CN111876763A - Chromium-free surface treatment liquid for zinc-aluminum-magnesium coated steel plate and preparation method thereof - Google Patents
Chromium-free surface treatment liquid for zinc-aluminum-magnesium coated steel plate and preparation method thereof Download PDFInfo
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- CN111876763A CN111876763A CN202010688335.2A CN202010688335A CN111876763A CN 111876763 A CN111876763 A CN 111876763A CN 202010688335 A CN202010688335 A CN 202010688335A CN 111876763 A CN111876763 A CN 111876763A
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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
Abstract
The invention relates to the field of surface treatment of a zinc-aluminum-magnesium coated steel plate, in particular to a chromium-free surface treatment liquid for a zinc-aluminum-magnesium coated steel plate and a preparation method thereof, the surface treatment liquid consists of 80-90 parts by mass of A and 1-20 parts by mass of B, wherein the component A comprises 100-150 parts by mass of organosilane and metal salt complex modified waterborne epoxy resin emulsion, 0.1-1 part by mass of waterborne defoaming agent, 0.5-2 parts by mass of waterborne lubricant and 100-200 parts by mass of deionized water, the component B is a waterborne curing agent, the water-based epoxy resin is prepared by compounding and modifying an organosilane coupling agent and a metal salt complex, the surface treatment liquid is prepared by mixing A, B two components according to a certain proportion before use, after the surface passivation treatment is carried out on the zinc-aluminum-magnesium plated steel plate, the obtained passivated plate has excellent corrosion resistance and excellent damp-heat black degeneration resistance.
Description
Technical Field
The invention relates to the technical field of zinc-aluminum-magnesium coated steel plate surface treatment materials, in particular to a chromium-free surface treatment liquid for a zinc-aluminum-magnesium coated steel plate and a preparation method thereof.
Background
The zinc-aluminum-magnesium coated steel plate is a novel high-corrosion-resistance steel plate, has excellent processing performance, high coating hardness and excellent damage resistance, has less coating adhesion but more excellent corrosion resistance compared with the common zinc-coated steel plate or aluminum-zinc coated steel plate, has good trimming corrosion resistance in the processing and using process, and has wide application fields including civil construction, agricultural livestock, electric power communication, industrial refrigeration and other industries. The zinc-aluminum-magnesium coating on the surface of the steel plate is easy to corrode and blacken in humid air, and the attractiveness and the coating property of the surface of a product are affected, so that the zinc-aluminum-magnesium coating steel plate needs to be subjected to surface passivation treatment. The traditional chromium-containing passivator is unfavorable to human bodies and environment and is gradually eliminated, the chromium-free passivator which is popular in the market at present has a good effect on a galvanized sheet, but when the surface of a zinc-aluminum-magnesium plated steel sheet is passivated, the corrosion resistance and the blackening resistance are poor, so that the chromium-free passivator specially used for the zinc-aluminum-magnesium plated steel sheet needs to be developed.
In patent applications with publication numbers CN107418328A and CN106752505A, single-component chromium-free passivator for a zinc-aluminum-magnesium coated steel sheet is developed by using resin, silane, metal salt and other components, during the film forming process of single-component aqueous resin, the crosslinking degree is low, the compactness of an organic film formed on the metal surface is limited, which results in insufficient blackening resistance of a passivation film of the zinc-aluminum-magnesium coated steel sheet in a hot and humid environment, after the zinc-aluminum-magnesium coated steel sheet treated by the treatment liquid in the two patent applications is placed in a hot and humid chamber with 50 ℃ and 95% RH for 120h, the surface color difference Δ E is greater than 10, and the surface is severely blackened. Therefore, a chromium-free passivator capable of forming an organic film with high crosslinking degree on the surface of the zinc-aluminum-magnesium coating needs to be developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a chromium-free surface treatment solution for a zinc-aluminum-magnesium plated steel plate, which has excellent corrosion resistance and blackening resistance, particularly excellent wet-heat blackening resistance and is environment-friendly, and a preparation method thereof.
