CN115261839B - Passivating solution for passivating high corrosion-resistant alloy - Google Patents
Passivating solution for passivating high corrosion-resistant alloy Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract
The invention belongs to the technical field of metal material surface treatment, and particularly relates to passivation solution for high corrosion resistance alloy passivation treatment. According to the invention, the passivation solution for passivation treatment of the high corrosion-resistant alloy is added with the modified glycidyl methacrylate, the aminated nano silicon dioxide and the phosphoric acid modified nano cellulose, and the modified glycidyl methacrylate and the phosphoric acid modified nano cellulose cooperate with each other, so that the adhesive force between a film layer and metal is greatly improved. Furthermore, the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane is adopted to modify the nano silicon dioxide, so that the dispersibility of the nano silicon dioxide in passivation solution can be improved, and the organic branched chain of the nano silicon dioxide contains a large amount of amino groups, so that the nano silicon dioxide can form hydrogen bonds with modified glycidyl methacrylate and phosphoric acid modified nano cellulose and is crosslinked into a network, the mechanical property of the film resin is greatly improved, and the adhesive force between the film and metal is further enhanced.
Description
Technical Field
The invention belongs to the technical field of metal material surface treatment, and particularly relates to passivation solution for high corrosion resistance alloy passivation treatment.
Background
The metal material is used as a foundation stone for the development of human society, and makes great contribution to the construction of substances and civilization in the modern society, and the problem of metal corrosion is one of the problems which cannot be thoroughly solved in the current society. In natural environment, corrosion of metals is proceeding from moment to moment, throughout the entire metal storage and application area. The world has not been fully counted, and the annual production of scrap metal material from corrosion is about 30% of the annual production of metal, resulting in direct economic losses of up to $7000 hundred million. Among them, galvanization of steel is a common, economical and effective method of corrosion protection, and nearly half of the world's production of metallic zinc is used for metal corrosion protection every year.
Galvanized sheet is widely used in household appliances, building materials, aerospace and other industries because of its excellent corrosion resistance. However, the zinc layer of the galvanized sheet is easily corroded in the natural environment, white corrosion products are generated, and the corrosion resistance of the galvanized sheet is greatly reduced. In order to improve the corrosion resistance of the galvanized sheet and prolong the service time of the galvanized sheet, passivation treatment is generally adopted on the surface zinc layer of the galvanized sheet. Among them, chromate passivation is widely used for passivation of galvanized sheet surface due to its advantages of simple process, low cost and excellent passivation effect. However, wherein Cr 6+ Is a highly toxic cancerogenic substance which is easy to be absorbed by human bodies and has direct destructiveness to natural environment, so that the research on chromium-free passivation is the trend of the current anti-corrosion field.
The surface layer of the metal to be protected is coated with a material with good corrosion resistance as a protective film layer, so that the metal to be protected is separated from the corrosion environment, and the purpose of slowing down the corrosion of the metal to be protected is achieved. The main treatment methods in industrial production are phosphating treatment, oxidation treatment, nonmetallic film layers, metallic film layers and the like. Wherein the nonmetallic film layer and the metallic film layer belong to the most commonly used anti-corrosion treatment method. However, since the passivation film obtained by the passivation process using the inorganic salt or the organic matter alone has no self-repairing capability, and the corrosion resistance of the passivation film has a certain gap compared with that of the chromate passivation, researchers begin to use the inorganic salt and the organic matter in combination to passivate the galvanized sheet, and as a result, the corrosion resistance of the composite passivation film is found to be obviously better than that of the passivation effect of the single inorganic salt or organic matter. The inorganic-organic composite chromium-free passivation film not only can reduce the defects of a single passivation film, but also integrates the advantages of the inorganic-organic composite chromium-free passivation film and can obviously improve the corrosion resistance of the passivation film. The research direction of the inorganic-organic composite chromium-free passivation technology at present mainly comprises the following steps: composite passivation of inorganic matters and organic acids, composite passivation of inorganic matters and organic silanes, composite passivation of inorganic matters and organic resins, composite passivation of inorganic matters, organic silanes, organic resins, and the like.
Although the passivation of the organic resin shows good corrosion resistance, the binding force between the resin purification film and the matrix metal is weak, and the film is easy to fall off, so that related researchers begin to carry out compound research of inorganic salt and organic resin, thereby improving the adhesive force and corrosion resistance of the passivation film.
CN 110565084B discloses an organic and inorganic composite passivation solution and passivation method. The citric acid and the phytic acid are adopted to replace the traditional nitric acid and chromate passivation, sodium molybdate and cerium nitrate are simultaneously introduced to conduct inorganic passivation, gamma- (2, 3-glycidoxy) propyl trimethoxy silane, water-based acrylic ester and nano silica sol are introduced to conduct organic passivation, so that inorganic and organic composite passivation is achieved, and the passivation effect is close to that of a passivation system of nitric acid and chromate. The method has no pertinence to research and optimize the binding force between the film layer and the matrix metal and the corrosion resistance of the film.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the passivation solution for the passivation treatment of the high corrosion-resistant alloy.
