Environment-friendly acrylic rust treatment material and rust removal method thereof

Abstract

This invention provides an environmentally friendly acrylic rust treatment material and its rust removal method, comprising an acrylic monomer component A, a nanofiller component B, and a photoinitiator component C. The acrylic monomer component A solution is prepared by mixing acrylic acid, acrylic acid derivatives, and a crosslinking agent in a mass ratio of 2–10:1–8:0.1–0.6. The nanofiller component B is prepared by mixing deionized water, polyvinylpyrrolidone, hydrazine hydrate, and a copper source in a mass ratio of 150–250:2–5:0.02–0.1:2–5. The nanofiller component B and the photoinitiator component C are added at mass ratios of 0.1:10–50 and 0.1:2.5–10 to component A, respectively. The reaction solvent, reaction atmosphere, reaction temperature, and reaction time parameters have been further optimized. Using rusted Q235 carbon steel substrate as a test object, this invention demonstrates the excellent rust treatment performance of this environmentally friendly acrylic material, which can effectively remove rust marks from the surface of Q235 carbon steel, and is of great significance for the subsequent protection of metal substrates. The rust removal ability of the system was improved by the reaction of acrylic acid with rust, the adsorption of acrylic hydrogel, and the addition of fillers. The rust removal formula with the greatest performance improvement was selected through parallel experiments, providing a new rust treatment strategy for the field of rust removal.

Description

Technical Field

[0001] This invention relates to the fields of polymer material synthesis technology and metal surface treatment technology, specifically to an environmentally friendly acrylic rust treatment material and its rust removal method. Background Technology

[0002] Metal resources are a vast treasure bestowed upon humankind by nature, but their inherent tendency to corrode has also inflicted heavy losses on humanity. Before applying a protective layer to a substrate surface, rust, scale, oil, and other impurities must be thoroughly removed to ensure cleanliness and a certain degree of roughness, guaranteeing effective adhesion between the coating and the substrate. Otherwise, as corrosion intensifies, the coating's corrosion resistance will significantly decrease.

[0003] Currently, rust removal technologies mainly include mechanical rust removal, sandblasting, flame rust removal, and chemical rust removal. These methods all have significant drawbacks. For example, mechanical manual rust removal is limited by the workpiece structure and easily causes dust pollution; the strong acids used in chemical rust removal can affect the properties of the substrate, and the waste liquid after rust removal is difficult to treat and pollutes the environment. To address these issues, the industry has conducted extensive research, and many new rust treatment materials, such as rust converters and rust-preventive coatings, have been widely reported. These materials typically use organic acids such as tannic acid as the main component of the system. However, tannic acid and its derivatives have poor permeability and strong acidity, which can affect the stability of the system. Therefore, it is necessary to select weaker acids for use in the field of rust treatment materials. Acrylic acid has extremely weak acidity (weaker than phosphoric acid, tannic acid, gallic acid, etc.), is inexpensive and readily available, and acrylic monomers can be cured into hydrogel materials through free radical polymerization under certain conditions. Hydrogels have extremely strong adsorption capacity and a high affinity for metal ions, effectively removing contaminants.

[0004] Here, we propose a novel rust removal method, distinct from any previous rust treatment approach. The main components of this rust removal system are extremely weak acidic acrylic acid and acrylic monomers, minimizing the impact on system stability. To enhance the rust removal effect, we mix cuprous oxide filler with acrylic monomers and a crosslinking agent, where the cuprous oxide is prepared via solution reduction. Then, a photoinitiator is added to the entire system, and the mixture is uniformly coated onto the rusted iron sheet. Rust removal is achieved through photoinitiated free radical polymerization under a 365nm UV lamp. The rust removal effect is excellent, and the resulting solidified waste material is easy to clean and recycle. Summary of the Invention

[0005] The technical objective of this invention is to address the shortcomings of existing technologies by providing a novel rust removal method that is highly effective in removing rust, low in cost, and environmentally friendly.

[0006] The innovations of this invention are mainly in the following aspects: 1. This invention is the first to propose a rust removal method that utilizes light-induced free radical polymerization under a 365nm ultraviolet lamp. The rust removal is completed after the hydrogel is cured, resulting in excellent rust removal effect and easy cleaning and recycling of the solidified waste material after the reaction.

[0007] 2. The acrylic acid used in this invention is extremely weak (weaker than phosphoric acid, tannic acid, gallic acid, etc.), which can react with rust while reducing the impact on the stability of the system.

[0008] 3. The acrylic monomers used in this invention can be cured into hydrogel materials through free radical polymerization under certain conditions. The hydrogels can effectively remove contaminants, have extremely strong adsorption capacity and a high affinity for metal ions, and exhibit excellent rust removal performance.

[0009] 4. By introducing cuprous oxide as a filler, a series of complex reactions will occur with acrylic monomers to generate monovalent copper complexes, which can participate in the reaction during rust removal to improve the rust removal effect.