The technical scheme of the invention is as follows:
a chromium-free surface treatment liquid for a zinc-aluminum-magnesium coated steel plate comprises 80-90 parts by mass of a component A and 1-20 parts by mass of a component B;
the component A comprises 100-150 parts by mass of organosilane and metal salt complex modified waterborne epoxy resin emulsion, 0.1-1 part by mass of waterborne defoaming agent, 0.5-2 parts by mass of waterborne lubricant and 100-200 parts by mass of deionized water;
the component B is a water-based curing agent;
preferably, the preparation method of the organosilane and metal salt complex modified aqueous epoxy resin emulsion comprises the following steps:
step 1, mixing 30-50 parts by mass of E44 epoxy resin and 50-70 parts by mass of E51 epoxy resin in a container, adding 20-50 parts by mass of gamma- (2, 3-glycidoxy) propyl trimethoxy silane and/or gamma- (2, 3-glycidoxy) propyl triethoxy silane, adding 40-100 parts by mass of polyethylene glycol with the molecular weight of 2000-4000 and 0.5-2 parts by mass of boron trifluoride diethyl etherate, heating to 70-100 ℃, and stirring for reacting for 5-8 hours;
step 2, cooling the reaction product in the container to 40-70 ℃, and dropwise adding 400-700 parts by mass of deionized water at a stirring speed of 500-2000 rpm to obtain the organosilane-modified waterborne epoxy resin emulsion;
step 3, taking 1-15 parts by mass of one or more of zirconium salt, titanium salt, nickel salt and molybdenum salt, adding deionized water to dissolve and dilute until the solid content of the solution is 1% -2% (wherein the solid content of the solution refers to the mass percentage of the residual components in the original solution after baking the solution at 100 ℃ for 2 hours), adding 1-3 parts by mass of phosphoric acid with the mass concentration of 85% and 5-15 parts by mass of triethylamine, and stirring for 20-40 minutes;
and 4, dropwise adding the mixed liquid obtained in the step 3 into the organosilane-modified waterborne epoxy resin emulsion obtained in the step 2, and stirring and reacting at the temperature of 0-40 ℃ for 30-60 minutes to obtain the organosilane-and-metal salt complex-modified waterborne epoxy resin emulsion.
Preferably, the zirconium salt is ammonium zirconium carbonate and/or zirconium acetate, the titanium salt is one or more of titanyl sulfate, ammonium fluotitanate and titanium sulfate, the nickel salt is one or more of nickel acetate, nickel nitrate and nickel sulfate, and the molybdenum salt is sodium molybdate and/or ammonium phosphomolybdate;
preferably, the aqueous defoaming agent consists of 80-95 parts by mass of polydimethylsiloxane and 0.1-10 parts by mass of silicon dioxide with the particle size of 30-100 nm;
preferably, the aqueous lubricant consists of 40-70 parts by mass of aqueous polyethylene and 40-50 parts by mass of aqueous polytetrafluoroethylene;
preferably, the aqueous curing agent comprises 40-60 parts by mass of phenolic aldehyde amine T31, 0.5-3 parts by mass of diethylenetriamine and 30-50 parts by mass of absolute ethyl alcohol.
A preparation method of the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate comprises the following steps: taking the organosilane and metal salt complex modified waterborne epoxy resin emulsion, the waterborne defoamer and the waterborne lubricant, adding deionized water, and stirring and mixing to obtain a component A; when in use, the component A and the component B are uniformly mixed to obtain the chromium-free surface treatment fluid for the zinc-aluminum-magnesium coated steel plate.
In the process of drying and film forming of the treatment liquid on the surface of a zinc-aluminum-magnesium coating steel plate, the epoxy resin and the water-based curing agent are subjected to a crosslinking reaction, and a silane coupling agent grafted on the epoxy resin structure can be hydrolyzed in water to form silicon hydroxyl which is combined with polar groups on the metal surface, so that an organic film formed by the epoxy resin is compactly adhered to the metal surface; in the drying film-forming process, zirconium salt, titanium salt, nickel salt and molybdenum salt not only react with the zinc-aluminum-magnesium coating to generate metal oxide and metal salt substances which are insoluble in water, and the metal oxide and the metal salt substances are mutually cooperated to form an inorganic conversion film, but also are complexed with a silane coupling agent on the epoxy resin to further improve the resin crosslinking degree, and finally a layer of compact organic resin film and an inorganic salt conversion film are formed on the surface of the zinc-aluminum-magnesium coating, so that the passivated zinc-aluminum-magnesium coating has stronger corrosion resistance.
Drawings
FIG. 1 is a graph showing the appearance of a Zn-Al-Mg plated steel sheet after being subjected to surface treatment by the surface treatment liquid in the example and then subjected to a salt spray resistance test for 120 hours.
Compared with the prior art, the invention has the technical advantages that:
the silane coupling agent is grafted on the aqueous epoxy resin, the aqueous epoxy resin is further modified by using the metal salt complex, when the A and B components are crosslinked and cured on the surface of the zinc-aluminum-magnesium coating, an organic film with a certain crosslinking degree can be formed, the metal salt complex has the function of a physical crosslinking point on the epoxy resin, the crosslinking degree of the organic film is further improved, meanwhile, zirconium oxide, titanium oxide and the like formed on the surface of the zinc-aluminum-magnesium coating by the metal salt and other inorganic salts are difficult to dissolve in water and cooperatively form an inorganic conversion film, and the inorganic conversion film has an inhibition effect on the permeation of water, oxygen and carbon dioxide, so that the passive film on the surface of the zinc-aluminum-magnesium coating steel plate has excellent corrosion resistance (salt mist resistance, solvent resistance, alkali resistance) and damp-heat black degeneration resistance.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way.
In the following examples, reagents not specifically described are conventional reagents, and some of the raw material manufacturers in the examples are as follows:
e44 epoxy resin, E51 epoxy resin and phenolic amine T31 manufacturers are the ba ling petrochemical;
the polyethylene glycol (PEG-2000, PEG-4000) manufacturer is petroleum chemical plant of Jiangsu Haian;
the manufacturer of the nano silicon dioxide with the particle size of 30-100 nm is New Material Co., Ltd of Hippocastidae;
the polydimethylsiloxane manufacturer is Dow Corning, USA, and the trade name is DC 193;
the manufacturer of the aqueous polyethylene is BASF corporation, and the trade name is WE 6;
the aqueous polytetrafluoroethylene was produced by Nippon Dajin industries, Ltd., and was designated by the reference number D-210.
Example 1:
in the embodiment, each mass part is 100 g;
the first step is as follows: preparation of aqueous epoxy resin emulsion modified by organosilane and metal salt complex
Mixing 50 parts by mass of E44 epoxy resin and 70 parts by mass of E51 epoxy resin in a container, adding 40 parts by mass of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 80 parts by mass of PEG-2000 and 1 part by mass of boron trifluoride diethyl etherate, heating to 80 ℃, and stirring for reacting for 6 hours;
secondly, cooling the reaction product in the container to 40 ℃, and dripping 500 parts by mass of deionized water at the stirring speed of 1200 revolutions per minute to obtain the organosilane modified waterborne epoxy resin emulsion;
taking 1.5 parts by mass of zirconium ammonium carbonate, 0.5 part by mass of titanyl sulfate, 0.5 part by mass of nickel nitrate and 1 part by mass of sodium molybdate, adding deionized water to dissolve, diluting until the solid content of the solution is 1.8% (wherein the solid content of the solution refers to the mass percentage of the residual components in the original solution after baking the solution at 100 ℃ for 2 hours, the following is the same, and the description is omitted), adding 2 parts by mass of phosphoric acid with the concentration of 85% by mass and 6 parts by mass of triethylamine, and stirring for 30 minutes;
dripping the mixed liquid obtained from the third step into the aqueous epoxy resin emulsion modified by the organic silane obtained from the fourth step, and stirring and reacting for 30 minutes at the temperature of 20 ℃ to obtain the aqueous epoxy resin emulsion modified by the organic silane and the metal salt complex.
The second step, preparation of water-based defoaming agent and water-based lubricant
Water-based defoaming agent: uniformly mixing 90 parts by mass of polydimethylsiloxane and 0.2 part by mass of silicon dioxide with the particle size of 30-100 nm;
aqueous lubricant: uniformly mixing 50 parts by mass of water-based polyethylene and 50 parts by mass of water-based polytetrafluoroethylene;
the third step: preparation of component A
Adding 145 parts by mass of deionized water into 140 parts by mass of the organosilane and metal salt complex modified waterborne epoxy resin emulsion prepared in the first step, 0.2 part by mass of the waterborne defoamer prepared in the second step and 1 part by mass of the waterborne lubricant, and stirring and mixing to obtain a component A;
the fourth step: preparation of component B
Taking 40 parts by mass of phenolic aldehyde amine T31, 1 part by mass of diethylenetriamine and 40 parts by mass of absolute ethyl alcohol, and stirring and mixing to obtain the component B.
The fifth step: a and B are compounded
When the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate is used, 85 parts by mass of the component A and 10 parts by mass of the component B are taken and uniformly mixed.
Example 2:
in the embodiment, each mass part is 200 g;
the first step is as follows: preparation of aqueous epoxy resin emulsion modified by organosilane and metal salt complex
Mixing 35 parts by mass of E44 epoxy resin and 65 parts by mass of E51 epoxy resin in a container, adding 35 parts by mass of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 100 parts by mass of PEG-4000 and 0.5 part by mass of boron trifluoride diethyl etherate, heating to 70 ℃, and stirring for reaction for 7 hours;
secondly, cooling the reaction product in the container to 45 ℃, and dripping 500 parts by mass of deionized water at the stirring speed of 1000 revolutions per minute to obtain the organosilane modified waterborne epoxy resin emulsion;
③ taking 1 part by mass of zirconium ammonium carbonate, 1 part by mass of titanyl sulfate, 1 part by mass of nickel nitrate and 1 part by mass of sodium molybdate, adding deionized water for dissolving, diluting until the solid content is 1.5%, then adding 1 part by mass of phosphoric acid with the concentration of 85% by mass and 5 parts by mass of triethylamine, and stirring for 20 minutes;
dripping the mixed liquid obtained from the third step into the aqueous epoxy resin emulsion modified by the organic silane obtained from the fourth step, and stirring and reacting for 30 minutes at the temperature of 25 ℃ to obtain the aqueous epoxy resin emulsion modified by the organic silane and the metal salt complex.
The second step, preparation of water-based defoaming agent and water-based lubricant
Water-based defoaming agent: taking 85 parts by mass of polydimethylsiloxane and 0.5 part by mass of silicon dioxide with the particle size of 30-100 nm, and uniformly mixing;
aqueous lubricant: uniformly mixing 40 parts by mass of aqueous polyethylene and 40 parts by mass of aqueous polytetrafluoroethylene;
the third step: preparation of component A
Adding 150 parts by mass of deionized water into 145 parts by mass of the organosilane and metal salt complex modified waterborne epoxy resin emulsion prepared in the first step, 0.4 part by mass of the waterborne defoamer prepared in the second step and 1.5 parts by mass of the waterborne lubricant, and stirring and mixing to obtain a component A;
the fourth step: preparation of component B
And (3) stirring and mixing 45 parts by mass of phenolic aldehyde amine T31, 0.5 part by mass of diethylenetriamine and 45 parts by mass of absolute ethyl alcohol to obtain the component B.
The fifth step: a and B are compounded
When the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate is used, 80 parts by mass of the component A and 8 parts by mass of the component B are taken and uniformly mixed.
Example 3:
in the embodiment, each part by mass is 500 g;
the first step is as follows: preparation of aqueous epoxy resin emulsion modified by organosilane and metal salt complex
Mixing 35 parts by mass of E44 epoxy resin and 60 parts by mass of E51 epoxy resin in a container, adding 30 parts by mass of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 95 parts by mass of PEG-2000 and 0.6 part by mass of boron trifluoride diethyl etherate, heating to 75 ℃, and stirring for reacting for 6 hours;
secondly, cooling the reaction product in the container to 50 ℃, and dripping 450 parts by mass of deionized water at the stirring speed of 1500 revolutions per minute to obtain the organosilane modified waterborne epoxy resin emulsion;
thirdly, 1 part by mass of zirconium ammonium carbonate, 0.5 part by mass of titanyl sulfate, 0.5 part by mass of ammonium fluotitanate, 1.5 parts by mass of nickel nitrate and 1 part by mass of sodium molybdate are taken, deionized water is added for dissolution and dilution until the solid content is 1.6 percent, 1 part by mass of phosphoric acid with the concentration of 85 percent by mass and 5 parts by mass of triethylamine are added, and stirring is carried out for 25 minutes;
dripping the mixed liquid obtained from the third step into the aqueous epoxy resin emulsion modified by the organic silane obtained from the fourth step, and stirring and reacting for 30 minutes at the temperature of 30 ℃ to obtain the aqueous epoxy resin emulsion modified by the organic silane and the metal salt complex.
The second step, preparation of water-based defoaming agent and water-based lubricant
Water-based defoaming agent: uniformly mixing 80 parts by mass of polydimethylsiloxane and 0.4 part by mass of silicon dioxide with the particle size of 30-100 nm;
aqueous lubricant: uniformly mixing 45 parts by mass of aqueous polyethylene and 45 parts by mass of aqueous polytetrafluoroethylene;
the third step: preparation of component A
Taking 150 parts by mass of the organosilane and metal salt complex modified waterborne epoxy resin emulsion prepared in the first step, 0.4 part by mass of the waterborne defoamer prepared in the second step and 2 parts by mass of the waterborne lubricant, adding 180 parts by mass of deionized water, and stirring and mixing to obtain a component A;
the fourth step: preparation of component B
Taking 40 parts by mass of phenolic aldehyde amine T31, 0.8 part by mass of diethylenetriamine and 40 parts by mass of absolute ethyl alcohol, and stirring and mixing to obtain the component B.
The fifth step: a and B are compounded
When the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate is used, 85 parts by mass of the component A and 10 parts by mass of the component B are taken and uniformly mixed.
Example 4:
in the embodiment, each part by mass is 1 kg;
the first step is as follows: preparation of aqueous epoxy resin emulsion modified by organosilane and metal salt complex
Mixing 50 parts by mass of E44 epoxy resin and 60 parts by mass of E51 epoxy resin in a container, adding 35 parts by mass of gamma- (2, 3-epoxypropoxy) propyl triethoxysilane, 100 parts by mass of PEG-2000 and 1 part by mass of boron trifluoride diethyl etherate, heating to 75 ℃, and stirring for reaction for 7 hours;
secondly, cooling the reaction product in the container to 40 ℃, and dripping 500 parts by mass of deionized water at the stirring speed of 1800 rpm to obtain the organosilane modified waterborne epoxy resin emulsion;
③ taking 1 part by mass of ammonium zirconium carbonate, 0.5 part by mass of zirconium acetate, 0.5 part by mass of titanyl sulfate, 0.5 part by mass of ammonium fluotitanate, 2 parts by mass of nickel nitrate and 1.5 parts by mass of ammonium phosphomolybdate, adding deionized water to dissolve and dilute until the solid content is 1.2 percent, then adding 2 parts by mass of phosphoric acid with the concentration of 85 percent by mass and 8 parts by mass of triethylamine, and stirring for 30 minutes;
dripping the mixed liquid obtained from the third step into the aqueous epoxy resin emulsion modified by the organic silane obtained from the fourth step, and stirring and reacting for 50 minutes at the temperature of 35 ℃ to obtain the aqueous epoxy resin emulsion modified by the organic silane and the metal salt complex.
The second step, preparation of water-based defoaming agent and water-based lubricant
Water-based defoaming agent: uniformly mixing 88 parts by mass of polydimethylsiloxane and 0.6 part by mass of silicon dioxide with the particle size of 50-85 nm;
aqueous lubricant: uniformly mixing 48 parts by mass of aqueous polyethylene and 48 parts by mass of aqueous polytetrafluoroethylene;
the third step: preparation of component A
Adding 175 parts by mass of deionized water into 148 parts by mass of the organosilane and metal salt complex modified waterborne epoxy resin emulsion prepared in the first step, 0.6 part by mass of the waterborne defoamer prepared in the second step and 1.8 parts by mass of the waterborne lubricant, and stirring and mixing to obtain a component A;
the fourth step: preparation of component B
And stirring and mixing 48 parts by mass of phenolic aldehyde amine T31, 0.6 part by mass of diethylenetriamine and 48 parts by mass of absolute ethyl alcohol to obtain the component B.
The fifth step: a and B are compounded
When the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate is used, 85 parts by mass of the component A and 20 parts by mass of the component B are taken and uniformly mixed.
To further illustrate the effects of the present invention, the following examples are comparative examples.
Example 5:
in the embodiment, each mass part is 100 g;
the first step is as follows: preparation of aqueous epoxy resin emulsion modified by organosilane and metal salt complex
Mixing 40 parts by mass of E44 epoxy resin and 60 parts by mass of E51 epoxy resin in a container, adding 20 parts by mass of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 20 parts by mass of PEG-2000 and 1 part by mass of boron trifluoride diethyl etherate, heating to 75 ℃, and stirring for reacting for 6 hours;
secondly, cooling the reaction product in the container to 40 ℃, and dripping 500 parts by mass of deionized water at the stirring speed of 1800 rpm to obtain the organosilane modified waterborne epoxy resin emulsion;
③ taking 1.8 parts by mass of ammonium zirconium carbonate, adding deionized water to dissolve and dilute the ammonium zirconium carbonate until the solid content is 1.5 percent, then adding 2.5 parts by mass of phosphoric acid with the mass percentage concentration of 85 percent and 8 parts by mass of triethylamine, and stirring for 30 minutes;
dripping the mixed liquid obtained from the third step into the aqueous epoxy resin emulsion modified by the organic silane obtained from the fourth step, and stirring and reacting for 40 minutes at the temperature of 35 ℃ to obtain the aqueous epoxy resin emulsion modified by the organic silane and the metal salt complex.
The second step, preparation of water-based defoaming agent and water-based lubricant
Water-based defoaming agent: uniformly mixing 87 parts by mass of polydimethylsiloxane and 0.5 part by mass of silicon dioxide with the particle size of 30-100 nm;
aqueous lubricant: uniformly mixing 47 parts by mass of aqueous polyethylene and 49 parts by mass of aqueous polytetrafluoroethylene;
the third step: preparation of component A
Adding 175 parts by mass of deionized water into 148 parts by mass of the organosilane and metal salt complex modified waterborne epoxy resin emulsion prepared in the first step, 0.6 part by mass of the waterborne defoamer prepared in the second step and 1.8 parts by mass of the waterborne lubricant, and stirring and mixing to obtain a component A;
the fourth step: preparation of component B
And stirring and mixing 48 parts by mass of phenolic aldehyde amine T31, 0.7 part by mass of diethylenetriamine and 49 parts by mass of absolute ethyl alcohol to obtain the component B.
The fifth step: a and B are compounded
When the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate is used, 85 parts by mass of the component A and 15 parts by mass of the component B are taken and uniformly mixed.
Example 6:
in the embodiment, each mass part is 100 g;
the first step is as follows: preparation of aqueous epoxy resin emulsion modified by organosilane and metal salt complex
Mixing 45 parts by mass of E44 epoxy resin and 55 parts by mass of E51 epoxy resin in a container, adding 25 parts by mass of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 120 parts by mass of PEG-2000 and 1 part by mass of boron trifluoride diethyl etherate, heating to 75 ℃, and stirring for reacting for 6 hours;
secondly, cooling the reaction product in the container to 40 ℃, and dripping 500 parts by mass of deionized water at the stirring speed of 1800 rpm to obtain the organosilane modified waterborne epoxy resin emulsion;
③ adding 1.5 parts by mass of zirconium acetate and 0.8 part by mass of titanyl sulfate into deionized water for dissolving and diluting until the solid content is 2 percent, then adding 3 parts by mass of phosphoric acid with the concentration of 85 percent by mass and 8 parts by mass of triethylamine, and stirring for 30 minutes;
dripping the mixed liquid obtained from the third step into the aqueous epoxy resin emulsion modified by the organic silane obtained from the fourth step, and stirring and reacting for 40 minutes at the temperature of 35 ℃ to obtain the aqueous epoxy resin emulsion modified by the organic silane and the metal salt complex.
The second step, preparation of water-based defoaming agent and water-based lubricant
Water-based defoaming agent: uniformly mixing 87 parts by mass of polydimethylsiloxane and 0.5 part by mass of silicon dioxide with the particle size of 30-100 nm;
aqueous lubricant: uniformly mixing 70 parts by mass of aqueous polyethylene and 40 parts by mass of aqueous polytetrafluoroethylene;
the third step: preparation of component A
Adding 183 parts by mass of deionized water into 140 parts by mass of the organosilane and metal salt complex modified waterborne epoxy resin emulsion prepared in the first step, 0.6 part by mass of the waterborne defoamer prepared in the second step and 1.8 parts by mass of the waterborne lubricant, and stirring and mixing to obtain a component A;
the fourth step: preparation of component B
Taking 45 parts by mass of phenolic aldehyde amine T31, 0.6 part by mass of diethylenetriamine and 50 parts by mass of absolute ethyl alcohol, and stirring and mixing to obtain the component B.
The fifth step: a and B are compounded
When the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate is used, 90 parts by mass of the component A and 20 parts by mass of the component B are taken and uniformly mixed.
Example 7:
in the embodiment, each mass part is 100 g;
the first step is as follows: preparation of aqueous epoxy resin emulsion modified by organosilane and metal salt complex
Mixing 35 parts by mass of E44 epoxy resin and 60 parts by mass of E51 epoxy resin in a container, adding 30 parts by mass of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 95 parts by mass of PEG-2000 and 0.6 part by mass of boron trifluoride diethyl etherate, heating to 75 ℃, and stirring for reacting for 6 hours;
secondly, cooling the reaction product in the container to 50 ℃, and dripping 450 parts by mass of deionized water at the stirring speed of 1500 revolutions per minute to obtain the organosilane modified waterborne epoxy resin emulsion;
③ taking 1 part by mass of phosphoric acid with the mass percent concentration of 85 percent and 5 parts by mass of triethylamine, and stirring and mixing for 20 minutes;
dripping the mixed liquid obtained from the third step into the aqueous epoxy resin emulsion modified by the organic silane obtained from the fourth step, and stirring and reacting for 30 minutes at the temperature of 30 ℃ to obtain the aqueous epoxy resin emulsion modified by the organic silane and the metal salt complex.
The second step, preparation of water-based defoaming agent and water-based lubricant
Water-based defoaming agent: uniformly mixing 80 parts by mass of polydimethylsiloxane and 0.4 part by mass of silicon dioxide with the particle size of 30-100 nm;
aqueous lubricant: uniformly mixing 45 parts by mass of aqueous polyethylene and 45 parts by mass of aqueous polytetrafluoroethylene;
the third step: preparation of component A
Taking 150 parts by mass of the organosilane and metal salt complex modified waterborne epoxy resin emulsion prepared in the first step, 0.4 part by mass of the waterborne defoamer prepared in the second step and 2 parts by mass of the waterborne lubricant, adding 180 parts by mass of deionized water, and stirring and mixing to obtain a component A;
the fourth step: preparation of component B
Taking 40 parts by mass of phenolic aldehyde amine T31, 0.8 part by mass of diethylenetriamine and 40 parts by mass of absolute ethyl alcohol, and stirring and mixing to obtain the component B.
The fifth step: a and B are compounded
When the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate is used, 85 parts by mass of the component A and 10 parts by mass of the component B are taken and uniformly mixed.
Example 8:
in the embodiment, each mass part is 100 g;
the first step is as follows: preparation of aqueous epoxy resin emulsion modified by organosilane and metal salt complex
Mixing 35 parts by mass of E44 epoxy resin and 60 parts by mass of E51 epoxy resin in a container, adding 30 parts by mass of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 95 parts by mass of PEG-2000 and 0.6 part by mass of boron trifluoride diethyl etherate, heating to 75 ℃, and stirring for reacting for 6 hours;
secondly, cooling the reaction product in the container to 50 ℃, and dripping 450 parts by mass of deionized water at the stirring speed of 1500 revolutions per minute to obtain the organosilane modified waterborne epoxy resin emulsion;
thirdly, 1 part by mass of zirconium ammonium carbonate, 0.5 part by mass of titanyl sulfate, 0.5 part by mass of ammonium fluotitanate, 1.5 parts by mass of nickel nitrate and 1 part by mass of sodium molybdate are taken, deionized water is added for dissolution and dilution until the solid content is 1.6 percent, 1 part by mass of phosphoric acid with the concentration of 85 percent by mass and 5 parts by mass of triethylamine are added, and stirring is carried out for 25 minutes;
dripping the mixed liquid obtained from the third step into the aqueous epoxy resin emulsion modified by the organic silane obtained from the fourth step, and stirring and reacting for 30 minutes at the temperature of 30 ℃ to obtain the aqueous epoxy resin emulsion modified by the organic silane and the metal salt complex.
The second step, preparation of water-based defoaming agent and water-based lubricant
Water-based defoaming agent: uniformly mixing 80 parts by mass of polydimethylsiloxane and 0.4 part by mass of silicon dioxide with the particle size of 30-100 nm;
aqueous lubricant: uniformly mixing 45 parts by mass of aqueous polyethylene and 45 parts by mass of aqueous polytetrafluoroethylene;
the third step: preparation of component A
Taking 150 parts by mass of the organosilane and metal salt complex modified waterborne epoxy resin emulsion prepared in the first step, 0.4 part by mass of the waterborne defoamer prepared in the second step and 2 parts by mass of the waterborne lubricant, adding 180 parts by mass of deionized water, and stirring and mixing to obtain a component A;
the fourth step: preparation of component B
Taking 40 parts by mass of phenolic aldehyde amine T31, 0.8 part by mass of diethylenetriamine and 40 parts by mass of absolute ethyl alcohol, and stirring and mixing to obtain the component B.
The fifth step: a and B are compounded
When the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate is used, 85 parts by mass of the component A and 0.5 part by mass of the component B are taken and uniformly mixed.
The effect test of the zinc-aluminum-magnesium coated steel plate treated by the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate of the invention comprises the following steps:
1. the test method is as follows:
respectively carrying out scraper treatment on the zinc-aluminum-magnesium coated steel plates produced by the martial steels by using the surface treatment liquids prepared in the examples 1 to 4, drying at 95 ℃ to form a film, controlling the thickness of the film to be 1000 +/-200 nm, standing for 24h to respectively obtain treated zinc-aluminum-magnesium coated steel plate samples, and testing each treated zinc-aluminum-magnesium coated steel plate sample according to the following method:
salt spray resistance test, 120 hours spray test (astm b117-2016 standard):
the treated zinc-aluminum-magnesium coated steel plate samples are required to be free from white rust for 48 hours; the area of white rust is less than or equal to 3 percent in 72 hours; the white rust area is less than or equal to 5 percent in 96 hours; the area of white rust is less than or equal to 8 percent within 120 hours;
testing solvent resistance:
respectively wiping each treated zinc-aluminum-magnesium coating steel plate sample back and forth for 10 times by using acetone and ethanol, and measuring the color difference value, wherein the surface of each zinc-aluminum-magnesium coating steel plate sample before and after wiping is required to have no obvious change, and the color difference delta E is less than or equal to 3;
thirdly, alkali resistance test:
spraying each zinc-aluminum-magnesium coating steel plate sample by using NaOH (with the pH value of about 12) alkaline solution at 40 ℃ for 2min, wherein each zinc-aluminum-magnesium coating steel plate sample is required to have no obvious change, and the color difference delta E is less than or equal to 3;
wet and heat resistant blackening
And (3) placing each treated zinc-aluminum-magnesium coated steel plate into a wet heat box with 50 ℃ and 95% RH for 120h, and testing the color difference before and after placing, wherein the color difference delta E of each zinc-aluminum-magnesium coated steel plate is required to be less than or equal to 3.
2. And (3) testing results:
the test results are given in table 1 below:
TABLE 1 treatment effect of different treatment solutions on Zn-Al-Mg coated steel sheet
In comparative example 5, since the amount of polyethylene glycol was too small and the hydrophilicity of the epoxy resin emulsion was too low, the particles were large when emulsified with water, and white precipitates were formed at the bottom of the emulsion for preparing a passivating agent, and a large amount of white particles remained on the surface after treating the steel plate, and could not be used; in comparative example 6, the consumption of polyethylene glycol is too much, and the hydrophilicity of the product is too strong, so that the water absorption of the final passivation film is too large, corrosive liquid is easy to permeate, and the corrosion resistance of the passivation film is poor; in comparative example 7, no metal salt corrosion inhibitor was used, resulting in insufficient corrosion resistance of the final treatment liquid; in comparative example 8, the use amount of the component B is too small, so that the crosslinking degree of the passivation film is too low, and the solvent resistance and the corrosion resistance of the passivation film are poor.
Examples 1 to 4 the surface treatment of the zinc-aluminum-magnesium coated steel sheet with the surface treatment liquid for a zinc-aluminum-magnesium coated steel sheet according to the present invention resulted in a zinc-aluminum-magnesium coated steel sheet having excellent salt spray resistance, solvent resistance, alkali resistance, and wet heat blackening resistance.
