CN112760629A - Environment-friendly chromium-free passivation solution suitable for metal surface treatment - Google Patents

Environment-friendly chromium-free passivation solution suitable for metal surface treatment Download PDF

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CN112760629A
CN112760629A CN202110100599.6A CN202110100599A CN112760629A CN 112760629 A CN112760629 A CN 112760629A CN 202110100599 A CN202110100599 A CN 202110100599A CN 112760629 A CN112760629 A CN 112760629A
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张晓峰
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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
    • 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
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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Abstract

The invention relates to the technical field of metal passivation, in particular to an environment-friendly chromium-free passivation solution suitable for metal surface treatment, which comprises the following components: the passivation solution prepared by the method effectively improves the neutral salt spray corrosion resistance of the carbon steel plate.

Description

Environment-friendly chromium-free passivation solution suitable for metal surface treatment
Technical Field
The invention relates to the technical field of metal passivation, in particular to an environment-friendly chromium-free passivation solution suitable for metal surface treatment.
Background
The iron and aluminum can be dissolved quickly in dilute nitric acid or dilute sulfuric acid, but the dissolution phenomenon in concentrated nitric acid or concentrated sulfuric acid is almost completely stopped, carbon steel is usually easy to rust, and if a proper amount of Ni and Cr is added into the steel, the steel becomes stainless steel. The phenomenon of a metal or alloy that is significantly enhanced in chemical stability by being affected by several factors is called passivation. The metal passivation phenomenon caused by certain passivation solutions is known as chemical passivation. Such as concentrated HNO3Concentrated H2SO4、HCIO3、K2Cr207、KMnO4The metal can be passivated by the oxidants, and after the metal is passivated, the electrode potential moves to the positive direction, so that the original characteristics of the metal are lost, for example, the passivated iron cannot replace copper in copper salt, the corrosion resistance of the metal can be improved by utilizing the metal passivation, the service life is prolonged, and the potential safety hazard is reduced.
Although the traditional passivation solution contains chromate, a passivation film formed by the chromate passivation solution has the advantages of good corrosion resistance, low cost, mature technology, good shielding effect, self-repairing function and the like, hexavalent chromium contained in chromate has high toxicity and great harm to human bodies and ecological environment, chromate passivation treatment becomes a process forbidden to use or strictly limited to use at home and abroad, and therefore, the development of an alternative environment-friendly chromate-free passivation solution is urgently needed at present.
Disclosure of Invention
Aiming at the problems, the invention provides an environment-friendly chromium-free passivation solution suitable for metal surface treatment.
In order to achieve the above object, the present invention adopts the following technical solutions:
an environment-friendly chromium-free passivation solution suitable for metal surface treatment comprises the following components in percentage by weight:
0.1 to 0.5 percent of fluorine-containing compound, 0.01 to 0.02 percent of silane coupling agent, 0.05 to 0.1 percent of titanium sulfate, 0.01 to 0.02 percent of sodium nitrate, 0.05 to 0.1 percent of copper sulfate, 0.03 to 0.05 percent of sodium formate, 0.02 to 0.04 percent of hydroxymethyl cellulose sodium, 0.1 to 1 percent of acetic acid, 0.01 to 0.02 percent of ammonium molybdate, 0.06 to 0.12 percent of sodium tripolyphosphate, 1 to 3 percent of rare earth load type porous graphene sealant, 3 to 6 percent of PMPO graft modified nano silicon dioxide, 0.5 to 1 percent of ethylene glycol monobutyl ether, 0.1 to 0.2 percent of alcohol ester, 0.012 to 0.016 percent of benzotriazole, 0.5 to 1 percent of microcrystalline paraffin, 0.05 to 0.1 percent of amino carboxylate complexing agent, 0.05 to 0.1 percent of complexing agent and the balance of deionized water.
Preferably, the environment-friendly chromium-free passivation solution consists of the following components in percentage by weight:
0.3 percent of fluorine-containing compound, 0.012 percent of silane coupling agent, 0.07 percent of titanium sulfate, 0.01 percent of sodium nitrate, 0.06 percent of copper sulfate, 0.03 percent of sodium formate, 0.02 percent of sodium carboxymethyl cellulose, 0.5 percent of acetic acid, 0.015 percent of ammonium molybdate, 0.12 percent of sodium tripolyphosphate, 3 percent of rare earth-loaded porous graphene sealant,
4% of PMPO grafting modified nano silicon dioxide, 0.6% of ethylene glycol monobutyl ether, 0.2% of alcohol ester, 0.016% of benzotriazole, 0.5% of microcrystalline paraffin, 0.1% of aminocarboxylate complexing agent, 0.1% of complexing agent and the balance of deionized water.
Preferably, the preparation method of the rare earth-supported porous graphene sealing agent is as follows:
(1) adding graphite into mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid in a weight ratio of 1:1 in ice bath, stirring and mixing uniformly, adding potassium hypochlorite, continuously stirring for 1-5h, removing the ice bath, recovering the room temperature, continuously stirring for 20-30h, heating to 40-50 ℃, stirring for 5-10h, cooling, performing suction filtration, washing the obtained solid with dilute hydrochloric acid for 3 times, fully washing with distilled water to neutrality, and performing vacuum drying at 60-80 ℃ to obtain a first intermediate;
(2) adding rare earth oxide and a first intermediate into deionized water, carrying out ultrasonic treatment for 1-2h, adding into a high-temperature high-pressure reaction kettle, reacting at the temperature of 3-5MPa and 400-500 ℃ for 5-10h, and carrying out suction filtration and water washing to obtain a second intermediate;
(3) drying the second intermediate at 40-50 ℃ for 10-20h, heating to 400-,
and cooling to 100-.
