Etching solution for alloy surface treatment and preparation method thereof

Abstract

The invention discloses an etching solution for alloy surface treatment and a preparation method thereof, and relates to the field of etching solutions. The preparation method comprises the following steps: firstly, preparing mesoporous titanium dioxide by a sol-gel method, modifying the mesoporous titanium dioxide by an amino coupling agent, loading green tea polyphenol and preparing a self-made corrosion inhibitor from konjac glucomannan grafted with quaternary ammonium groups, adsorbing dopamine by utilizing electrostatic interaction, and polymerizing to form pH response hydrophilic particles; in the etching process, when the solution is slightly acidic, the corrosion inhibitor is released to inhibit excessive etching; meanwhile, carboxymethyl cellulose is grafted with sulfonic acid groups, N-(phosphonomethyl) iminodiacetic acid modified chitosan is used for preparing complexing agents A and B, and after compounding, the complexing agents A and B are mixed with components such as hydrophilic particles to obtain etching liquid; the compound complexing agent can form a strong coordination bond with metal ions and can also be chelated with heavy metal ions; chitosan, phosphonic acid groups and hydrophilic particles cooperate with one another, so that the surface hydrophilicity of the alloy is improved, and hydrolytic precipitation and scale attachment are effectively inhibited. The prepared etching liquid for alloy surface treatment has the effects of high efficiency and uniform etching.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of etching solution, in particular to an etching solution for alloy surface treatment and a preparation method thereof. BACKGROUND

[0002] In the field of etching solution, the performance of the etching solution directly affects the quality of the alloy surface. In the prior art, the etching solution is prone to cause excessive etching under acidic conditions, and the hydrolysis and precipitation of metal ions can easily cause fouling, resulting in a rough surface. At the same time, the traditional complexing agent has insufficient coordination ability for metal ions, and cannot inhibit the complexation competition caused by the accumulation of heavy metal ions, and the material surface has poor hydrophilicity, and the fouling adhesion problem is prominent. In addition, the existing corrosion inhibitor release mechanism lacks pH responsiveness, and cannot accurately control the release timing, resulting in poor etching uniformity. Therefore, developing an etching solution with pH-responsive corrosion inhibition, metal ion chelation and surface hydrophilic modification functions is the key to solving the problems of excessive etching and fouling adhesion in the alloy etching process. SUMMARY

[0003] The purpose of the present application is to provide an etching solution for alloy surface treatment and a preparation method thereof to solve the problems in the prior art.

[0004] In order to solve the above technical problems, the present application provides the following technical scheme: an etching solution for alloy surface treatment, comprising the following steps: (1) mixing green tea polyphenol, grafted quaternary ammonium group konjac glucomannan and deionized water in a mass ratio of 1:1:200, stirring at 60°C for 2h, filtering and washing, and drying at 60°C for 12h to obtain a self-made corrosion inhibitor, which is loaded on mesoporous titanium dioxide prepared by sol-gel method and modified with amino coupling agent; mixing mesoporous titanium dioxide, dopamine and buffer A in a mass ratio of 5:1:50, stirring at room temperature for 24h in the dark, centrifuging for 10min, and freeze-drying for 12h to obtain self-made hydrophilic particles; (2) mixing carboxymethyl cellulose and deionized water in a mass ratio of 1-2:20, stirring at room temperature for 1-2h, then adding 0.2-0.4 times the mass of carboxymethyl cellulose of sodium vinyl sulfonate, bubbling with high-purity nitrogen at a rate of 0.5L / min for 30min, heating to 65-75°C, adding 0.02-0.04 times the mass of carboxymethyl cellulose of initiator, stirring for 6-8h, adjusting the pH to 7-8 with buffer B, dialyzing, and then freeze-drying for 24h to obtain complexing agent A; (3) Mix glyphosate and activation solution at a mass ratio of 2~4:100 and stir at room temperature for 2h to obtain activated glyphosate solution; mix chitosan, 1,6-hexanediamine and buffer C at a mass ratio of 1~2:0.1~0.2:20, maintain pH at 6.0, stir at room temperature for 10min, add 15~20 times the mass of activated glyphosate solution of chitosan at a rate of 1 drop / s, stir at room temperature for 12~14h, centrifuge for 10min to wash, and dry at 60℃ for 12h to obtain complexing agent B; (4) Mix 2-4 parts by weight of hydrophilic particles, 15-20 parts by weight of complexing agent A, 10-15 parts by weight of complexing agent B, 4-6 parts by weight of etchant and 55-70 parts by weight of deionized water, and stir at room temperature for 30 minutes to obtain an etching solution for alloy surface treatment.

[0005] Furthermore, the amino coupling agent in step (1) is 3-aminopropyltriethoxysilane.

[0006] Furthermore, the pore size and particle size of the mesoporous titanium dioxide in step (1) are: pore size 5nm, particle size 100nm.

[0007] Furthermore, the buffer A in step (1) is a 50mM Tris-HCl buffer with pH=8.5.

[0008] Furthermore, the initiator in step (2) is ammonium persulfate.

[0009] Furthermore, the buffer solution B in step (2) is a 1M sodium hydroxide solution.

