstation (CHI-760E China). A three-electrode system was formed by the sample, platinum sheet, and calomel electrode with saturated KCI solution. Electrochemical impedance spectroscopy was tested at 10−2–105 Hz range and used 10 mV amplitude. During testing, the sample was tested with a 1 cm2 bare leakage area.

3. Results and Discussion

3.1. Scanning Electron Microscope and X-ray Spectroscopy Analysis

SEM images of phenolic resin coatings with different mass fractions of nano-titanium are shown in Figure 2. The bright-colored dots are titanium nanopowders in Figure 2. It can be seen that the nano-titanium has not agglomerated in the form of spheres. As shown in Figure 2a,b, there were some holes and a large number of defects in the coating with 3% titanium nanopowder. Some of the titanium nanopowder was not dispersed uniformly, and agglomerates were formed, which attenuates the small size effect of the nanomaterials. As shown in Figure 2c,d, there were holes and a small number of defects in the coating with 4% nano-titanium powder. The addition of nano-titanium powder increased the roughness of the coating. There is no obvious agglomeration, although the distribution of nano-titanium powder is more scattered. As shown in Figure 2e,f, there were holes and a large number of defects in the coating with 5% nano-titanium powder. The agglomeration of nano-titanium powder was the most serious phenomenon, which may be due to the high mass fraction of nano-titanium powder relative to the phenolic resin. According to the above surface morphology, it can be inferred that the coating containing 4% nano-titanium powder has fewer holes and defects, and the dispersion degree of the nano-titanium powder and the phenolic resin is the largest. The compatibility of the interaction between them is good so that the nanoparticles can give full play to their roles.
EDS analysis was used to understand the distribution of titanium nanoparticles in Ti-PF coatings. As shown in Figure 3, the black part was PF and the bright part was titanium nanoparticles. As shown in the red areas of Figure 3b,d,f, it can be seen that the 3% Ti-PF coating had very little titanium nanoparticles and obvious agglomeration. The 4% Ti-PF coating had high titanium nanoparticle content and a more uniform distribution, with only a small portion of aggregation. The 5% Ti-PF coating had an uneven distribution of titanium nanoparticles and an obvious agglomeration phenomenon. The agglomeration phenomenon was attributed to the different chemical properties of PF and titanium nanoparticles, which caused titanium nanoparticles to self-polymerize. Overall, the distribution of titanium nanoparticles in PF was more uniform when the content of titanium nanoparticles was 4%. The anti-corrosion effect was the best.

3.2. Fourier Transform Infrared Spectroscopy and Raman Spectrum Characterization

The FTIR spectra of the modified phenolic resin coatings with different titanium nanoparticle content are shown in Figure 4. By comparison, it was found that the Ti-PF coatings showed IR absorption peaks specific to phenolic resin. The stretching vibration peaks of benzene ring C-H bond at 3448 cm−1 and aldehyde group -CH2 at 2971 and 2859 cm−1 were found. A new absorption peak appeared in the KH550 modification, which was different from the pure PF coatings. The C-O-C asymmetric vibration peak at 1050 cm−1 and the Si-O-Ti asymmetric vibration peak at 642 cm−1 were found in the Ti-PF coatings, indicating a silane coupler in the phenolic resin. Si-O-Ti, with a characteristic absorption peak at 642 cm−1, indicated that silane coupling agent KH550 was grafted with titanium nanopowder [31], and nano-titanium-modified phenolic resin was prepared. The 4% Ti-PF coating with a characteristic absorption peak at 642 cm−1 had the highest absorption intensity, which indicated that the surface grafting was maximally accomplished with 4% nano-titanium content. When the nano-titanium content was 3%, less grafting and coating were carried out with phenolic resin due to the small amount of nano-titanium content. When the nano-titanium content was 5%, agglomeration of nano-titanium and phenolic resin took place, and only a small portion of the grafting and coating was accomplished.
The Raman spectra of the modified phenolic resin coatings with different nano-titanium contents are shown in Figure 5. Compared with the pure PF coatings, absorption peaks appeared for 3%, 4% and 5% nano-titanium-modified phenolic resin coatings. The nano-titanium and phenolic resin completed the grafting, but no obvious characteristic peaks appeared, which may be due to the agglomeration of nano-titanium. Only a small amount of nano-titanium and phenolic resin completed the grafting, and a large amount of phenolic resin still existed. When the content of nano-titanium is 4%, the wave peak is the highest, and the amount of nano-titanium grafted with phenolic resin is the largest. This result is consistent with the FTIR spectrum results.