[0010] The technical solution adopted by this invention to solve its technical problem is: 1. An environmentally friendly acrylic rust treatment material and its rust removal method, comprising an acrylic monomer component A, a nanofiller component B, and a photoinitiator component C: The acrylic monomer component A solution is prepared by mixing acrylic acid, acrylic acid derivatives, and crosslinking agent in a mass ratio of 2–10:1–8:0.1–0.6. The nanofiller component B is prepared by mixing deionized water, polyvinylpyrrolidone, hydrazine hydrate, and copper source in a mass ratio of 150–250:2–5:0.02–0.1:2–5. The nanofiller component B and the photoinitiator component C are added in mass ratios of 0.1:10–50 and 0.1:2.5–10 with component A, respectively. Mix and stir the acrylic monomer component A, nanofiller component B, and photoinitiator component C until homogeneous. Quickly transfer the mixed solution to the surface of the rusted steel sheet. First, set the distance between the mold and the UV lamp to 5–20 cm and the UV lamp power to 60–120 W. After UV curing for 1–4 hours, the rust removal will be completed.

[0011] 2. This invention also provides a method for preparing an environmentally friendly acrylic rust treatment material, the specific steps of which are as follows: 1) Synthesis of acrylic monomer solution (Component A): Acrylic acid, acrylic derivatives, and crosslinking agent are weighed in a mass ratio of 2–10:1–8:0.1–0.6. The order of addition of the reagents is as follows: 1.1) Acrylic acid and acrylic derivatives are mixed first and stirred at a speed of 300–1000 rpm for 0.5–3 hours within a temperature range of 20–35°C. 1.2) Then add the crosslinking agent and stir at a speed of 200–500 rpm for 0.5–2 hours within a temperature range of 20–35℃. 2) Preparation of Nanofiller Component B: Deionized water, polyvinylpyrrolidone, hydrazine hydrate, and copper source were weighed in a mass ratio of 150–250:2–5:0.02–0.1:2–5. The mixture was stirred at 300–700 rpm for 10–50 minutes to completely dissolve the polyvinylpyrrolidone. Then, the copper source was added to the mixture, and the mixture was stirred at 300–700 rpm for 10–50 minutes to ensure homogeneity. The mixture was shielded from light using aluminum foil, and then hydrazine hydrate was added. The mixture was ultrasonicated for 20–90 minutes to obtain the reactant. Finally, the resulting brick-red precipitate was washed with deionized water and anhydrous ethanol, and dried at 50–80°C for 6–10 hours to obtain the desired filler Cu2O.

[0012] 3) Preparation of rust removal solution: Weigh out nanofiller component B and acrylic monomer component A at a mass ratio of 0.1:10–50, and stir at 300–1000 rpm for 0.5–3 hours within a temperature range of 20–35℃. Add photoinitiator component C at a mass ratio of 0.1:2.5–10 to component A; then quickly shield from light and stir at 300–1000 rpm for 1–10 minutes within a temperature range of 20–35℃.

[0013] 4) Rust treatment method and steps: A rusted Q235 steel plate, PU pad, silicone oil film, and glass plate are stacked sequentially to form a mold for the polymerization and curing of acrylic hydrogel. A gap of 8 × 4 × 0.05 cm is left between the Q235 steel plate and the glass plate. 3 The cavity. Transfer the rust removal solution into the assembled mold, avoiding the formation of air bubbles. Irradiate the mold under a UV lamp, specifically: 4.1) First, set the distance between the mold and the UV lamp to 5–20cm, and the UV lamp power to 60–120W.

[0014] 4.2) Rust removal is completed after UV curing for 1–4 hours. According to embodiments of the present invention, the acrylic derivative may be selected from one or more of methyl acrylate, ethyl acrylate, acrylamide, etc.

[0015] According to embodiments of the present invention, the crosslinking agent may be selected from one or more of divinylbenzene and diisocyanate, N,N-methylenebisacrylamide and 1,4-bis(acryloyloxy)butane.

[0016] According to an embodiment of the present invention, the copper source is any one or more of copper nitrate, copper acetate, copper chloride, copper carbonate, and copper sulfate.

[0017] According to embodiments of the present invention, the initiator may be selected from one or more of 1-hydroxycyclohexylphenyl ketone (184), 2-hydroxy-2-methyl-1-phenylpropanone (HMPP, 1173), and methyl benzoylformate (MBF).

[0018] 3. Among them, the metal substrate for surface rust removal treatment can be widely used steel, or other metal materials such as iron.

[0019] The present invention provides an environmentally friendly acrylic rust treatment material and its rust removal method, which, compared with the prior art, have the following advantages: 1. The acrylic acid used in this invention is extremely weak (weaker than phosphoric acid, tannic acid, gallic acid, etc.), thus solving the problem that phosphoric acid, tannic acid, gallic acid, etc., affect the stability of the system. Acrylic acid can react with rust while minimizing its impact on system stability. Simultaneously, acrylic monomers can be cured into hydrogel materials through free radical polymerization under certain conditions. The hydrogel effectively removes contaminants, possesses extremely strong adsorption capacity and a high affinity for metal ions, exhibiting excellent rust removal performance.

[0020] 2. This invention introduces cuprous oxide filler into the rust removal system. The filler will undergo a series of complex reactions with acrylic monomers to generate monovalent copper complexes, which can participate in the reaction during rust removal to improve the rust removal effect.

[0021] 3. Experiments show that the rust treatment method provided by this invention has excellent rust removal effect. Furthermore, this method is low-cost and environmentally friendly. The hydrogel generated during the rust treatment process can be quickly and easily removed from the substrate surface, avoiding problems such as waste liquid disposal that can easily cause secondary pollution. This provides a new rust treatment strategy for the field of rust removal. Attached Figure Description

[0022] Appendix Figure 1 These are scanning electron microscope images and EDS energy dispersive spectroscopy (EDS) images of Cu2O synthesized in Example 1 of this invention.