[0010] Furthermore, the activation solution in step (3) is: the concentration of EDC in the activation solution is 50 g / L, the concentration of NHS is 30 g / L, and the solvent is a 0.1 M MES buffer solution with pH=6.0.

[0011] Furthermore, the buffer solution C in step (3) is a 2wt% aqueous solution of acetic acid.

[0012] Furthermore, the etching agent in step (4) is a mixture of 10wt% hydrogen peroxide, malonic acid, succinic acid and phenylurea in a mass ratio of 10:1.5:2.5:0.2.

[0013] Furthermore, the application of an etching solution for alloy surface treatment is characterized in that the alloy material is first subjected to gradient annealing pretreatment, then immersed in the etching solution, ultrasonically assisted etching at 20kHz for 5 minutes, the alloy surface is rinsed with ethanol, and dried at 60°C for 6 hours to obtain the treated alloy material.

[0014] Furthermore, the alloy material is 6061 aluminum alloy.

[0015] Compared with the prior art, the present application has the following beneficial effects: The present application realizes the effect of efficient and uniform etching by mixing the self-made hydrophilic particles and the self-made complexing agent and other ingredients.

[0016] Firstly, the self-made corrosion inhibitor is prepared by loading green tea polyphenols and konjac glucomannan grafted with quaternary ammonium groups on mesoporous titanium dioxide prepared by sol-gel method after modification by amino coupling agent, and then using surface electrostatic adsorption to form pH-responsive hydrophilic particles by polymerizing dopamine. The hydrophilicity of polydopamine can enhance the penetration of the etching solution on the alloy surface; during the etching process, when the solution is slightly acidic, the surface force between polydopamine and particles weakens, and the particles fall off from the surface, thereby releasing the self-made corrosion inhibitor to inhibit excessive etching, and the mesoporous structure of titanium dioxide adsorbs metal ions to inhibit their local aggregation and hydrolysis and precipitation, thereby avoiding surface roughness caused by fouling; Secondly, the modified carboxymethyl cellulose is obtained by grafting sulfonic acid groups on carboxymethyl cellulose by free radical polymerization, which is complexing agent A; the modified chitosan is prepared by grafting 1,6-hexanediamine onto chitosan after EDC / NHS activation of bisphosphonate, which is complexing agent B, and then the complexing agents A and B are compounded and mixed with hydrophilic particles and other ingredients to obtain the etching solution for alloy surface treatment; the complexing agent can form strong coordination bonds with metal ions to inhibit their hydrolysis and precipitation, and can also chelate heavy metal ions to prevent them from accumulating in the solution to form complex competition; in addition, the inherent superhydrophilicity of chitosan, the strong hydration ability of phosphonic acid groups and the contribution of hydrophilic particles significantly improve the hydrophilicity of the alloy material surface during the treatment process, effectively inhibiting the adhesion of fouling. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0018] In order to more clearly illustrate the method provided by the present application, the following embodiments are described in detail. The test methods of various indexes of an etching solution for alloy surface treatment prepared in the following embodiments are as follows: Etching performance test: the 6061 aluminum alloy was first heated to 400℃ at a heating rate of 5℃ / min, then kept for 1.5h, then cooled to 200℃ at a cooling rate of 10℃ / min, kept for 30min, and then naturally cooled to room temperature to complete the gradient annealing pretreatment. Then, the alloy was immersed in the etching solution of Examples 1-3 and Comparative Examples 1-7, and etched for 5min with the aid of 20kHz ultrasonic. After that, the alloy surface was rinsed with ethanol, and dried at 60℃ under a vacuum degree of 0.1kPa for 6h to obtain the treated 6061 aluminum alloy. The thickness of the 6061 aluminum alloy after gradient annealing was the initial thickness, and the thickness of the 6061 aluminum alloy after etching was the final thickness. The etching rate of Examples 1-3 and Comparative Examples 1-7 was calculated. A contact angle measuring instrument was used to measure the contact angle between the water droplet and the surface of the 6061 alloy sheet etched with the etching solution of Examples 1-3 and Comparative Examples 1-7. The smaller the contact angle, the stronger the hydrophilicity, indicating that the etching solution has better penetration ability and better anti-fouling effect. A scanning electron microscope was used to observe the surface morphology of the 6061 alloy sheet etched with the etching solution of Examples 1-3 and Comparative Examples 1-7. The surface brightness and flatness were observed, and the results are shown in Table 1.

[0019] pH response performance test of hydrophilic particles: four 6061 aluminum alloys that had completed gradient annealing pretreatment were immersed in the etching solution of Examples 2, Comparative Example 1, Comparative Example 2 and Comparative Example 3 with magnetic stirring at room temperature. The etching time was controlled at 1min, 3min and 5min, respectively. After that, the 6061 aluminum alloy was taken out and the alloy surface was rinsed with ethanol, and then dried at 60℃ under a vacuum degree of 0.1kPa for 6h. The etching rate was measured and calculated, and the pH value was monitored. The results are shown in Table 2.

