CN115558915A - Magnesium alloy high-corrosion-resistance hydrophobic sealant and preparation method thereof - Google Patents
Magnesium alloy high-corrosion-resistance hydrophobic sealant and preparation method thereof Download PDFInfo
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- CN115558915A CN115558915A CN202211219869.6A CN202211219869A CN115558915A CN 115558915 A CN115558915 A CN 115558915A CN 202211219869 A CN202211219869 A CN 202211219869A CN 115558915 A CN115558915 A CN 115558915A
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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
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Abstract
The invention relates to the technical field of alloy surface treatment, in particular to a magnesium alloy high-corrosion-resistance hydrophobic sealing agent and a preparation method thereof. The magnesium alloy high-corrosion-resistance 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 obtained polymer film has excellent salt mist resistance, corrosion resistance and other performances, the appearance of the film is uniform and has no heterochrosis, the conductivity of the product is not affected, the main raw materials are all water-based components, and the environment-friendly performance is excellent.
Description
Technical Field
The invention relates to the technical field of alloy surface treatment, in particular to a magnesium alloy high-corrosion-resistance hydrophobic sealing agent and a preparation method thereof.
Background
The magnesium alloy is formed by adding other elements into magnesium as a base, and has the characteristics of low density, high strength, good shock absorption performance, good electric and heat conduction performance, good process performance and the like. The density of the magnesium alloy is only 1.7kg/m 3 2/3 of aluminum and 1/4 of steel, higher strength than aluminum alloy and steel, and specific stiffness close to 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.
However, magnesium metal has very active properties, very low electrode potential, and very high chemical activity and electrochemical activity. The surfaces of magnesium and magnesium alloy are exposed in the air and are easily corroded by the atmosphere; and when magnesium and magnesium alloy are in contact with other metals, galvanic corrosion occurs as an anode. This causes the magnesium alloy to have insufficient performance, and severely limits the industrial application of the magnesium alloy. Therefore, the proper surface treatment of the magnesium alloy to improve the corrosion resistance and beautify the decorative function has very important significance.
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 being corroded, and has low cost and simple process and is widely applied. However, hexavalent chromium ions are toxic and strongly carcinogenic, seriously harming 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 magnesium alloy surface corrosion prevention technology has been studied in the prior art, the defects of unsatisfactory corrosion prevention effect, high production cost, complex process, poor environmental protection performance of raw materials and the like exist, so the magnesium alloy surface corrosion prevention technology still needs to be studied, 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-resistance 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 obtained polymer film has excellent salt mist resistance, corrosion resistance and other performances, the appearance of the film is uniform and has no heterochrosis, the conductivity of the product is not affected, the main raw materials are all water-based components, and the environment-friendly performance is excellent.
In order to achieve the purpose, the invention adopts the following technical scheme:
the magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized by comprising the following components in parts by weight: 30-60 parts of water-based 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 water-based resin, 10 parts of silane coupling agent, 5 parts of silicon-containing agent, 20 parts of alkaline compound and the balance of water.
Preferably, the composition comprises the following components in parts by weight: 60 parts of water-based resin, 20 parts of silane coupling agent, 10 parts of silicon-containing agent, 40 parts of alkaline compound and the balance of water.
Preferably, the composition comprises the following components in parts by weight: 50 parts of water-based resin, 15 parts of silane coupling agent, 8 parts of silicon-containing agent, 35 parts of alkaline compound and the balance of water.
Further, the water-based resin is selected from one or more of water-based organic silicon resin, water-based fluorocarbon resin and water-based phenolic resin.
Further, the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane and N-aminoethyl-gamma-aminopropyltrimethoxysilane.
Further, the silicon-containing agent is selected from one or more of nano silica sol, water-based silicone oil and water-based nano silicon dioxide.
Further, the alkaline compound is selected from one or more of triethanolamine, monoethanolamine and ammonia monohydrate.
In addition, the application also provides a using method of the magnesium alloy high-corrosion-resistance 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-resistance hydrophobic sealing agent, and the mass percentage of the magnesium alloy high-corrosion-resistance hydrophobic sealing agent in the soaking solution is 10% -20%.
Further, after the magnesium alloy product is placed into the soaking solution for soaking, the magnesium alloy product is placed into an oven for baking for 15-20 minutes at the constant temperature of 150 ℃.