3.3. UV Spectrum Analysis

Figure 6 shows the UV spectra of pure PF coatings and modified phenolic resin coatings with different titanium nanoparticle content. It can be seen that both PF coatings with and without modification have similar absorbance in the range of ≤185 nm. This may be due to the fact that phenolic resins have an aromatic ring containing unbonded electrons of oxygen and π-bonds formed by C=O. In the UV region of 185–400 nm, the absorption of nano-titanium-modified coatings is higher than that of pure PF coating. This indicates that the addition of modified titanium nanoparticles is beneficial to increase the absorption of the coatings.

3.4. Electrochemical Performance of Coatings

Figure 7 shows the electrochemical Tafel curves, the self-corrosion potentials and the self-corrosion currents of different coatings. There was a very small difference in the self-corrosion potentials among pure PF, 3%, 4% and 5% Ti-PF coatings. However, the difference in the self-corrosion currents was large. Among them, the 4% Ti-PF coating had the lowest self-corrosion current, indicating the best corrosion resistance. Figure 8 shows the impedance diagrams of pure PF coatings and modified phenolic resin coatings with different titanium nanoparticle content. It can be seen that the pure PF, 3%, 4% and 5% Ti-PF coatings have semicircular shaped impedance arcs, but the impedance arc diameter of the Ti-PF coating was significantly larger than that of the pure PF coating, and the impedance arc diameter of the 4% Ti-PF coating was much larger than that of the pure PF coating. This was because the higher the impedance value of the coating, the larger the arc diameter of the coating was. The 4% Ti-PF coating had the highest impedance value and, thus, the largest arc diameter. The impedance data were fitted by the equivalent circuit, and the fitting parameters for the impedance spectra of coatings are shown in Table 3. The equivalent circuit consisted of the solution resistance (Rs), the polarization resistance (R1) and the non-ideal capacitor (CPE1). Polarization resistance (R1) was used to measure the corrosion resistance of the coating [32]. It can be seen that the addition of nano-titanium increases the polarization resistance value of the coatings. One of the 4% Ti-PF coatings had the largest polarization resistance value, indicating the best corrosion resistance. The results are consistent with the impedance plots. Figure 9 shows the bode plots of nano-titanium composite coatings with different contents. It can be seen that the impedance modulus in the low-frequency region (|Z|0.01 Hz) of all the Ti-PF coatings with different contents is significantly higher than that of the pure PF coating [33]. The 4% Ti-PF coating has the largest impedance modulus, which is about 1.08 × 104 Ω cm2. Normally, the impedance modulus at low frequency (|Z|0.01 Hz) is an important parameter for evaluating the corrosion resistance of the organic coatings. It is shown that the incorporation of nano-titanium significantly enhances the corrosion resistance of the pure PF coating. Similarly, the phase angle In the high-frequency region (|Z|103–104 Hz) also reflects the corrosion resistance of the coatings well, which decreases gradually for the pure PF coatings but hardly changes for the Ti-PF coatings [34]. The 4% Ti-PF coating showed the slowest decreasing trend, which indicates the best corrosion protection.