[0020] Example 1; (1) 5g of Konjac Glucomannan with model KJ-30 and 30ml of isopropyl alcohol were mixed, 125ml of 1M sodium hydroxide aqueous solution was added dropwise at a rate of 20ml / min, stirred at a speed of 200rpm, and heated to 60℃ at a rate of 8℃ / min, 2.5g of 3-chloro-2-hydroxypropyl trimethylammonium chloride was added, and the reaction was continued to stir for 2h, then the pH was adjusted to 6.0 with 1M hydrochloric acid aqueous solution, ethanol was added to make the ethanol concentration reach 80% of the total solution volume, and it was left to stand for 30min, 4000rpm centrifugation for 10min to collect the precipitate and washed with ethanol for 3 times, and dried at 50℃ for 12h to obtain the konjac glucomannan grafted with quaternary ammonium groups; green tea polyphenol, konjac glucomannan grafted with quaternary ammonium groups and deionized water were mixed according to the mass ratio of 1:1:20, stirred at 60℃ at a speed of 300rpm for 2h, filtered and washed with deionized water for 3 times, and dried at 60℃ for 12h to obtain the self-made corrosion inhibitor; in a 40℃ constant temperature water bath, 4.5g of cetyl trimethylammonium bromide was mixed with 20ml of deionized water to form a liquid crystal by stirring at a speed of 500rpm, 25mL of tetrabutyl titanate and 50mL of anhydrous ethanol were mixed and added dropwise into the liquid crystal at a speed of 3s / drop, after the dropwise addition was completed, 200mL of a mixture of ethanol and 4mL of deionized water was added at a speed of 1s / drop, and the distillation was continued at 90℃ until a gel was formed, the gel was dried at 80℃ for 4h, then put into a Soxhlet extractor, extracted with anhydrous ethanol for 48h, and calcined at 500℃ for 2h to obtain mesoporous titanium dioxide with a pore size of 5nm and a particle size of 100nm; 20mg of mesoporous titanium dioxide was weighed, 60μL of 3-aminopropyl triethoxysilane and 5mL of methanol were added, and stirred at a speed of 200rpm in the dark at room temperature for 12h, then centrifuged at 8000rpm for 10min and the solid product was washed with deionized water for 3 times, and dried at 60℃ for 8h to obtain aminated mesoporous titanium dioxide nanoparticles; 10mg of aminated mesoporous titanium dioxide nanoparticles was weighed, 3mg of self-made corrosion inhibitor and 3mL of 0.1M phosphate buffer were added, and stirred at a speed of 300rpm for 24h, then centrifuged at 10000rpm for 5min and washed with deionized water for 3 times, and dried at 60℃ for 10h to obtain mesoporous titanium dioxide nanoparticles loaded with self-made corrosion inhibitor; the mesoporous titanium dioxide nanoparticles loaded with self-made corrosion inhibitor, dopamine and 50mM, pH=8.5 Tris-HCl buffer were mixed according to the mass ratio of 5:1:50, stirred at a speed of 200rpm in the dark at room temperature for 24h, centrifuged at a speed of 8000rpm for 10min, and the solid material was washed with deionized water for 3 times, then freeze-dried at-50℃ for 12h to obtain the self-made hydrophilic particles; (2) Carboxymethyl cellulose and deionized water were mixed at a mass ratio of 1:20, stirred at room temperature at a speed of 500 rpm for 1 h, 0.2 times the mass of carboxymethyl cellulose of sodium vinyl sulfonate was added, and high-purity nitrogen was bubbled at a rate of 0.5 L / min for 30 min; after the dissolved oxygen was discharged, the temperature was raised to 65°C, 0.02 times the mass of carboxymethyl cellulose of ammonium persulfate was added, and stirred at a speed of 300 rpm for 6 h, then 1M sodium hydroxide solution was added to adjust the pH to 7.0, and dialyzed for 48 h with a dialysis bag with a molecular weight cutoff of 3500 Da using deionized water as the mobile phase, and then replaced every 8 h, and then freeze-dried at -50°C for 24 h to obtain complexing agent A; (3) The glufosinate-ammonium and the activation solution were mixed at a mass ratio of 2:100, the EDC concentration in the activation solution was 50 g / L, the NHS concentration was 30 g / L, the solvent was a pH=6.0, 0.1M MES buffer, and the mixture was stirred at room temperature at a speed of 300 rpm for 2 h to obtain an activated glufosinate-ammonium solution; chitosan, 1,6-hexanediamine, and 2wt% acetic acid aqueous solution were mixed at a mass ratio of 1:0.1:20, the pH was maintained at 6.0, and the mixture was stirred at room temperature at a speed of 300 rpm for 10 min, then the activated glufosinate-ammonium solution was added at a rate of 1 drop / s, the mass of the chitosan was 15 times, and the mixture was stirred at room temperature at a speed of 300 rpm for 12 h, then centrifuged at a speed of 6000 rpm for 10 min, the solid material was washed with deionized water for 3 times, and then dried at 60°C for 12 h to obtain complexing agent B; (4) 2 parts by weight of hydrophilic particles, 15 parts by weight of complexing agent A, 10 parts by weight of complexing agent B, 4 parts by weight of etching agent, and 70 parts by weight of deionized water were mixed, the etching agent was prepared by mixing 10wt% hydrogen peroxide, malonic acid, succinic acid, and phenylurea at a mass ratio of 10:1.5:2.5:0.2, and then stirred at room temperature at a speed of 500 rpm for 30 min to obtain an etching solution for alloy surface treatment.