The invention has the beneficial effects that:
the water-based resin can be used for attaching a layer of hydrophobic protective film on the surface of the magnesium alloy, the silicon-containing reagent is used for assisting in film formation, the performance of a high 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, the components in a system are ensured to exert corresponding effects, the pH value is adjusted to be neutral by the alkaline compound, and unnecessary corrosion to a base material caused by too large or too small pH value is avoided. According to the invention, through scientific collocation of a proper amount of components, the inhibition effect among the components is avoided, so that the finally obtained polymer film has excellent salt spray resistance, corrosion resistance and other properties, the film has uniform appearance and no heterochrosis, no adverse effect is caused on the conductivity of the product, the main raw materials are water-based components, and the environment-friendly performance is excellent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The following specific embodiments further describe the present invention.
Example 1
A magnesium alloy high-corrosion-resistance hydrophobic sealing agent comprises the following components in parts by weight: 30 parts of water-based organic silicon resin, 10 parts of gamma- (2,3-glycidoxy) propyl trimethoxy silane, 5 parts of water-based silicone oil, 20 parts of triethanolamine and 935 parts of water.
The preparation method of the sealant comprises the following steps: sequentially adding water, water-based organic silicon resin, water-based silicone oil and gamma- (2,3-epoxypropoxy) propyl trimethoxy silane into a stirring kettle, stirring for 20-30 minutes until the system is uniform and transparent, adding triethanolamine to adjust the pH value to 6.5-7.5, and discharging to obtain the product.
Example 2
A magnesium alloy high-corrosion-resistance hydrophobic sealing agent comprises the following components in parts by weight: 60 parts of water-based fluorocarbon resin, 20 parts of gamma-aminopropyltriethoxysilane, 10 parts of nano silica sol, 40 parts of monoethanolamine and 870 parts of water.
The preparation method of the sealant comprises the following steps: sequentially adding water, water-based fluorocarbon resin, nano silica sol and gamma-aminopropyltriethoxysilane into a stirring kettle, stirring for 20-30 minutes until the system is uniform and transparent, adding monoethanolamine to adjust the pH value to 6.5-7.5, and discharging to obtain the product.
Example 3
A magnesium alloy high-corrosion-resistance hydrophobic sealing agent comprises the following components in parts by weight: 50 parts of water-based phenolic resin, 15 parts of N-aminoethyl-gamma-aminopropyltrimethoxysilane, 8 parts of water-based nano silicon dioxide, 35 parts of ammonia monohydrate and 892 parts of water.
The preparation method of the sealant comprises the following steps: sequentially adding water, water-based phenolic resin, water-based nano silicon dioxide and N-aminoethyl-gamma-aminopropyltrimethoxysilane into a stirring kettle, stirring for 20-30 minutes until the system is uniform and transparent, adding ammonium monohydrate to adjust the pH value to 6.5-7.5, and discharging to obtain the product.
Example 4
A magnesium alloy high-corrosion-resistance 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-aminopropyltrimethoxysilane, 6 parts of nano silica sol, 25 parts of monoethanolamine and 921 parts of water.
The preparation method of the sealant comprises the following steps: sequentially adding water, water-based organic silicon resin, nano silica sol and N-aminoethyl-gamma-aminopropyltrimethoxysilane into a stirring kettle, stirring for 20-30 minutes until the system is uniform and transparent, adding monoethanolamine to adjust the pH value to 6.5-7.5, and discharging to obtain the product.
Example 5
A magnesium alloy high-corrosion-resistance hydrophobic sealing agent comprises the following components in parts by weight: 45 parts of water-based fluorocarbon resin, 14 parts of gamma- (2,3-glycidoxy) propyl trimethoxy silane, 7 parts of water-based nano silicon dioxide, 30 parts of ammonia monohydrate and 904 parts of water.
The preparation method of the sealant comprises the following steps: sequentially adding water, water-based fluorocarbon resin, water-based nano silicon dioxide and gamma- (2,3-epoxypropoxy) propyl trimethoxy silane into a stirring kettle, stirring for 20-30 minutes until the system is uniform and transparent, adding ammonia monohydrate to adjust the pH value to 6.5-7.5, and discharging to obtain the product.