Wherein the rare earth oxide is selected from lanthanum oxide, cerium oxide or yttrium oxide.
Preferably, the preparation method of the PMPO grafted modified nano-silica comprises the following steps:
(1) washing the nano silicon dioxide with diluted hydrochloric acid, and activating at the temperature of 150 ℃ and 160 ℃ for 1-5 h;
(2) adding activated nano silicon dioxide into anhydrous toluene, performing ultrasonic dispersion, then dropwise adding glycidyl ether trimethoxy silane, performing reflux reaction for 20-25h, and washing with anhydrous toluene after the reaction is finished to obtain pretreated nano silicon dioxide;
(3) adding the pretreated nano silicon dioxide into a carbonate buffer solution of polyether polyol, stirring and reacting for 20-25h at room temperature, and washing with deionized water and drying after the reaction is finished.
Preferably, the fluorine-containing compound is one or more of fluotitanic acid, fluozirconic acid, potassium fluozirconate, sodium fluosilicate, sodium fluoride or magnesium fluoride.
Preferably, the silane coupling agent is one or more of KH-540, KH-550, KH-560, KH-151, KH-792 and KH-602.
Preferably, the amino carboxylate complexing agent is EDTA and DTPA according to the weight ratio of (1-10): (1-10) mixing.
Preferably, the complexing agent is one or more of citric acid and salts thereof, tartaric acid and salts thereof, lactic acid and salts thereof, malonic acid and salts thereof, succinic acid and salts thereof, gluconic acid and salts thereof, maleic acid and salts thereof, and glycolic acid and salts thereof.
Preferably, the preparation method of the environment-friendly chromium-free passivation solution is as follows:
(1) adding a silane coupling agent into deionized water, and uniformly stirring to obtain a solution A;
(2) heating the solution A to 40-50 ℃, sequentially adding sodium carboxymethylcellulose, acetic acid, ethylene glycol monobutyl ether and alcohol ester twelve, and stirring for 30-50min at the speed of 100-200r/min to obtain solution B;
(3) and heating the solution B to 60-65 ℃, increasing the rotating speed to 200-one-step operation for 300r/min, sequentially adding the rare earth-loaded porous graphene sealant, the PMPO grafted modified nano-silica, the fluorine-containing compound, titanium sulfate, sodium nitrate, copper sulfate, sodium formate, ammonium molybdate, sodium tripolyphosphate, benzotriazole, microcrystalline paraffin, the complexing agent and the aminocarboxylate complexing agent, stirring for 1-3h, and recovering the room temperature.
The invention has the beneficial effects that:
the invention provides an environment-friendly chromium-free passivation solution suitable for metal surface treatment, which is more green and environment-friendly compared with the traditional chromate passivation solution, and the rare earth supported porous graphene sealant in the components can be suspended in the passivation solution and is included in a passivation film when the passivation film is formed, so that the thickness of the passivation film can be increased, and Cl is retarded-And SO42-The technical scheme of adding graphene oxide into the passivation solution is also disclosed in the comparison document CN108642484B, but the innovation point of the present application lies in that rare earth oxide is loaded into the pore channels of porous graphene, which can effectively avoid the occurrence of pitting corrosion process, and the passivation film can extend into the pore channels of porous graphene to fill up the gaps,the passive film is more compact; the nano silicon dioxide is used as an auxiliary sealing agent, is better compatible with other components of passivation solution after being grafted and modified by PMPO, and the formed passivation film is more uniform and compact, and can be solidified into gel in a passivation film forming stage after being added, so that on one hand, the adhesive force of the passivation film, an alloy substrate and a subsequent coating is improved, and the nano silicon dioxide also has certain isolation capacity, so that outer-layer water vapor and acid gas can be effectively prevented from entering the interior of the passivation film to improve the corrosion resistance, in addition, the silane coupling agent has larger influence on the performance of the formed passivation film, the silane coupling agent has alkoxy groups, silanol generated after hydrolysis can be effectively combined with a metal substrate, the active groups can react with hydroxyl groups in the PMPO and active groups in a coating to form a net structure, and a bridge is erected between an inorganic filler and an organic film to improve the compactness of the passivation film, the passivation solution prepared by the invention effectively improves the neutral salt spray corrosion resistance of the carbon steel plate, and the comparison shows that the rare earth loaded porous graphene sealing agent and PMPO grafted modified nano-silica in the passivation solution can further improve the passivation effect of the passivation solution and improve the corrosion resistance of the carbon steel plate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1:
an environment-friendly chromium-free passivation solution suitable for metal surface treatment comprises the following components in percentage by weight:
0.3% of fluotitanic acid, 0.07% of silane coupling agent KH-5500.012%, 0.07% of titanium sulfate, 0.01% of sodium nitrate, 0.06% of copper sulfate, 0.03% of sodium formate, 0.02% of sodium carboxymethylcellulose, 0.5% of acetic acid, 0.015% of ammonium molybdate, 0.12% of sodium tripolyphosphate, 3% of rare earth-supported porous graphene sealant, 4% of PMPO grafted modified nano-silica, 0.6% of ethylene glycol monobutyl ether, 0.2% of alcohol ester, 0.016% of benzotriazole, 0.5% of microcrystalline paraffin, EDTA and DTPA according to the weight ratio of 1:1, 0.1 percent of complexing agent sodium citrate and the balance of deionized water.