3.5. Salt Spray Resistance Test

The results of the salt spray test are shown in Figure 10. After 480 h of exposure, the pure PF coatings showed severe corrosion damage at the scratches and blistering, rusting and pitting on the surface, which indicated that the pure PF coatings had poor corrosion resistance. After the addition of titanium nanoparticles, the corrosion damage of the Ti-PF coatings with different contents was greatly reduced after 480 h of exposure, which indicated that the salt spray resistance of the pure PF coatings could be significantly improved by the addition of nano-titanium nanoparticles. Among them, the surface of 4% Ti-PF coating again showed only a small amount of pitting corrosion, no blistering or corrosion diffusion, almost intact. This phenomenon was consistent with the results of the EIS test, indicating that the addition of nano-titanium nanoparticles can significantly improve the salt spray resistance of pure PF coatings. When the addition of titanium nanoparticles was 4%, the Ti-PF coating had the best salt spray resistance performance.
In a further study of its corrosion resistance, 4% nano-titanium-modified phenolic resin coating was subjected to a salt spray resistance test for 768 h. The specific experimental process parameters are shown in Table 4. As shown in Figure 11, it can be seen that after 768 h of continuous spraying, the 4% Ti-PF coating showed crack-like corrosion, and the coating was completely destroyed in the corrosive medium. The corrosion resistance of the phenolic resin coating can be significantly improved by adding titanium nanoparticles. The nano-titanium-modified phenolic resin coatings first started to corrode from the periphery, which was due to the fact that the coating samples were not completely enclosed around the samples, and the sample substrates were exposed to the salt spray environment. The loss of solvents or volatiles in the coating, as well as the degradation and aging of the coating molecular chains, lead to changes in the surface state of the coating, which reduces the gloss of the coating.

3.6. Adhesion Test

The adhesion of the modified phenolic resin coatings with different contents of nano-titanium is shown in Figure 12 and Figure 13. It can be seen that the adhesion grade of the pure PF coating was grade 2, and the adhesion grade of the Ti-PF coatings was grade 1. The addition of titanium nanoparticles can improve the adhesion of the coating. The nano-titanium can form stable physical or chemical bonds with the substrate, which improves the cross-linking density of the coating, thus consolidating the adhesion and showing a better adhesion grade [35].

3.7. Anti-Corrosion Mechanism of Composite Coating

The addition of nanomaterials can precisely fill the pores in traditional coatings, which fundamentally blocks the penetration of external corrosive substances into the coating [36,37]. Nano-titanium will form a dense oxide film at room temperature, which has excellent corrosion resistance. So, the introduction of nano-titanium in anti-corrosion coatings can enhance the corrosion resistance of the coating.
A nano-titanium-modified polymer was prepared by a physicochemical method in this study. Nano-titanium powder and phenolic resin were combined through a chemical bonding force to form a spatial mesh structure during magnetic stirring. The adhesion and hydrophobicity of the coating were enhanced by the modification. It was difficult for corrosive mediums to be adsorbed on the surface of the coating. The barrier ability of the coating was thus enhanced to the corrosive mediums [38].
The nano-titanium-modified phenolic resin can disperse nano-titanium uniformly in the system. A mesh structure was formed and effectively filled the defects in the coating. The infiltration of corrosive mediums was slowed down, and the “labyrinth effect” was increased [39]. Therefore, the anti-corrosion effect of the coating was improved by the nano-titanium [40].

4. Conclusions

In this work, a nano-titanium-modified phenolic resin coating with high corrosion resistance was developed. The microstructure, elemental distribution, optical properties, corrosion behavior and adhesion were investigated. Some conclusions can be drawn as follows:
(1)
Through the comparative analysis of the corrosion resistance of Ti-PF coatings and pure PF coating, it was confirmed that the addition of nano-titanium could effectively enhance the corrosion resistance of pure PF coating, and the optimum addition amount of nano-titanium was determined to be 4%.
(2)
By comparing the adhesion of Ti-PF coatings and pure PF coating, it was confirmed that the addition of nano-titanium could improve the degree of adhesion of pure PF coatings, and all the Ti-PF coatings showed excellent adhesion.
(3)
The impedance value of the Ti-PF coatings was much larger than that of the pure PF coating, among which the impedance value of the 4% Ti-PF coatings was the largest; the 4% Ti-PF coatings were almost intact after 480 h of salt spray resistance test, which showed excellent corrosion resistance.
However, cracks still appeared in the coating. Some work on synergizing fiber materials and titanium nanoparticles should be conducted in future work.