TABLE 1 examples 1-5 compositions 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-aminopropyltriethoxysilane | 20 | ||||
| Gamma- (2,3-glycidoxy) propyl trimethoxy silane | 10 | 14 | |||
| N-aminoethyl-gamma-aminopropyltrimethoxysilane | 15 | 13 | |||
| Nano silica sol | 10 | 6 | |||
| Water-based silicone oil | 5 | ||||
| Aqueous nano silicon dioxide | 8 | 7 | |||
| Triethanolamine | 20 | ||||
| Monoethanolamine | 40 | 25 | |||
| Ammonia monohydrate | 35 | 30 | |||
| Water (W) | 935 | 870 | 892 | 921 | 904 |
Water-based silicone resin: COATOSIL DRI available from Shanghai Kangqing New materials science and technology, inc.;
water-based fluorocarbon resin: DF-M05, available from jaboticaba cary chemical technologies, ltd;
water-based phenolic resin: HY654546, available from shandong haoyao new materials, inc;
gamma-aminopropyltriethoxysilane: KH550, available from jonan first pass chemical technology ltd;
gamma- (2,3-glycidoxy) propyltrimethoxysilane: KH560, available from jonan first pass chemical technology ltd;
n-aminoethyl- γ -aminopropyltrimethoxysilane: KH792, available from profov biotechnology limited, wuhan;
nano silica sol: WV33, available from aksunobel corporation;
water-based silicone oil: ST101, available from intellectual silicone materials ltd, available from foshan;
water-based nano-silica: PH-40, available from Shenzhen, tongtai chemical technology, inc.
Comparative example 1
Compared with the embodiment 1, the magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized in that: comparative example 1 contained no gamma- (2,3-glycidoxy) propyltrimethoxysilane, 35 parts of a water-based silicone resin and 10 parts of a water-based silicone oil.
Comparative example 2
Compared with the embodiment 1, the magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized in that: comparative example 2 contains no water-based silicone resin, 25 parts of gamma- (2,3-glycidoxy) propyltrimethoxysilane and 20 parts of water-based silicone oil.
Comparative example 3
Compared with the embodiment 1, the magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized 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
Compared with the embodiment 1, the magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized in that: comparative example 4a non-aqueous epoxy resin was used instead of an aqueous silicone resin.
Comparative example 5
Compared with the embodiment 1, the magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized in that: comparative example 5 a non-aqueous polyurethane resin was used instead of an aqueous silicone resin.
Comparative example 6
Compared with the embodiment 1, the magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized 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 is processed by adopting the product and the method in embodiment 1 of the Chinese invention patent CN 112029394A.
Comparative example 8: the sample plate to be tested is processed by adopting the product and the method in embodiment 1 of the Chinese invention patent CN 114058230A.
Comparative example 9
Compared with the embodiment 1, the magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized in that: comparative example 9 sodium carbonate was used instead of triethanolamine.
Comparative example 10
Compared with the embodiment 1, the magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized in that: comparative example 10 sodium hydroxide was used 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 | ||||||||
| Non-aqueous silicone resin | 30 | ||||||||
| Gamma- (2,3-glycidoxy) 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 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | ||
| Sodium carbonate | 20 | ||||||||
| Sodium hydroxide | 20 | ||||||||
| Water (W) | 935 | 935 | 935 | 935 | 935 | 935 | 935 | 935 | 935 |
Non-aqueous epoxy resin: e-51, available from Jining Sanshi Biotech, inc.;
non-aqueous polyurethane resin: HKW-3100 available from Jining Biao Yi chemical Co., ltd;
non-aqueous silicone resin: SH-9601, available from chemical industries, inc. of the New four seas, hubei.
Performance testing
And (2) cleaning the magnesium alloy sample plate with water, and soaking the magnesium alloy sample plate in soaking solutions prepared by the sealing agents of the examples and the comparative examples at normal temperature for 6 minutes, wherein the soaking solutions are prepared by adding water to the sealing agents of the examples and the comparative examples, and the mass percent of each sealing agent in the soaking solutions is 20%. And (4) 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 (4) 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 carried out according to the GB/T10125-2021 standard under the set conditions of the temperature of a salt spray test box being 35 +/-1 ℃, the saturated air being 47 +/-1 ℃, the concentration of the salt water being 5 +/-l%, the pH value being 6.5-7.2 and the spraying amount being 1-2 ml/80 square centimeters/hour.
(2) Sulfur dioxide resistance test
Reference is made to GB/T9789-2008.
(3) Corrosion resistance test
And (3) testing the corrosion resistance of the sample to be tested by adopting a titration method, uniformly selecting 5 points of each sample plate to be tested for titration, observing the color change of the base material at the titration position, and recording the time required for color change.
(4) Conductivity test
Testing the conductivity by using a microohm meter, contacting two electrodes with the surface of a sample plate to be tested, measuring two points on the surface of the sample for 5 times, and taking an average value; in the test, the electrode area is 1cm 2 The electrode pressure was 1.4MPa.
