CN115558915B - Magnesium alloy high corrosion-resistant hydrophobic sealing agent and preparation method thereof - Google Patents
Magnesium alloy high corrosion-resistant hydrophobic sealing agent and preparation method thereof Download PDFInfo
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- CN115558915B CN115558915B CN202211219869.6A CN202211219869A CN115558915B CN 115558915 B CN115558915 B CN 115558915B CN 202211219869 A CN202211219869 A CN 202211219869A CN 115558915 B CN115558915 B CN 115558915B
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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
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention relates to the technical field of alloy surface treatment, in particular to a magnesium alloy high corrosion-resistant hydrophobic sealing agent and a preparation method thereof. The magnesium alloy high corrosion-resistant hydrophobic sealing agent comprises water-based resin, a silicon-containing reagent, a silane coupling agent and an alkaline compound, and the components are scientifically compounded according to specific dosage to obtain a sealing agent product with excellent corrosion resistance and antifouling performance. The polymer film obtained by the method has the advantages of excellent salt spray resistance, corrosion resistance and the like, uniform appearance of the film, no abnormal color, no adverse effect on the conductivity of the product, water-based components as main raw materials and excellent environmental protection performance.
Description
Technical Field
The invention relates to the technical field of alloy surface treatment, in particular to a magnesium alloy high corrosion-resistant hydrophobic sealing agent and a preparation method thereof.
Background
The magnesium alloy is an alloy which is formed by adding other elements based on magnesium, and has the characteristics of low density, high strength, good shock absorption performance, good electric conduction and heat conduction performance, good technological performance and the like. The density of the magnesium alloy is only 1.7kg/m 3 Is 2/3 of aluminum, 1/4 of steel, has higher strength than aluminum alloy and steel, has specific rigidity close to that of aluminum alloy and steel, and is the lightest metal structural material. Therefore, the magnesium alloy has wide development prospect in the fields of electronic products, automobiles, aerospace and the like which need high-specific-strength metal materials.
But magnesium metal has very active property, low electrode potential and extremely high chemical activity and electrochemical activity. Magnesium and magnesium alloy surfaces are exposed to air and are easily corroded by the atmosphere; and when magnesium and magnesium alloy are contacted with other metals, galvanic corrosion occurs as an anode. Therefore, the excellent performance of the magnesium alloy is not fully exerted, and the industrial application of the magnesium alloy is severely limited. Therefore, the magnesium alloy is of great significance in improving the corrosion resistance and beautifying and decorating functions by proper surface treatment.
Common methods for corrosion prevention of magnesium alloy surfaces include chemical conversion coating, anodic oxidation, micro-arc oxidation, electroplating, electrophoresis and the like, wherein the chemical conversion coating treatment is the treatment method with the simplest process and the lowest cost. The traditional chemical conversion treatment technology mainly adopts hexavalent chromium ions to form a layer of compact protective film on the surface of the magnesium alloy, can effectively protect the base material from corrosion, and has low cost, simple process and wide application. Hexavalent chromium ions are toxic and highly carcinogenic, severely damaging the ecological environment and human health. Therefore, the green and environment-friendly magnesium alloy treatment process is an important research direction. A protective layer with high corrosion resistance and hydrophobicity is formed on the surface of the magnesium alloy product, so that the corrosion of the magnesium alloy can be effectively delayed, the reject ratio of the product is reduced, and the economic benefit is improved.
Although the prior art has researches on the magnesium alloy surface corrosion prevention technology, the prior art has the defects of unsatisfactory corrosion prevention effect, high production cost, complex process, poor environment-friendly performance of raw materials and the like, so that the researches on the magnesium alloy surface corrosion prevention technology are still needed, and the application prospect of the magnesium alloy material is further expanded.
Disclosure of Invention
The invention aims to provide a magnesium alloy high corrosion-resistant hydrophobic sealing agent, which comprises water-based resin, a silicon-containing reagent, a silane coupling agent and an alkaline compound, wherein the components are scientifically compounded according to specific dosage to obtain a sealing agent product with excellent corrosion resistance and antifouling performance. The polymer film obtained by the method has the advantages of excellent salt spray resistance, corrosion resistance and the like, uniform appearance of the film, no abnormal color, no adverse effect on the conductivity of the product, water-based components as main raw materials and excellent environmental protection performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the high corrosion-resistant hydrophobic sealing agent for the magnesium alloy is characterized by comprising the following components in parts by weight: 30-60 parts of aqueous resin, 10-20 parts of silane coupling agent, 5-10 parts of silicon-containing reagent, 20-40 parts of alkaline compound and the balance of water.