[0021] Example 2; (1) 5g of Konjac Glucomannan with model KJ-30 and 30ml of isopropyl alcohol were mixed, 125ml of 1M sodium hydroxide aqueous solution was added dropwise at a rate of 20ml / min, stirred at a speed of 200rpm, and heated to 60℃ at a rate of 8℃ / min, 2.5g of 3-chloro-2-hydroxypropyl trimethylammonium chloride was added, and the reaction was continued to stir for 2h, then the pH was adjusted to 6.0 with 1M hydrochloric acid aqueous solution, ethanol was added to make the ethanol concentration reach 80% of the total solution volume, and it was left to stand for 30min, 4000rpm centrifugation for 10min to collect the precipitate and washed with ethanol for 3 times, and dried at 50℃ for 12h to obtain the konjac glucomannan grafted with quaternary ammonium groups; green tea polyphenols, konjac glucomannan grafted with quaternary ammonium groups and deionized water were mixed according to the mass ratio of 1:1:20, stirred at 300rpm at 60℃ for 2h, filtered and washed with deionized water for 3 times, and dried at 60℃ for 12h to obtain the self-made corrosion inhibitor; in a 40℃ constant temperature water bath, 4.5g of cetyl trimethylammonium bromide was mixed with 20ml of deionized water to form a liquid crystal by stirring at a speed of 500rpm, 25mL of tetrabutyl titanate and 50mL of anhydrous ethanol were mixed and added dropwise into the liquid crystal at a speed of 3s / drop, after the dropwise addition was completed, 200mL of a mixture of ethanol and 4mL of deionized water was added at a speed of 1s / drop, and the distillation was continued at 90℃ until a gel was formed, the gel was dried at 80℃ for 4h, then put into a Soxhlet extractor, extracted with anhydrous ethanol for 48h, and calcined at 500℃ for 2h to obtain mesoporous titanium dioxide with a pore size of 5nm and a particle size of 100nm; 20mg of mesoporous titanium dioxide was weighed, 60μL of 3-aminopropyl triethoxysilane and 5mL of methanol were added, and stirred at a speed of 200rpm at room temperature in the dark for 12h, then centrifuged at 8000rpm for 10min and the solid product was washed with deionized water for 3 times, and dried at 60℃ for 8h to obtain aminated mesoporous titanium dioxide nanoparticles; 10mg of aminated mesoporous titanium dioxide nanoparticles was weighed, 3mg of self-made corrosion inhibitor and 3mL of 0.1M phosphate buffer were added, and stirred at a speed of 300rpm for 24h, then centrifuged at 10000rpm for 5min and washed with deionized water for 3 times, and dried at 60℃ for 10h to obtain mesoporous titanium dioxide nanoparticles loaded with self-made corrosion inhibitor; the mesoporous titanium dioxide nanoparticles loaded with self-made corrosion inhibitor, dopamine and 50mM, pH=8.5 Tris-HCl buffer were mixed according to the mass ratio of 5:1:50, stirred at a speed of 200rpm at room temperature in the dark for 24h, centrifuged at a speed of 8000rpm for 10min, and the solid material was washed with deionized water for 3 times, then freeze-dried at-50℃ for 12h to obtain the self-made hydrophilic particles; (2) mixing carboxymethyl cellulose and deionized water according to a mass ratio of 1.5:20, stirring at a speed of 500 rpm for 1.5 h at room temperature, adding sodium vinyl sulfonate with a mass of 0.3 times that of the carboxymethyl cellulose, and then bubbling high-purity nitrogen at a rate of 0.5 L / min for 30 min; after the dissolved oxygen is discharged, the temperature is raised to 70°C, and ammonium persulfate with a mass of 0.03 times that of the carboxymethyl cellulose is added, and stirring is performed at a speed of 300 rpm for 7 h; then, 1M sodium hydroxide solution is added to adjust the pH to 7.5, and dialysis is performed for 48 h through a dialysis bag with a molecular weight cut-off of 3500 Da using deionized water as the mobile phase, and the dialysis bag is replaced every 8 h; and then, freeze-drying is performed at -50°C for 24 h to obtain the complexing agent A; (3) mixing glufosinate-ammonium and an activation solution according to a mass ratio of 3:100, wherein the concentration of EDC in the activation solution is 50 g / L, the concentration of NHS is 30 g / L, and the solvent is a MES buffer solution with a pH of 6.0 and a concentration of 0.1M, stirring at a speed of 300 rpm for 2 h at room temperature to obtain an activated glufosinate-ammonium solution; mixing chitosan, 1,6-hexanediamine, and 2wt% acetic acid aqueous solution according to a mass ratio of 1.5:0.15:20, maintaining the pH at 6.0, stirring at a speed of 300 rpm for 10 min at room temperature, and then adding the activated glufosinate-ammonium solution with a mass of 18 times that of the chitosan at a rate of 1 drop / s, stirring at a speed of 300 rpm for 13 h at room temperature, centrifuging at a speed of 6000 rpm for 10 min, washing the solid material with deionized water for 3 times, and then drying at 60°C for 12 h to obtain the complexing agent B; (4) mixing 3 parts by weight of hydrophilic particles, 18 parts by weight of the complexing agent A, 12 parts by weight of the complexing agent B, 5 parts by weight of an etching agent, and 60 parts by weight of deionized water, wherein the etching agent is obtained by mixing 10wt% hydrogen peroxide, malonic acid, succinic acid, and phenylurea according to a mass ratio of 10:1.5:2.5:0.2, and then stirring at a speed of 500 rpm for 30 min at room temperature to obtain the etching solution for alloy surface treatment.