The results of the performance tests are shown in tables 3 and 4.
TABLE 3
| Test items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Salt spray resistance per hour | 760 | 745 | 745 | 750 | 745 |
| Resistance to sulfur dioxide/h | 590 | 570 | 575 | 575 | 580 |
| Corrosion resistance/s | 25 | 23 | 24 | 24 | 23 |
| Conductivity test/m Ω | 6 | 7 | 6 | 7 | 7 |
| Appearance of the product | Uniform and no different color | Uniform and no different color | Uniform and no different color | Uniform and no foreign color | Uniform and no different color |
The results in table 3 show that the sealant of the invention has excellent salt spray resistance, sulfur dioxide resistance and corrosion resistance, wherein the time of no obvious oxidation phenomenon in the salt spray resistance test can reach more than 745h, the time of sulfur dioxide resistance is more than 570h, the time of color change of the base material in the corrosion resistance test is more than 23s, the sample plate coated with the sealant has good conductivity, the appearance is uniform and has no heterochrosis, and no adverse effect on the appearance of the product is caused.
TABLE 4
| Test items | Example 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 spray resistance per hour | 760 | 425 | 130 | 455 | 410 | 430 | 480 | 470 | 415 | 605 | 620 |
| Resistance to oxidation by dioxide Sulfur/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 meter Test/m omega | 6 | 19 | 34 | 16 | 17 | 16 | 13 | 15 | 20 | 12 | 12 |
| Appearance of the product | Is uniform and has no Different colors | Is uniform and has no Different colors | Is uneven and hard Poor in degree | Is uniform and has no Different colors | Is uniform and has no Different colors | Is uniform and has no Different colors | Is uniform and has no Different colors | Is uniform and has no Different colors | Is uniform and has no Different colors | Is uniform and has no Different colors | Is uniform and has no Different colors |
As can be seen from the test results in Table 4, the waterborne resin, the coupling agent and the silicon-containing agent are very important and have no choice but to exert the excellent efficacy of the sealant of the invention. Comparative example 1, which contains no coupling agent, contains an aqueous resin and a silicon-containing agent, and has significant differences in properties from example 1, and the possible reason is that although the aqueous resin can form a polymer film on the surface of a sample plate, the silicon-containing agent also has a certain auxiliary film-forming effect, the aqueous resin and the silicon-containing agent are relatively poor in compatibility due to lack of bridging effect of the coupling agent, and it is difficult to fully exert their respective performance effects in a unified system, so the performance test result of comparative example 1 without the coupling agent is even worse than that of comparative example 3 with the aqueous resin and without the silicon-containing agent; comparative example 2 contains no water-based resin, contains coupling agent and silicon-containing agent, and from the above, it is known that the silicon-containing agent only exerts an auxiliary film-forming effect in the system, and in the case of lacking the water-based resin as the main film-forming component, a dense polymer film cannot be formed only by the silicon-containing agent and the coupling agent, and the film formed therefrom has problems of poor uniformity and low hardness, and cannot be put into use; comparative example 3 contains no silicon-containing agent, contains an aqueous resin and a coupling agent, and although the lack of the silicon-containing agent can avoid the problem of poor compatibility with the aqueous resin, the lack of the auxiliary film-forming effect of the silicon-containing agent also results in no significant difference from the performance test result of comparative example 3 in comparison with comparative example 1. The magnesium alloy surface treatment agent comprises the water-based resin, the coupling agent and the silicon-containing reagent, the compatibility of all components 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 surface treatment is obviously improved.
Comparative examples 4 to 6 each use a non-aqueous resin instead of the aqueous resin of example 1, and it is clear from the test results in table 4 that excellent product properties cannot be obtained by using the non-aqueous resin in the present invention. The reason is probably that the non-aqueous resin raw material contains a large amount of organic solvent, so that the resin and the silicon-containing agent of the invention cannot be well mutually dissolved, and the non-aqueous resin generally has relatively high viscosity and poor dispersibility in the system of the invention, and can be excessively aggregated in a certain area on the surface of the sample plate, so that the distribution of the polymer film is not uniform, and the performance test result is poor. According to the characteristics of a component system, the water-based resin is added, so that the components are well compatible, the water-based resin forms a high molecular film, the silicon-containing reagent can further improve the film forming effect, can fill microcracks and gaps on the surface of the magnesium alloy, and has excellent performances such as salt spray resistance and corrosion resistance. Further, it was found in the performance test that example 1 using the aqueous silicone resin was relatively superior in performance to examples 2 to 5 using other aqueous resins, probably because the aqueous silicone resin and the silicon-containing agent were compatible with each other to a greater extent than those of the silicone-based component, and it can be seen from the results of the performance test of comparative example 6 that although the non-aqueous resin used in comparative example 6 was inferior in performance test to those of examples using the aqueous resin, the final performance was slightly superior to those of comparative examples 4 and 5 using other non-aqueous resins because it used the silicone resin.