Author Contributions

X.Y. conceived the idea and supervised this project. C.Z., F.C. and X.L. performed experiments. C.Z., X.W. (Xiaoliang Wang) and X.W. (Xuegang Wang) analyzed the data and wrote the manuscript. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Graduate Program Construction Project of Shandong University of Architecture (YZKG201603, ALK201602, ALK201710, ALK201808), Shandong Province Higher Education Institutions Science and Technology Program (J17KA017), Doctoral Fund of Shandong University of Architecture (XNBS1625), Shandong Province Social Science Planning Research Program (19CHYJ12), and Research on corrosion-resistant support technology for high salt water in the Jinqiao coal mine (H23180Z0101).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

The authors acknowledge the full financial support for this work provisioned by the Shandong Province Higher Education Institutions Science and Technology Program.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. The High Cost of Corrosion. Focus Powder Coat. 2019, 2019, 1. [CrossRef]
  2. Gnedenkov, A.S.; Sinebryukhov, S.L.; Filonina, V.S.; Plekhova, N.G.; Gnedenkov, S.V. Smart composite antibacterial coatings with active corrosion protection of magnesium alloys. J. Magnes. Alloys 2022, 10, 3589–3611. [Google Scholar] [CrossRef]
  3. Wang, G.G.; Wen, S.G.; Qin, S.P.; Wang, J.H.; Wang, C.R.; Chen, Y.B. Synthesis of novel nano hyperbranched polymer resin and its corrosion resistance in coatings. Prog. Org. Coat. 2020, 140, 105496. [Google Scholar] [CrossRef]
  4. Neto, A.G.C.; Pellanda, A.C.; Jorge, A.R.D.C. Preparation and evaluation of corrosion resistance of a self-healing alkyd coating based on microcapsules containing Tung oil. Prog. Org. Coat. 2020, 147, 105874. [Google Scholar] [CrossRef]
  5. Yao, H.; Zhang, X.; Shen, L.M.; Bao, Z.N. Tribological and anticorrosion properties of polyvinyl butyral (PVB) coating reinforced with phenol formaldehyde resin (PF). Prog. Org. Coat. 2021, 158, 106382. [Google Scholar] [CrossRef]
  6. Fan, X.G.; Xia, Y.Z.; Wu, S.; Zhang, D.; Oliver, S.S.; Chen, X.N.; Lei, L.; Shi, S.X. Covalently immobilization of modified graphene oxide with waterborne hydroxyl acrylic resin for anticorrosive reinforcement of its coatings. Prog. Org. Coat. 2022, 163, 106685. [Google Scholar] [CrossRef]
  7. Xue, D.; Meng, Q.B.; Lu, X.Y.; Ling, L.; Wei, H.Y.; Liu, B.L. Achieving high performance anticorrosive coating via in situ polymerization of polyurethane and poly(propylene oxide) grafted graphene oxide composites. Corros. Sci. 2020, 176, 109055. [Google Scholar] [CrossRef]
  8. Honarvar, N.M.; Zhang, Y.; Mahmoodi, A.; Xu, G.; Wu, L.J.; Shi, X.M. Nanocomposite organic coatings for corrosion protection of metals: A review of recent advances. Prog. Org. Coat. Int. Rev. J. 2022, 162, 106573. [Google Scholar] [CrossRef]
  9. El-Shamy, O.A.A.; Deyab, M.A. Novel anticorrosive coatings based on nanocomposites of epoxy, chitosan and silver. Mater. Lett. 2023, 330, 133298. [Google Scholar] [CrossRef]
  10. Li, W.; Sheng, Z.; He, D.M.; Cai, M.; He, C.; Fan, X.Q. Ti3C2@ZnO-reinforced interpenetrating polymer network coating toward harsh wear/corrosion protection. Tribol. Int. 2023, 188, 108877. [Google Scholar] [CrossRef]
  11. Kumar, S.S.A.; Ma, I.W.; Ramesh, K.; Ramesh, S. Development of graphene incorporated acrylic-epoxy composite hybrid anti-corrosion coatings for corrosion protection. Mater. Chem. Phys. 2023, 303, 127731. [Google Scholar] [CrossRef]