[0022] Example 3; (1) 5g of Konjac Glucomannan with model KJ-30 and 30ml of isopropyl alcohol were mixed, 125ml of 1M sodium hydroxide aqueous solution was added dropwise at a rate of 20ml / min, stirred at a speed of 200rpm, and heated to 60℃ at a rate of 8℃ / min, 2.5g of 3-chloro-2-hydroxypropyl trimethylammonium chloride was added, and the reaction was continued to stir for 2h, then the pH was adjusted to 6.0 with 1M hydrochloric acid aqueous solution, ethanol was added to make the ethanol concentration reach 80% of the total solution volume, and it was left to stand for 30min, 4000rpm centrifugation for 10min to collect the precipitate and washed with ethanol for 3 times, and dried at 50℃ for 12h to obtain the konjac glucomannan grafted with quaternary ammonium groups; green tea polyphenols, konjac glucomannan grafted with quaternary ammonium groups and deionized water were mixed according to the mass ratio of 1:1:20, stirred at 300rpm at 60℃ for 2h, filtered and washed with deionized water for 3 times, and dried at 60℃ for 12h to obtain the self-made corrosion inhibitor; in a 40℃ constant temperature water bath, 4.5g of cetyl trimethylammonium bromide was mixed with 20ml of deionized water to form a liquid crystal by stirring at a speed of 500rpm, 25mL of tetrabutyl titanate and 50mL of anhydrous ethanol were mixed and added dropwise into the liquid crystal at a speed of 3s / drop, after the dropwise addition was completed, 200mL of a mixture of ethanol and 4mL of deionized water was added at a speed of 1s / drop, and the distillation was continued at 90℃ until a gel was formed, the gel was dried at 80℃ for 4h, then put into a Soxhlet extractor, extracted with anhydrous ethanol for 48h, and calcined at 500℃ for 2h to obtain mesoporous titanium dioxide with a pore size of 5nm and a particle size of 100nm; 20mg of mesoporous titanium dioxide was weighed, 60μL of 3-aminopropyl triethoxysilane and 5mL of methanol were added, and stirred at a speed of 200rpm at room temperature in the dark for 12h, then centrifuged at 8000rpm for 10min and the solid product was washed with deionized water for 3 times, and dried at 60℃ for 8h to obtain aminated mesoporous titanium dioxide nanoparticles; 10mg of aminated mesoporous titanium dioxide nanoparticles was weighed, 3mg of self-made corrosion inhibitor and 3mL of 0.1M phosphate buffer were added, and stirred at a speed of 300rpm for 24h, then centrifuged at 10000rpm for 5min and washed with deionized water for 3 times, and dried at 60℃ for 10h to obtain mesoporous titanium dioxide nanoparticles loaded with self-made corrosion inhibitor; the mesoporous titanium dioxide nanoparticles loaded with self-made corrosion inhibitor, dopamine and 50mM, pH=8.5 Tris-HCl buffer were mixed according to the mass ratio of 5:1:50, stirred at a speed of 200rpm at room temperature in the dark for 24h, centrifuged at a speed of 8000rpm for 10min, and the solid material was washed with deionized water for 3 times, then freeze-dried at-50℃ for 12h to obtain the self-made hydrophilic particles; (2) Carboxymethyl cellulose and deionized water were mixed in a mass ratio of 2:20, stirred at room temperature at a speed of 500 rpm for 2 h, then 0.4 times the mass of carboxymethyl cellulose of sodium vinyl sulfonate was added, and high-purity nitrogen was bubbled at a rate of 0.5 L / min for 30 min; after the dissolved oxygen was discharged, the temperature was raised to 75°C, 0.04 times the mass of carboxymethyl cellulose of ammonium persulfate was added, and stirred at a speed of 300 rpm for 8 h; then 1M sodium hydroxide solution was added to adjust the pH to 8.0, and dialysis was performed for 48 h using a dialysis bag with a molecular weight cutoff of 3500 Da and deionized water as the mobile phase, and the dialysis was replaced every 8 h; then the mixture was freeze-dried at -50°C for 24 h to obtain complexing agent A; (3) The glufosinate-ammonium and the activation solution were mixed in a mass ratio of 4:100, the EDC concentration in the activation solution was 50 g / L, the NHS concentration was 30 g / L, the solvent was a pH 6.0, 0.1M MES buffer, and the mixture was stirred at room temperature at a speed of 300 rpm for 2 h to obtain an activated glufosinate-ammonium solution; chitosan, 1,6-hexanediamine, and 2 wt% acetic acid aqueous solution were mixed in a mass ratio of 2:0.2:20, the pH was maintained at 6.0, and the mixture was stirred at room temperature at a speed of 300 rpm for 10 min; then 20 times the mass of chitosan of the activated glufosinate-ammonium solution was added dropwise at a rate of 1 drop / s, and the mixture was stirred at room temperature at a speed of 300 rpm for 14 h; then the mixture was centrifuged at a speed of 6000 rpm for 10 min, the solid material was washed with deionized water for 3 times, and the mixture was dried at 60°C for 12 h to obtain complexing agent B; (4) 4 parts by weight of hydrophilic particles, 20 parts by weight of complexing agent A, 15 parts by weight of complexing agent B, 6 parts by weight of etching agent, and 55 parts by weight of deionized water were mixed to obtain an etching solution for alloy surface treatment, wherein the etching agent was obtained by mixing 10 wt% hydrogen peroxide, malonic acid, succinic acid, and phenylurea in a mass ratio of 10:1.5:2.5:0.2, and the mixture was stirred at room temperature at a speed of 500 rpm for 30 min.