The preparation method of the rare earth-loaded porous graphene sealing agent comprises the following steps:
adding graphite into mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 1:1 under ice bath, stirring and mixing uniformly, adding potassium hypochlorite, stirring for 2 hr, removing ice bath, recovering room temperature, stirring for 25 hr, heating to 50 deg.C, stirring for 8 hr, cooling, vacuum filtering, washing the obtained solid with diluted hydrochloric acid for 3 times, washing with distilled water to neutrality, vacuum drying at 70 deg.C to obtain first intermediate, adding cerium oxide and the first intermediate into deionized water, ultrasonic treating for 1 hr, adding into high temperature high pressure reaction kettle, reacting at 5MPa and 500 ℃ for 8h, filtering, washing with water to obtain a second intermediate, drying the second intermediate at 45 ℃ for 10h, heating to 400 ℃ for one time, preserving heat for 5h, and heating to 1100 ℃ for the second time, preserving heat for 2h, cooling to 110 ℃, and preserving heat for 10h to obtain the rare earth-supported porous graphene sealing agent.
The preparation method of PMPO grafted modified nano-silica comprises the following steps:
washing nano-silica with diluted hydrochloric acid, activating at 150 ℃ for 2h, adding the activated nano-silica into anhydrous toluene, performing ultrasonic dispersion, dropwise adding glycidyl ether trimethoxy silane, performing reflux reaction for 20h, washing with the anhydrous toluene after the reaction is finished to obtain pretreated nano-silica, adding the pretreated nano-silica into a carbonate buffer solution of polyether polyol, stirring at room temperature for reaction for 20h, and washing with deionized water and drying after the reaction is finished.
The preparation method of the environment-friendly chromium-free passivation solution comprises the following steps:
adding a silane coupling agent KH-550 into deionized water, uniformly stirring to obtain solution A, heating the solution A to 45 ℃, sequentially adding sodium carboxymethylcellulose, acetic acid, ethylene glycol monobutyl ether and alcohol ester twelve, stirring at 150r/min for 50min to obtain solution B, heating the solution B to 65 ℃, increasing the rotating speed to 200r/min, sequentially adding a rare earth-loaded porous graphene sealing agent, PMPO grafted modified nano-silica, fluotitanic acid, titanium sulfate, sodium nitrate, copper sulfate, sodium formate, ammonium molybdate, sodium tripolyphosphate, benzotriazole, microcrystalline paraffin, a complexing agent sodium citrate and an amino carboxylate complexing agent, stirring for 3h, and recovering the room temperature.
Example 2:
an environment-friendly chromium-free passivation solution suitable for metal surface treatment comprises the following components in percentage by weight:
0.1-0.5% of potassium fluorozirconate, 0.06% of silane coupling agent KH-5600.01%, 0.06% of titanium sulfate, 0.015% of sodium nitrate, 0.1% of copper sulfate, 0.04% of sodium formate, 0.02% of sodium hydroxymethyl cellulose, 0.7% of acetic acid, 0.02% of ammonium molybdate, 0.1% of sodium tripolyphosphate, 1% of rare earth-supported porous graphene sealant, 4% of PMPO grafted modified nano silicon dioxide, 0.6% of ethylene glycol monobutyl ether, 0.13% of alcohol ester, 0.016% of benzotriazole, 0.7% of microcrystalline paraffin, EDTA and DTPA according to the weight ratio of 2: 1, 0.05 percent of complexing agent citric acid and the balance of deionized water.
The preparation method of the rare earth-loaded porous graphene sealing agent comprises the following steps:
adding graphite into mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 1:1 under ice bath, stirring and mixing uniformly, adding potassium hypochlorite, stirring for 5 hr, removing ice bath, recovering room temperature, stirring for 25 hr, heating to 40 deg.C, stirring for 6 hr, cooling, vacuum filtering, washing the obtained solid with diluted hydrochloric acid for 3 times, washing with distilled water to neutrality, vacuum drying at 70 deg.C to obtain first intermediate, adding cerium oxide and the first intermediate into deionized water, ultrasonic treating for 1 hr, adding into high temperature high pressure reaction kettle, reacting for 6h under 5MPa at 450 ℃, filtering, washing with water to obtain a second intermediate, drying the second intermediate at 45 ℃ for 20h, heating to 450 ℃ for one time, preserving heat for 5h, and heating to 1200 ℃ for the second time, preserving heat for 2.5 hours, cooling to 110 ℃, and preserving heat for 6 hours to obtain the rare earth-loaded porous graphene sealing agent.
The preparation method of PMPO grafted modified nano-silica comprises the following steps:
washing nano-silica with diluted hydrochloric acid, activating at 150 ℃ for 5h, adding the activated nano-silica into anhydrous toluene, performing ultrasonic dispersion, dropwise adding glycidyl ether trimethoxy silane, performing reflux reaction for 20h, washing with the anhydrous toluene after the reaction is finished to obtain pretreated nano-silica, adding the pretreated nano-silica into a carbonate buffer solution of polyether polyol, stirring at room temperature for reaction for 25h, washing with deionized water after the reaction is finished, and drying.