Preferably, the composition comprises the following components in parts by weight: 30 parts of aqueous resin, 10 parts of silane coupling agent, 5 parts of silicon-containing reagent, 20 parts of alkaline compound and the balance of water.
Preferably, the composition comprises the following components in parts by weight: 60 parts of aqueous resin, 20 parts of silane coupling agent, 10 parts of silicon-containing reagent, 40 parts of alkaline compound and the balance of water.
Preferably, the composition comprises the following components in parts by weight: 50 parts of aqueous resin, 15 parts of silane coupling agent, 8 parts of silicon-containing reagent, 35 parts of alkaline compound and the balance of water.
Further, the aqueous resin is selected from one or more of aqueous organic silicon resin, aqueous fluorocarbon resin and aqueous phenolic resin.
Further, the silane coupling agent is selected from one or more of gamma-aminopropyl triethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane and N-aminoethyl-gamma-aminopropyl trimethoxysilane.
Further, the silicon-containing reagent is selected from one or more of nano silica sol, water-based silicone oil and water-based nano silica.
Further, the alkaline compound is selected from one or more of triethanolamine, monoethanolamine and ammonia monohydrate.
In addition, the application also provides a use method of the magnesium alloy high corrosion-resistant hydrophobic sealing agent, which is characterized in that a magnesium alloy product is placed into a soaking solution to be soaked for 6-10 minutes; the soaking solution is prepared by adding water into the magnesium alloy high corrosion-resistant hydrophobic sealing agent, wherein the mass percentage of the magnesium alloy high corrosion-resistant hydrophobic sealing agent in the soaking solution is 10% -20%.
Further, after the magnesium alloy product is placed into the soaking liquid for soaking, the magnesium alloy product is placed into an oven for baking at the constant temperature of 150 ℃ for 15-20 minutes.
The invention has the beneficial effects that:
the water-based resin can be attached with a layer of hydrophobic protective film on the surface of the magnesium alloy, and the silicon-containing reagent assists in forming the film, so that the performance of the polymer film is further improved, microcracks and gaps on the surface of the magnesium alloy can be filled, the silane coupling agent can improve the compatibility of the water-based resin and the silicon-containing reagent, ensure that each component in the system plays a corresponding role, and the alkaline compound adjusts the pH value to be neutral so as to avoid unnecessary corrosion to a base material caused by overlarge or overlarge pH value. According to the invention, by selecting a proper amount of components for scientific collocation, the inhibition effect among the components is avoided, so that the finally obtained polymer film has excellent salt spray resistance, corrosion resistance and other performances, the appearance of the film is uniform and has no abnormal color, the conductivity of the product is not adversely affected, the main raw materials are all water-based components, and the environment-friendly performance is excellent.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The invention is further described in the following detailed description.
Example 1
The magnesium alloy high corrosion-resistant hydrophobic sealing agent comprises the following components in parts by weight: 30 parts of aqueous organic silicon resin, 10 parts of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, 5 parts of aqueous silicone oil, 20 parts of triethanolamine and 935 parts of water.
The preparation method of the sealing agent comprises the following steps: adding water, water-based organic silicon resin, water-based silicone oil and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into a stirring kettle in sequence, stirring for 20-30 minutes until the system is uniform and transparent, adding triethanolamine, regulating the pH to 6.5-7.5, and discharging.
Example 2
The magnesium alloy high corrosion-resistant hydrophobic sealing agent comprises the following components in parts by weight: 60 parts of aqueous fluorocarbon resin, 20 parts of gamma-aminopropyl triethoxysilane, 10 parts of nano silica sol, 40 parts of monoethanolamine and 870 parts of water.
The preparation method of the sealing agent comprises the following steps: adding water, water-based fluorocarbon resin, nano silica sol and gamma-aminopropyl triethoxysilane into a stirring kettle in sequence, stirring for 20-30 minutes until the system is uniform and transparent, adding monoethanolamine to regulate pH to 6.5-7.5, and discharging to obtain the product.
Example 3
The magnesium alloy high corrosion-resistant hydrophobic sealing agent comprises the following components in parts by weight: 50 parts of aqueous phenolic resin, 15 parts of N-aminoethyl-gamma-aminopropyl trimethoxysilane, 8 parts of aqueous nano silicon dioxide, 35 parts of ammonia monohydrate and 892 parts of water.
The preparation method of the sealing agent comprises the following steps: adding water, water-based phenolic resin, water-based nano silicon dioxide and N-aminoethyl-gamma-aminopropyl trimethoxysilane into a stirring kettle in sequence, stirring for 20-30 minutes until the system is uniform and transparent, adding ammonia monohydrate to adjust the pH to 6.5-7.5, and discharging to obtain the aqueous phenolic resin.
Example 4
The magnesium alloy high corrosion-resistant hydrophobic sealing agent comprises the following components in parts by weight: 35 parts of water-based organic silicon resin, 13 parts of N-aminoethyl-gamma-aminopropyl trimethoxy silane, 6 parts of nano silica sol, 25 parts of monoethanolamine and 921 parts of water.
The preparation method of the sealing agent comprises the following steps: adding water, water-based organic silicon resin, nano silica sol and N-aminoethyl-gamma-aminopropyl trimethoxy silane into a stirring kettle in sequence, stirring for 20-30 minutes until the system is uniform and transparent, adding monoethanolamine to regulate the pH value to 6.5-7.5, and discharging to obtain the nano-silica gel.
Example 5
The magnesium alloy high corrosion-resistant hydrophobic sealing agent comprises the following components in parts by weight: 45 parts of aqueous fluorocarbon resin, 14 parts of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, 7 parts of aqueous nano silicon dioxide, 30 parts of ammonia monohydrate and 904 parts of water.
The preparation method of the sealing agent comprises the following steps: adding water, water-based fluorocarbon resin, water-based nano silicon dioxide and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into a stirring kettle in sequence, stirring for 20-30 minutes until the system is uniform and transparent, adding ammonia monohydrate to adjust the pH to 6.5-7.5, and discharging to obtain the nano-silica gel.
TABLE 1 examples 1-5 Components and amounts
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Aqueous silicone resin | 30 | 35 | |||
| Aqueous fluorocarbon resin | 60 | 45 | |||
| Aqueous phenolic resin | 50 | ||||
| Gamma-aminopropyl triethoxy silane | 20 | ||||
| Gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane | 10 | 14 | |||
| N-aminoethyl-gamma-aminopropyl trimethoxysilane | 15 | 13 | |||
| Nano silica sol | 10 | 6 | |||
| Water-based silicone oil | 5 | ||||
| Aqueous nanosilica | 8 | 7 | |||
| Triethanolamine salt | 20 | ||||
| Monoethanolamine | 40 | 25 | |||
| Ammonia monohydrate | 35 | 30 | |||
| Water and its preparation method | 935 | 870 | 892 | 921 | 904 |
Aqueous silicone resin: COATOSIL DRI, available from Shanghai Kaiju New Material technologies Co., ltd;
aqueous fluorocarbon resin: DF-M05, available from Shandong Jiayi chemical technology Co., ltd;
aqueous phenolic resin: HY654546, available from Shandong Haohao New Material Co., ltd;
gamma-aminopropyl triethoxysilane: KH550, available from atactic first pass chemical technology limited;
gamma- (2, 3-glycidoxy) propyltrimethoxysilane: KH560, available from atactic first pass chemical technology limited;
n-aminoethyl-gamma-aminopropyl trimethoxysilane: KH792, available from wuhan pluronic biotechnology limited;
nano silica sol: WV33, available from aku norbeol;
aqueous silicone oil: ST101, available from the intellect silicone materials limited in the bergamot;
aqueous nanosilica: PH-40, available from Shenzhen Tongtai chemical technology Co., ltd.
Comparative example 1
The magnesium alloy high corrosion-resistant hydrophobic sealing agent is different from the embodiment 1 in that: comparative example 1 does not contain gamma- (2, 3-glycidoxy) propyltrimethoxysilane, the aqueous silicone resin is 35 parts, and the aqueous silicone oil is 10 parts.
Comparative example 2
The magnesium alloy high corrosion-resistant hydrophobic sealing agent is different from the embodiment 1 in that: comparative example 2 contains no aqueous silicone resin, 25 parts of gamma- (2, 3-glycidoxy) propyltrimethoxysilane and 20 parts of aqueous silicone oil.
Comparative example 3
The magnesium alloy high corrosion-resistant hydrophobic sealing agent is different from the embodiment 1 in that: comparative example 3 contains no aqueous silicone oil, 32.5 parts of aqueous silicone resin and 12.5 parts of gamma- (2, 3-glycidoxy) propyltrimethoxysilane.
Comparative example 4
The magnesium alloy high corrosion-resistant hydrophobic sealing agent is different from the embodiment 1 in that: comparative example 4a non-aqueous epoxy resin was used instead of an aqueous silicone resin.
Comparative example 5
The magnesium alloy high corrosion-resistant hydrophobic sealing agent is different from the embodiment 1 in that: comparative example 5 a non-aqueous polyurethane resin was used instead of an aqueous silicone resin.
Comparative example 6
The magnesium alloy high corrosion-resistant hydrophobic sealing agent is different from the embodiment 1 in that: comparative example 6 a non-aqueous silicone resin was used instead of an aqueous silicone resin.
Comparative example 7: the sample plate to be tested described in the application is processed by adopting the product and the method of the example 1 of the Chinese invention patent CN 112029394A.
Comparative example 8: the sample plate to be tested described in the application is processed by adopting the product and the method of the example 1 of the Chinese invention patent CN 114058230A.
Comparative example 9
The magnesium alloy high corrosion-resistant hydrophobic sealing agent is different from the embodiment 1 in that: comparative example 9 uses sodium carbonate instead of triethanolamine.
Comparative example 10
The magnesium alloy high corrosion-resistant hydrophobic sealing agent is different from the embodiment 1 in that: comparative example 10 uses sodium hydroxide instead of triethanolamine.
TABLE 2 example 1, comparative examples 1-6 Components and amounts
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 9 | Comparative example 10 | |
| Aqueous silicone resin | 30 | 35 | 32.5 | 30 | 30 | ||||
| Non-aqueous epoxy resin | 30 | ||||||||
| Non-aqueous polyurethane resin | 30 | ||||||||
| Nonaqueous silicone resins | 30 | ||||||||
| Gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane | 10 | 25 | 12.5 | 10 | 10 | 10 | 10 | 10 | |
| Water-based silicone oil | 5 | 10 | 20 | 5 | 5 | 5 | 5 | 5 | |
| Triethanolamine salt | 20 | 20 | 20 | 20 | 20 | 20 | 20 | ||
| Sodium carbonate | 20 | ||||||||
| Sodium hydroxide | 20 | ||||||||
| Water and its preparation method | 935 | 935 | 935 | 935 | 935 | 935 | 935 | 935 | 935 |
Non-aqueous epoxy resin: e-51, obtained from Jining Sanshi biotechnology Co., ltd;
non-aqueous polyurethane resin: HKW-3100, available from Jining Tang Yi chemical Co., ltd;
nonaqueous silicone resin: SH-9601, available from Hubei New Sihai chemical Co., ltd.
Performance testing
The magnesium alloy sample plate is cleaned by water and is placed into soaking solutions prepared by the sealing agents of the examples and the comparative examples to be soaked for 6 minutes, wherein the soaking temperature is normal temperature, the soaking solutions are prepared by adding water into the sealing agents of the examples and the comparative examples, and the mass percentage of each sealing agent in the soaking solutions is 20%. And (3) placing the soaked sample plate into an oven, and baking for 15 minutes at a constant temperature of 150 ℃ to obtain a sample plate to be tested. The following performance tests are carried out on the sample plate to be tested:
(1) Salt spray resistance test
And placing the sample plate to be tested in a salt spray test box, and recording the time when the sample plate is obviously oxidized. The test is based on GB/T10125-2021 standard, the set condition is that the temperature of a salt spray test box is 35+/-1 ℃, saturated air is 47+/-1 ℃, the salt water concentration is 5+/-l%, the pH is 6.5-7.2, and the spraying amount is 1-2 ml/80 square cm/h.
(2) Sulfur dioxide resistance test
Reference is made to GB/T9789-2008.
(3) Corrosion resistance test
And testing the corrosion resistance of the sample to be tested by adopting a titration method, uniformly selecting 5 points on each sample plate to be tested for titration, observing the color change of a substrate at the titration position, and recording the time required for color change.
(4) Conductivity test
The conductivity is tested by using a microohm meter, two electrodes are contacted with the surface of a sample plate to be tested, two points are taken at any position on the surface of the sample for measurement, the total test is carried out for 5 times, and the average value is taken; in the test, the electrode area was 1cm 2 The electrode pressure was 1.4MPa.
The performance test results are shown in tables 3 and 4.
TABLE 3 Table 3
| Test item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Salt mist/h resistance | 760 | 745 | 745 | 750 | 745 |
| Sulfur dioxide/h resistance | 590 | 570 | 575 | 575 | 580 |
| Corrosion resistance/s | 25 | 23 | 24 | 24 | 23 |
| Conductivity test/mΩ | 6 | 7 | 6 | 7 | 7 |
| Appearance of | Uniform and free of different colors | Uniform and free of different colors | Uniform and free of different colors | Uniform and free of different colors | Uniform and free of different colors |
As shown in the results of Table 3, the sealing agent of the invention has excellent salt spray resistance, sulfur dioxide resistance and corrosion resistance, wherein the time for no obvious oxidation phenomenon in the salt spray test can reach more than 745h, the sulfur dioxide resistance time is more than 570h, the color change time of the corrosion resistance test base material is more than 23s, the conductivity of the sample plate coated with the sealing agent is good, the appearance is uniform and has no abnormal color, and the appearance of the product is not affected.
TABLE 4 Table 4
| Test item Order of (A) | Examples 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 |
| Salt mist resistance- h | 760 | 425 | 130 | 455 | 410 | 430 | 480 | 470 | 415 | 605 | 620 |
| Dioxygen resistance Sulfur conversion/h | 590 | 305 | 105 | 320 | 310 | 315 | 365 | 350 | 290 | 490 | 505 |
| Corrosion resistance- s | 25 | 8 | 3 | 10 | 8 | 9 | 14 | 12 | 7 | 11 | 13 |
| Conductivity of conductive material Test/m Ω | 6 | 19 | 34 | 16 | 17 | 16 | 13 | 15 | 20 | 12 | 12 |
| Appearance of | The uniformity of the product is achieved, no abnormal color | The uniformity of the product is achieved, no abnormal color | The non-uniformity of the particles is achieved, poor hardness | The uniformity of the product is achieved, no abnormal color | The uniformity of the product is achieved, no abnormal color | The uniformity of the product is achieved, no abnormal color | The uniformity of the product is achieved, no abnormal color | The uniformity of the product is achieved, no abnormal color | The uniformity of the product is achieved, no abnormal color | The uniformity of the product is achieved, no abnormal color | The uniformity of the product is achieved, no abnormal color |
As can be seen from the test results in Table 4, the aqueous resin, the coupling agent, and the silicon-containing agent are essential for the excellent effect of the blocking agent of the present invention. The reason why the comparative example 1 contains no coupling agent, contains both aqueous resin and siliceous agent, and has a remarkable difference in various properties from example 1 is probably because, although the aqueous resin can form a polymer film on the surface of the sample plate, the siliceous agent also has a certain auxiliary film-forming effect, but because of the lack of bridging effect of the coupling agent, the aqueous resin has relatively poor compatibility with siliceous agent, and it is difficult to fully exert the respective property effects in a unified system, so the result of the property test of the comparative example 1 without the coupling agent is even worse than that of the comparative example 3 containing the aqueous resin without the siliceous agent; from the above, it is clear that the comparative example 2 contains no aqueous resin and contains a coupling agent and a silicon-containing agent, and that the silicon-containing agent only plays an auxiliary film-forming role in the system, and in the case of the absence of an aqueous resin as a main film-forming component, a relatively dense polymer film cannot be formed only by the silicon-containing agent and the coupling agent, and the resulting film has problems of poor uniformity and low hardness, and cannot be put into use; comparative example 3 does not contain a siliceous agent, contains an aqueous resin and a coupling agent, and although the lack of the siliceous agent can avoid the problem of poor compatibility with the aqueous resin, it also lacks the auxiliary film-forming action of the siliceous agent, so that the performance test results of comparative example 3 are not significantly different from those of comparative example 1. The embodiment 1 contains the water-based resin, the coupling agent and the silicon-containing reagent, the compatibility of each component of the system is good, the excellent performance of each component is facilitated, and the coupling agent and the silicon-containing reagent can fill microcracks and gaps on the surface of the magnesium alloy, so that the corrosion resistance of the magnesium alloy after the surface treatment is obviously improved.
Comparative examples 4 to 6 each use a non-aqueous resin instead of the aqueous resin in example 1, and as can be seen from the test results in Table 4, excellent product properties cannot be obtained by using the non-aqueous resin in the present invention. It is possible that the non-aqueous resin raw material contains a relatively large amount of organic solvent, so that the resin and the silicon-containing reagent of the invention are not well mutually soluble, and the non-aqueous resin is generally relatively large in viscosity, poor in dispersibility in the system of the invention, and possibly excessively aggregated in a certain area of the surface of the sample plate, so that the polymer film is not uniformly distributed, and the performance test result is poor. According to the invention, the aqueous resin is added according to the characteristics of a component system, so that all components are well compatible, the aqueous resin forms a high polymer film, the silicon-containing reagent can further improve the film forming effect, and can fill microcracks and gaps on the surface of the magnesium alloy, and the performances of salt spray resistance, corrosion resistance and the like are excellent. In addition, it was found that the performance of example 1 using the aqueous silicone resin was relatively better than that of examples 2 to 5 using other aqueous resins, probably because the aqueous silicone resin and the silicon-containing agent were of the same silicon-based composition and the compatibility therebetween was better, and it was also seen from the performance test results of comparative example 6 that although the non-aqueous resin was used in comparative example 6, the performance test results were inferior to those of the examples using the aqueous resin, but the final performance was slightly better than those of comparative examples 4 and 5 using other non-aqueous resins because the silicone resin was used.
Comparative example 7 is example 1 of CN112029394a, which relates to a system for forming a magnesium-lithium alloy surface corrosion-resistant coating, using a high-density ductile resin, a lithium salt inorganic substance, a sheet-like shielding material to form a corrosion-resistant primer, using a high-density resin to form a sealing varnish, and then using the corrosion-resistant primer and the sealing varnish in sequence to spray and cure a sample plate. From the results of the performance test, it is possible that the comparative example 7 adopts two film-forming sealing treatments, and the performances of salt spray resistance, corrosion resistance and the like are slightly better than those of most comparative examples, but a significant difference still exists compared with the embodiment of the invention. In addition, as the comparative example 7 adopts two film forming sealing treatments, the complex process degree, the parameter control difficulty and the like are increased, and the actual production and application difficulty is higher.
Comparative example 8 is example 1 of CN114058230a, which relates to an anticorrosion method for an aluminum alloy surface, adding various resins and organic solvents, carbon fibers, copper oxide, and the like, preparing an anticorrosion soak solution by heating and stirring or melting, then soaking the aluminum alloy in the anticorrosion soak solution, and forming a thin film layer with adhesiveness, heat resistance, weather resistance and corrosion resistance on the aluminum alloy surface. However, the antiseptic soaking solution contains too many resin types and also contains inorganic matters such as copper oxide, so that the system is more complicated in structure, and antagonism or inhibition can occur between components. The performance test results also show that each performance of comparative example 8 is poor, and the complex composition of the system truly influences the expected effects of each component, and although various resins are theoretically expected to form different polymer films to complement each other, in fact, too many component types prevent the film layer with good performance from being obtained.
The alkaline reagent generally plays a role in regulating the pH of the system, and generally has no obvious influence on the performance of the system, however, in the research and development process of the invention, it is found that under the condition that other conditions are the same, the use of certain alkaline reagents can cause obvious degradation of the salt spray resistance, corrosion resistance and other performances of the product. As the test results of comparative examples 9, 10 show, the replacement of triethanolamine with equal amounts of sodium carbonate or sodium hydroxide, the product performance is significantly reduced, unlike the usual expected results. The possible reasons are that sodium carbonate and sodium hydroxide are inorganic salts, so that a large amount of free metal ions are easily generated in water, and the resin has a certain adsorption and clamping capacity on the metal ions, thereby preventing the resin from forming a film normally, and resulting in poor performance of a finally formed polymer film. The use of the basic compounds triethanolamine, monoethanolamine, ammonia monohydrate according to the invention avoids the problems described above.
The invention avoids the inhibition effect of each component by selecting proper amount of components to scientifically match, and the coupling agent is added to ensure that the film-forming component aqueous resin is well compatible with the auxiliary component silicon-containing reagent, so that the finally obtained polymer film has excellent corrosion resistance and other performances, and the appearance of the film is uniform without different colors and has no adverse effect on the conductivity of the product.
Further, the surface contact angle test was conducted on the sample plates of examples 1 to 5 and comparative examples 1 to 8, and the results are shown in tables 5 and 6.
TABLE 5
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| Contact angle/° | 165.3 | 163.2 | 163.5 | 163.7 | 164.7 | 150.6 | 142.5 | 153.8 | 154.1 | 156.3 | 158.4 | 152.0 | 150.6 |
TABLE 6
| Comparative example 9 | Comparative example 10 | |
| Contact angle/° | 151.3 | 152.8 |
As is clear from the results of tables 5 and 6, except comparative example 2, the contact angle of the surface of each sample plate is above 150 degrees, and the hydrophobic property is good, while the contact angle of the surface of each sample plate in the embodiment of the invention is above 160 degrees, up to above 165 degrees, and the hydrophobic property is relatively better, so that the surface of a product can be effectively prevented from being polluted by moisture, sweat and the like, and the sample plate has excellent antifouling property.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (8)
1. The high corrosion-resistant hydrophobic sealing agent for the magnesium alloy is characterized by comprising the following components in parts by weight: 30-60 parts of aqueous resin, 10-20 parts of silane coupling agent, 5-10 parts of silicon-containing reagent, 20-40 parts of alkaline compound and the balance of water; the aqueous resin is one or more selected from aqueous organic silicon resin, aqueous fluorocarbon resin and aqueous phenolic resin; the silicon-containing reagent is one or more selected from nano silica sol, water-based silicone oil and water-based nano silica; the alkaline compound is selected from one or more of triethanolamine, monoethanolamine and ammonia monohydrate.
2. The magnesium alloy high corrosion resistant hydrophobic sealing agent according to claim 1, which is characterized by comprising the following components in parts by weight: 30 parts of aqueous resin, 10 parts of silane coupling agent, 5 parts of silicon-containing reagent, 20 parts of alkaline compound and the balance of water.
3. The magnesium alloy high corrosion resistant hydrophobic sealing agent according to claim 1, which is characterized by comprising the following components in parts by weight: 60 parts of aqueous resin, 20 parts of silane coupling agent, 10 parts of silicon-containing reagent, 40 parts of alkaline compound and the balance of water.
4. The magnesium alloy high corrosion resistant hydrophobic sealing agent according to claim 1, which is characterized by comprising the following components in parts by weight: 50 parts of aqueous resin, 15 parts of silane coupling agent, 8 parts of silicon-containing reagent, 35 parts of alkaline compound and the balance of water.
5. The magnesium alloy high corrosion resistant hydrophobic blocking agent according to claim 1, wherein the silane coupling agent is selected from one or more of gamma-aminopropyl triethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane, and N-aminoethyl-gamma-aminopropyl trimethoxysilane.
6. The magnesium alloy high corrosion resistant hydrophobic sealing agent according to claim 2, which is characterized by comprising the following components in parts by weight: 30 parts of aqueous organic silicon resin, 10 parts of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, 5 parts of aqueous silicone oil, 20 parts of triethanolamine and the balance of water.
7. A method for using the high corrosion-resistant hydrophobic sealing agent for magnesium alloy according to any one of claims 1 to 6, wherein the magnesium alloy product is placed into a soaking solution for soaking for 6 to 10 minutes; the soaking solution is prepared by adding water into the magnesium alloy high corrosion-resistant hydrophobic sealing agent, wherein the mass percentage of the magnesium alloy high corrosion-resistant hydrophobic sealing agent in the soaking solution is 10% -20%.
8. The method of claim 7, wherein after immersing the magnesium alloy product in the immersion liquid, the magnesium alloy product is baked in an oven at a constant temperature of 150 ℃ for 15-20 minutes.
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