[0023] Comparative Example 1; Comparative Example 1 differs from Example 2 in that step (1) is changed to: 4.5 g of cetyltrimethylammonium bromide is mixed with 20 ml of deionized water in a 40 °C constant temperature water bath, stirred uniformly at a speed of 500 rpm to form a liquid crystal, 25 mL of a mixture of tetrabutyl titanate and 50 mL of anhydrous ethanol is added dropwise to the liquid crystal at a speed of 3 s / drop, after the dropwise addition is completed, 200 mL of a mixture of ethanol and 4 mL of deionized water is added at a speed of 1 s / drop, and distillation is carried out at 90 °C until a gel is formed, the gel is dried at 80 °C for 4 h, then placed in a Soxhlet extractor, extracted with anhydrous ethanol for 48 h, and calcined at 500 °C for 2 h to obtain mesoporous titanium dioxide with a pore size of 5 nm and a particle size of 100 nm; 20 mg of mesoporous titanium dioxide is weighed, 60 μL of 3-aminopropyltriethoxysilane and 5 mL of methanol are added, stirred at a speed of 200 rpm in the dark at room temperature for 12 h, centrifuged at 8000 rpm for 10 min, and the solid product is washed with deionized water 3 times, dried at 60 °C for 8 h to obtain aminated mesoporous titanium dioxide nanoparticles; 10 mg of aminated mesoporous titanium dioxide nanoparticles is weighed, 3 mg of a self-made corrosion inhibitor and 3 mL of 0.1 M phosphate buffer are added, stirred at a speed of 300 rpm for 24 h, centrifuged at 10,000 rpm for 5 min, and washed with deionized water 3 times, dried at 60 °C for 10 h to obtain mesoporous titanium dioxide nanoparticles loaded with a self-made corrosion inhibitor; the mesoporous titanium dioxide nanoparticles loaded with a self-made corrosion inhibitor, dopamine, and 50 mM, pH = 8.5 Tris-HCl buffer are mixed at a mass ratio of 5:1:50, stirred at a speed of 200 rpm in the dark at room temperature for 24 h, centrifuged at a speed of 8000 rpm for 10 min, the solid material is washed with deionized water 3 times, and then freeze-dried at -50 °C for 12 h to obtain a self-made hydrophilic particle, and the remaining steps are the same as in Example 2.

[0024] Comparative Example 2; Comparative Example 2 differs from Example 2 in that step (1) and step (4) are different, step (1) is changed to: 5 g of Konjac Glucomannan with model KJ-30 is mixed with 30 ml of isopropyl alcohol, 125 ml of 1 M sodium hydroxide aqueous solution is added dropwise at a rate of 20 ml / min, stirring at a speed of 200 rpm, and heating at a rate of 8 ℃ / min to 60 ℃, 2.5 g of 3-chloro-2-hydroxypropyl trimethylammonium chloride is added, and the reaction is continued to stir for 2 h, then 1 M hydrochloric acid aqueous solution is added to adjust the pH to 6.0, ethanol is added to make the ethanol concentration reach 80% of the total solution volume, and the mixture is allowed to stand for 30 min, and the precipitate is collected by centrifugation at 4000 rpm for 10 min and washed with ethanol for 3 times, and dried at 50 ℃ for 12 h to obtain the Konjac Glucomannan grafted with quaternary ammonium groups; green tea polyphenols, Konjac Glucomannan grafted with quaternary ammonium groups and deionized water are mixed in a mass ratio of 1:1:20, stirred at 300 rpm at 60 ℃ for 2 h, filtered and washed with deionized water for 3 times, and dried at 60 ℃ for 12 h to obtain the self-made corrosion inhibitor; in a constant temperature water bath at 40 ℃, 4.5 g of cetyl trimethylammonium bromide is mixed with 20 ml of deionized water to form a liquid crystal by stirring at a speed of 500 rpm, 25 mL of tetrabutyl titanate and 50 mL of anhydrous ethanol are added dropwise into the liquid crystal at a rate of 3 s / drop, and after the dropwise addition is completed, 200 mL of a mixture of ethanol and 4 mL of deionized water is added at a rate of 1 s / drop, and the mixture is distilled at 90 ℃ until a gel is formed, the gel is dried at 80 ℃ for 4 h, and then placed in a Soxhlet extractor, extracted with anhydrous ethanol for 48 h, and calcined at 500 ℃ for 2 h to obtain mesoporous titanium dioxide with a pore size of 5 nm and a particle size of 100 nm; 20 mg of the mesoporous titanium dioxide is weighed, 60 μL of 3-aminopropyl triethoxysilane and 5 mL of methanol are added, and the mixture is stirred at a speed of 200 rpm in the dark at room temperature for 12 h, then centrifuged at 8000 rpm for 10 min and the solid product is washed with deionized water for 3 times, and dried at 60 ℃ for 8 h to obtain aminated mesoporous titanium dioxide nanoparticles; 10 mg of the aminated mesoporous titanium dioxide nanoparticles is weighed, 3 mg of the self-made corrosion inhibitor and 3 mL of 0.1 M phosphate buffer are added, and the mixture is stirred at a speed of 300 rpm for 24 h, then centrifuged at 10000 rpm for 5 min and washed with deionized water for 3 times, and dried at 60 ℃ for 10 h to obtain mesoporous titanium dioxide nanoparticles loaded with the self-made corrosion inhibitor; step (4) is changed to: 5 parts by weight of mesoporous titanium dioxide nanoparticles loaded with the self-made corrosion inhibitor, 2.5 parts by weight of complexing agent A, 1.5 parts by weight of complexing agent B, 0.8 parts by weight of hydrogen peroxide and 90 parts by weight of deionized water are mixed, and the mixture is stirred at a speed of 500 rpm at room temperature for 30 min to obtain an etching solution for alloy surface treatment, and the remaining steps are the same as in Example 2.