  12. Zhao, Y.M.; Zhang, P.Y.; Gu, X.Q.; Zhang, X.L.; Huo, M.D. Preparation of PVDF-PDMS-SiO2 multi-stage rough superhydrophobic coating with excellent anti-corrosion and drag reduction performance via one-step cold spraying. Surf. Coat. Technol. 2023, 471, 129882. [Google Scholar] [CrossRef]
  13. George, J.S.; Paduvilan, J.K.; Salim, N.; Sunarso, J.; Kalarikkal, N.; Hameed, N.; Thomas, S. Advances and future outlook in epoxy/graphene composites for anticorrosive applications. Prog. Org. Coat. 2022, 162, 106571. [Google Scholar] [CrossRef]
  14. Ammar, S.; Ramesh, K.; Ma IA, W.; Farah, Z.; Vengadaesvaran, B.; Ramesh, S.; Arof, A.K. Studies on SiO2-hybrid polymeric nanocomposite coatings with superior corrosion protection and hydrophobicity. Surf. Coat. Technol. 2017, 324, 536–545. [Google Scholar] [CrossRef]
  15. Tang, G.; Zhang, K.; Yan, Z.; Ma, L.; Huang, X. A self-curing, thermosetting resin based on epoxy and organic titanium chelate as an anticorrosive coating matrix for heat exchangers: Preparation and properties. Prog. Org. Coat. Int. Rev. J. 2017, 102, 225–230. [Google Scholar] [CrossRef]
  16. Wang, J.X.; Huan, Y.; Zhu, M.; Xie, B.Q.; Yu, X.R.; Su, G.H.; Wang, L. Epoxy coating with excellent anticorrosion and pH-responsive performances based on DEAEMA modified mesoporous silica nanomaterials. Colloids Surf. A Physicochem. Eng. Asp. 2021, 634, 127951. [Google Scholar] [CrossRef]
  17. Yao, H.R.; Li, L.J.; Li, W.S.; Qi, D.; Fu, W.L.; Wang, N. Application of nanomaterials in waterborne coatings: A review. Resour. Chem. Mater. 2022, 1, 184–200. [Google Scholar] [CrossRef]
  18. Zhao, H.R.; Ding, J.H.; Liu, P.L.; Yu, H.B. Boron nitride-epoxy inverse “nacre-like” nanocomposite coatings with superior anticorrosion performance. Corros. Sci. 2021, 183, 109333. [Google Scholar] [CrossRef]
  19. Chen, Y.X.; Bai, W.B.; Chen, J.P.; Zhao, J.; Wei, F.F.; Jian, R.K.; Zheng, X.X.; Xu, Y.L. In-situ intercalation of montmorillonite/urushiol titanium polymer nanocomposite for anti-corrosion and anti-aging of epoxy coatings. Prog. Org. Coat. 2022, 165, 106738. [Google Scholar] [CrossRef]
  20. Guo, H.; Yang, C.; Sun, H.; Xiang, N.; Li, C.; Wang, C. Silane coupling agent modified layered double hydroxide/graphene oxide preparation of intelligent anticorrosive coating. Surf. Coat. Technol. 2023, 467, 129728. [Google Scholar] [CrossRef]
  21. Lin, J.D.; Li, X.Q.; Chen, J.K. Synthesis and characterization of molybdenum/phenolic resin composites binding with aluminum nitride particles for diamond cutters. Appl. Surf. Sci. 2013, 284, 297–307. [Google Scholar] [CrossRef]
  22. Tang, K.H.; Zhang, A.L.; Ge, T.J.; Liu, X.F.; Tang, X.J.; Li, Y.J. Research progress on modification of phenolic resin. Mater. Today Commun. 2020, 26, 101879. [Google Scholar] [CrossRef]
  23. Wei, X.; Li, J.J.; Zhang, S.H.; Jiang, C.; Feng, Y.Y.; Zhao, J.; Lin, Z.X.; Huang, X.L.; Wang, T.; He, J.P. In situ synthesis of graphene-phenol formaldehyde composites and their highly-efficient radical scavenging effects under the γ irradiation. Corros. Sci. 2019, 159, 108139. [Google Scholar]
  24. Dai, Y.X.; Lv, F.N.; Wang, B.; Chen, Y. Thermoresponsive phenolic formaldehyde amines with strong intrinsic photoluminescence: Preparationcharacterization and application as hardeners in waterborne epoxy resin formulations. Polymer 2018, 145, 454–462. [Google Scholar] [CrossRef]
  25. Chen, S.; Zhao, S.; Chen, M.Y.; Zhang, X.; Zhang, J.; Li, X.; Zhang, H.; Shen, X.L. The anticorrosion mechanism of phenolic conversion coating applied on magnesium implants. Appl. Surf. Sci. 2018, 463, 953–967. [Google Scholar] [CrossRef]