The preparation method of the environment-friendly chromium-free passivation solution comprises the following steps:
adding a silane coupling agent KH-560 into deionized water, uniformly stirring to obtain solution A, heating the solution A to 40 ℃, sequentially adding sodium hydroxymethyl cellulose, acetic acid, ethylene glycol monobutyl ether and alcohol ester twelve, stirring at 200r/min for 50min to obtain solution B, heating the solution B to 60 ℃, increasing the rotating speed to 250r/min, sequentially adding a rare earth-loaded porous graphene sealing agent, PMPO graft modified nano-silica, potassium fluorozirconate, titanium sulfate, sodium nitrate, copper sulfate, sodium formate, ammonium molybdate, sodium tripolyphosphate, benzotriazole, microcrystalline paraffin, a complexing agent citric acid and an amino carboxylate complexing agent, stirring for 2h, and recovering the room temperature.
Example 3:
an environment-friendly chromium-free passivation solution suitable for metal surface treatment comprises the following components in percentage by weight:
0.1% of sodium fluosilicate, 0.1% of silane coupling agent KH-5500.015%, 0.08% of titanium sulfate, 0.01% of sodium nitrate, 0.06% of copper sulfate, 0.05% of sodium formate, 0.02% of sodium carboxymethylcellulose, 0.1% of acetic acid, 0.01% of ammonium molybdate, 0.12% of sodium tripolyphosphate, 2% of rare earth-supported porous graphene sealant, 3% of PMPO grafted modified nano-silica, 0.5% of ethylene glycol monobutyl ether, 0.12% of alcohol ester, 0.015% of benzotriazole, 0.5% of microcrystalline paraffin, EDTA and DTPA according to the weight ratio of 1: 2, 0.08 percent of complexing agent, 0.1 percent of complexing agent sodium citrate and the balance of deionized water.
The preparation method of the rare earth-loaded porous graphene sealing agent comprises the following steps:
adding graphite into mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 1:1 under ice bath, stirring and mixing uniformly, adding potassium hypochlorite, stirring for 4 hr, removing ice bath, recovering room temperature, stirring for 25 hr, heating to 50 deg.C, stirring for 6 hr, cooling, vacuum filtering, washing the obtained solid with diluted hydrochloric acid for 3 times, washing with distilled water to neutrality, vacuum drying at 70 deg.C to obtain first intermediate, adding cerium oxide and the first intermediate into deionized water, ultrasonic treating for 1 hr, adding into high temperature high pressure reaction kettle, reacting at 5MPa and 480 ℃ for 5h, filtering, washing with water to obtain a second intermediate, drying the second intermediate at 50 ℃ for 15h, heating to 450 ℃ for one time, preserving heat for 5h, and (3) heating to 1000 ℃ for the second time, preserving heat for 2h, cooling to 110 ℃, and preserving heat for 6h to obtain the rare earth-supported porous graphene sealing agent.
The preparation method of PMPO grafted modified nano-silica comprises the following steps:
washing nano-silica with diluted hydrochloric acid, activating at 150 ℃ for 5h, adding the activated nano-silica into anhydrous toluene, performing ultrasonic dispersion, dropwise adding glycidyl ether trimethoxy silane, performing reflux reaction for 22h, washing with the anhydrous toluene after the reaction is finished to obtain pretreated nano-silica, adding the pretreated nano-silica into a carbonate buffer solution of polyether polyol, stirring at room temperature for reaction for 25h, washing with deionized water after the reaction is finished, and drying.
The preparation method of the environment-friendly chromium-free passivation solution comprises the following steps:
adding a silane coupling agent KH-550 into deionized water, uniformly stirring to obtain solution A, heating the solution A to 45 ℃, sequentially adding sodium carboxymethylcellulose, acetic acid, ethylene glycol monobutyl ether and alcohol ester twelve, stirring at 120r/min for 50min to obtain solution B, heating the solution B to 65 ℃, increasing the rotating speed to 200r/min, sequentially adding a rare earth-loaded porous graphene sealing agent, PMPO graft modified nano-silica, sodium fluosilicate, titanium sulfate, sodium nitrate, copper sulfate, sodium formate, ammonium molybdate, sodium tripolyphosphate, benzotriazole, microcrystalline paraffin, a complexing agent sodium citrate and an amino carboxylate complexing agent, stirring for 3h, and recovering the room temperature.
Example 4:
an environment-friendly chromium-free passivation solution suitable for metal surface treatment comprises the following components in percentage by weight:
0.1% of fluotitanic acid, 0.1% of silane coupling agent KH-5500.01%, 0.05% of titanium sulfate, 0.01% of sodium nitrate, 0.05% of copper sulfate, 0.03% of sodium formate, 0.02% of sodium carboxymethylcellulose, 0.1% of acetic acid, 0.01% of ammonium molybdate, 0.06% of sodium tripolyphosphate, 1% of rare earth-supported porous graphene sealant, 3% of PMPO grafted modified nano silicon dioxide, 0.5% of ethylene glycol monobutyl ether, 0.1% of alcohol ester, 0.012% of benzotriazole, 0.5% of microcrystalline paraffin, EDTA and DTPA according to the weight ratio of 1:1, 0.05 percent of complexing agent sodium citrate and the balance of deionized water.
The preparation method of the rare earth-loaded porous graphene sealing agent comprises the following steps:
adding graphite into mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 1:1 under ice bath, stirring and mixing uniformly, adding potassium hypochlorite, stirring for 1 hr, removing ice bath, stirring at room temperature for 20 hr, heating to 40 deg.C, stirring for 5 hr, cooling, vacuum filtering, washing the obtained solid with diluted hydrochloric acid for 3 times, washing with distilled water to neutrality, vacuum drying at 60 deg.C to obtain first intermediate, adding cerium oxide and the first intermediate into deionized water, ultrasonic treating for 1 hr, adding into high temperature high pressure reaction kettle, reacting at 3MPa and 400 ℃ for 5h, filtering, washing with water to obtain a second intermediate, drying the second intermediate at 40 ℃ for 10h, heating to 400 ℃ for one time, keeping the temperature for 3h, and (3) heating to 1000 ℃ for the second time, preserving heat for 2h, cooling to 100 ℃, and preserving heat for 5h to obtain the rare earth-supported porous graphene sealing agent.