The passivation solution for the passivation treatment of the high corrosion-resistant alloy comprises the following raw materials in parts by mass: 90-120 parts of bisphenol A epoxy diacrylate, 10-20 parts of modified glycidyl methacrylate, 10-20 parts of aminated nano silicon dioxide, 10-20 parts of phosphoric acid modified nano cellulose, 10-100 parts of absolute ethyl alcohol, 20-50 parts of water-soluble hydrogen-containing silicone oil, 0.01-5 parts of surfactant, 0.1-5 parts of flatting agent, 5-10 parts of metal film forming agent, 0.5-5 parts of stabilizing agent, 4-6 parts of acetic acid, 6-8 parts of ammonia water and 200-400 parts of water.
The surfactant is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl diphenyl ether disulfonate and disodium hexadecyl sulfophenoxy benzene sulfonate.
The leveling agent is at least one of hydroxymethyl cellulose, fluorine leveling agent and acrylic leveling agent; preferably, the leveling agent is an acrylic leveling agent.
The metal film forming agent is one or two of ammonium fluotitanate and sodium tungstate; preferably, the metal film forming agent is ammonium fluotitanate and sodium tungstate according to the mass ratio of (1-2): (1-2) and mixing.
The stabilizer is at least one of sodium citrate or sodium tetraborate.
The preparation method of the modified glycidyl methacrylate comprises the following steps:
10-20 parts of tannic acid, 90-110 parts of water and 10-20 parts of glycidyl methacrylate are mixed according to parts by mass, 0.5-1 part of tetrabutylammonium bromide is added into the mixture, 0.1-0.2 part of hydroquinone is added into the mixture, the mixture is stirred for 3-5min at a rotating speed of 100-200r/min, the mixture is placed at a temperature of 85-95 ℃ for reaction for 3-5h, ethyl acetate is used for extraction, an upper organic phase is taken, and the mixture is subjected to reduced pressure rotary evaporation to obtain the modified glycidyl methacrylate.
The preparation method of the phosphoric acid modified nanocellulose comprises the following steps:
s1, crushing the dried bamboo pulp paper, mixing the crushed bamboo pulp paper with water according to the mass ratio of 1 (1) to 2), treating the crushed bamboo pulp paper for 120 to 150 minutes by adopting a homogenizer at the rotating speed of 18000 rpm to 20000rpm, and drying the crushed bamboo pulp paper to obtain bamboo pulp;
s2, mixing 5-15 parts of bamboo pulp, 3-4 parts of phosphoric acid, 10-15 parts of urea and 15-20 parts of water according to parts by weight, performing ultrasonic treatment for 60-90min under the power of 1300-1500W by using an ultrasonic breaker, and then adding 50-60 parts of water for dilution to obtain a suspension;
s3, regulating the pH value of the suspension obtained in the step S2 to 10-12 by using 4-6wt% sodium hydroxide aqueous solution, stirring for 20-40min at the rotating speed of 100-200r/min, filtering to obtain precipitate, washing with water, and drying to obtain the phosphoric acid modified nanocellulose.
The preparation method of the aminated nano silicon dioxide comprises the following steps:
(1) Adding 20-40 parts by mass of polyvinylpyrrolidone into 200-300 parts by mass of absolute ethyl alcohol, then adding 50-100 parts by mass of ammonia water with the concentration of 20-24wt%, stirring for 5-10min at the speed of 100-200r/min, adding 10-20 parts by mass of tetraethyl orthosilicate, continuously stirring for 2-3h at the speed of 100-200r/min, filtering to obtain a filter cake, washing and drying to obtain nano silicon dioxide;
(2) Mixing 90-110 parts of toluene and 10-20 parts of nano silicon dioxide according to parts by mass, ultrasonically dispersing for 4-6min, adding 3-6 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, stirring for 1-3min at 8000-12000r/min, refluxing for 20-30h at 100-200 ℃, filtering to obtain a filter cake, washing and drying to obtain the aminated nano silicon dioxide.
The power of the ultrasonic wave is 50-70W, and the frequency is 70-90kHz.
A preparation method of a passivation solution for passivation treatment of high corrosion resistance alloy comprises the following steps: 100-200 parts of modified glycidyl methacrylate, 10-20 parts of aminated nano silicon dioxide, 10-20 parts of phosphoric acid modified nano cellulose, 10-100 parts of absolute ethyl alcohol, 20-50g of water-soluble hydrogen-containing silicone oil, 0.01-5 parts of surfactant, 0.1-5 parts of flatting agent, 5-10 parts of metal film forming agent, 0.5-5 parts of stabilizer, 4-6 parts of acetic acid, 6-8 parts of ammonia water and 200-400 parts of water are mixed according to the mass parts, and the mixture is stirred for 5-10min at a rotating speed of 100-200r/min, so that the passivation solution for passivation treatment of the high corrosion-resistant alloy is obtained.
Although good corrosion resistance is shown for organic resin passivation, the binding force between the resin purification film and the matrix metal is weak, and the film is easy to fall off, so that the invention starts to carry out the compounding research of inorganic salt and organic resin, thereby improving the adhesive force and corrosion resistance of the passivation film.
Tannic Acid (TA) is a biological base containing a plurality of catechol groups, has high annual output and low price, can generate adhesion effect with various metal surfaces, and can effectively improve the adhesion of a film layer to a metal plate, however, tannic acid contains a structure with a large number of benzene rings, has extremely poor compatibility with resin and has no photosensitive group, and cannot be directly applied to a photo-curing coating. Therefore, the invention grafts tannic acid on glycidyl methacrylate by ring-opening reaction between tannic acid and glycidyl methacrylate, improves the resin compatibility, and can well promote the adhesive force of the film layer and the metal substrate by adding the tannic acid into passivation solution. The modified glycidyl methacrylate is adopted independently, so that the adhesive force between the film layer and metal is improved to a certain extent, but the corrosion resistance is slightly poor, and the film layer is easy to fall off along with the deepening of the corrosion degree.