[0025] Comparative Example 3; Comparative Example 3 is different from Example 2 in that there is no step (1), and step (4) is changed to: 18 parts by weight of complexing agent A, 12 parts by weight of complexing agent B, 5 parts by weight of etching agent, and 60 parts by weight of deionized water are mixed, the etching agent is obtained by mixing 10 wt% hydrogen peroxide, malonic acid, succinic acid, and phenylurea in a mass ratio of 10:1.5:2.5:0.2, and stirring at room temperature at a speed of 500 rpm for 30 min to obtain an etching solution for alloy surface treatment, and the remaining steps are the same as in Example 2.

[0026] Comparative Example 4; Comparative Example 4 is different from Example 2 in that there is no step (2), and step (4) is changed to: 3 parts by weight of hydrophilic particles, 12 parts by weight of complexing agent B, 5 parts by weight of etching agent, and 60 parts by weight of deionized water are mixed, the etching agent is obtained by mixing 10 wt% hydrogen peroxide, malonic acid, succinic acid, and phenylurea in a mass ratio of 10:1.5:2.5:0.2, and stirring at room temperature at a speed of 500 rpm for 30 min to obtain an etching solution for alloy surface treatment, and the remaining steps are the same as in Example 2.

[0027] Comparative Example 5; Comparative Example 5 is different from Example 2 in that there is no step (3), and step (4) is changed to: 3 parts by weight of hydrophilic particles, 18 parts by weight of complexing agent A, 5 parts by weight of etching agent, and 60 parts by weight of deionized water are mixed, the etching agent is obtained by mixing 10 wt% hydrogen peroxide, malonic acid, succinic acid, and phenylurea in a mass ratio of 10:1.5:2.5:0.2, and stirring at room temperature at a speed of 500 rpm for 30 min to obtain an etching solution for alloy surface treatment, and the remaining steps are the same as in Example 2.

[0028] Comparative Example 6; Comparative Example 6 is different from Example 2 in that there is no step (2) or (3), and step (4) is changed to: 3 parts by weight of hydrophilic particles, 5 parts by weight of etching agent, and 60 parts by weight of deionized water are mixed, the etching agent is obtained by mixing 10 wt% hydrogen peroxide, malonic acid, succinic acid, and phenylurea in a mass ratio of 10:1.5:2.5:0.2, and stirring at room temperature at a speed of 500 rpm for 30 min to obtain an etching solution for alloy surface treatment, and the remaining steps are the same as in Example 2.

[0029] Comparative Example 7; Comparative Example 7 is a blank group, specifically: 5 parts by weight of etching agent and 60 parts by weight of deionized water are mixed, the etching agent is obtained by mixing 10 wt% hydrogen peroxide, malonic acid, succinic acid, and phenylurea in a mass ratio of 10:1.5:2.5:0.2, and stirring at room temperature at a speed of 500 rpm for 30 min to obtain an etching solution for alloy surface treatment.

[0030] Effect Example The performance analysis results of an etching solution for alloy surface treatment using one of Examples 1 to 3 and Comparative Examples 1 to 7 of the present application are shown in Table 1 below.

[0031] Table 1

[0032] The pH response performance analysis results of the hydrophilic particles in the etching solution for alloy surface treatment using the alloy of Example 2 and Comparative Examples 1 to 3 of the present application are given in Table 2 below.