FIG. 1 is a surface treatment liquid for zinc-aluminum-magnesium steel plate of the above embodiment, and the surface treatment liquid is subjected to salt spray resistance test for 120 hours, wherein in example 5, the passivation plate cannot be used due to a large amount of particles on the surface of the passivation film, and no relevant performance test is performed; in fig. 1, the upper row of plates are the zinc-aluminum-magnesium passivated plates after the salt spray resistance tests of examples 1 to 4 from left to right; the lower plate is a zinc-aluminum-magnesium passivation plate after the salt spray resistance test of the embodiments 6 to 8 from left to right. As can be seen from FIG. 1, after 120 hours of salt spray testing, the surfaces of the passivated panels of examples 1-4 had no significant white rust; white rust appeared on the surfaces of examples 6 to 8, and the corrosion area was large.
Claims (6)
1. The chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate is characterized by comprising 80-90 parts by mass of A and 1-20 parts by mass of B, wherein the A is composed of 100-150 parts by mass of organosilane and metal salt complex modified water-based epoxy resin emulsion, 0.1-1 part by mass of water-based defoaming agent, 0.5-2 parts by mass of water-based lubricant and 100-200 parts by mass of deionized water, and the B is a water-based curing agent.
2. The chromium-free surface treatment liquid for a zinc-aluminum-magnesium coated steel sheet according to claim 1, wherein the component B comprises 40 to 60 parts by mass of phenalkamine T31, 0.5 to 3 parts by mass of diethylenetriamine, and 30 to 50 parts by mass of absolute ethyl alcohol.
3. The chromium-free surface treatment liquid for a zinc aluminum magnesium coated steel sheet according to claim 1, wherein the method for preparing the aqueous epoxy resin emulsion modified with the organosilane and metal salt complex comprises the steps of:
step 1, mixing 30-50 parts by mass of E44 epoxy resin and 50-70 parts by mass of E51 epoxy resin in a container, adding 20-50 parts by mass of gamma- (2, 3-glycidoxy) propyl trimethoxy silane and/or gamma- (2, 3-glycidoxy) propyl triethoxy silane, adding 40-100 parts by mass of polyethylene glycol with the molecular weight of 2000-4000 and 0.5-2 parts by mass of boron trifluoride diethyl etherate, heating to 70-100 ℃, and stirring for reacting for 5-8 hours;
step 2, cooling the reaction product in the container to 40-70 ℃, and dropwise adding 400-700 parts by mass of deionized water at a stirring speed of 500-2000 rpm to obtain the organosilane-modified waterborne epoxy resin emulsion;
step 3, taking 1-15 parts by mass of zirconium salt, titanium salt, nickel salt and/or molybdenum salt, adding deionized water for dissolving and diluting until the solid content of the solution is 1% -2%, adding 1-3 parts by mass of phosphoric acid with the mass percentage concentration of 85% and 5-15 parts by mass of triethylamine, and stirring for 20-40 minutes;
and 4, dropwise adding the mixed liquid obtained in the step 3 into the organosilane-modified waterborne epoxy resin emulsion obtained in the step 2, and stirring and reacting at the temperature of 0-40 ℃ for 30-60 minutes to obtain the organosilane-and-metal salt complex-modified waterborne epoxy resin emulsion.
4. The chromium-free surface treatment liquid for a zinc-aluminum-magnesium-coated steel sheet according to claim 3, wherein the zirconium salt is ammonium zirconium carbonate and/or zirconium acetate; the titanium salt is one or more of titanyl sulfate, ammonium fluotitanate and titanium sulfate; the nickel salt is one or more of nickel acetate, nickel nitrate and nickel sulfate; the molybdenum salt is sodium molybdate and/or ammonium phosphomolybdate.
5. The chromium-free surface treatment liquid for a zinc-aluminum-magnesium coated steel sheet according to claim 1, wherein the aqueous defoaming agent comprises 80 to 95 parts by mass of polydimethylsiloxane and 0.1 to 10 parts by mass of silica having a particle size of 30 to 100 nm; the water-based lubricant is composed of 40-70 parts by mass of water-based polyethylene and 40-50 parts by mass of water-based polytetrafluoroethylene.
6. The method for preparing a chromium-free surface treatment liquid for a zinc aluminum magnesium plated steel sheet according to any one of claims 1 to 5, comprising the steps of: taking the organosilane and metal salt complex modified waterborne epoxy resin emulsion, the waterborne defoamer and the waterborne lubricant, adding deionized water, and stirring and mixing to obtain a component A; and uniformly mixing the component A and the component B to obtain the chromium-free surface treatment liquid for the zinc-aluminum-magnesium coated steel plate.
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| CN114774905A (en) * | 2022-03-30 | 2022-07-22 | 马鞍山钢铁股份有限公司 | Special environment-friendly passivator and passivation process for chromium-free galvanized aluminum-magnesium steel plate |
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