[0023] Appendix Figure 2 This is the XRD pattern of Cu2O synthesized in Example 1 of this invention.

[0024] Appendix Figure 3 These are actual photos comparing the steel sheet after rust treatment and the rusted Q235 steel sheet in Embodiment 1 of the present invention.

[0025] Appendix Figure 4 These are optical morphology and surface roughness diagrams of the steel sheet after rust treatment and the rusted Q235 steel sheet in Embodiment 1 of the present invention.

[0026] Appendix Figure 5These are scanning electron microscope images, elemental distribution spectrum, and mapping diagrams of the steel sheet after rust treatment and the rusted Q235 steel sheet in Embodiment 1 of the present invention.

[0027] Appendix Figure 6 This is a micro-area electrochemical data diagram of the boundary area between the rust-removed and unrust-removed parts of the steel sheet after rust treatment in Embodiment 2 of the present invention.

[0028] Appendix Figure 7 This is a comparison of the Raman spectra of a steel sheet treated with rust and a rusted Q235 steel sheet, as shown in Embodiment 2 of the present invention.

[0029] Appendix Figure 8 These are XPS spectra of the steel sheet after rust treatment and the rusted Q235 steel sheet in Embodiment 3 of the present invention.

[0030] Appendix Figure 9 These are comparative photographs of steel sheets after rust treatment and rusted Q235 steel sheets, taken in Embodiment 3 of the present invention.

[0031] Appendix Figure 10 These are comparative photographs of steel sheets after rust treatment and rusted Q235 steel sheets, taken in Embodiment 4 of the present invention.

[0032] Appendix Figure 11 These are FT-IR spectra of the hydrogel cured on the surface of the steel sheet after rust treatment in Embodiment 4 of the present invention, and the hydrogel cured by ultraviolet light alone.

[0033] Appendix Figure 12 This is an XPS spectrum fitting diagram of Cu 2p in the steel sheet after rust treatment in Embodiment 4 of the present invention and in the hydrogel generated by simple ultraviolet light curing.

[0034] Appendix Figure 13 This is an open-circuit voltage curve of steel sheet after rust treatment, bare steel, and rusted Q235 steel sheet according to Embodiment 5 of the present invention.

[0035] Appendix Figure 14 The results are electrochemical impedance spectroscopy analysis of steel sheets after rust treatment, bare steel, and rusted Q235 steel sheets in Embodiment 5 of the present invention.

[0036] Appendix Figure 15 This is a Tafel polarization curve diagram of steel sheet after rust treatment, bare steel, and rusted Q235 steel sheet in Embodiment 5 of the present invention. Detailed Implementation

[0037] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0038] This invention provides an environmentally friendly acrylic rust treatment material and its rust removal method, comprising an acrylic monomer component A, a nanofiller component B, and a photoinitiator component C: The acrylic monomer component A solution is prepared by mixing acrylic acid, acrylic acid derivatives, and crosslinking agent in a mass ratio of 2–10:1–8:0.1–0.6. The nanofiller component B is prepared by mixing deionized water, polyvinylpyrrolidone, hydrazine hydrate, and copper source in a mass ratio of 150–250:2–5:0.02–0.1:2–5. The nanofiller component B and the photoinitiator component C are added in mass ratios of 0.1:10–50 and 0.1:2.5–10 with component A, respectively. Mix and stir the acrylic monomer component A, nanofiller component B, and photoinitiator component C until homogeneous. Quickly transfer the mixed solution to the surface of the rusted steel sheet. First, set the distance between the mold and the UV lamp to 5–20 cm and the UV lamp power to 60–120 W. After UV curing for 1–4 hours, the rust removal will be completed.

[0039] This invention also provides a method for preparing an environmentally friendly acrylic rust treatment material, the specific steps of which are as follows: 1) Synthesis of acrylic monomer solution (Component A): Acrylic acid, acrylic derivatives, and crosslinking agent are weighed in a mass ratio of 2–10:1–8:0.1–0.6. The order of addition of the reagents is as follows: 1.1) Acrylic acid and acrylic derivatives are mixed first and stirred at a speed of 300–1000 rpm for 0.5–3 hours within a temperature range of 20–35°C. 1.2) Then add the crosslinking agent and stir at a speed of 200–500 rpm for 0.5–2 hours within a temperature range of 20–35℃. 2) Preparation of Nanofiller Component B: Deionized water, polyvinylpyrrolidone, hydrazine hydrate, and copper source were weighed in a mass ratio of 150–250:2–5:0.02–0.1:2–5. The mixture was stirred at 300–700 rpm for 10–50 minutes to completely dissolve the polyvinylpyrrolidone. Then, the copper source was added to the mixture, and the mixture was stirred at 300–700 rpm for 10–50 minutes to ensure homogeneity. The mixture was shielded from light using aluminum foil, and then hydrazine hydrate was added. The mixture was ultrasonicated for 20–90 minutes to obtain the reactant. Finally, the resulting brick-red precipitate was washed with deionized water and anhydrous ethanol, and dried at 50–80°C for 6–10 hours to obtain the desired filler Cu2O.