[0033] Table 2

[0034] From the experimental data comparison of the etching rate of the examples and comparative examples in Table 1 and Table 2, it can be found that the self-made corrosion inhibitor prepared by first preparing mesoporous titanium dioxide by sol-gel method, then loading green tea polyphenol and konjac glucomannan grafted with quaternary ammonium groups after modification by amino coupling agent, adsorbing dopamine polymerization by surface electrostatic action to form pH-responsive hydrophilic particles, releasing corrosion inhibitor to inhibit excessive etching when the solution is slightly acidic during etching; at the same time, complexing agents A and B are prepared by grafting sulfonic acid groups and double glycol phosphonated chitosan, respectively, and then mixed with hydrophilic particles and other components to obtain the etching solution after compounding; the compounding complexing agent can form strong coordination bond with metal ions and chelate with heavy metal ions, significantly improving the etching ability; from the experimental data comparison of the contact angle of the examples and comparative examples in Table 1, it can be found that the mesoporous titanium dioxide is wrapped with dopamine polymerization by surface electrostatic action to obtain hydrophilic particles, which synergistically act with chitosan and phosphonic acid groups to significantly improve the hydrophilicity of the alloy material surface during the treatment process, effectively inhibiting the adhesion of scale; from the experimental data comparison of the surface morphology after etching of the examples and comparative examples in Table 1, it can be found that the etching solution for alloy surface treatment prepared by the present application has the effect of efficient and uniform etching.

[0035] It will be obvious to a person skilled in the art that, without departing from the spirit or essential characteristics of the application, the present application can be carried out in other specific forms than those described and exemplified herein. The present embodiments are therefore to be construed in all aspects as illustrative only and not restrictive, the scope of the application being indicated by the appended claims rather than by the description presented herein before, it being intended that all changes enabling a technical solution that falls within the framework of the equivalent elements of the claims come within the scope of the present application. Any reference signs in the claims should not be construed as limiting the claims concerned.

Claims

1. An etching solution for alloy surface treatment, characterized in that, Includes the following steps: (1) Green tea polyphenols, konjac glucomannan grafted with quaternary ammonium groups and deionized water were mixed in a mass ratio of 1:1:200, stirred at 60°C for 2 h, filtered and washed, and dried at 60°C for 12 h to obtain a self-made corrosion inhibitor, which was loaded onto mesoporous titanium dioxide prepared by sol-gel method and modified with amino coupling agent; mesoporous titanium dioxide, dopamine and buffer A were mixed in a mass ratio of 5:1:50, stirred at room temperature in the dark for 24 h, centrifuged for 10 min, and freeze-dried for 12 h to obtain self-made hydrophilic particles; (2) After mixing carboxymethyl cellulose and deionized water at a mass ratio of 1~2:20, stir at room temperature for 1~2 hours, add sodium vinyl sulfonate at a mass ratio of 0.2~0.4 times that of carboxymethyl cellulose, bubble with high-purity nitrogen at a rate of 0.5 L / min for 30 minutes, heat to 65~75℃, add initiator at a mass ratio of 0.02~0.04 times that of carboxymethyl cellulose, stir for 6~8 hours, add buffer B to adjust the pH to 7~8, dialyze, and freeze dry for 24 hours to obtain complexing agent A; (3) Mix glyphosate and activation solution at a mass ratio of 2-4:100 and stir at room temperature for 2 hours to obtain activated glyphosate solution; mix chitosan, 1,6-hexanediamine and buffer C at a mass ratio of 1-2:0.1-0.2:20, maintain pH at 6.0, stir at room temperature for 10 minutes, add 15-20 times the mass of activated glyphosate solution of chitosan at a rate of 1 drop / s, stir at room temperature for 12-14 hours, centrifuge for 10 minutes to wash, and dry at 60°C for 12 hours to obtain complexing agent B; (4) Mix 2-4 parts by weight of hydrophilic particles, 15-20 parts by weight of complexing agent A, 10-15 parts by weight of complexing agent B, 4-6 parts by weight of etchant and 55-70 parts by weight of deionized water, and stir at room temperature for 30 minutes to obtain an etching solution for alloy surface treatment.

2. The etching solution for alloy surface treatment according to claim 1, characterized in that, The amino coupling agent in step (1) is 3-aminopropyltriethoxysilane.

3. The etching solution for alloy surface treatment according to claim 1, characterized in that, The pore size and particle size of the mesoporous titanium dioxide in step (1) are: pore size 5nm, particle size 100nm.

4. The etching solution for alloy surface treatment according to claim 1, characterized in that, The buffer A in step (1) is a 50mM Tris-HCl buffer with pH=8.

5.

5. The etching solution for alloy surface treatment according to claim 1, characterized in that, The initiator in step (2) is ammonium persulfate.

6. The etching solution for alloy surface treatment according to claim 1, characterized in that, The buffer solution B in step (2) is a 1M sodium hydroxide solution.

7. The etching solution for alloy surface treatment according to claim 1, characterized in that, The activation solution in step (3) is: the concentration of EDC in the activation solution is 50 g / L, the concentration of NHS is 30 g / L, and the solvent is a 0.1 M MES buffer solution with pH=6.

0.

8. The etching solution for alloy surface treatment according to claim 1, characterized in that, The buffer solution C in step (3) is a 2wt% aqueous solution of acetic acid.

9. The etching solution for alloy surface treatment according to claim 1, characterized in that, The etching agent in step (4) is a mixture of 10wt% hydrogen peroxide, malonic acid, succinic acid and phenylurea in a mass ratio of 10:1.5:2.5:0.

2.

10. The application of an etching solution for alloy surface treatment, characterized in that, After the alloy material is pretreated by gradient annealing, it is immersed in etching solution and etched with ultrasonic assistance at 20 kHz for 5 min. The alloy surface is then rinsed with ethanol and dried at 60 ℃ for 6 h to obtain the treated alloy material.

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