The preparation method of PMPO grafted modified nano-silica comprises the following steps:
the method comprises the steps of washing nano-silica with dilute hydrochloric acid, activating at 150 ℃ for 1h, adding the activated nano-silica into anhydrous toluene, performing ultrasonic dispersion, dropwise adding glycidyl ether trimethoxy silane, performing reflux reaction for 20h, washing with the anhydrous toluene after the reaction is finished to obtain pretreated nano-silica, adding the pretreated nano-silica into a carbonate buffer solution of polyether polyol, stirring at room temperature for reaction for 20h, and washing with deionized water and drying after the reaction is finished.
The preparation method of the environment-friendly chromium-free passivation solution comprises the following steps:
adding a silane coupling agent KH-550 into deionized water, uniformly stirring to obtain solution A, heating the solution A to 40 ℃, sequentially adding sodium carboxymethylcellulose, acetic acid, ethylene glycol monobutyl ether and alcohol ester twelve, stirring at 100r/min for 30min to obtain solution B, heating the solution B to 60 ℃, increasing the rotating speed to 200r/min, sequentially adding a rare earth-loaded porous graphene sealing agent, PMPO graft modified nano-silica, a fluorine-containing compound, titanium sulfate, sodium nitrate, copper sulfate, sodium formate, ammonium molybdate, sodium tripolyphosphate, benzotriazole, microcrystalline paraffin, a complexing agent sodium citrate and an amino carboxylate complexing agent, stirring for 1h, and recovering the room temperature.
Example 5:
an environment-friendly chromium-free passivation solution suitable for metal surface treatment comprises the following components in percentage by weight:
0.5% of fluotitanic acid, 0.5% of silane coupling agent KH-5500.02%, 0.1% of titanium sulfate, 0.02% of sodium nitrate, 0.1% of copper sulfate, 0.05% of sodium formate, 0.04% of sodium carboxymethylcellulose, 1% of acetic acid, 0.02% of ammonium molybdate, 0.12% of sodium tripolyphosphate, 3% of rare earth-supported porous graphene sealant, 6% of PMPO grafted modified nano-silica, 1% of ethylene glycol monobutyl ether, 0.2% of alcohol ester dodeca, 0.016% of benzotriazole, 1% of microcrystalline paraffin, EDTA and DTPA according to a weight ratio of 5: 1, 0.1 percent of complexing agent sodium citrate and the balance of deionized water.
The preparation method of the rare earth-loaded porous graphene sealing agent comprises the following steps:
adding graphite into mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 1:1 under ice bath, stirring and mixing uniformly, adding potassium hypochlorite, stirring for 5 hr, removing ice bath, stirring at room temperature for 30 hr, heating to 50 deg.C, stirring for 10 hr, cooling, vacuum filtering, washing the obtained solid with diluted hydrochloric acid for 3 times, washing with distilled water to neutrality, vacuum drying at 80 deg.C to obtain first intermediate, adding cerium oxide and the first intermediate into deionized water, ultrasonic treating for 1-2 hr, adding into high temperature high pressure reaction kettle, reacting at 5MPa and 500 ℃ for 10h, filtering, washing with water to obtain a second intermediate, drying the second intermediate at 50 ℃ for 20h, heating to 500 ℃ for one time, preserving heat for 5h, and heating to 1200 ℃ for the second time, preserving heat for 2.5 hours, cooling to 120 ℃, and preserving heat for 10 hours to obtain the rare earth-loaded porous graphene sealing agent.
The preparation method of PMPO grafted modified nano-silica comprises the following steps:
washing nano-silica with dilute hydrochloric acid, activating at 160 ℃ for 5h, adding the activated nano-silica into anhydrous toluene, performing ultrasonic dispersion, dropwise adding glycidyl ether trimethoxy silane, performing reflux reaction for 25h, washing with the anhydrous toluene after the reaction is finished to obtain pretreated nano-silica, adding the pretreated nano-silica into a carbonate buffer solution of polyether polyol, stirring at room temperature for reaction for 25h, washing with deionized water after the reaction is finished, and drying.
The preparation method of the environment-friendly chromium-free passivation solution comprises the following steps:
adding a silane coupling agent KH-550 into deionized water, uniformly stirring to obtain solution A, heating the solution A to 50 ℃, sequentially adding sodium carboxymethylcellulose, acetic acid, ethylene glycol monobutyl ether and alcohol ester twelve, stirring at 200r/min for 50min to obtain solution B, heating the solution B to 65 ℃, increasing the rotating speed to 300r/min, sequentially adding a rare earth-loaded porous graphene sealing agent, PMPO graft modified nano-silica, a fluorine-containing compound, titanium sulfate, sodium nitrate, copper sulfate, sodium formate, ammonium molybdate, sodium tripolyphosphate, benzotriazole, microcrystalline paraffin, a complexing agent sodium citrate and an amino carboxylate complexing agent, stirring for 3h, and recovering the room temperature.