  26. Ambale, M.M.; Kikkeri, N.S.M.; Mahesh, B.H.; Saurav, R.N.; Kamalon, R.; Ningappa, K.S. Development of Al2O3.ZnO/GO-phenolic formaldehyde amine derivative nanocomposite: A new hybrid anticorrosion coating material for mild steel. Colloids Surf. A Physicochem. Eng. Asp. 2020, 601, 125036. [Google Scholar]
  27. Ashish, S.; Chavvakula, M.M.; Pravin, K.S.; Piyush, C.V. Titanium-based materials: Synthesis, properties, and applications. Mater. Proc. 2022, 56, 412–419. [Google Scholar]
  28. Pei, L.C.; Lin, D.; Wang, R.T.; Yuan, S.C.; Lu, R.J.; Li, H.Z.; Zhu, J.J.; Jiang, Y.X.; Deng, J.P.; Zhu, Y.J.; et al. Ti3C2Tx MXene@STPP novel waterborne long-term anti-corrosion coating with “3 + 1” multiple high-performance active-passive protection barrier mechanisms. Prog. Org. Coat. 2023, 184, 107874. [Google Scholar] [CrossRef]
  29. ISO 2409:2020; Paints and Varnishes—Cross-Cut Test. International Organization for Standardization: Genève, Switzerland, 2020.
  30. ISO 9227:2017; Corrosion Tests in Artificial Atmospheres—Salt Spray Tests. International Organization for Standardization: Genève, Switzerland, 2017.
  31. Xun, L.L.; Ren, J.; Lu, J.H.; Tong, X.Q.; Zhao, T.T.; Bang, L.T.; Shi, X.L. Preparation of double linked waterborne epoxy resin coating using Titanium curing agent and aminopropyltriethoxysilane and its anticorrosive properties. Int. J. Electrochem. Sci. 2021, 16, 210768. [Google Scholar]
  32. Wan, C.Y.; Chen, B.Q. Synthesis and characterization of biomimetic hydroxyapatite/sepiolite nanocomposites. Nanoscale 2011, 3, 693–700. [Google Scholar] [CrossRef]
  33. Tian, W.L.; Meng, F.D.; Liu, L.; Li, Y.; Wang, F.H. The failure behaviour of a commercial highly pigmented epoxy coating under marine alternating hydrostatic pressure. Prog. Org. Coat. 2015, 82, 101–112. [Google Scholar] [CrossRef]
  34. Li, Y.; Yang, Z.Z.; Qiu, H.X.; Dai, Y.G.; Zheng, Q.B.; Li, J.; Yang, J.H. Self-aligned graphene as anticorrosive barrier in waterborne polyurethane composite coatings. J. Mater. Chem. A 2014, 2, 14139–14145. [Google Scholar] [CrossRef]
  35. Qiu, C.C.; Liu, D.M.; Jin, K.; Fang, L.; Sha, T.D. Corrosion resistance and micro-tribological properties of nickel hydroxide-graphene oxide composite coating, Diamond and Related Materials. Diam. Relat. Mater. 2017, 76, 150–156. [Google Scholar] [CrossRef]
  36. Zhang, Y.Y.; Wang, X.J.; Tian, H.; Xing, J.J.; Liu, L. Epoxy composite coating with excellent anti-corrosion and self-healing properties based on mesoporous silica nano-containers. J. Mol. Struct. 2023, 1294, 136538. [Google Scholar] [CrossRef]
  37. Wu, D.Q.; Su, Q.; Chen, L.; Cui, H.X.; Zhao, Z.C.; Wu, Y.P.; Zhou, H.D.; Chen, J.M. Achieving high anti-wear and corrosion protection performance of phenoxy-resin coatings based on reinforcing with functional graphene oxide. Appl. Surf. Sci. 2022, 601, 154156. [Google Scholar] [CrossRef]
  38. Dong, H.Y.; Zhan, Y.Q.; Chen, Y.W.; Li, Y.L.; Sun, A.; Chen, X.M.; Zhu, F.; Jia, H.S. Fabrication of hydrophobic and enhanced anticorrosion performance of epoxy coating through the synergy of functionalized graphene oxide and nano-silica binary fillers. Colloids Surf. A Physicochem. Eng. Asp. 2023, 664, 131086. [Google Scholar] [CrossRef]
  39. Huang, Z.W.; Chen, S.L.; Lin, Q.; Shen, B. Improved anticorrosive and tribological performance of Ti-6Al-4V alloys via a mussel-inspired graphene/phenol-formaldehyde resin nanocomposite coating. Prog. Org. Coat. 2022, 601, 154156. [Google Scholar] [CrossRef]
