CN111349923B - Chromium-free environment-friendly passivation treating fluid for zinc layer surface and preparation method and application thereof - Google Patents
Chromium-free environment-friendly passivation treating fluid for zinc layer surface and preparation method and application thereof Download PDFInfo
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- CN111349923B CN111349923B CN202010177001.9A CN202010177001A CN111349923B CN 111349923 B CN111349923 B CN 111349923B CN 202010177001 A CN202010177001 A CN 202010177001A CN 111349923 B CN111349923 B CN 111349923B
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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
- C23C22/68—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 solutions with pH between 6 and 8
Abstract
The invention provides a chromium-free environment-friendly passivation treating fluid for a zinc layer surface as well as a preparation method and application thereof, wherein the passivation treating fluid comprises the following components: 1-10% of special doped resin, 1-8% of coupling agent, 1-10% of aqueous nano sol, 0.5-5% of modified hydroxyl nano layered silicate powder, 0.1-3% of metal chelating agent, 5-20% of diluent, 0.5-3% of dispersant, 0.5-3% of thickening agent, 0.3-2% of pH regulator and the balance of water. The invention utilizes a resin doping process, uses special hybrid resin as a film forming agent, and uses a coupling agent to embed organic high molecular material into inorganic SiO 2 In the reticular three-dimensional film layer, the reticular three-dimensional film layer is further filled and wrapped by using the modified hydroxyl nano layered silicate to realize inorganic-organic composite passivation, solve the compatibility problem of organic components and inorganic components, improve the stability of the passivation treatment solution, form a compact corrosion-resistant passivation layer when being coated on the surface of the zinc layer, and have the advantages of low film-forming drying temperature, simple and convenient treatment process, high solution stability, acid and alkali corrosion resistance, capability of realizing chromium-free environment-friendly treatment and the like.
Description
Technical Field
The invention relates to the field of metal surface treatment, in particular to a chromium-free environment-friendly passivation treating fluid for a zinc layer surface, and a preparation method and application thereof.
Background
The problem of corrosion failure of metal substrates is an important factor influencing national economic development, particularly in the industries of aviation, electric power, transportation, machinery and the like, and performance failure caused by corrosion of metal components causes failure of equipment and production lines and loss of lives and properties of people, so that the problem is highly concerned and valued by government departments in various places at present.
The protective layer treatment of the metal substrate surface by using zinc metal is one of the most common and effective anticorrosion modes at present, and the main processes comprise galvanizing, hot dipping, thermal diffusion zinc impregnation, zinc-aluminum coating and the like. However, in a damp and hot environment, because the standard electrode potential of zinc is-0.76V, is more negative than the potential of iron (0.44V) and is more active, a zinc layer can be subjected to corrosion reaction preferentially to generate black or gray specks and white loose corrosion products, the compactness and the corrosion resistance of a zinc protective layer are seriously influenced, and if the zinc protective layer is not further protected, the substrate can be corroded and damaged for a long time to generate red rust.
In order to further improve the corrosion resistance of the zinc-containing protective layer, the zinc protective layer needs to be passivated or sealed, and inert deposition or barriers are used for forming a compact protective film to delay the corrosion rate of the zinc layer, so that the effect of protecting the zinc layer is achieved. The traditional passivation process mainly adopts chromic anhydride passivation solution containing hexavalent chromium, the passivation layer of the passivation solution has certain self-repairability, but because the hexavalent chromium has high carcinogenicity to human bodies, the passivation sealing solution is completely forbidden to contain hexavalent chromium ions at present, and instead, trivalent chromium is used for substitution, but the treatment effect of the trivalent chromium passivation solution is not ideal, and the formed passivation layer can be converted into the hexavalent chromium under certain conditions, so the trivalent chromium passivation is not a completely environment-friendly post-treatment process.
Therefore, a chromium-free environment-friendly passivation treatment method is urgently needed at the present stage, the research on chromium-free passivation is more at home and abroad, and the inorganic passivation technology, the organic passivation technology and the inorganic-organic composite passivation technology are mainly used, wherein the inorganic passivation technology mainly comprises the passivation of molybdate, tungstate, titanate, zirconate, manganate, modified silicate and rare earth metal salt; after a pure inorganic matter is passivated to form a film, the film is relatively thin, and the elasticity and the toughness are poor, so that the tension of the film is insufficient, and the compactness and the continuity are poor. Organic matter passivation mainly comprises organic acid passivation, organic silane passivation, a high polymer material passivation film and the like, but the adhesion of a high polymer material after organic passivation to a metal matrix is poor, and the outdoor ultraviolet aging resistance performance is poor, so the current environment-friendly chromium-free passivation research is more inclined to an inorganic-organic composite passivation process, the inorganic-organic composite passivation process utilizes inorganic components to improve the aging resistance and low-temperature rapid film forming property of the film, improves the toughness of the film, enhances the tension of the film and improves the acid and alkali resistance through organic components, so that the composite passivation film has various characteristics of environment protection and corrosion resistance, but the problem of the inorganic-organic composite passivation process mainly shows the compatibility problem of the organic components and the inorganic components, how to combine the organic components and the inorganic components together stably is realized, the stability of the passivating agent is improved, and the industrial production is the main direction of the inorganic-organic composite passivation research at the present stage.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a brand-new zinc layer surface chromium-free environment-friendly passivation treating fluid and a preparation method and application thereof 2 In the reticular three-dimensional film layer, the reticular three-dimensional film layer is further filled and wrapped by the nano layered silicate, so that inorganic-organic composite passivation is realized, the problem of compatibility of organic components and inorganic components is solved, the stability of the passivation treatment solution is improved, a compact corrosion-resistant passivation layer can be formed when the inorganic-organic composite passivation treatment solution is coated on the surface of the zinc layer, and the inorganic-organic composite passivation treatment solution has the unique advantages of low film-forming drying temperature, simple and convenient treatment process, high solution stability, acid and alkali corrosion resistance, capability of realizing chromium-free environment-friendly treatment and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer comprises the following components in percentage by mass: 1-10% of special doped resin, 1-8% of coupling agent, 1-10% of aqueous nano sol, 0.5-5% of modified hydroxyl nano layered silicate powder, 0.1-3% of metal chelating agent, 5-20% of diluent, 0.5-3% of dispersant, 0.5-3% of thickening agent, 0.3-2% of pH regulator and the balance of water.
The invention further provides the chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer, wherein the chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer comprises the following components in percentage by mass: 5-10% of special doped resin, 1-4% of coupling agent, 5-10% of aqueous nano sol, 1-4% of modified hydroxyl nano layered silicate powder, 0.3-2% of metal chelating agent, 10-20% of diluent, 1-2% of dispersant, 1-2% of thickening agent, 0.3-2% of pH regulator and the balance of water.
The invention further provides a chromium-free environment-friendly passivation treatment liquid for the surface of a zinc layer, wherein the specially doped resin is selected from the following group: one or a mixture of more of acrylate organic silicon hybrid resin, polyurethane organic silicon hybrid resin, epoxy organic silicon hybrid resin, silicone alkyne hybrid resin, organic silicon-inorganic silicon hybrid resin, titanium oxide modified MQ hybrid resin, acrylate modified polyurethane resin, alkyd organic silicon hybrid resin, silsesquioxane polyethylene silicon resin, polyester modified alkyd organic silicon hybrid resin, epoxy modified alkyd organic silicon hybrid resin, silane terminated polyether hybrid resin, styrene-acrylate resin, pure acrylate organic silicon hybrid resin, polyester modified acrylate organic silicon hybrid resin, acrylic acid modified alkyd organic silicon hybrid resin and organic silicon modified fluorocarbon resin.
The chromium-free environment-friendly passivation treatment fluid for the surface of the zinc layer is further characterized in that the coupling agent is one or a mixture of silane coupling agent and bimetallic coupling agent; further preferably, the coupling agent is selected from one or a mixture of KH550, KH560, KH570, KH580, KH590, KH151 and TPM.
Further, according to the chromium-free environment-friendly passivation treatment liquid for the surface of the zinc layer, the water-based nano sol is one or more of nano silicon dioxide, nano zirconium dioxide and nano titanium dioxide, wherein the particle size of the nano silicon dioxide, the nano zirconium dioxide and the nano titanium dioxide is 1-99nm.
Further, according to the chromium-free environment-friendly passivation treatment liquid for the surface of the zinc layer, the modified hydroxyl nano layered silicate powder is prepared by modifying one or a mixture of more of serpentine, hectorite, attapulgite, sericite and montmorillonite.
Further, according to the chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer, the preparation method of the modified hydroxyl nano layered silicate powder comprises the following steps:
firstly, carrying out coarse crushing, airflow crushing, ball milling and screening treatment on lamellar silicate to obtain lamellar silicate powder with the average particle size of less than 20 microns, wherein the lamellar silicate is selected from one or more of serpentine, hectorite, attapulgite, sericite and montmorillonite;
then, putting the phyllosilicate powder into a ball mill, and ball-milling for 12-24 hours at different rotating speeds of 500-1400rad/min to prepare nano phyllosilicate powder with the particle size of 20-100 nanometers;
then, mixing the nano layered silicate powder and a coupling agent according to the mass ratio of 1;
and finally, heating and drying the slurry after the reaction is finished to obtain the modified hydroxyl nano layered silicate powder.
The chromium-free environment-friendly passivation treatment solution for the surface of the zinc layer is further characterized in that the metal chelating agent is one or a mixture of more of sodium gluconate, EDTA sodium salt, HEDP sodium salt, citric acid and tannic acid; wherein the diluent is one or a mixture of ethanol, glycol, glycerol and tetraethoxysilane; wherein the dispersant is one or a mixture of more of stearate, polyoxyethylene octyl phenol ether-10, polyethylene glycol, polypropylene glycol, tween 20 and tween 80; wherein the thickening agent is one or a mixture of more of cellulose ether, polyacrylate and polyvinylpyrrolidone; wherein the pH regulator is one or a mixture of more of ammonia water, tartaric acid, acetic acid and triethanolamine.
A preparation method of chromium-free environment-friendly passivation treating fluid for a zinc layer surface comprises the following steps:
the method comprises the following steps: weighing the following raw material components in percentage by weight: 1-10% of special doped resin, 1-8% of coupling agent, 1-10% of aqueous nano sol, 0.5-5% of modified hydroxyl nano layered silicate powder, 0.1-3% of metal chelating agent, 5-20% of diluent, 0.5-3% of dispersant, 0.5-3% of thickening agent, 0.3-2% of pH regulator and the balance of water;
step two: adding the modified hydroxyl nano layered silicate powder and one third of the diluent by weight into a first reaction kettle, mixing to prepare first slurry, then placing the first reaction kettle into a constant-temperature water bath kettle at 60-80 ℃, keeping the temperature of the first slurry at 60-80 ℃, slowly dripping the coupling agent by weight into the first slurry, stirring for 20-50 minutes at the rotation speed of a stirring rotor of 900-1200rad/min, and dispersing for 5-20 minutes by using ultrasonic waves to prepare first mixed solution;
step three: adding the special doped resin and two thirds of diluent by weight into a second reaction kettle, mixing at room temperature to prepare second slurry, then sequentially adding the aqueous nano sol and the metal chelating agent by weight into the second slurry, stirring for 20-50 minutes at the rotation speed of a stirring rotor of 900-1200rad/min, and then dispersing for 10-30 minutes by using ultrasonic waves to prepare second mixed solution;
step four: adding the first mixed solution into the second mixed solution at the temperature of 50-80 ℃, fully and uniformly stirring, adding half weight of water, adding the dispersant and the thickening agent, stirring for 10-30 minutes at the rotating speed of a stirring rotor of 500-800rad/min, adding the PH regulator and the residual water to regulate the PH to be between 6 and 7, and preparing a third mixed solution;
step five: and keeping the temperature of the third mixed solution constant between 50 and 80 ℃, uniformly stirring for 50 to 80 minutes under the condition that the rotating speed of a stirring rotor is 600 to 1200rad/min, and finally performing ultrasonic dispersion for 20 to 60 minutes to prepare the chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer.
The invention discloses application of the chromium-free environment-friendly passivation treating fluid on the surface of a zinc layer, wherein the chromium-free environment-friendly passivation treating fluid on the surface of the zinc layer is uniformly coated on the surface of the zinc layer through a roller coating, dip coating or spraying process; the method comprises the steps of carrying out hydrolytic condensation on aqueous nano sol in the chromium-free environment-friendly passivation treatment solution on the surface of a zinc layer to form a three-dimensional cross-linked silicon-oxygen bond, reacting hydroxyl on organic silicon with hydroxyl on the surface of the zinc layer to form a bond by using a coupling agent under the coordination of a cross network structure formed by polycondensation of a special doped resin film-forming agent, modifying the surface of nano layered silicate by using the coupling agent, filling and wrapping the nano layered silicate on the surface of a three-dimensional mesh organic-inorganic composite passivation film, and detecting neutral salt mist of the passivation film for more than 360 hours.
Compared with the prior art, the invention has the following outstanding advantages.
(1) The invention provides a brand-new zinc layer surface chromium-free environment-friendly passivation treating fluid and a preparation technology thereof, innovating an inorganic-organic composite passivation process, initiatively utilizing a resin doping process in inorganic-organic composite passivation, embedding an organic high polymer material into inorganic SiO by using a special hybrid resin as a film forming agent and a coupling agent 2 In the reticular three-dimensional film layer, the reticular three-dimensional film layer is further filled and wrapped by the nano layered silicate, a brand new inorganic-organic composite passivation process is realized, the compatibility and stability of organic components and inorganic components in the passivation solution are improved, and the brand new chromium-free environment-friendly passivation treatment solution for the surface of the zinc layer is provided based on the new inorganic-organic composite passivation process, so that the novel passivation treatment solution has wide popularization and application prospects.
(2) The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer is an aqueous environment-friendly solution, does not contain chromium, molybdenum, manganese and national banned heavy metals, has the advantages of environmental protection and no emission, has good stability of forming a film on the surface of a zinc material, is suitable for production of various processes such as roller coating, dip coating, spray coating and the like, can be cured at normal temperature of about 1min after passivation, and has the advantages of simple operation and suitability for batch production and operation.
(3) The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer has the unique properties closely related to the specific components: the nano sol forms three-dimensional cross-linked silicon-oxygen bonds through hydrolytic condensation, under the coordination of a cross network structure formed by polycondensation of a special doped resin film forming agent, hydroxyl on organic silicon and hydroxyl on the surface of a zinc layer react to form bonds by using a coupling agent to form an organic-inorganic composite film, the binding force of a passivation film layer and a zinc layer matrix is enhanced, the surface of the nano layered silicate is modified by using the coupling agent, the nano layered silicate is filled and wrapped on the surface of the three-dimensional mesh organic-inorganic composite passivation film, the passivation film has excellent corrosion resistance, humidity resistance, heat resistance and weather resistance, and after the zinc layer is passivated, the neutral salt spray detection is longer than 360 hours.
Detailed Description
The following detailed description of the technical solutions of the present invention is provided to enable those skilled in the art to more clearly understand the present invention, but not to limit the scope of the present invention.
The invention provides a chromium-free environment-friendly passivation treating fluid for a zinc layer surface and a preparation method thereof, wherein the chromium-free environment-friendly passivation treating fluid for the zinc layer surface comprises the following components in percentage by mass: 1-10% of special doped resin, 1-8% of coupling agent, 1-10% of aqueous nano sol, 0.5-5% of modified hydroxyl nano layered silicate powder, 0.1-3% of metal chelating agent, 5-20% of diluent, 0.5-3% of dispersant, 0.5-3% of thickening agent, 0.3-2% of pH regulator and the balance of water.
Wherein the special doped resin is: one or a mixture of more of acrylate organic silicon hybrid resin, polyurethane organic silicon hybrid resin, epoxy organic silicon hybrid resin, silicone alkyne hybrid resin, organic silicon-inorganic silicon hybrid resin, titanium oxide modified MQ hybrid resin, acrylate modified polyurethane resin, alkyd organic silicon hybrid resin, silsesquioxane polyethylene silicon resin, polyester modified alkyd organic silicon hybrid resin, epoxy modified alkyd organic silicon hybrid resin, silane terminated polyether hybrid resin, styrene-acrylate resin, pure acrylate organic silicon hybrid resin, polyester modified acrylate organic silicon hybrid resin, acrylic acid modified alkyd organic silicon hybrid resin and organic silicon modified fluorocarbon resin.
Wherein the coupling agent is one or a mixture of more of a silane coupling agent and a bimetallic coupling agent. The coupling agent is preferably one or more selected from the group consisting of KH550, KH560, KH570, KH580, KH590, KH151 and TPM.
The water-based nano sol is one or a mixture of more of nano silicon dioxide, nano zirconium dioxide and nano titanium dioxide, and the particle size of the nano silicon dioxide, the nano zirconium dioxide and the nano titanium dioxide is 1-99nm.
The modified hydroxyl nano layered silicate powder is prepared by modifying one or a mixture of more of serpentine powder, hectorite powder, attapulgite powder, sericite powder and montmorillonite powder, the modification process can be based on common coupling modification, and the particle size of the modified hydroxyl nano layered silicate powder is preferably 20-100 microns. The preferable preparation method of the modified hydroxyl nano layered silicate powder comprises the following steps: firstly, the finished product is purchased or lamellar silicate (one or more of serpentine, hectorite, attapulgite, sericite and montmorillonite) is subjected to coarse crushing, airflow crushing, ball milling and screening to prepare lamellar silicate powder with the average particle size of less than 20 microns, and the lamellar silicate powder can also be directly purchased. Then the phyllosilicate powder with the average grain diameter less than 20 microns is put into a ball mill and is ball milled for 12 to 24 hours under different rotating speeds of 500 to 1400rad/min, and the nanometer phyllosilicate powder with the grain diameter of 20 to 100 nanometers is prepared. And then further modifying the nano layered silicate powder by using a coupling agent and tetraethoxysilane, specifically mixing the nano layered silicate powder and the coupling agent (a common silane coupling agent can be used) according to the mass fraction of 1 Mixture of ) After being mixed, the tetraethoxysilane is magnetically stirred for 40 minutes at the rotating speed of 300-600rad/min, is ultrasonically dispersed for 30 minutes and then is added into a reaction kettle to react at the temperature of 120 DEG CAnd finally heating and drying the slurry after the reaction is finished for 40 minutes to obtain the modified hydroxyl nano layered silicate powder with the particle size of 20-100 micrometers.
The metal chelating agent is one or a mixture of more of sodium gluconate, EDTA sodium salt, HEDP sodium salt, citric acid and tannin.
Wherein the diluent is one or more of ethanol, ethylene glycol, glycerol and ethyl orthosilicate
Wherein the dispersant is one or a mixture of more of stearate, polyoxyethylene octyl phenol ether-10, polyethylene glycol, polypropylene glycol, tween 20 and Tween 80.
Wherein the thickening agent is one or a mixture of more of cellulose ether, polyacrylate and polyvinylpyrrolidone.
Wherein the pH regulator is one or a mixture of more of ammonia water, tartaric acid, acetic acid and triethanolamine.
The invention further provides a preparation method of the chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer, which comprises the following steps:
the method comprises the following steps: weighing the following raw material components in percentage by weight: 1-10% of special doped resin, 1-8% of coupling agent, 1-10% of aqueous nano sol, 0.5-5% of modified hydroxyl nano layered silicate powder, 0.1-3% of metal chelating agent, 5-20% of diluent, 0.5-3% of dispersant, 0.5-3% of thickening agent, 0.3-2% of pH regulator and the balance (calculated by 100%) of water.
Step two: adding the modified hydroxyl nano layered silicate powder and one third of the diluent by weight into a first reaction kettle, mixing to prepare first slurry, then placing the first reaction kettle into a constant-temperature water bath kettle with the temperature of 60-80 ℃ (preferably 70 ℃), slowly dropwise adding the coupling agent by weight into the first slurry under the condition that the temperature of the first slurry is kept at 60-80 ℃ (preferably 70 ℃), stirring for 20-50 minutes (preferably 35 minutes) under the condition that the rotating speed of a stirring rotor is 900-1200rad/min, and then dispersing for 5-20 minutes (preferably 10 minutes) by ultrasonic waves to prepare a first mixed solution A.
Step three: adding the weight of the special doped resin and two thirds of the weight of the diluent into a second reaction kettle, mixing at room temperature to prepare second slurry, then sequentially adding the weight of the aqueous nano sol and the weight of the metal chelating agent into the second slurry, stirring for 20-50 minutes (preferably 30 minutes) under the condition of the rotation speed of a stirring rotor being 900-1200rad/min, and then dispersing for 10-30 minutes (preferably 20 minutes) by using ultrasonic waves to prepare a second mixed solution B.
Step four: adding the first mixed solution A into the second mixed solution B at the temperature of 50-80 ℃ (preferably 60 ℃), fully stirring uniformly, adding half weight of water, adding the dispersant and the thickener, stirring for 10-30 minutes (preferably 20 minutes) at the rotation speed of a stirring rotor of 500-800rad/min, adding the pH regulator and the water with the rest weight to regulate the pH to 6-7 to obtain a third mixed solution C, finally controlling the temperature of the third mixed solution C to be constant between 50-80 ℃, uniformly stirring for 50-80 minutes (preferably 60 minutes) at the rotation speed of the stirring rotor of 600-1200rad/min, and finally performing ultrasonic dispersion for 20-60 minutes (preferably 30 minutes) to obtain the chromium-free environment-friendly passivation treatment solution for the surface of the zinc layer.
In the above embodiments of the present invention, the materials used are not limited in the present invention, and may be commercially available as they are or prepared by a conventional method.
Compared with the prior art, the invention has the following outstanding advantages.
(1) The chromium-free environment-friendly passivation treating solution for the surface of the zinc layer is an aqueous environment-friendly solution, does not contain chromium, molybdenum, manganese and national banned heavy metals, has the advantages of environmental protection and no emission, has good stability of forming a film on the surface of a zinc material, is suitable for various processes such as roller coating, dip coating, spray coating and the like, can be cured at normal temperature of about 1min after passivation, and has the advantages of simple operation and suitability for batch production and operation.
(2) In the chromium-free environment-friendly passivation treatment liquid for the surface of the zinc layer, the water-based nano sol forms three-dimensional cross-linked silicon-oxygen bonds through hydrolytic condensation, the hydroxyl on the organic silicon and the hydroxyl on the surface of the zinc layer react to form bonds by using the coupling agent under the coordination of a cross network structure formed by polycondensation of a special doped resin film forming agent, so that an organic-inorganic composite film is formed, the bonding force between the passivation film layer and a zinc layer matrix is improved and enhanced, the surface of the nano layered silicate is modified by the coupling agent, so that the nano layered silicate is filled and wrapped on the surface of the three-dimensional mesh organic-inorganic composite passivation film, the passivation film has excellent corrosion resistance, humidity resistance and weather resistance, and the neutral salt spray detection is more than 360 hours after the zinc layer is passivated.
The present invention will be described in further detail with reference to specific examples.
The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer described in the first to fifth embodiments is an aqueous environment-friendly solution, and respectively comprises the following components in percentage by weight in the following table 1:
table 1 examples one to five examples the composition components of the chromium-free environmental passivation treating solution for zinc layer surface
| Ingredient Unit (g) | Example one | Example two | EXAMPLE III | Example four | EXAMPLE five |
| Special doped resins | 7.5 | 6 | 6.5 | 8 | 5.5 |
| Coupling agent | 2.4 | 1.9 | 1.4 | 3 | 1.2 |
| Aqueous nanosol | 5.5 | 6.5 | 6.2 | 5 | 7.5 |
| Modified nano-layered silicate | 2.5 | 1.5 | 2 | 3 | 1 |
| Metal chelating agents | 1 | 0.4 | 0.8 | 1.5 | 0.8 |
| Diluent | 20 | 11 | 13 | 16 | 15 |
| Dispersing agent | 1.4 | 1 | 1 | 1.5 | 0.8 |
| Thickening agent | 1.2 | 1.1 | 1.6 | 1.8 | 1.2 |
| PH regulator | 1 | 0.6 | 1 | 1.2 | 1 |
| Water (I) | 57.5 | 70 | 66.5 | 59 | 66 |
| In total (g) | 100 | 100 | 100 | 100 | 100 |
Examples one to five the preparation methods of the chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer are as follows (the preparation process of each example is the same, and the difference is only the content of each component):
the method comprises the following steps: the components corresponding to each example were weighed out respectively according to the weights in table 1: special doped resin, coupling agent, nano sol, nano layered silicate, metal chelating agent, pH regulator, diluent, dispersant, thickener and water.
Step two: adding the modified hydroxyl nano layered silicate powder and one third of diluent by weight into a first reaction kettle, mixing to prepare first slurry, then placing the first reaction kettle into a constant-temperature water bath kettle at 70 ℃, keeping the temperature of the first slurry at 70 ℃, slowly dripping the coupling agent by weight into the first slurry, stirring for 30 minutes at the rotation speed of a stirring rotor of 900-1200rad/min, and then dispersing for 10 minutes by ultrasonic waves to prepare a first mixed solution A.
Step three: adding the special doped resin and two thirds of diluent by weight into a second reaction kettle, mixing at room temperature to prepare second slurry, then sequentially adding the aqueous nano sol and the metal chelating agent by weight into the second slurry, stirring for 30 minutes under the condition of the rotating speed of a stirring rotor of 900-1200rad/min, and then dispersing for 20 minutes by using ultrasonic waves to prepare second mixed solution B.
Step four: adding the first mixed solution A into the second mixed solution B at the temperature of 60 ℃, fully and uniformly stirring, adding half weight of water, adding the dispersant and the thickener, stirring for 20 minutes at the rotation speed of a stirring rotor of 500-800rad/min, adding the pH regulator and the residual water to regulate the pH to 6-7 to obtain a third mixed solution C, finally controlling the temperature of the third mixed solution C to be constant at about 60 ℃, uniformly stirring for 60 minutes at the rotation speed of the stirring rotor of 600-1200rad/min, and finally performing ultrasonic dispersion for 30 minutes to obtain the environment-friendly passivation treating solution for the surface of the zinc layer corresponding to each embodiment of the invention.
Further to illustrate the outstanding technical effects of the invention, the chromium-free environment-friendly passivation treatment solution for the surface of the zinc layer prepared in the above embodiments is applied respectively, and the application effects are measured, specifically as follows:
the use method of the chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer prepared by the embodiments of the invention comprises the following steps:
the zinc impregnation test plate is produced by using various processes such as roller coating, dip coating, spray coating and the like, the chromium-free environment-friendly passivation treating solution prepared in each embodiment is uniformly coated and wrapped on the surface of the zinc layer of the zinc impregnation test plate for 1min, the using environment temperature of the solution is 0-35 ℃, and after coating, the zinc impregnation test plate is dried at the temperature of 50-100 ℃ for 20 min.
In order to further verify the gain effect of the chromium-free passivation composite coating prepared in each embodiment of the invention, the zinc impregnation test plate coated with the chromium-free environment-friendly passivation treatment solution on the surface of the zinc layer described in the embodiment 1-embodiment 5 is dried and then subjected to neutral salt spray 360-hour test rating, and the performance rating is shown in the following table 2:
table 2, the performance rating of the zinc layer surface chromium-free environmental passivation solution after being coated on the zincification test plate by roll coating, dip coating and spray coating
The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer provided by the embodiment of the invention has very good film forming stability on the surface of a zinc material, is suitable for various processes such as roller coating, dip coating and spray coating, can be cured at normal temperature of about 1min after passivation, and has the advantages of being simple to operate and suitable for batch production and operation.
Finally, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer is characterized by comprising the following components in percentage by mass: 1-10% of special doped resin, 1-8% of coupling agent, 1-10% of aqueous nano sol, 0.5-5% of modified hydroxyl nano layered silicate powder, 0.1-3% of metal chelating agent, 5-20% of diluent, 0.5-3% of dispersant, 0.5-3% of thickening agent, 0.3-2% of pH regulator and the balance of water;
the special doped resin is selected from: one or a mixture of more of acrylate silicone hybrid resin, polyurethane silicone hybrid resin, epoxy silicone hybrid resin, silicone alkyne hybrid resin, silicone-inorganic silicone hybrid resin, titanium oxide modified MQ hybrid resin, acrylate modified polyurethane resin, alkyd silicone hybrid resin, silsesquioxane polyethylene silicone resin, polyester modified alkyd silicone hybrid resin, epoxy modified alkyd silicone hybrid resin, silane terminated polyether hybrid resin, styrene-acrylate resin, pure acrylate silicone hybrid resin, polyester modified acrylate silicone hybrid resin, acrylic acid modified alkyd silicone hybrid resin and silicone modified fluorocarbon resin;
the modified hydroxyl nano layered silicate powder is prepared by modifying one or a mixture of more of serpentine, hectorite, attapulgite and sericite, and the specific preparation method comprises the following steps:
firstly, carrying out coarse crushing, airflow crushing, ball milling and screening treatment on lamellar silicate to obtain lamellar silicate powder with the average particle size of less than 20 microns, wherein the lamellar silicate is selected from one or more of serpentine, hectorite, attapulgite and sericite;
then, putting the phyllosilicate powder into a ball mill, and ball-milling for 12-24 hours at different rotating speeds of 500-1400rad/min to prepare nano phyllosilicate powder with the particle size of 20-100 nanometers;
then, mixing the nano layered silicate powder and a coupling agent according to the mass ratio of 1;
and finally, heating and drying the slurry after the reaction is finished to obtain the modified hydroxyl nano layered silicate powder.
2. The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer as claimed in claim 1, which is characterized by comprising the following components in percentage by mass: 5-10% of special doped resin, 1-4% of coupling agent, 5-10% of aqueous nano sol, 1-4% of modified hydroxyl nano layered silicate powder, 0.3-2% of metal chelating agent, 10-20% of diluent, 1-2% of dispersant, 1-2% of thickening agent, 0.3-2% of pH regulator and the balance of water.
3. The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer as claimed in claim 1, wherein the coupling agent is one or a mixture of silane coupling agent and bimetallic coupling agent.
4. The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer as claimed in claim 3, wherein the coupling agent is selected from one or a mixture of KH550, KH560, KH570, KH580, KH590, KH151 and TPM.
5. The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer as claimed in claim 1, wherein the aqueous nano sol is one or more of nano silicon dioxide, nano zirconium dioxide and nano titanium dioxide, and the particle size of the nano silicon dioxide, the nano zirconium dioxide and the nano titanium dioxide is 1-99nm.
6. The chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer as claimed in claim 1, wherein the metal chelating agent is one or a mixture of more of sodium gluconate, sodium EDTA, HEDP sodium salt, citric acid and tannic acid; wherein the diluent is one or a mixture of more of ethanol, glycol, glycerol and ethyl orthosilicate; wherein the dispersant is one or a mixture of more of stearate, polyoxyethylene octyl phenol ether-10, polyethylene glycol, polypropylene glycol, tween 20 and tween 80; wherein the thickening agent is one or a mixture of more of cellulose ether, polyacrylate and polyvinylpyrrolidone; wherein the pH regulator is one or a mixture of more of ammonia water, tartaric acid, acetic acid and triethanolamine.
7. A preparation method of the chromium-free environment-friendly passivation treating fluid for the surface of the zinc layer as defined in any one of claims 1 to 6 is characterized by comprising the following steps:
the method comprises the following steps: weighing the following raw material components in percentage by weight: 1-10% of special doped resin, 1-8% of coupling agent, 1-10% of aqueous nano sol, 0.5-5% of modified hydroxyl nano layered silicate powder, 0.1-3% of metal chelating agent, 5-20% of diluent, 0.5-3% of dispersant, 0.5-3% of thickening agent, 0.3-2% of pH regulator and the balance of water;
step two: adding the modified hydroxyl nano-layered silicate powder and one third of the diluent by weight into a first reaction kettle, mixing to prepare first slurry, then placing the first reaction kettle into a constant-temperature water bath kettle at 60-80 ℃, keeping the temperature of the first slurry at 60-80 ℃, slowly dripping the coupling agent by weight into the first slurry, stirring for 20-50 minutes at the rotation speed of a stirring rotor of 900-1200rad/min, and then dispersing for 5-20 minutes by using ultrasonic waves to prepare a first mixed solution;
step three: adding the special doped resin and two-thirds of diluent by weight into a second reaction kettle, mixing at room temperature to prepare second slurry, then sequentially adding the aqueous nano sol and the metal chelating agent by weight into the second slurry, stirring at the rotating speed of a stirring rotor of 900-1200rad/min for 20-50 minutes, and dispersing for 10-30 minutes by using ultrasonic waves to prepare second mixed solution;
step four: adding the first mixed solution into the second mixed solution at the temperature of 50-80 ℃, fully and uniformly stirring, adding half weight of water, adding the dispersant and the thickening agent with the weight, stirring for 10-30 minutes at the rotating speed of a stirring rotor of 500-800rad/min, adding the pH regulator with the weight and the water with the residual weight, and adjusting the pH value to 6-7 to prepare a third mixed solution;
step five: and keeping the temperature of the third mixed solution constant between 50 and 80 ℃, uniformly stirring for 50 to 80 minutes under the condition that the rotation speed of a stirring rotor is 600 to 1200rad/min, and finally performing ultrasonic dispersion for 20 to 60 minutes to prepare the chromium-free environment-friendly passivation treatment solution for the surface of the zinc layer.
8. The use of the chromium-free environment-friendly passivation treatment solution for the surface of the zinc layer as defined in any one of claims 1 to 6 or the chromium-free environment-friendly passivation treatment solution prepared by the preparation method as defined in claim 7 is characterized in that the chromium-free environment-friendly passivation treatment solution for the surface of the zinc layer is uniformly coated on the surface of the zinc layer by a roller coating, dip coating or spray coating process; the method comprises the steps of carrying out hydrolytic condensation on aqueous nano sol in the chromium-free environment-friendly passivation treatment solution on the surface of a zinc layer to form a three-dimensional cross-linked silicon-oxygen bond, reacting hydroxyl on organic silicon with hydroxyl on the surface of the zinc layer to form a bond by using a coupling agent under the coordination of a special doped resin film-forming agent polycondensation to form a cross network structure, forming an organic-inorganic composite film, modifying the surface of the nano layered silicate by using the coupling agent, filling and wrapping the nano layered silicate on the surface of a three-dimensional mesh organic-inorganic composite passivation film, and detecting neutral salt fog of the passivation film for more than 360 hours.
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| CN112517052B (en) * | 2020-12-07 | 2023-03-28 | 陕西天元智能再制造股份有限公司 | ZnCl 2 -H modified molecular sieve composite catalyst and preparation method and application thereof |
| CN112941498A (en) * | 2021-01-26 | 2021-06-11 | 东莞市卓越新材料科技有限公司 | Aluminum foil surface treatment process for aluminum plastic film |
| CN113690401B (en) * | 2021-10-26 | 2021-12-31 | 中南大学 | Zinc phosphate-silane composite passive film modified zinc metal negative electrode and preparation method and application thereof |
| CN114921775A (en) * | 2022-05-16 | 2022-08-19 | 浙江遂昌奥美化工科技有限公司 | Environment-friendly coating agent and preparation method thereof |
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