Example 6:
an environment-friendly chromium-free passivation solution suitable for metal surface treatment comprises the following components in percentage by weight:
0.1% of fluotitanic acid, 0.1% of silane coupling agent KH-5500.02%, 0.05% of titanium sulfate, 0.02% of sodium nitrate, 0.05% of copper sulfate, 0.05% of sodium formate, 0.02% of sodium carboxymethylcellulose, 1% of acetic acid, 0.01% of ammonium molybdate, 0.12% of sodium tripolyphosphate, 1% of rare earth-supported porous graphene sealant, 6% of PMPO grafted modified nano-silica, 0.5% of ethylene glycol monobutyl ether, 0.2% of alcohol ester, 0.012% of benzotriazole, 1% of microcrystalline paraffin, EDTA and DTPA according to a weight ratio of 1: 10, 0.05 percent of complexing agent, 0.1 percent of complexing agent sodium citrate and the balance of deionized water.
The preparation method of the rare earth-loaded porous graphene sealing agent comprises the following steps:
adding graphite into mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 1:1 under ice bath, stirring and mixing uniformly, adding potassium hypochlorite, stirring for 1 hr, removing ice bath, stirring at room temperature for 30 hr, heating to 40 deg.C, stirring for 10 hr, cooling, vacuum filtering, washing the obtained solid with diluted hydrochloric acid for 3 times, washing with distilled water to neutrality, vacuum drying at 60 deg.C to obtain first intermediate, adding cerium oxide and the first intermediate into deionized water, ultrasonic treating for 2 hr, adding into high temperature high pressure reaction kettle, reacting at 3MPa and 500 ℃ for 5h, filtering, washing with water to obtain a second intermediate, drying the second intermediate at 50 ℃ for 10h, heating to 500 ℃ for one time, preserving heat for 3h, and heating to 1200 ℃ for the second time, preserving heat for 2h, cooling to 120 ℃, and preserving heat for 5h to obtain the rare earth-supported porous graphene sealing agent.
The preparation method of PMPO grafted modified nano-silica comprises the following steps:
the method comprises the steps of washing nano-silica with dilute hydrochloric acid, activating at 160 ℃ for 1h, adding the activated nano-silica into anhydrous toluene, performing ultrasonic dispersion, dropwise adding glycidyl ether trimethoxy silane, performing reflux reaction for 25h, washing with the anhydrous toluene after the reaction is finished to obtain pretreated nano-silica, adding the pretreated nano-silica into a carbonate buffer solution of polyether polyol, stirring at room temperature for reaction for 20h, and washing with deionized water and drying after the reaction is finished.
The preparation method of the environment-friendly chromium-free passivation solution comprises the following steps:
adding a silane coupling agent KH-550 into deionized water, uniformly stirring to obtain solution A, heating the solution A to 50 ℃, sequentially adding sodium carboxymethylcellulose, acetic acid, ethylene glycol monobutyl ether and alcohol ester twelve, stirring at 100r/min for 50min to obtain solution B, heating the solution B to 60 ℃, increasing the rotating speed to 300r/min, sequentially adding a rare earth-loaded porous graphene sealing agent, PMPO grafted modified nano silicon dioxide, a fluorine-containing compound, titanium sulfate, sodium nitrate, copper sulfate, sodium formate, ammonium molybdate, sodium tripolyphosphate, benzotriazole, microcrystalline paraffin, a complexing agent sodium citrate and an amino carboxylate complexing agent, stirring for 1h, and recovering the room temperature.
Example 7:
an environment-friendly chromium-free passivation solution suitable for metal surface treatment comprises the following components in percentage by weight:
0.1% of fluotitanic acid, 0.1% of silane coupling agent KH-5500.01%, 0.1% of titanium sulfate, 0.02% of sodium nitrate, 0.05% of copper sulfate, 0.03% of sodium formate, 0.04% of sodium carboxymethylcellulose, 1% of acetic acid, 0.01% of ammonium molybdate, 0.12% of sodium tripolyphosphate, 2% of rare earth-supported porous graphene sealant, 5% of PMPO grafted modified nano-silica, 1% of ethylene glycol monobutyl ether, 0.1% of alcohol ester dodeca, 0.015% of benzotriazole, 1% of microcrystalline paraffin, EDTA and DTPA according to a weight ratio of 1:1, 0.05 percent of complexing agent, 0.1 percent of complexing agent sodium citrate and the balance of deionized water.
The preparation method of the rare earth-loaded porous graphene sealing agent comprises the following steps:
adding graphite into mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid according to the weight ratio of 1:1 under ice bath, stirring and mixing uniformly, adding potassium hypochlorite, stirring for 5 hr, removing ice bath, recovering room temperature, stirring for 25 hr, heating to 50 deg.C, stirring for 8 hr, cooling, vacuum filtering, washing the obtained solid with diluted hydrochloric acid for 3 times, washing with distilled water to neutrality, vacuum drying at 60 deg.C to obtain first intermediate, adding cerium oxide and the first intermediate into deionized water, ultrasonic treating for 1 hr, adding into high temperature high pressure reaction kettle, reacting for 5h under 5MPa at 450 ℃, filtering, washing with water to obtain a second intermediate, drying the second intermediate at 50 ℃ for 20h, heating to 450 ℃ for one time, preserving heat for 5h, and heating to 1100 ℃ for the second time, preserving heat for 2h, cooling to 100 ℃ and preserving heat for 10h to obtain the rare earth-supported porous graphene sealing agent.
The preparation method of PMPO grafted modified nano-silica comprises the following steps:
washing nano-silica with diluted hydrochloric acid, activating at 150 ℃ for 5h, adding the activated nano-silica into anhydrous toluene, performing ultrasonic dispersion, dropwise adding glycidyl ether trimethoxy silane, performing reflux reaction for 20h, washing with the anhydrous toluene after the reaction is finished to obtain pretreated nano-silica, adding the pretreated nano-silica into a carbonate buffer solution of polyether polyol, stirring at room temperature for reaction for 20h, washing with deionized water after the reaction is finished, and drying.
The preparation method of the environment-friendly chromium-free passivation solution comprises the following steps:
adding a silane coupling agent KH-550 into deionized water, uniformly stirring to obtain solution A, heating the solution A to 50 ℃, sequentially adding sodium carboxymethylcellulose, acetic acid, ethylene glycol monobutyl ether and alcohol ester twelve, stirring at 200r/min for 50min to obtain solution B, heating the solution B to 60 ℃, increasing the rotating speed to 250r/min, sequentially adding a rare earth-loaded porous graphene sealing agent, PMPO graft modified nano-silica, a fluorine-containing compound, titanium sulfate, sodium nitrate, copper sulfate, sodium formate, ammonium molybdate, sodium tripolyphosphate, benzotriazole, microcrystalline paraffin, a complexing agent sodium citrate and an amino carboxylate complexing agent, stirring for 3h, and recovering the room temperature.
Comparative example 1:
comparative example 1 is substantially the same as example 1 except that the rare earth-supported porous graphene blocking agent is not added.
Comparative example 2:
comparative example 2 is substantially the same as example 1 except that PMPO was not added to graft-modify the nano-silica.
Comparative example 3:
comparative example 3 is substantially the same as example 1 except that a rare earth-supported porous graphene blocking agent is replaced with general porous graphene.
Comparative example 4:
comparative example 4 is substantially the same as example 1 except that the conventional nano-silica is used instead of the PMPO graft-modified nano-silica.
Neutral salt spray corrosion test:
taking 12 commercial Q235 cold-rolled carbon steel plates of 50 multiplied by 50cm, repeatedly polishing the surfaces of the 12 commercial Q235 cold-rolled carbon steel plates by using abrasive paper until the surfaces of the 12 commercial Q235 cold-rolled carbon steel plates have metallic luster, removing oil by using medium-temperature alkaline, cleaning, immersing the 12 commercial Q235 cold-rolled carbon steel plates into a 5% (volume fraction) nitric acid solution, activating at room temperature for 15s, finally washing the 12 commercial Q235 cold-rolled carbon steel plates by using deionized water, and wiping the surfaces by using;
taking 7 test pieces, respectively immersing the test pieces in the passivation solution prepared in the embodiments 1-7 of the invention, treating the test pieces at room temperature for 10min, opening the test pieces into a constant-temperature drying oven to dry the test pieces for 10h at 100 ℃, and respectively marking the test pieces as test groups 1-7;
respectively soaking 4 test pieces into the passivation solution prepared in comparative examples 1-4 of the invention, treating for 10min at room temperature, opening the test pieces into a constant temperature drying oven for drying treatment for 10h at 100 ℃, and respectively marking as comparative groups 1-4;
and (3) immersing the rest 1 test piece into deionized water, immersing for 10min at room temperature, and after the immersion is finished, putting the test piece into a constant-temperature drying oven for drying treatment for 10h at 100 ℃ to serve as a blank group.
Carrying out a neutral salt spray corrosion test on the sample by adopting a continuous spraying mode:
the corrosion solution is NaCl solution (50 +/-5) g/L, prepared by deionized water, and the settling amount of the salt spray is 1.0-2.0 mL/(80 cm)2H), the temperature in the oven is (35 +/-2) ° C; continuously spraying for 24h as 1 period for 5 periods; the spraying frequency is 8s at intervals of 10s, after each test period is finished, the corrosion area percentage of the test sample is calculated to evaluate the corrosion resistance, and the test results are shown in the following table 1:
table 1:
Figure DEST_PATH_IMAGE002
the neutral salt spray corrosion test shows that the passivation solution prepared in the embodiments 1 to 7 of the present invention effectively improves the neutral salt spray corrosion resistance of the carbon steel plate, and the comparison shows that the rare earth supported porous graphene sealant and the PMPO grafted modified nano silica in the passivation solution can further improve the passivation effect of the passivation solution and improve the corrosion resistance of the carbon steel plate.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (9)

1. The environment-friendly chromium-free passivation solution suitable for metal surface treatment is characterized by comprising the following components in percentage by weight:
0.1 to 0.5 percent of fluorine-containing compound, 0.01 to 0.02 percent of silane coupling agent, 0.05 to 0.1 percent of titanium sulfate, 0.01 to 0.02 percent of sodium nitrate, 0.05 to 0.1 percent of copper sulfate, 0.03 to 0.05 percent of sodium formate, 0.02 to 0.04 percent of hydroxymethyl cellulose sodium, 0.1 to 1 percent of acetic acid, 0.01 to 0.02 percent of ammonium molybdate, 0.06 to 0.12 percent of sodium tripolyphosphate, 1 to 3 percent of rare earth load type porous graphene sealant, 3 to 6 percent of PMPO graft modified nano silicon dioxide, 0.5 to 1 percent of ethylene glycol monobutyl ether, 0.1 to 0.2 percent of alcohol ester, 0.012 to 0.016 percent of benzotriazole, 0.5 to 1 percent of microcrystalline paraffin, 0.05 to 0.1 percent of amino carboxylate complexing agent, 0.05 to 0.1 percent of complexing agent and the balance of deionized water.
2. The environment-friendly chromium-free passivation solution as claimed in claim 1, which is characterized by comprising the following components in percentage by weight:
0.3% of fluorine-containing compound, 0.012% of silane coupling agent, 0.07% of titanium sulfate, 0.01% of sodium nitrate, 0.06% of copper sulfate, 0.03% of sodium formate, 0.02% of sodium carboxymethylcellulose, 0.5% of acetic acid, 0.015% of ammonium molybdate, 0.12% of sodium tripolyphosphate, 3% of rare earth-supported porous graphene sealant, 4% of PMPO grafted modified nano silicon dioxide, 0.6% of ethylene glycol monobutyl ether, 0.2% of alcohol ester, 0.016% of benzotriazole, 0.5% of microcrystalline paraffin, 0.1% of aminocarboxylate complexing agent, 0.1% of complexing agent and the balance of deionized water.
3. The environment-friendly chromium-free passivation solution according to claim 1, wherein the preparation method of the rare earth-supported porous graphene sealant comprises the following steps:
(1) adding graphite into mixed acid consisting of concentrated sulfuric acid and concentrated nitric acid in a weight ratio of 1:1 in ice bath, stirring and mixing uniformly, adding potassium hypochlorite, continuously stirring for 1-5h, removing the ice bath, recovering the room temperature, continuously stirring for 20-30h, heating to 40-50 ℃, stirring for 5-10h, cooling, performing suction filtration, washing the obtained solid with dilute hydrochloric acid for 3 times, fully washing with distilled water to neutrality, and performing vacuum drying at 60-80 ℃ to obtain a first intermediate;
(2) adding rare earth oxide and a first intermediate into deionized water, carrying out ultrasonic treatment for 1-2h, adding into a high-temperature high-pressure reaction kettle, reacting at the temperature of 3-5MPa and 400-500 ℃ for 5-10h, and carrying out suction filtration and water washing to obtain a second intermediate;
(3) drying the second intermediate at 40-50 ℃ for 10-20h, heating to 400-,
and cooling to 100-.
4. The environment-friendly chromium-free passivation solution according to claim 1, wherein the preparation method of the PMPO graft modified nano silica is as follows:
(1) washing the nano silicon dioxide with diluted hydrochloric acid, and activating at the temperature of 150 ℃ and 160 ℃ for 1-5 h;
(2) adding activated nano silicon dioxide into anhydrous toluene, performing ultrasonic dispersion, then dropwise adding glycidyl ether trimethoxy silane, performing reflux reaction for 20-25h, and washing with anhydrous toluene after the reaction is finished to obtain pretreated nano silicon dioxide;
(3) adding the pretreated nano silicon dioxide into a carbonate buffer solution of polyether polyol, stirring and reacting for 20-25h at room temperature, and washing with deionized water and drying after the reaction is finished.
5. The environment-friendly chromium-free passivation solution according to claim 1, wherein the fluorine-containing compound is one or more of fluotitanic acid, fluozirconic acid, potassium fluozirconate, sodium fluosilicate, sodium fluoride or magnesium fluoride.
6. The environment-friendly chromium-free passivation solution according to claim 1, wherein the silane coupling agent is one or more of KH-540, KH-550, KH-560, KH-151, KH-792 and KH-602.
7. The environment-friendly chromium-free passivation solution according to claim 1, wherein the aminocarboxylate complexing agent is EDTA and DTPA according to a weight ratio of (1-10): (1-10) mixing.
8. The environment-friendly chromium-free passivation solution according to claim 1, wherein the complexing agent is one or more of citric acid and salts thereof, tartaric acid and salts thereof, lactic acid and salts thereof, malonic acid and salts thereof, succinic acid and salts thereof, gluconic acid and salts thereof, maleic acid and salts thereof, and glycolic acid and salts thereof.
9. The environment-friendly chromium-free passivation solution according to claim 1, characterized in that the preparation method comprises the following steps:
(1) adding a silane coupling agent into deionized water, and uniformly stirring to obtain a solution A;
(2) heating the solution A to 40-50 ℃, sequentially adding sodium carboxymethylcellulose, acetic acid, ethylene glycol monobutyl ether and alcohol ester twelve, and stirring for 30-50min at the speed of 100-200r/min to obtain solution B;
(3) and heating the solution B to 60-65 ℃, increasing the rotating speed to 200-one-step operation for 300r/min, sequentially adding the rare earth-loaded porous graphene sealant, the PMPO grafted modified nano-silica, the fluorine-containing compound, titanium sulfate, sodium nitrate, copper sulfate, sodium formate, ammonium molybdate, sodium tripolyphosphate, benzotriazole, microcrystalline paraffin, the complexing agent and the aminocarboxylate complexing agent, stirring for 1-3h, and recovering the room temperature.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114932064A (en) * 2022-03-07 2022-08-23 泉州市微米电子科技有限公司 Spraying method for processing automobile parts to improve corrosion resistance
CN116121573A (en) * 2023-03-14 2023-05-16 创拓精工(江苏)有限公司 Nut with composite coating on surface and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114932064A (en) * 2022-03-07 2022-08-23 泉州市微米电子科技有限公司 Spraying method for processing automobile parts to improve corrosion resistance
CN116121573A (en) * 2023-03-14 2023-05-16 创拓精工(江苏)有限公司 Nut with composite coating on surface and preparation method thereof
CN116121573B (en) * 2023-03-14 2024-01-02 创拓精工(江苏)有限公司 Nut with composite coating on surface and preparation method thereof

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