  40. Liu, L.S.; Zhao, M.Y.; Pei, X.Y.; Liu, S.K.; Luo, S.G.; Yan, M.J.; Shao, R.Q.; Sun, Y.; Xu, W.; Xu, Z.W. Improving corrosion resistance of epoxy coating by optimizing the stress distribution and dispersion of SiO2 filler. Prog. Org. Coat. 2023, 179, 107522. [Google Scholar] [CrossRef]
Coatings 13 01703 g001
Figure 1. Schematic illustration of the preparation of Ti-PF coatings.
Figure 1. Schematic illustration of the preparation of Ti-PF coatings.
Coatings 13 01703 g001
Coatings 13 01703 g002
Figure 2. SEM images of (a) 3% Ti-PF and (b) the enlarged view of the red section in (a), SEM images of (c) 4% Ti-PF and (d) the enlarged view of the red section in (c), SEM images of (e) 5% Ti-PF and (f) the enlarged view of the red section in (e).
Figure 2. SEM images of (a) 3% Ti-PF and (b) the enlarged view of the red section in (a), SEM images of (c) 4% Ti-PF and (d) the enlarged view of the red section in (c), SEM images of (e) 5% Ti-PF and (f) the enlarged view of the red section in (e).
Coatings 13 01703 g002
Coatings 13 01703 g003
Figure 3. (a) SEM and (b) Ti spectra of 3% Ti-PF coating, (c) SEM and (d) Ti spectra of 4% Ti-PF coating, (e) SEM and (f) Ti spectra of 5% Ti-PF coating.
Figure 3. (a) SEM and (b) Ti spectra of 3% Ti-PF coating, (c) SEM and (d) Ti spectra of 4% Ti-PF coating, (e) SEM and (f) Ti spectra of 5% Ti-PF coating.
Coatings 13 01703 g003
Coatings 13 01703 g004
Figure 4. Infrared spectra of modified phenolic resin coatings with different titanium nanoparticle contents.
Figure 4. Infrared spectra of modified phenolic resin coatings with different titanium nanoparticle contents.
Coatings 13 01703 g004
Coatings 13 01703 g005
Figure 5. Raman spectra of modified phenolic resin coatings with different titanium nanoparticle contents.
Figure 5. Raman spectra of modified phenolic resin coatings with different titanium nanoparticle contents.
Coatings 13 01703 g005
Coatings 13 01703 g006
Figure 6. UV spectra of nano-titanium composite coatings with different contents.
Figure 6. UV spectra of nano-titanium composite coatings with different contents.
Coatings 13 01703 g006
Coatings 13 01703 g007
Figure 7. Tafel curves and related data for nano-titanium composite coatings with different contents.
Figure 7. Tafel curves and related data for nano-titanium composite coatings with different contents.
Coatings 13 01703 g007
Coatings 13 01703 g008
Figure 8. Impedance plot of nano-titanium composite coatings with different contents.
Figure 8. Impedance plot of nano-titanium composite coatings with different contents.
Coatings 13 01703 g008
Coatings 13 01703 g009
Figure 9. Bode plot of nano-titanium composite coatings with different contents.
Figure 9. Bode plot of nano-titanium composite coatings with different contents.
Coatings 13 01703 g009
Coatings 13 01703 g010
Figure 10. Optical images of PF (a,e), 3% Ti-PF (b,f), 4% Ti-PF (c,g), and 5% Ti-PF (d,h) coated tinplate before and after salt spray test.
Figure 10. Optical images of PF (a,e), 3% Ti-PF (b,f), 4% Ti-PF (c,g), and 5% Ti-PF (d,h) coated tinplate before and after salt spray test.
Coatings 13 01703 g010
Coatings 13 01703 g011
Figure 11. Photographs of salt spray resistance test of phenolic resin coating modified with 4% titanium nanoparticles: (a) 0 h; (b) 96 h; (c) 192 h; (d) 288 h; (e) 384 h; (f) 480 h; (g) 576 h; (h) 672 h; (i) 768 h.