Thus, the present invention further employs phosphoric acid modified nanocellulose and adds it to the passivation solution. Nanocellulose has high tensile strength, and good mechanical properties in filling applications of composite reinforcement materials, which are also reflected in large specific surface area and large long diameter of nanocellulose. The film layer obtained by adding the material into the passivation solution has good mechanical properties. In addition, since nanocellulose contains a large number of glucose residues, the nanocellulose can well react with phosphoric acid to obtain phosphorylated nanocellulose. And the phosphoric acid can react with metal to generate various salt which can be chelated with the surface of the metal, thereby further improving the adhesive force between the film layer and the metal substrate. Compared with phosphate resin prepared by taking phosphorus pentoxide or phosphorus oxychloride as raw materials in the prior art, the method has the advantages of low requirement on synthesis conditions of the phosphorylated nanocellulose, safety and no pollution. In addition, the phosphoric acid modified nanocellulose can form a stable colloid in the water-soluble reagent, which is beneficial to improving the stability of the passivation solution.
Still further, in order to improve the wear resistance of the passivation solution, the nano silicon dioxide is added into the passivation solution as an additive, but the nano silicon dioxide has poor dispersibility and is easy to agglomerate, so that the stability of the passivation solution is influenced, the surface of the film layer is not smooth, and the adhesive force is reduced. Therefore, the invention adopts various silane coupling agents to modify nano silicon dioxide, and finally discovers that the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane is adopted to modify nano silicon dioxide, so that the dispersibility of the nano silicon dioxide in passivation solution can be improved, and as the organic branched chain contains a large amount of amino groups, the nano silicon dioxide can form hydrogen bonds with modified glycidyl methacrylate and phosphoric acid modified nano cellulose and form a network through crosslinking, the mechanical property of film resin is greatly improved, and the adhesive force between the film and metal is further enhanced.
When the modified glycidyl methacrylate, the phosphoric acid modified nano cellulose and the aminated nano silicon dioxide are added into the passivation solution at the same time, the three are synergistic, so that the passivation solution shows excellent corrosion resistance and adhesive force.
The invention has the beneficial effects that:
according to the invention, the compound research of inorganic salt and organic resin is carried out, the tannic acid and glycidyl methacrylate are adopted to react, so that the resin compatibility of tannic acid is improved, phosphoric acid modified nanocellulose is used for replacing phosphoric acid ester resin prepared by taking phosphorus pentoxide or phosphorus oxychloride as raw materials, and the reaction condition is low in requirement, safer and pollution-free. The modified glycidyl methacrylate and the phosphoric acid modified nanocellulose cooperate to greatly improve the adhesive force between the film layer and the metal. Furthermore, the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane is adopted to modify the nano silicon dioxide, so that the dispersibility of the nano silicon dioxide in passivation solution can be improved, and the organic branched chain of the nano silicon dioxide contains a large amount of amino groups, so that the nano silicon dioxide can form hydrogen bonds with modified glycidyl methacrylate and phosphoric acid modified nano cellulose and is crosslinked into a network, the mechanical property of the film resin is greatly improved, and the adhesive force between the film and metal is further enhanced.
Detailed Description
Bisphenol a epoxy diacrylate, CAS number: 89297-97-2.
Bamboo pulp paper, goods number: PC-400, bamboo pulp paper extraction purchased from North Beijing from paper products Limited.
Polyvinylpyrrolidone, model: PVPK30, ulan Ind.
N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, CAS number: 1760-24-3.
Water-soluble hydrogen-containing silicone oil, model: HY-6, hongYejie technology Co., ltd.
Acrylic leveling agent, model: KMT-5519, manufactured by Pick, germany.
The concentration of phosphoric acid used in the examples was 85% by weight.
The concentration of acetic acid used in the examples was 25wt%.
Example 1
A preparation method of a passivation solution for passivation treatment of high corrosion resistance alloy comprises the following steps: 100 parts of bisphenol A epoxy diacrylate, 50 parts of absolute ethyl alcohol, 30 parts of water-soluble hydrogen-containing silicone oil, 3 parts of surfactant, 3 parts of flatting agent, 8 parts of metal film forming agent, 3 parts of stabilizing agent, 5 parts of acetic acid, 7 parts of 24wt% ammonia water and 300 parts of water are mixed according to parts by mass, and stirring is carried out for 6 minutes at a rotating speed of 180r/min, so that the passivation solution for passivation treatment of the high corrosion-resistant alloy is obtained.
The surfactant is sodium dodecyl benzene sulfonate.
The leveling agent is an acrylic leveling agent.
The metal film forming agent is ammonium fluotitanate and sodium tungstate according to the mass ratio of 1:1, and mixing.
The stabilizer is sodium citrate.
Example 2
A preparation method of a passivation solution for passivation treatment of high corrosion resistance alloy comprises the following steps: 100 parts of bisphenol A epoxy diacrylate, 15 parts of modified glycidyl methacrylate, 50 parts of absolute ethyl alcohol, 30 parts of water-soluble hydrogen-containing silicone oil, 3 parts of surfactant, 3 parts of flatting agent, 8 parts of metal film forming agent, 3 parts of stabilizer, 5 parts of acetic acid, 7 parts of 24wt% ammonia water and 300 parts of water are mixed according to parts by mass, and stirring is carried out for 6 minutes at a rotating speed of 180r/min, so that the passivation solution for passivation of the high corrosion resistance alloy is obtained.
The surfactant is sodium dodecyl benzene sulfonate.
The leveling agent is an acrylic leveling agent.
The metal film forming agent is ammonium fluotitanate and sodium tungstate according to the mass ratio of 1:1, and mixing.
The stabilizer is sodium citrate.
The preparation method of the modified glycidyl methacrylate comprises the following steps:
17 parts of tannic acid, 100 parts of water and 14 parts of glycidyl methacrylate are mixed according to parts by mass, 0.6 part of tetrabutylammonium bromide is added into the tannic acid, 0.15 part of hydroquinone is added into the mixture, the mixture is stirred for 4min at a rotating speed of 180r/min, the mixture is placed at a temperature of 90 ℃ for reaction for 4h, ethyl acetate is used for extraction, an upper organic phase is taken, and the organic phase is subjected to reduced pressure rotary evaporation to obtain modified glycidyl methacrylate.
Example 3
A preparation method of a passivation solution for passivation treatment of high corrosion resistance alloy comprises the following steps: 100 parts of bisphenol A epoxy diacrylate, 15 parts of aminated nano silicon dioxide, 50 parts of absolute ethyl alcohol, 30 parts of water-soluble hydrogen-containing silicone oil, 3 parts of surfactant, 3 parts of flatting agent, 8 parts of metal film forming agent, 3 parts of stabilizer, 5 parts of acetic acid, 7 parts of 24wt% ammonia water and 300 parts of water are mixed according to parts by mass, and stirring is carried out for 6 minutes at a rotating speed of 180r/min, so that the passivation solution for passivation treatment of the high corrosion-resistant alloy is obtained.
The surfactant is sodium dodecyl benzene sulfonate.
The leveling agent is an acrylic leveling agent.
The metal film forming agent is ammonium fluotitanate and sodium tungstate according to the mass ratio of 1:1, and mixing.
The stabilizer is sodium citrate.
The preparation method of the aminated nano silicon dioxide comprises the following steps:
(1) Adding 30 parts by mass of polyvinylpyrrolidone into 270 parts by mass of absolute ethyl alcohol, then adding 75 parts by mass of ammonia water with the concentration of 20wt% into the absolute ethyl alcohol, stirring the mixture for 10min at the rotation speed of 180r/min, adding 15 parts by mass of tetraethyl orthosilicate, continuously stirring the mixture for 2.5h at the rotation speed of 180r/min, filtering to obtain a filter cake, washing and drying the filter cake to obtain nano silicon dioxide;
(2) Mixing 100 parts of toluene and 15 parts of nano silicon dioxide according to parts by mass, ultrasonically dispersing for 5min, adding 4 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, stirring for 2min at a rotating speed of 10000r/min, refluxing for 24h at 160 ℃, filtering to obtain a filter cake, washing and drying to obtain the amino nano silicon dioxide; the power of the ultrasonic wave is 60W, and the frequency is 80kHz.
Example 4
A preparation method of a passivation solution for passivation treatment of high corrosion resistance alloy comprises the following steps: 100 parts of bisphenol A epoxy diacrylate, 15 parts of phosphoric acid modified nanocellulose, 50 parts of absolute ethyl alcohol, 30 parts of water-soluble hydrogen-containing silicone oil, 3 parts of surfactant, 3 parts of flatting agent, 8 parts of metal film forming agent, 3 parts of stabilizer, 5 parts of acetic acid, 7 parts of 24wt% ammonia water and 300 parts of water are mixed according to parts by mass, and stirring is carried out for 6 minutes at a rotating speed of 180r/min, so that the passivation solution for passivation of the high corrosion-resistant alloy is obtained.
The surfactant is sodium dodecyl benzene sulfonate.
The leveling agent is an acrylic leveling agent.
The metal film forming agent is ammonium fluotitanate and sodium tungstate according to the mass ratio of 1:1, and mixing.
The stabilizer is sodium citrate.
The preparation method of the phosphoric acid modified nanocellulose comprises the following steps:
s1, crushing the dried bamboo pulp paper, mixing the crushed bamboo pulp paper with water according to a mass ratio of 1:2, treating the crushed bamboo pulp paper with a homogenizer at a rotating speed of 20000rpm for 120min, and drying the crushed bamboo pulp paper to obtain bamboo pulp;
s2, mixing 10 parts of bamboo pulp, 3.8 parts of phosphoric acid, 12 parts of urea and 15.7 parts of water according to parts by mass, performing ultrasonic treatment for 75 minutes by using an ultrasonic breaker under the power of 1500W, and then adding 55 parts of water for dilution to obtain a suspension;
and S3, regulating the pH value of the suspension obtained in the step S2 to 11 by using 5wt% sodium hydroxide aqueous solution, stirring for 30min at a rotating speed of 180r/min, filtering to obtain precipitate, washing with water, and drying to obtain the phosphoric acid modified nanocellulose.
Example 5
A preparation method of a passivation solution for passivation treatment of high corrosion resistance alloy comprises the following steps: 100 parts of bisphenol A epoxy diacrylate, 15 parts of modified glycidyl methacrylate, 15 parts of aminated nano silicon dioxide, 50 parts of absolute ethyl alcohol, 30 parts of water-soluble hydrogen-containing silicone oil, 3 parts of surfactant, 3 parts of flatting agent, 8 parts of metal film forming agent, 3 parts of stabilizer, 5 parts of acetic acid, 7 parts of 24wt% ammonia water and 300 parts of water are mixed according to parts by mass, and stirring is carried out for 6 minutes at a rotating speed of 180r/min, so that the passivation solution for passivation of the high corrosion-resistant alloy is obtained.
The surfactant is sodium dodecyl benzene sulfonate.
The leveling agent is an acrylic leveling agent.
The metal film forming agent is ammonium fluotitanate and sodium tungstate according to the mass ratio of 1:1, and mixing.
The stabilizer is sodium citrate.
The preparation method of the modified glycidyl methacrylate comprises the following steps:
17 parts of tannic acid, 100 parts of water and 14 parts of glycidyl methacrylate are mixed according to parts by mass, 0.6 part of tetrabutylammonium bromide is added into the tannic acid, 0.15 part of hydroquinone is added into the mixture, the mixture is stirred for 4min at a rotating speed of 180r/min, the mixture is placed at a temperature of 90 ℃ for reaction for 4h, ethyl acetate is used for extraction, an upper organic phase is taken, and the organic phase is subjected to reduced pressure rotary evaporation to obtain modified glycidyl methacrylate.
The preparation method of the aminated nano silicon dioxide comprises the following steps:
(1) Adding 30 parts by mass of polyvinylpyrrolidone into 270 parts by mass of absolute ethyl alcohol, then adding 75 parts by mass of ammonia water with the concentration of 20wt% into the absolute ethyl alcohol, stirring the mixture for 10min at the rotation speed of 180r/min, adding 15 parts by mass of tetraethyl orthosilicate, continuously stirring the mixture for 2.5h at the rotation speed of 180r/min, filtering to obtain a filter cake, washing and drying the filter cake to obtain nano silicon dioxide;
(2) Mixing 100 parts of toluene and 15 parts of nano silicon dioxide according to parts by mass, ultrasonically dispersing for 5min, adding 4 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, stirring for 2min at a rotating speed of 10000r/min, refluxing for 24h at 160 ℃, filtering to obtain a filter cake, washing and drying to obtain the amino nano silicon dioxide; the power of the ultrasonic wave is 60W, and the frequency is 80kHz.
Example 6
A preparation method of a passivation solution for passivation treatment of high corrosion resistance alloy comprises the following steps: 100 parts of bisphenol A epoxy diacrylate, 15 parts of modified glycidyl methacrylate, 15 parts of phosphoric acid modified nanocellulose, 50 parts of absolute ethyl alcohol, 30 parts of water-soluble hydrogen-containing silicone oil, 3 parts of surfactant, 3 parts of flatting agent, 8 parts of metal film forming agent, 3 parts of stabilizer, 5 parts of acetic acid, 7 parts of 24wt% ammonia water and 300 parts of water are mixed according to parts by mass, and stirring is carried out for 6 minutes at a rotating speed of 180r/min, so that the passivation solution for passivation of the high corrosion-resistant alloy is obtained.
The surfactant is sodium dodecyl benzene sulfonate.
The leveling agent is an acrylic leveling agent.
The metal film forming agent is ammonium fluotitanate and sodium tungstate according to the mass ratio of 1:1, and mixing.
The stabilizer is sodium citrate.
The preparation method of the modified glycidyl methacrylate comprises the following steps:
17 parts of tannic acid, 100 parts of water and 14 parts of glycidyl methacrylate are mixed according to parts by mass, 0.6 part of tetrabutylammonium bromide is added into the tannic acid, 0.15 part of hydroquinone is added into the mixture, the mixture is stirred for 4min at a rotating speed of 180r/min, the mixture is placed at a temperature of 90 ℃ for reaction for 4h, ethyl acetate is used for extraction, an upper organic phase is taken, and the organic phase is subjected to reduced pressure rotary evaporation to obtain modified glycidyl methacrylate.
The preparation method of the phosphoric acid modified nanocellulose comprises the following steps:
s1, crushing the dried bamboo pulp paper, mixing the crushed bamboo pulp paper with water according to a mass ratio of 1:2, treating the crushed bamboo pulp paper with a homogenizer at a rotating speed of 20000rpm for 120min, and drying the crushed bamboo pulp paper to obtain bamboo pulp;
s2, mixing 10 parts of bamboo pulp, 3.8 parts of phosphoric acid, 12 parts of urea and 15.7 parts of water according to parts by mass, performing ultrasonic treatment for 75 minutes by using an ultrasonic breaker under the power of 1500W, and then adding 55 parts of water for dilution to obtain a suspension;
and S3, regulating the pH value of the suspension obtained in the step S2 to 11 by using 5wt% sodium hydroxide aqueous solution, stirring for 30min at a rotating speed of 180r/min, filtering to obtain precipitate, washing with water, and drying to obtain the phosphoric acid modified nanocellulose.
Example 7
A preparation method of a passivation solution for passivation treatment of high corrosion resistance alloy comprises the following steps: 100 parts of bisphenol A epoxy diacrylate, 15 parts of aminated nano silicon dioxide, 15 parts of phosphoric acid modified nano cellulose, 50 parts of absolute ethyl alcohol, 30 parts of water-soluble hydrogen-containing silicone oil, 3 parts of surfactant, 3 parts of flatting agent, 8 parts of metal film forming agent, 3 parts of stabilizer, 5 parts of acetic acid, 7 parts of 24wt% ammonia water and 300 parts of water are mixed according to parts by mass, and stirring is carried out for 6 minutes at a rotating speed of 180r/min, so that the passivation solution for passivation treatment of the high corrosion-resistant alloy is obtained.
The surfactant is sodium dodecyl benzene sulfonate.
The leveling agent is an acrylic leveling agent.
The metal film forming agent is ammonium fluotitanate and sodium tungstate according to the mass ratio of 1:1, and mixing.
The stabilizer is sodium citrate.
The preparation method of the phosphoric acid modified nanocellulose comprises the following steps:
s1, crushing the dried bamboo pulp paper, mixing the crushed bamboo pulp paper with water according to a mass ratio of 1:2, treating the crushed bamboo pulp paper with a homogenizer at a rotating speed of 20000rpm for 120min, and drying the crushed bamboo pulp paper to obtain bamboo pulp;
s2, mixing 10 parts of bamboo pulp, 3.8 parts of phosphoric acid, 12 parts of urea and 15.7 parts of water according to parts by mass, performing ultrasonic treatment for 75 minutes by using an ultrasonic breaker under the power of 1500W, and then adding 55 parts of water for dilution to obtain a suspension;
and S3, regulating the pH value of the suspension obtained in the step S2 to 11 by using 5wt% sodium hydroxide aqueous solution, stirring for 30min at a rotating speed of 180r/min, filtering to obtain precipitate, washing with water, and drying to obtain the phosphoric acid modified nanocellulose.
The preparation method of the aminated nano silicon dioxide comprises the following steps:
(1) Adding 30 parts by mass of polyvinylpyrrolidone into 270 parts by mass of absolute ethyl alcohol, then adding 75 parts by mass of ammonia water with the concentration of 20wt% into the absolute ethyl alcohol, stirring the mixture for 10min at the rotation speed of 180r/min, adding 15 parts by mass of tetraethyl orthosilicate, continuously stirring the mixture for 2.5h at the rotation speed of 180r/min, filtering to obtain a filter cake, washing and drying the filter cake to obtain nano silicon dioxide;
(2) Mixing 100 parts of toluene and 15 parts of nano silicon dioxide according to parts by mass, ultrasonically dispersing for 5min, adding 4 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, stirring for 2min at a rotating speed of 10000r/min, refluxing for 24h at 160 ℃, filtering to obtain a filter cake, washing and drying to obtain the amino nano silicon dioxide; the power of the ultrasonic wave is 60W, and the frequency is 80kHz.
Example 8
A preparation method of a passivation solution for passivation treatment of high corrosion resistance alloy comprises the following steps: 100 parts of bisphenol A epoxy diacrylate, 15 parts of modified glycidyl methacrylate, 15 parts of aminated nano silicon dioxide, 15 parts of phosphoric acid modified nano cellulose, 50 parts of absolute ethyl alcohol, 30 parts of water-soluble hydrogen-containing silicone oil, 3 parts of surfactant, 3 parts of leveling agent, 8 parts of metal film forming agent, 3 parts of stabilizer, 5 parts of acetic acid, 7 parts of 24wt% ammonia water and 300 parts of water are mixed according to the mass parts, and stirring is carried out for 6 minutes at a rotating speed of 180r/min, so that the passivation solution for passivation treatment of the high corrosion-resistant alloy is obtained.
The surfactant is sodium dodecyl benzene sulfonate.
The leveling agent is an acrylic leveling agent.
The metal film forming agent is ammonium fluotitanate and sodium tungstate according to the mass ratio of 1:1, and mixing.
The stabilizer is sodium citrate.
The preparation method of the modified glycidyl methacrylate comprises the following steps:
17 parts of tannic acid, 100 parts of water and 14 parts of glycidyl methacrylate are mixed according to parts by mass, 0.6 part of tetrabutylammonium bromide is added into the tannic acid, 0.15 part of hydroquinone is added into the mixture, the mixture is stirred for 4min at a rotating speed of 180r/min, the mixture is placed at a temperature of 90 ℃ for reaction for 4h, ethyl acetate is used for extraction, an upper organic phase is taken, and the organic phase is subjected to reduced pressure rotary evaporation to obtain modified glycidyl methacrylate.
The preparation method of the phosphoric acid modified nanocellulose comprises the following steps:
s1, crushing the dried bamboo pulp paper, mixing the crushed bamboo pulp paper with water according to a mass ratio of 1:2, treating the crushed bamboo pulp paper with a homogenizer at a rotating speed of 20000rpm for 120min, and drying the crushed bamboo pulp paper to obtain bamboo pulp;
s2, mixing 10 parts of bamboo pulp, 3.8 parts of phosphoric acid, 12 parts of urea and 15.7 parts of water according to parts by mass, performing ultrasonic treatment for 75 minutes by using an ultrasonic breaker under the power of 1500W, and then adding 55 parts of water for dilution to obtain a suspension;
and S3, regulating the pH value of the suspension obtained in the step S2 to 11 by using 5wt% sodium hydroxide aqueous solution, stirring for 30min at a rotating speed of 180r/min, filtering to obtain precipitate, washing with water, and drying to obtain the phosphoric acid modified nanocellulose.
The preparation method of the aminated nano silicon dioxide comprises the following steps:
(1) Adding 30 parts by mass of polyvinylpyrrolidone into 270 parts by mass of absolute ethyl alcohol, then adding 75 parts by mass of ammonia water with the concentration of 20wt% into the absolute ethyl alcohol, stirring the mixture for 10min at the rotation speed of 180r/min, adding 15 parts by mass of tetraethyl orthosilicate, continuously stirring the mixture for 2.5h at the rotation speed of 180r/min, filtering to obtain a filter cake, washing and drying the filter cake to obtain nano silicon dioxide;
(2) Mixing 100 parts of toluene and 15 parts of nano silicon dioxide according to parts by mass, ultrasonically dispersing for 5min, adding 4 parts of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, stirring for 2min at a rotating speed of 10000r/min, refluxing for 24h at 160 ℃, filtering to obtain a filter cake, washing and drying to obtain the amino nano silicon dioxide; the power of the ultrasonic wave is 60W, and the frequency is 80kHz.
Test example 1
Cutting the low-carbon steel plate into the size required by the experiment by using a plate shearing machine, smoothing the fourth Zhou Damo steel plate by using a grinder to prevent burrs, and cleaning the cut steel plate by using clear water.
Preparing a certain amount of acetone according to a proportion, immersing a low-carbon steel plate into the acetone, repeatedly brushing the surface by using a soft brush until oil stains on the surface are completely removed, washing the low-carbon steel plate cleaned by using tap water for multiple times to prevent the acetone from remaining on the surface, and finally putting the low-carbon steel plate into a blast drying oven with the temperature of 100 ℃ for about 3min, drying, taking out and cooling to obtain a clean low-carbon steel plate; and (3) coating the passivation solution for passivation treatment of the high corrosion-resistant alloy prepared in the examples 1-8 on a clean low-carbon steel plate by using a frame type film coater to prepare a passivation film layer, leveling the passivation film layer at 50 ℃ for 30min, and drying the passivation film layer at normal temperature for 24h to obtain a sample plate for testing.
Neutral salt spray test: the salt spray resistance of the test panels described above was tested with reference to GB/T1771-2007 determination of neutral salt spray resistance of paints and varnishes. The size of the plate is as follows: 150 mm.100 mm, a film thickness of 74 μm, a salt spray box temperature of 35 ℃, a salt spray collection rate of 2mL/h, and a sodium chloride concentration of 50g/L. The time at which pitting occurred was recorded.
Table 1: neutral salt spray test results
| Salt spray resistance time/h | |
| Example 1 | 371 |
| Example 2 | 457 |
| Example 3 | 459 |
| Example 4 | 463 |
| Example 5 | 546 |
| Example 6 | 502 |
| Example 7 | 541 |
| Example 8 | 620 |
It can be seen from table 1 that the passivation solution for passivation treatment of high corrosion resistant alloy prepared in example 8 has the best salt spray corrosion resistance effect, while the passivation solutions for passivation treatment of high corrosion resistant alloy used in examples 4, 5 and 6 have slightly poorer effects, which indicates that the three components of modified glycidyl methacrylate, phosphoric acid modified nanocellulose and aminated nano silicon dioxide act synergistically, so that the passivation solution shows excellent corrosion resistance and adhesive force. The modified glycidyl methacrylate forms extremely strong adhesion effect through tannic acid and the metal substrate, the modified glycidyl methacrylate can be better compatible with resin, so that the effect of enhancing adhesion is exerted, the phosphoric acid modified nano cellulose can form chelation, covalent bonds and other chemical bonds through the phosphate radical and the metal substrate, the adhesion force of a film layer and the metal substrate is enhanced, the contact between a film and a steel plate is increased by the improvement of the adhesion force, the damage of a corrosive medium to a film layer/metal interface is reduced, and the salt spray resistance is enhanced. In addition, the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane is adopted to modify the nano silicon dioxide, so that the dispersibility of the nano silicon dioxide in passivation solution can be improved, and as the organic branched chain of the nano silicon dioxide contains a large amount of amino groups, the nano silicon dioxide can form hydrogen bonds with modified glycidyl methacrylate and phosphoric acid modified nano cellulose and is crosslinked into a network, the mechanical property of the film resin is greatly improved, and the adhesive force between the film and metal is further enhanced. The three are cooperated, so that the film layer and the metal substrate are tightly connected, salt mist cannot invade, and the salt mist resistance of the film layer is greatly improved. Thus, in examples 2,3 and 4, respectively, the modified glycidyl methacrylate, the phosphoric acid modified nanocellulose or the aminated nano silica was singly used, and the salt spray resistance was further lowered.
Test example 2
Adhesion test: the environmental-friendly color steel sheets prepared in examples 1 to 8 were tested for film adhesion with reference to GB/T9286-2021, paint and varnish cross-cut test. Adopting an electrically driven multi-blade cutting tool, wherein the blade spacing is 1mm; the test was performed using the test panel prepared in test example 1.