[0040] 3) Preparation of rust removal solution: Weigh out nanofiller component B and acrylic monomer component A at a mass ratio of 0.1:10–50, and stir at 300–1000 rpm for 0.5–3 hours within a temperature range of 20–35℃. Add photoinitiator component C at a mass ratio of 0.1:2.5–10 to component A; then quickly shield from light and stir at 300–1000 rpm for 1–10 minutes within a temperature range of 20–35℃.

[0041] 4) Rust treatment method and steps: A rusted Q235 steel plate, PU pad, silicone oil film, and glass plate are stacked sequentially to form a mold for the polymerization and curing of acrylic hydrogel. A gap of 8 × 4 × 0.05 cm is left between the Q235 steel plate and the glass plate. 3 The cavity. Transfer the rust removal solution into the assembled mold, avoiding the formation of air bubbles. Irradiate the mold under a UV lamp, specifically: 4.1) First, set the distance between the mold and the UV lamp to 5–20cm, and the UV lamp power to 60–120W.

[0042] 4.2) After UV curing for 1–4 hours, rust removal can be completed.

[0043] The acrylic derivatives mentioned in step 1) can be selected from one or more of methyl acrylate, ethyl acrylate, acrylamide, etc.

[0044] The crosslinking agent mentioned in step 1) may be selected from one or more of divinylbenzene and diisocyanate, N,N-methylenebisacrylamide and 1,4-bis(acryloyloxy)butane.

[0045] The copper source mentioned in step 2) is any one or more of copper nitrate, copper acetate, copper chloride, copper carbonate, and copper sulfate.

[0046] The initiator mentioned in step 3) can be selected from one or more of 1-hydroxycyclohexylphenyl ketone (184), 2-hydroxy-2-methyl-1-phenylpropanone (HMPP, 1173), and methyl benzoylformate (MBF).

[0047] Among them, the metal substrate for surface rust removal treatment can be widely used steel, or other metal materials such as iron.

[0048] Example 1 This invention provides an environmentally friendly acrylic rust treatment material and its rust removal method, comprising an acrylic monomer component A, a nanofiller component B, and a photoinitiator component C. The specific steps are as follows: 1) Synthesis of acrylic monomer solution (Component A): Acrylic acid, acrylic derivatives, and crosslinking agent were weighed in a mass ratio of 5:4:0.225. The order of addition of the reagents was as follows: 1.1) Add 8g of acrylamide to 10g of acrylic acid solution and stir at 500rpm for 1 hour at 25℃.

[0049] 1.2) Then add 0.45g of crosslinking agent N,N′-methylenebisacrylamide, and stir at 500rpm for 30 minutes at 25℃. 2) Preparation of Nanofiller Component B: First, 3g of polyvinylpyrrolidone was dissolved in 200mL of deionized water and stirred at 500rpm for 20 minutes to ensure complete dissolution. Then, 4.3g of copper nitrate was added to the mixture, and the mixture was stirred at 500rpm for 20 minutes to ensure homogeneity. The mixture was then shielded from light using aluminum foil, followed by the addition of 80μL of hydrazine hydrate. The mixture was ultrasonicated for 30 minutes to obtain the reactants. Finally, the resulting brick-red precipitate was washed with deionized water and anhydrous ethanol, and dried at 60℃ for 8 hours to obtain the desired filler Cu2O.

[0050] 3) Preparation of rust removal solution: Weigh 0.18g of nanofiller component B and stir at 500 rpm for 1 hour at 25℃. Then add 400μL of photoinitiator HMPP; then quickly shield from light and stir at 500 rpm for 1 minute at 25℃.

[0051] 4) Rust treatment method and steps: A rusted Q235 steel plate, PU pad, silicone oil film, and glass plate are stacked sequentially to form a mold for the polymerization and curing of acrylic hydrogel. A gap of 8 × 4 × 0.05 cm is left between the Q235 steel plate and the glass plate. 3 The cavity. Transfer the rust removal solution into the assembled mold, avoiding the formation of air bubbles. Irradiate the mold under a UV lamp, specifically: 4.1) First, set the distance between the mold and the UV lamp to 10cm and the UV lamp power to 80W.

[0052] 4.2) Rust removal can be completed after UV curing for 2 hours.

[0053] The synthesized filler Cu2O and the rust-treated sample were characterized as follows: Scanning electron microscope (SEM) images and EDS (energy dispersive spectroscopy) analyses of the synthesized filler Cu2O are shown below. Figure 1 As shown, Cu2O has a relatively uniform spherical structure, and the Cu and O elements are evenly distributed in the EDS energy spectrum, indicating that the filler Cu2O was successfully prepared.

[0054] The XRD pattern of the synthetic filler Cu2O is as follows: Figure 2 As shown, the XRD pattern exhibits high-intensity diffraction peaks, which correspond to the characteristic peaks of Cu2O. The diffraction peaks at 2θ values ​​of 29.5°, 36.4°, 42.3°, 61.4°, and 73.5° are consistent with the (110), (111), (200), (220), and (311) crystal planes of Cu2O (JCPDS No. 78-2076). Comparison with the standard card confirms the successful synthesis of Cu2O.

[0055] Photos of rusted Q235 steel sheets and steel sheets after rust removal are shown below. Figure 3 As shown in the before and after photos, it can be seen that the rust layer was cleaned very thoroughly after treatment. The surface of the steel sheet after rust removal is cleaner and tidier compared to the rusted surface, demonstrating a significant rust removal effect.

[0056] The optical morphology and surface roughness of rusted Q235 steel sheets and rust-treated steel sheets are as follows: Figure 4 As shown, the surface of the steel sheet before rust treatment was uneven, covered with loose, unevenly distributed rust, exhibiting a highly rough state. The height distribution diagram shows a large height difference on the substrate surface, indicating significant unevenness. The surface of the steel sheet after rust treatment is noticeably smoother and cleaner than the steel sheet before treatment. Although traces of corrosion remain, the loose rust has disappeared. The height distribution diagram shows that the height difference on the substrate surface is much smaller than that of the steel sheet before rust treatment, demonstrating a significant rust removal effect.

[0057] Scanning electron microscope (SEM) images of rusted Q235 steel sheets and steel sheets after rust treatment, including elemental distribution spectra and mapping diagrams, are shown below. Figure 5As shown, the steel sheet surface before rust treatment had obvious rust, with large granular areas observable. After rust treatment, the granular and needle-like substances on the steel sheet surface basically disappeared, and the roughness of the steel sheet was greatly reduced, demonstrating a very obvious rust removal effect. The elemental distribution spectrum and mapping diagram show that Na was uniformly distributed on the surface of the steel sheet matrix before rust treatment and had a high content, which is due to the residual NaCl on the rusted steel sheet surface. The high O content is because the steel sheet matrix was extensively oxidized, forming iron oxides. The Na content decreased from 9.2% to 0% and the O content decreased from 21.44% to 8.9% after rust treatment, proving that impurities such as NaCl on the rusted steel sheet surface were basically completely removed, and the main component of rust, iron oxide, was also largely reacted. This rust removal method has a significant rust removal effect.

[0058] Example 2 This invention provides an environmentally friendly acrylic rust treatment material and its rust removal method, comprising an acrylic monomer component A, a nanofiller component B, and a photoinitiator component C. The specific steps are as follows: 1) Synthesis of acrylic monomer solution (Component A): Acrylic acid, acrylic derivatives, and crosslinking agent were weighed in a mass ratio of 2:1:0.06. The order of addition of the reagents was as follows: 1.1) Add 5g of acrylamide to 10g of acrylic acid solution and stir at 500rpm for 1 hour at 25℃.

[0059] 1.2) Then add 0.3g of crosslinking agent N,N′-methylenebisacrylamide, and stir at 500rpm for 30 minutes at 25℃. 2) Preparation of Nanofiller Component B: First, 3g of polyvinylpyrrolidone was dissolved in 200mL of deionized water and stirred at 500rpm for 20 minutes to ensure complete dissolution. Then, 4g of copper nitrate was added to the mixture, and the mixture was stirred at 500rpm for 20 minutes to ensure homogeneity. The mixture was then shielded from light using aluminum foil, followed by the addition of 80μL of hydrazine hydrate. The mixture was ultrasonicated for 30 minutes to obtain the reactants. Finally, the resulting brick-red precipitate was washed with deionized water and anhydrous ethanol, and dried at 60℃ for 8 hours to obtain the desired filler Cu2O.

[0060] 3) Preparation of rust removal solution: Weigh 0.12 g of nanofiller component B and stir at 500 rpm for 1 hour at 25°C. Then add 400 μL of photoinitiator HMPP; then quickly shield from light and stir at 500 rpm for 1 minute at 25°C.

[0061] 4) Rust treatment method and steps: A rusted Q235 steel plate, PU pad, silicone oil film, and glass plate are stacked sequentially to form a mold for the polymerization and curing of acrylic hydrogel. A gap of 8 × 4 × 0.05 cm is left between the Q235 steel plate and the glass plate. 3 The cavity. Transfer the rust removal solution into the assembled mold, avoiding the formation of air bubbles. Irradiate the mold under a UV lamp, specifically: 4.1) First, set the distance between the mold and the UV lamp to 15cm and the UV lamp power to 100W.

[0062] 4.2) After UV curing for 1.5 hours, rust removal can be completed.

[0063] The samples treated with the above rust were characterized as follows: The micro-electrochemical results at the interface between the rust-removed and unremoved areas are as follows: Figure 6 As shown, due to the presence of corrosion products, the average height of the untreated area is higher than that of the treated area. Furthermore, the unevenness of the untreated area causes fluctuations in the potential difference between the sample surface and the probe, resulting in different voltage potentials at different interface regions. Images of different interface regions show that the voltage potential of the treated area is significantly lower than that of the untreated area, exhibiting a stepwise decrease in voltage potential from the untreated area to the treated area. This demonstrates the substantial removal of rust from the steel sheet surface after rust treatment, indicating the significant effectiveness of this rust treatment method.

[0064] Raman spectra of rusted Q235 steel sheets and rust-treated steel sheets are as follows: Figure 7 As shown, the rust layer of the corroded steel sheet mainly contains oxides such as Fe2O3, Fe3O4, α-FeOOH, and γ-FeOOH. The Raman spectra of the steel sheets before and after rust treatment clearly show that the Raman peak intensities of various oxides and hydroxyl oxides on the steel sheet substrate surface are significantly reduced or disappear after rust treatment, indicating excellent rust treatment results.

[0065] Example 3 This invention provides an environmentally friendly acrylic rust treatment material and its rust removal method, comprising an acrylic monomer component A, a nanofiller component B, and a photoinitiator component C. The specific steps are as follows: 1) Synthesis of acrylic monomer solution (Component A): Acrylic acid, acrylic derivatives, and crosslinking agent were weighed in a mass ratio of 10:7:0.45. The order of addition of the reagents was as follows: 1.1) Add 7g of methyl acrylate to 10g of acrylic acid solution and stir at 500rpm for 1 hour at 25℃.

[0066] 1.2) Then add 0.45g of crosslinking agent divinylbenzene, and stir at 500rpm for 30 minutes at 25℃; 2) Preparation of Nanofiller Component B: First, 3g of polyvinylpyrrolidone was dissolved in 200mL of deionized water and stirred at 500rpm for 20 minutes to ensure complete dissolution. Then, 4g of copper carbonate was added to the mixture, and the mixture was stirred at 500rpm for 20 minutes to ensure homogeneity. The mixture was then shielded from light using aluminum foil, followed by the addition of 60μL of hydrazine hydrate. The mixture was then sonicated for 30 minutes to obtain the reactants. Finally, the resulting brick-red precipitate was washed with deionized water and anhydrous ethanol, and dried at 60℃ for 8 hours to obtain the desired filler Cu2O.

[0067] 3) Preparation of rust removal solution: Weigh 0.12g of nanofiller component B and stir at 500 rpm for 1 hour at 25℃. Then add 400μL of photoinitiator 1-hydroxycyclohexylphenyl ketone; then quickly shield from light and stir at 500 rpm for 1 minute at 25℃.

[0068] 4) Rust treatment method and steps: A rusted Q235 steel plate, PU pad, silicone oil film, and glass plate are stacked sequentially to form a mold for the polymerization and curing of acrylic hydrogel. A gap of 8 × 4 × 0.05 cm is left between the Q235 steel plate and the glass plate. 3 The cavity. Transfer the rust removal solution into the assembled mold, avoiding the formation of air bubbles. Irradiate the mold under a UV lamp, specifically: 4.1) First, set the distance between the mold and the UV lamp to 10cm and the UV lamp power to 80W.

[0069] 4.2) Rust removal can be completed after UV curing for 2 hours.

[0070] The samples treated with the above rust were characterized as follows: XPS spectra of steel sheets before and after rust treatment are as follows Figure 8 As shown, C, O, and Fe elements were detected in the steel sheet before rust treatment, while C, O, Fe, and Cu elements were detected in the steel sheet after rust treatment. From the XPS spectrum, we can see that the binding energy of O and Fe elements in the rust-treated steel sheet is significantly reduced compared to the rusted steel sheet, indicating excellent rust removal effect.

[0071] Photos of rusted Q235 steel sheets and steel sheets after rust removal are shown below. Figure 9 As shown in the before and after photos, it can be seen that a large amount of rust layer was removed after treatment. The surface of the steel sheet after rust removal is cleaner and tidier compared to the rusted steel sheet surface, and the rust removal effect is significant.

[0072] Example 4 This invention provides an environmentally friendly acrylic rust treatment material and its rust removal method, comprising an acrylic monomer component A, a nanofiller component B, and a photoinitiator component C. The specific steps are as follows: 1) Synthesis of acrylic monomer solution (Component A): Acrylic acid, acrylic derivatives, and crosslinking agent were weighed in a mass ratio of 5:4:0.225. The order of addition of the reagents was as follows: 1.1) Add 8g of methyl acrylate to 10g of acrylic acid solution and stir at 500rpm for 1 hour at 25℃.

[0073] 1.2) Then add 0.45g of crosslinking agent 1,4-bis(acryloyloxy)butane, and stir at 500rpm for 30 minutes at 25°C. 2) Preparation of Nanofiller Component B: First, 4g of polyvinylpyrrolidone was dissolved in 200mL of deionized water and stirred at 500rpm for 20 minutes to ensure complete dissolution. Then, 3.5g of copper sulfate was added to the mixture, and the mixture was stirred at 500rpm for 20 minutes to ensure homogeneity. The mixture was then shielded from light using aluminum foil, and 70μL of hydrazine hydrate was added. The mixture was then sonicated for 30 minutes to obtain the reactants. Finally, the resulting brick-red precipitate was washed with deionized water and anhydrous ethanol, and dried at 70℃ for 8 hours to obtain the desired filler Cu2O.

[0074] 3) Preparation of rust removal solution: Weigh 0.09g of nanofiller component B and stir at 500 rpm for 1 hour at 25℃. Then add 400μL of photoinitiator methyl benzoylformate (MBF); then quickly shield the solution from light and stir at 500 rpm for 1 minute at 25℃.

[0075] 4) Rust treatment method and steps: A rusted Q235 steel plate, PU pad, silicone oil film, and glass plate are stacked sequentially to form a mold for the polymerization and curing of acrylic hydrogel. A gap of 8 × 4 × 0.05 cm is left between the Q235 steel plate and the glass plate. 3 The cavity. Transfer the rust removal solution into the assembled mold, avoiding the formation of air bubbles. Irradiate the mold under a UV lamp, specifically: 4.1) First, set the distance between the mold and the UV lamp to 10cm and the UV lamp power to 80W.

[0076] 4.2) Rust removal can be completed after UV curing for 2 hours.

[0077] The samples treated with the above rust were characterized as follows: Photos of rusted Q235 steel sheets and steel sheets after rust removal are shown below. Figure 10As shown in the before and after photos, it can be seen that the rust layer was almost completely removed after treatment. The surface of the steel sheet after rust removal is cleaner and tidier compared to the rusted surface, demonstrating a significant rust removal effect.

[0078] FT-IR spectral analysis of hydrogels cured on the surface of steel sheets after rust treatment and hydrogels cured by UV light alone, as follows: Figure 11 As shown, the FT-IR spectrum exhibits multiple absorption peaks. At 3400 cm⁻¹... –1 and 3200cm –1 The peak values ​​between these points correspond to the tensile vibrations of -NH2. 2937cm –1 The characteristic peak of the hydrogel at this location indicates the presence of CH. The peak value is at approximately 1660 cm⁻¹. –1 and 1596cm –1 The characteristic absorption peak at 534 cm⁻¹ is attributed to the stretching vibration of the carbonyl group (C=O) in the hydrogel. –1 The absorption peak at 534 cm⁻¹ is due to the stretching vibration of Cu-O, proving the successful introduction of copper. However, the hydrogel formed on the surface of the steel sheet after rust treatment shows an absorption peak at 534 cm⁻¹. –1 The absorption peak at that location disappeared, indicating that copper participated in the rust treatment reaction.

[0079] XPS spectral fitting results of Cu 2p in hydrogels cured on the surface of rust-treated steel sheets and hydrogels cured by UV light alone are as follows: Figure 12 As shown in the figure, the high-resolution XPS spectrum of Cu 2p in the hydrogel sample that did not participate in rust removal can be decomposed into two spin orbital doublets. The spin orbital doublets with binding energies of 932.2 eV and 952.1 eV are attributed to Cu. + 2p 3 / 2 and Cu + 2p 1 / 2 This indicates that copper exists in a monovalent form after being added to the mixed solution of acrylic acid and acrylamide. In the rust-treated steel sheet sample, the Cu 2p electronic state has two peaks at 934.4 eV and 954.2 eV, corresponding to Cu... 2+ 2p3 / 2 and Cu 2+ The 2p1 / 2 spin orbital indicates that copper participated in the reaction and its valence state changed to divalent during the rust treatment process.

[0080] Example 5 This invention provides an environmentally friendly acrylic rust treatment material and its rust removal method, comprising an acrylic monomer component A, a nanofiller component B, and a photoinitiator component C. The specific steps are as follows: 1) Synthesis of acrylic monomer solution (Component A): Acrylic acid, acrylic derivatives, and crosslinking agent were weighed in a mass ratio of 2:1:0.06. The order of addition of the reagents was as follows: 1.1) Add 5g of ethyl acrylate to 10g of acrylic acid solution and stir at 500rpm for 1 hour at 25℃.

[0081] 1.2) Then add 0.3g of crosslinking agent diisocyanate, and stir at 500rpm for 30 minutes at 25℃; 2) Preparation of Nanofiller Component B: First, 3.5g of polyvinylpyrrolidone was dissolved in 200mL of deionized water and stirred at 500rpm for 20 minutes to ensure complete dissolution. Then, 3g of copper acetate was added to the mixture, and the mixture was stirred at 500rpm for 20 minutes to ensure homogeneity. The mixture was then shielded from light using aluminum foil, followed by the addition of 60μL of hydrazine hydrate. The mixture was ultrasonicated for 30 minutes to obtain the reactants. Finally, the resulting brick-red precipitate was washed with deionized water and anhydrous ethanol, and dried at 65℃ for 7 hours to obtain the desired filler Cu2O.

[0082] 3) Preparation of rust removal solution: Weigh 0.09g of nanofiller component B and stir at 500 rpm for 1 hour at 25℃. Then add 200μL of photoinitiator HMPP; then quickly shield from light and stir at 500 rpm for 1 minute at 25℃.

[0083] 4) Rust treatment method and steps: A rusted Q235 steel plate, PU pad, silicone oil film, and glass plate are stacked sequentially to form a mold for the polymerization and curing of acrylic hydrogel. A gap of 8 × 4 × 0.05 cm is left between the Q235 steel plate and the glass plate. 3 The cavity. Transfer the rust removal solution into the assembled mold, avoiding the formation of air bubbles. Irradiate the mold under a UV lamp, specifically: 4.1) First, set the distance between the mold and the UV lamp to 15cm and the UV lamp power to 120W.

[0084] 4.2) After UV curing for 1.5 hours, rust removal can be completed.

[0085] The samples treated with the above rust were characterized as follows: The open-circuit potential-time curves of rusted steel sheets, rust-treated steel sheets, and bare steel are shown below. Figure 13 As shown, the open-circuit voltage stability of the bare steel is approximately -0.55V, while the open-circuit voltage stability of the steel sheet treated with the new rust treatment method is -0.57V, slightly lower than that of the bare steel but significantly higher than that of the rusted steel sheet (-0.67V). Compared with the rusted steel sheet, the stability of the entire system is enhanced after rust treatment, and the corrosion rate of Q235 steel is reduced.

[0086] EIS data for rusted steel sheets, rust-treated steel sheets, and bare steel are as follows: Figure 14As shown, for corroded steel sheets, porous rust readily reacts and exhibits the lowest impedance. The impedance of the treated steel sheet is significantly higher than that of the corroded steel sheet. EIS data also demonstrate that the stability and corrosion resistance of the entire system are enhanced compared to the corroded steel sheet.

[0087] Tafel polarization curves of rusted steel sheets, rust-treated steel sheets, and bare steel are as follows: Figure 15 As shown, the corrosion current density of the steel sample treated by the new rust treatment method was significantly reduced compared to the rusted steel sheet, from 1.29 × 10⁻⁶. –6 mA / cm 2 Reduced to 1.84×10 –7 mA / cm 2 The corrosion potential shifted significantly to the positive side, rising from -0.944V to -0.87V, indicating that the rust treatment method has a significant rust removal effect, and the stability and corrosion resistance of the steel sheet after rust treatment are enhanced.

[0088] Although preferred embodiments of this application have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of this application.

[0089] Obviously, those skilled in the art can make various modifications and variations to this application without departing from the spirit and scope of this application. Therefore, if such modifications and variations fall within the scope of the claims of this application and their equivalents, this application also intends to include such modifications and variations.

[0090] Except for the technical features described in the specification, all other technologies are known to those skilled in the art.

Claims

1. An environmentally friendly acrylic rust treatment material, comprising acrylic monomer component A, nanofiller component B, and photoinitiator component C: The acrylic monomer component A is composed of acrylic acid, acrylic acid derivatives, and crosslinking agents in a mass ratio of 2–10:1–8:0.1–0.

6. The nanofiller component B is prepared from deionized water, polyvinylpyrrolidone, hydrazine hydrate, and copper source in a mass ratio of 150–250:2–5:0.02–0.1:2–5. The nanofiller component B and the photoinitiator component C are added at mass ratios of 0.1:10–50 and 0.1:2.5–10 to the acrylic monomer component A, respectively. in, The acrylic derivative is selected from one or more of methyl acrylate, ethyl acrylate, and acrylamide; the crosslinking agent is selected from one or more of divinylbenzene, diisocyanate, N,N-methylenebisacrylamide, and 1,4-bis(acryloyloxy)butane; the copper source is one or more of copper nitrate, copper acetate, copper chloride, copper carbonate, and copper sulfate; and the photoinitiator C component is one or more of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, and methyl benzoylformate.

2. The rust removal method using the environmentally friendly acrylic rust treatment material according to claim 1, comprising the following steps: The acrylic monomer component A, nanofiller component B, and photoinitiator component C as described in claim 1 are mixed and stirred evenly to obtain a mixed solution; a rusted Q235 steel plate, PU pad, silicone oil film, and glass plate are stacked sequentially to form a mold, with a gap of 8 × 4 × 0.05 cm between the Q235 steel plate and the glass plate. 3 The cavity; Transfer the mixed solution into the mold, avoiding the formation of air bubbles; irradiate the mold under a UV lamp, with a distance of 5–20 cm between the mold and the UV lamp, and a UV lamp power of 60–120W; Rust removal is completed after UV curing for 1–4 hours.

3. The preparation method of the environmentally friendly acrylic rust treatment material according to claim 1, comprising the following steps: 1) Synthesis of acrylic monomer component A: Weigh acrylic acid, acrylic derivatives, and crosslinking agent in a mass ratio of 2–10:1–8:0.1–0.

6. The order of addition of raw materials is as follows: 1.1) Acrylic acid and acrylic derivatives are mixed first and stirred at 300–1000 rpm for 0.5–3 hours within a temperature range of 20–35°C. 1.2) Then add the crosslinking agent and stir at 200–500 rpm for 0.5–2 hours within the temperature range of 20–35℃. 2) Preparation of Nanofiller Component B: Deionized water, polyvinylpyrrolidone, hydrazine hydrate, and copper source were weighed in a mass ratio of 150–250:2–5:0.02–0.1:2–5. Polyvinylpyrrolidone was added to deionized water and stirred at 300–700 rpm for 10–50 minutes to completely dissolve the polyvinylpyrrolidone and obtain a mixed solution. Then, copper source was added to the mixed solution and stirred at 300–700 rpm for 10–50 minutes to ensure uniform mixing of the raw materials. The mixed solution with copper source was shielded from light using tin foil, and then hydrazine hydrate was added. The mixture was ultrasonicated for 20–90 minutes to obtain a brick-red precipitate. Finally, the brick-red precipitate was washed with deionized water and anhydrous ethanol and dried at 50–80℃ for 6–10 hours to obtain the desired nanofiller component B. 3) Preparation of rust treatment material: Weigh the nanofiller component B and acrylic monomer component A at a mass ratio of 0.1:10–50, and stir at a speed of 300–1000 rpm for 0.5–3 hours within a temperature range of 20–35℃; add the photoinitiator component C at a mass ratio of 0.1:2.5–10 to the acrylic monomer component A; then quickly shield the material from light, and stir at a speed of 300–1000 rpm for 1–10 minutes within a temperature range of 20–35℃ to obtain the rust treatment material.

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