Figure 11. Photographs of salt spray resistance test of phenolic resin coating modified with 4% titanium nanoparticles: (a) 0 h; (b) 96 h; (c) 192 h; (d) 288 h; (e) 384 h; (f) 480 h; (g) 576 h; (h) 672 h; (i) 768 h.
Coatings 13 01703 g011
Coatings 13 01703 g012
Figure 12. Surface morphology of coatings with different titanium nanoparticles after scribing (a) 0%, (b) 3%, (c) 4% and (d) 5%.
Figure 12. Surface morphology of coatings with different titanium nanoparticles after scribing (a) 0%, (b) 3%, (c) 4% and (d) 5%.
Coatings 13 01703 g012
Coatings 13 01703 g013
Figure 13. Adhesion test of nano-titanium composite coatings with different contents.
Figure 13. Adhesion test of nano-titanium composite coatings with different contents.
Coatings 13 01703 g013
Table 1. Reference formulations of nano-titanium-modified phenolic resins.
Table 1. Reference formulations of nano-titanium-modified phenolic resins.
Serial NumberIngredientContent (wt.%)
1Titanium nanopowder20–30
2Silane coupling agent KH55010–15
3Phenolic resin (chemistry)55–70
Table 2. Reference formulations for nano-titanium phenolic resin coatings.
Table 2. Reference formulations for nano-titanium phenolic resin coatings.
Serial NumberIngredientContent (wt.%)
1Nano-titanium-modified phenolic resin40~50
2Phenolic resin (chemistry)40~45
3Deionized water6~10
4Curing agent1~2
5Leveling agent1~1.5
6Thickener1~1.5
Table 3. Equivalent circuit fitting parameters for impedance spectra of coatings.
Table 3. Equivalent circuit fitting parameters for impedance spectra of coatings.
CoatingRs/Ω·cm2CPE-T/Ω−1 cm−2·snR1/Ω·cm2
PF6.825.21 × 10−51102
3% Ti-PF7.013.36 × 10−57104
4% Ti-PF12.166.00 × 10−515,452
5% Ti-PF16.275.00 × 10−511,747
Table 4. Process parameters for salt spray resistance test of coatings.
Table 4. Process parameters for salt spray resistance test of coatings.
Corrosion Time/hNano-Titanium-Modified Phenolic Resin Coating
0Coating intact
96Coating intact
192Coating intact
288Coating intact
384Discoloration of the coating and rust spots on the surface of the boards
480Discoloration of the coating and rust spots on the surface of the boards
576Discoloration of the coating and rust spots on the surface of the boards
Light rusting at scratches, rusting on the lower side of boards
672Discoloration of the coating and rust spots on the surface of the boards
Rust at scratches, rust spreading on the lower side of the panel and also on the left side
768Discoloration of coating, spreading of rust at scratches
Cracked rust on panel
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Zheng, C.; Yuan, X.; Li, X.; Wang, X.; Cui, F.; Wang, X. Research on Nano-Titanium Modified Phenolic Resin Coating and Corrosion Resistance. Coatings 2023, 13, 1703. https://doi.org/10.3390/coatings13101703

AMA Style

Zheng C, Yuan X, Li X, Wang X, Cui F, Wang X. Research on Nano-Titanium Modified Phenolic Resin Coating and Corrosion Resistance. Coatings. 2023; 13(10):1703. https://doi.org/10.3390/coatings13101703

Chicago/Turabian Style

Zheng, Chengwu, Xingdong Yuan, Xiaojing Li, Xuegang Wang, Fadong Cui, and Xiaoliang Wang. 2023. "Research on Nano-Titanium Modified Phenolic Resin Coating and Corrosion Resistance" Coatings 13, no. 10: 1703. https://doi.org/10.3390/coatings13101703

APA Style

Zheng, C., Yuan, X., Li, X., Wang, X., Cui, F., & Wang, X. (2023). Research on Nano-Titanium Modified Phenolic Resin Coating and Corrosion Resistance. Coatings, 13(10), 1703. https://doi.org/10.3390/coatings13101703

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop