CN108315728B - Metal anticorrosion treating agent and application method thereof - Google Patents
Metal anticorrosion treating agent and application method thereof Download PDFInfo
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- CN108315728B CN108315728B CN201711396719.1A CN201711396719A CN108315728B CN 108315728 B CN108315728 B CN 108315728B CN 201711396719 A CN201711396719 A CN 201711396719A CN 108315728 B CN108315728 B CN 108315728B
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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
- C23C22/34—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 fluorides or complex fluorides
- C23C22/36—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 fluorides or complex fluorides containing also phosphates
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Abstract
The invention relates to the technical field of corrosion prevention, and particularly relates to a metal corrosion prevention treating agent, a metal corrosion prevention part and a preparation method thereof. A metal anticorrosion treating agent comprises the following raw materials, by weight, 0.1% -2% of metal villiaumite, 0.2% -3% of phosphate, 0.2% -2% of phosphoric acid, 0.2% -2% of high-molecular polymer and the balance of water; the pH value of the antiseptic treatment agent is 3-4. The metal villiaumite and the phosphate of the metal anticorrosion treating agent can form a compact anticorrosion protective layer on the surface of a metal base material under the action of a high molecular polymer, so that the effect of preventing the surface of the metal base material from being corroded is achieved, and the raw materials are good in environmental friendliness and good in anticorrosion effect. The application method of the metal anticorrosion treating agent disclosed by the invention has the advantages that the metal anticorrosion treating agent is directly coated on the surface of a metal substrate without being activated in advance and dried, the process is simple, the environmental friendliness is good, and the anticorrosion effect is good.
Description
Technical Field
The invention relates to the technical field of corrosion prevention, in particular to a metal corrosion prevention treating agent and an application method thereof.
Background
To reduce or prevent corrosion of the metal, the most common method is to apply a corrosion-resistant coating to the metal surface to isolate the corrosive medium from contacting the metal substrate. The existing metal surface corrosion prevention is mainly characterized in that chromate and the like are adopted to carry out chemical treatment on a metal base material, a layer of compact chemical passivation film is formed on the surface of the metal base material to achieve the purpose of protecting the metal, and the general process flow comprises the following steps: degreasing, washing, passivating, washing, drying and the like, the process is complex, and meanwhile, industrial wastewater containing heavy metal ions is generated, so that the environment is not environment-friendly.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a metal anticorrosion treating agent which is good in environmental protection property and good in anticorrosion effect.
The invention also aims to provide an application method of the metal anti-corrosion treatment agent, which is simple in process and convenient for industrial production.
One of the purposes of the invention is realized by the following technical scheme: a metal anticorrosion treating agent, which comprises the following raw materials in percentage by weight,
the pH value of the antiseptic treatment agent is 3-4.
The metal villiaumite provides fluorinion and metal ion, the fluorinion makes the metal anticorrosion treating agent of the invention stable, the metal ion forms a layer of compact protective layer on the surface of the metal substrate under the action of the high molecular polymer, namely the anticorrosion protective layer, the high molecular polymer has better viscosity, so that the formed anticorrosion protective layer is not easy to fall off from the surface of the metal substrate, and the better anticorrosion protection effect is achieved, if the content of the metal villiaumite is less than 0.1%, the anticorrosion performance of the anticorrosion protective layer further obtained by using the obtained metal anticorrosion treating agent is poorer, and if the content of the metal villiaumite is more than 2%, the problems of incomplete dissolution of the metal salt or over high concentration of the metal salt can be generated; if the content of the high molecular polymer is less than 0.2%, an anticorrosive protective layer with a required thickness cannot be easily formed on the surface of the metal substrate, so that the anticorrosive performance of the anticorrosive coating or the anticorrosive part provided by the invention cannot be achieved, and if the content of the high molecular polymer is more than 2%, the appearance of the protective layer obtained from the high molecular polymer is relatively cloudy, so that the appearance of the obtained anticorrosive part is obviously poor; the existence of phosphoric acid can adjust the pH value of the metal anticorrosion treating agent to 3-4, and the existence of a small amount of phosphoric acid can improve the viscosity of the surface of the high molecular polymer and the metal base material; when the pH value of the metal anticorrosion treating agent is more than 4, the corrosion resistance of an anticorrosion protective layer and a metal anticorrosion piece obtained by the metal anticorrosion treating agent is poor, so that the corrosion resistance of the anticorrosion protective layer or the metal anticorrosion piece provided by the invention cannot be achieved.
Preferably, the metal fluoride salt is one or more of zirconium fluoride, chromium fluoride and hafnium fluoride. According to the invention, the metal villiaumite is selected to be one or more of zirconium fluoride, chromium fluoride and hafnium fluoride, the solubility of the metal villiaumite in water is low, so that the introduction of excessive other metal ions on the metal surface is avoided, the solubility is low, a compact anticorrosion protective layer can be formed on the surface of a metal substrate under the action of a high molecular polymer, and more preferably, the metal villiaumite is chromium fluoride. More preferably, 0.1 to 0.3 weight percent of cerium fluoride can be added into the metal anticorrosion treating agent, and fluoride ions are further introduced, so that the stability of the metal anticorrosion treating agent is improved.
Preferably, the phosphate is one or more of zirconium phosphate, chromium phosphate and hafnium phosphate. The metal ions of the phosphate selected by the invention are consistent with those of the fluoride salt, so that other metal ions are avoided being introduced, the stability of the solution is reduced, and the metal fluoride salt, the phosphate and the phosphoric acid are used for being matched with a high molecular polymer to form a compact anticorrosive protective layer on the surface of a metal base material.
Preferably, the high molecular polymer is one or more of polytetrafluoroethylene, polyacrylate, epoxy resin, phenolic resin and polyimide. According to the invention, the high-molecular polymer is selected, so that the protective film can be quickly formed on the surface of the metal base material, and the protective film has strong adhesion with the metal base material and cannot fall off. More preferably, the high molecular polymer is prepared by compounding epoxy resin, phenolic resin and polyimide according to the mass ratio of 1-2:1-3: 1.
Preferably, the metal preservative treatment agent further comprises 0.05% -2.0% of a surfactant, wherein the surfactant is one or more of a nonionic surfactant, an anionic surfactant and a zwitterionic surfactant.
The nonionic surfactant in the invention is one or more of polyoxyethylene type nonionic surfactant, polyol type nonionic surfactant, alkylolamide type nonionic surfactant, fluorocarbon type nonionic surfactant, organosilicon type nonionic surfactant and modified organosilicon type nonionic surfactant; the anionic surfactant is one or more of carboxylate anionic surfactant, sulfonate anionic surfactant, sulfate anionic surfactant and phosphate anionic surfactant; the zwitterionic surfactant is one or more of amino acid type zwitterionic surfactant, betaine type zwitterionic surfactant and imidazoline type zwitterionic surfactant. According to the invention, by adding the surfactant, the high molecular polymer has better viscosity with metal villiaumite, phosphate and the surface of the metal base material, and a compact anticorrosion protective layer is further prepared on the surface of the metal base material. More preferably, the surfactant is a nonionic surfactant and an anionic surfactant which are compounded according to the weight ratio of 1-3:1, and the specific nonionic surfactant is a polyoxyethylene type nonionic surfactant, a polyol type nonionic surfactant and a fluorocarbon type nonionic surfactant which are compounded according to the mass ratio of 2-3:1-3: 1; the anionic surfactant is formed by compounding a carboxylate anionic surfactant and a phosphate anionic surfactant according to the mass ratio of 2-3: 1.
Preferably, the metal preservative treatment agent further comprises 0.5-3 wt% of polyethylene glycol, and the molecular weight of the polyethylene glycol is in the range of 400-2000-.
The surface hardening efficiency of the metal antiseptic treatment agent solution is reduced by adding polyethylene glycol, the solubility of the metal fluoride salt can be further regulated and controlled according to the molecular weight range and the weight percentage of the added polyethylene glycol, and the metal antiseptic treatment agent of the metal fluoride salt with the suitable solubility is obtained, more preferably, the molecular weight of the polyethylene glycol is 800-1200, and the adding amount of the polyethylene glycol is 0.8-1%.
The preparation method of the metal anticorrosion treating agent comprises the following steps:
(1) firstly, adding phosphate and phosphoric acid into water, and uniformly stirring;
(2) adding metal villiaumite into the solution obtained in the step (1), and uniformly stirring;
(3) adding polyethylene glycol into the solution obtained in the step (2), and uniformly stirring;
(4) and (4) adding a high molecular polymer and a surfactant into the solution obtained in the step (3), and uniformly stirring to obtain the metal anticorrosion treating agent.
Wherein, the temperature in the step (1) is 25-30 ℃, and the stirring speed is 500-1000 r/min; the temperature in the step (2) is 45-60 ℃, and the stirring speed is 1000-; the temperature in the step (3) is 50-65 ℃, and the stirring speed is 1000-; the temperature in the step 4) is 25-35 ℃, and the stirring speed is 800-. In the step (2), the temperature is properly raised, and the stirring speed is high, so that the improvement of the solubility of the metal villiaumite is facilitated; in the step (3), polyethylene glycol is added for further adjusting the solubility of the metal fluoride salt; in the step (3), the high molecular polymer is added, the temperature of the solution is reduced, and the stirring speed is reduced, so that the mixture of the high molecular polymer and the metal villiaumite and other substances is uniform, and the metal anticorrosion treating agent disclosed by the invention is favorable for forming a compact anticorrosion protective layer on the surface of a metal substrate.
The second purpose of the invention is realized by the following technical scheme: an application method of a metal anticorrosion treating agent comprises the steps of coating the metal anticorrosion treating agent on the surface of a metal base material, and forming an anticorrosion protective layer on the surface of the metal base material after drying.
The anti-corrosion protective layer is a coating obtained by drying the metal anti-corrosion treating agent disclosed by the invention, and the anti-corrosion protective layer is completely or partially free of water, and preferably completely free of water and other organic solvents. The anti-corrosion protective layer has good corrosion resistance. The anti-corrosion protection layer can have any thickness as required, for example, the thickness range can be 100-1000nm, or 200-800nm, or 300-600 nm.
Preferably, the coating process is as follows: one or more of dip coating, spray coating, roll coating, and brush coating. The metal anti-corrosion treatment agent can be coated on the surface of a metal base material only by a coating mode, and the metal anti-corrosion treatment agent is simple to operate, simple in equipment, low in production cost and suitable for production and popularization.
Preferably, the drying temperature is 150 ℃ to 250 ℃. The drying temperature of the invention can be selected to dry the metal anti-corrosion treatment agent coated on the metal base material in a short time, and can avoid the invalidation of high molecular polymers and the like in the raw materials, and the drying temperature is more preferably 150-200 ℃.
Preferably, the base material is one or more of a stainless steel base material, an aluminum base material and an aluminum alloy base material. More preferably, the substrate is an aluminum substrate, and the metal corrosion prevention treatment agent of the present invention is mainly used for treating a soft packaging film for a lithium battery.
Preferably, the surface of the metal substrate is cleaned with alcohol before the metal corrosion inhibitor is applied to the surface of the metal substrate. And removing grease or other pollutants on the surface of the metal substrate by using alcohol to prevent the formation of an anti-corrosion protective layer from being influenced.
The invention has the beneficial effects that: the metal villiaumite and the phosphate of the metal anticorrosion treating agent can form a compact anticorrosion protective layer on the surface of a metal base material under the action of a high molecular polymer, so that the effect of preventing the surface of the metal base material from being corroded is achieved, and the raw materials are good in environmental friendliness and good in anticorrosion effect.
The application method of the metal anticorrosion treating agent disclosed by the invention has the advantages that the metal anticorrosion treating agent is directly coated on the surface of a metal substrate without being activated in advance and dried, the process is simple, the environmental friendliness is good, and the anticorrosion effect is good.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The metal anticorrosion treating agent comprises the following raw materials in percentage by weight: 0.3% of zirconium fluoride, 0.6% of zirconium phosphate, 0.5% of phosphoric acid, 0.5% of polyacrylate and the balance of water; and brushing and coating the metal anticorrosion treating agent on the surface of an aluminum foil substrate, and drying at 180 ℃ for 5min to obtain the metal anticorrosion part of the embodiment.
Example 2
The metal anticorrosion treating agent comprises the following raw materials in percentage by weight: 2% of chromium fluoride, 3% of chromium phosphate, 2% of phosphoric acid, 2% of phenolic resin and the balance of water; and (3) coating the metal anticorrosion treating agent on the surface of a stainless steel substrate in a roll coating manner, and drying at 250 ℃ for 5min to obtain the metal anticorrosion part of the embodiment.
Example 3
The metal anticorrosion treating agent comprises the following raw materials in percentage by weight: 0.1% of hafnium fluoride, 0.2% of hafnium phosphate, 0.2% of phosphoric acid, 0.2% of polytetrafluoroethylene and the balance of water; and dip-coating the metal anticorrosion treating agent on the surface of an aluminum alloy substrate, and drying at 150 ℃ for 5min to obtain the metal anticorrosion part of the embodiment.
Example 4
The metal anticorrosion treating agent comprises the following raw materials in percentage by weight: 1% of chromium fluoride, 1.5% of chromium phosphate, 1.2% of phosphoric acid and 2% of high-molecular polymer, wherein the high-molecular polymer is prepared by compounding epoxy resin, phenolic resin and polyimide according to the mass ratio of 1:1:1, and the balance is water; and spraying the metal anticorrosion treating agent on the surface of a paint spraying base material, and drying at 180 ℃ for 5min to obtain the metal anticorrosion part of the embodiment.
Example 5
The metal anticorrosion treating agent comprises the following raw materials in percentage by weight: 0.3 percent of zirconium fluoride, 0.6 percent of zirconium phosphate, 0.5 percent of phosphoric acid, 0.5 percent of polyacrylate and 0.05 percent of surfactant, wherein the surfactant is a nonionic surfactant and an anionic surfactant which are compounded according to the weight ratio of 1:1, and the specific nonionic surfactant is a polyoxyethylene type nonionic surfactant, a polyhydric alcohol type nonionic surfactant and a fluorocarbon type nonionic surfactant which are compounded according to the mass ratio of 2:1: 1; the anionic surfactant is formed by compounding a carboxylate anionic surfactant and a phosphate anionic surfactant according to the mass ratio of 2:1, 0.5% of polyethylene glycol, the molecular weight range of the polyethylene glycol is 400-800, and the balance is water; and brushing and coating the metal anticorrosion treating agent on the surface of an aluminum foil substrate, and drying at 180 ℃ for 5min to obtain the metal anticorrosion part of the embodiment.
Example 6
The metal anticorrosion treating agent comprises the following raw materials in percentage by weight: 1% of chromium fluoride, 1.5% of chromium phosphate, 1.2% of phosphoric acid and 2% of high molecular polymer, wherein the high molecular polymer is prepared by compounding epoxy resin, phenolic resin and polyimide according to the mass ratio of 1:1:1, the surfactant is 2.0%, the surfactant is a nonionic surfactant and an anionic surfactant according to the weight ratio of 3:1, and the specific nonionic surfactant is prepared by compounding a polyoxyethylene type nonionic surfactant, a polyalcohol type nonionic surfactant and a fluorocarbon type nonionic surfactant according to the mass ratio of 3:3: 1; the anionic surfactant is formed by compounding a carboxylate anionic surfactant and a phosphate anionic surfactant according to the mass ratio of 3:1, the polyethylene glycol accounts for 3%, the molecular weight range of the polyethylene glycol is 800-2000, and the balance is water; and spraying the metal anticorrosion treating agent on the surface of a paint spraying base material, and drying at 180 ℃ for 5min to obtain the metal anticorrosion part of the embodiment.
Example 7
The metal corrosion-resistant part obtained in the example 1 is compounded with nylon and CPP to prepare the aluminum-plastic composite film for the lithium battery.
The invention mainly tests and evaluates the corrosion resistance of the metal corrosion-resistant part through the salt spray resistance.
The metal corrosion-resistant parts in examples 1 to 6 were subjected to a salt spray test by cutting a "x" on the surface of the metal corrosion-resistant part with a blade, placing the cut pieces in a salt spray box, and performing the salt spray test.
Salt spray testing was performed according to ASTM B117. And taking out every 10 hours, cleaning the steel plate by using clean water, drying the steel plate by using compressed air, and visually observing whether the corrosion of more than 2mm exists along the edge of the X-shaped cut, whether the anticorrosive coating has rusty spots or not, or whether the anticorrosive coating peels off. If any one of the conditions occurs, stopping the test and recording the total test time; if none of the above occurs, the salt spray test is continued until the total test time reaches 1000 hours and the total test time is recorded as 1000 hours. For example, if there was no peeling after 30 hours of removal and peeling after 40 hours of removal, the salt spray resistance time was recorded as 40 hours. If the measured time of the salt spray resistance of a certain anticorrosive part is more than or equal to 250 hours, the anticorrosive part has good salt spray resistance, and the specific test effect is shown in table 1.
Table 1, results of testing the milk salt spray performance of the metal corrosion inhibitors of examples 1-6.
As can be seen from Table 1, the anti-salt fog time of the anti-corrosion metal parts prepared according to the embodiments 1 to 6 can reach more than 250 hours and can also reach 800 hours at least, so that the anti-corrosion metal parts related to the embodiments 1 to 6 have good anti-salt fog performance and good anti-corrosion effect.
After the aluminum-plastic film obtained in example 7 is corroded by the aqueous electrolyte at 85 ℃ for 48 hours, the bonding strength between the aluminum foil and the CPP is still good, which shows that the aluminum-plastic film obtained in example 7 has a good HF (hydrogen fluoride) prevention effect.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (6)
1. A metal corrosion prevention treatment agent is characterized in that: comprises the following raw materials in percentage by weight,
the balance of water;
the pH value of the antiseptic treatment agent is 3-4;
the metal fluoride salt is one or more of zirconium fluoride, chromium fluoride and hafnium fluoride;
the metal ions of the phosphate are identical to the metal ions of the metal fluoro salt;
the high molecular polymer is prepared by compounding epoxy resin, phenolic resin and polyimide according to the mass ratio of 1-2:1-3: 1;
the metal preservative treatment agent also comprises 0.5-3 wt% of polyethylene glycol, and the molecular weight range of the polyethylene glycol is 400-2000-.
2. The metal corrosion preventive treatment agent according to claim 1, characterized in that: the metal preservative treatment agent also comprises 0.05-2.0 wt% of surfactant, wherein the surfactant is one or more of nonionic surfactant, anionic surfactant and zwitterionic surfactant.
3. An application method of a metal anticorrosion treating agent is characterized in that: the metal corrosion prevention treatment agent according to any one of claims 1 to 2 is applied to the surface of a metal substrate, and after drying, a corrosion prevention protective layer is formed on the surface of the metal substrate.
4. The method of using the metal corrosion preventive treatment agent according to claim 3, characterized in that: the coating process comprises the following steps: one or more of dip coating, spray coating, roll coating, and brush coating.
5. The method of using the metal corrosion preventive treatment agent according to claim 3, characterized in that: the drying temperature is 150-250 ℃.
6. The method of using the metal corrosion preventive treatment agent according to claim 3, characterized in that: before coating the metal anti-corrosion treatment agent on the surface of the metal base material, cleaning the surface of the metal base material by using alcohol.
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| CN113481494A (en) * | 2021-07-01 | 2021-10-08 | 深圳市中科墨磷科技有限公司 | Metal material anticorrosion treating agent and application thereof |
| CN115101862A (en) * | 2022-06-10 | 2022-09-23 | 江苏睿捷新材料科技有限公司 | Corrosion-resistant metal-plastic composite film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157336A (en) * | 1995-11-20 | 1997-08-20 | 日本涂料公司 | Surface treatment composition, surface treatment solution and surface treatment method for aluminum and its alloys |
| CN103060788A (en) * | 2013-01-31 | 2013-04-24 | 宝山钢铁股份有限公司 | Single-sided electro-galvanized non-chrome surface treatment steel plate for fuel tank and surface treating agent |
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| JP5721307B2 (en) * | 2007-10-17 | 2015-05-20 | 関西ペイント株式会社 | Multi-layer coating method and coated article |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157336A (en) * | 1995-11-20 | 1997-08-20 | 日本涂料公司 | Surface treatment composition, surface treatment solution and surface treatment method for aluminum and its alloys |
| CN103060788A (en) * | 2013-01-31 | 2013-04-24 | 宝山钢铁股份有限公司 | Single-sided electro-galvanized non-chrome surface treatment steel plate for fuel tank and surface treating agent |
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Effective date of registration: 20230920 Address after: 411100 High tech Industrial Development Zone, Shaoshan City, Xiangtan City, Hunan Province (Building 2, No. 28 Jingui Road) Patentee after: Hunan Besterui New Material Technology Co.,Ltd. Address before: 410600 No. 020 Jinshui West Road, Ningxiang High tech Industrial Park, Changsha City, Hunan Province Patentee before: HUNAN XINNENG NEW MATERIAL CO.,LTD. |