Table 2: adhesion test results
| Adhesive force grading | |
| Example 1 | 3 |
| Example 2 | 2 |
| Example 3 | 2 |
| Example 4 | 2 |
| Example 5 | 0 |
| Example 6 | 1 |
| Example 7 | 0 |
| Example 8 | 0 |
As can be seen from table 2, the film layer of the sample plate prepared in example 8 has the best adhesion, because the passivation solution shows the best adhesion due to the synergistic effect of the modified glycidyl methacrylate, the phosphoric acid modified nanocellulose and the aminated nano silicon dioxide. The passivation film prepared by adding the aminated nano-silica and the phosphoric acid modified nano-cellulose in the example 7, and adding the modified glycidyl methacrylate and the aminated nano-silica in the example 5 also has extremely strong adhesive force, and the passivation solution prepared by adding the modified glycidyl methacrylate and the phosphoric acid modified nano-cellulose in the example 6 has lower adhesive force. This comparison can be seen to be due to the aminated nanosilica. Therefore, the invention speculates that the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane is adopted to modify the nano silicon dioxide, so that the dispersibility of the nano silicon dioxide in passivation solution can be improved, and as the organic branched chain of the nano silicon dioxide contains a large amount of amino groups, the nano silicon dioxide can form hydrogen bonds with modified glycidyl methacrylate and phosphoric acid modified nano cellulose and form a network through crosslinking, the adhesive force between the film layer and the metal substrate is enhanced, and the mechanical property of the film layer is enhanced, so that the film layer is more difficult to damage.
Claims (9)
1. The preparation method of the passivation solution for the passivation treatment of the high corrosion-resistant alloy is characterized by comprising the following steps of: 90-120 parts of bisphenol A epoxy diacrylate, 10-20 parts of modified glycidyl methacrylate, 10-20 parts of aminated nano silicon dioxide, 10-20 parts of phosphoric acid modified nano cellulose, 10-100 parts of absolute ethyl alcohol, 20-50 parts of water-soluble hydrogen-containing silicone oil, 0.01-5 parts of surfactant, 0.1-5 parts of flatting agent, 5-10 parts of metal film forming agent, 0.5-5 parts of stabilizing agent, 4-6 parts of acetic acid, 6-8 parts of ammonia water and 200-400 parts of water are mixed and stirred to obtain the passivation solution for passivation treatment of the high corrosion-resistant alloy;
the preparation method of the modified glycidyl methacrylate comprises the following steps:
10-20 parts of tannic acid, 90-110 parts of water and 10-20 parts of glycidyl methacrylate are mixed according to parts by mass, 0.5-1 part of tetrabutylammonium bromide is added into the mixture, 0.1-0.2 part of hydroquinone is added into the mixture, the mixture is stirred for 3-5min at a rotating speed of 100-200r/min, the mixture is placed at a temperature of 85-95 ℃ for reaction for 3-5h, ethyl acetate is used for extraction, an upper organic phase is taken, and the mixture is subjected to reduced pressure rotary evaporation to obtain the modified glycidyl methacrylate.
2. The method for preparing a passivation solution for passivation of highly corrosion-resistant alloy according to claim 1, wherein the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl diphenyl ether disulfonate, and disodium hexadecyl sulfophenoxy benzene sulfonate.
3. The method for preparing a passivation solution for passivation of a highly corrosion resistant alloy according to claim 1, wherein the leveling agent is at least one of a hydroxymethyl cellulose, a fluorine-based leveling agent, and an acrylic leveling agent.
4. The method for preparing the passivation solution for passivation of high corrosion resistance alloy according to claim 1, wherein the metal film forming agent is one or two of ammonium fluotitanate and sodium tungstate.
5. The method for preparing a passivation solution for passivation of highly corrosion resistant alloy according to claim 1, wherein the stabilizer is at least one of sodium citrate or sodium tetraborate.
6. The method for preparing the passivation solution for the passivation treatment of the high corrosion resistant alloy according to claim 1, wherein the method for preparing the phosphoric acid modified nanocellulose comprises the following steps:
s1, crushing the dried bamboo pulp paper, mixing the crushed bamboo pulp paper with water, treating the crushed bamboo pulp paper by a homogenizer, and drying the crushed bamboo pulp paper to obtain bamboo pulp;
s2, mixing bamboo pulp, phosphoric acid, urea and water, treating by using an ultrasonic breaker, and then adding water for dilution to obtain a suspension;
and S3, regulating the pH of the suspension obtained in the step S2 by using a sodium hydroxide aqueous solution, stirring, filtering to obtain a precipitate, washing with water, and drying to obtain the phosphoric acid modified nanocellulose.
7. The method for preparing the passivation solution for passivation treatment of the high corrosion resistant alloy according to claim 1, wherein the preparation method of the aminated nano silicon dioxide comprises the following steps:
(1) Adding polyvinylpyrrolidone into absolute ethyl alcohol, then adding ammonia water, stirring, adding tetraethyl orthosilicate, stirring, filtering to obtain a filter cake, washing and drying to obtain nano silicon dioxide;
(2) Mixing toluene and nano silicon dioxide, performing ultrasonic dispersion, adding N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane, stirring, refluxing, filtering to obtain a filter cake, washing and drying to obtain the amino nano silicon dioxide.
8. The method for preparing a passivation solution for passivation of highly resistant alloy according to claim 7, wherein the power of the ultrasonic wave is 50-70W and the frequency is 70-90kHz.
9. The passivation solution for passivation of high corrosion resistance alloy is characterized in that the passivation solution is prepared by the preparation method of the passivation solution for passivation of high corrosion resistance alloy according to any one of claims 1 to 8.
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