Comparative example 7 is example 1 of CN112029394a, which relates to a method for forming an anticorrosive coating system on a magnesium-lithium alloy surface, using high-density toughness resin, lithium salt inorganic matter and sheet shielding material to form an anticorrosive primer, using high-density resin to form a sealing varnish, and then using the anticorrosive primer and the sealing varnish to perform spraying, curing and other treatments on a sample plate in sequence. From the results of the performance test, it is probably because the comparative example 7 adopts two film-forming sealing treatments, the salt spray resistance, the corrosion resistance and other performances are slightly better than those of most comparative examples, but a relatively obvious gap exists compared with the examples of the invention. In addition, just as comparative example 7 adopts two film-forming sealing treatments, the complexity of the process, the difficulty of parameter control and the like are correspondingly increased, and the difficulty of practical production and application is higher.
Comparative example 8 is example 1 of CN114058230a, which relates to a method for corrosion prevention of an aluminum alloy surface, adding various resins and organic solvents, carbon fiber, copper oxide, etc., stirring or melting by heating to prepare a corrosion prevention soaking solution, and then soaking the aluminum alloy in the corrosion prevention soaking solution to form a thin film layer with adhesiveness, heat resistance, weather resistance and corrosion resistance on the aluminum alloy surface. However, the antiseptic soak solution contains too many kinds of resins and inorganic substances such as copper oxide, which makes the system complex and may have antagonistic or inhibitory effects among the components. It can be seen from the performance test results that each performance of comparative example 8 is poor, and it can be seen that the complex structure of the system actually affects the expected efficacy of each component, although theoretically it is expected that a plurality of resins can form different polymer films, and the components are too many to make up for each other, but actually the components are too many to prevent obtaining a film with good performance.
The alkaline agent generally plays a role in adjusting the pH of the system, and generally has no significant influence on the performance of the system, however, in the development process of the invention, the use of certain alkaline agents under the same other conditions is found to cause obvious deterioration of the salt spray resistance, corrosion resistance and other performances of the product. As the test results of comparative examples 9, 10 show, replacing triethanolamine with an equal amount of sodium carbonate or sodium hydroxide, the product performance drops significantly, unlike the normally expected results. The probable reason is that sodium carbonate and sodium hydroxide are inorganic salts, are easily dissolved in water to generate a large amount of free metal ions, and the resin has certain adsorption and entrapment capacity on the metal ions, so that the normal film forming of the resin is hindered, and the finally formed polymer film has poor performance. The alkaline compounds triethanolamine, monoethanolamine and ammonia monohydrate of the present invention can be used to avoid the above problems.
According to the invention, by selecting a proper amount of components for scientific collocation, the inhibition effect among the components is avoided, and the coupling agent is added, so that the water-based resin of the film forming component is well compatible with the silicon-containing reagent of the auxiliary component, and the finally obtained polymer film has excellent performances such as corrosion resistance and the like, and the film has uniform appearance without heterochrosis and has no adverse effect on the conductivity of the product.
Further, the test pieces of examples 1 to 5 and comparative examples 1 to 8 were subjected to surface contact angle tests, 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 |
From the results in tables 5 and 6, it can be seen that, except for comparative example 2, the contact angle of the surface of each sample plate is more than 150 °, and the hydrophobic property is good, whereas the contact angle of the surface of the sample plate in the example of the present invention is more than 160 °, and can reach more than 165 ° at most, and the hydrophobic property is relatively better, so that the surface of the product can be effectively prevented from being polluted by moisture, sweat, etc., and the antifouling property is excellent.
The above-described embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. The magnesium alloy high-corrosion-resistance hydrophobic sealing agent is characterized by comprising the following components in parts by weight: 30-60 parts of water-based 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 water-based resin is selected from one or more of water-based organic silicon resin, water-based fluorocarbon resin and water-based phenolic resin.
2. The magnesium alloy high-corrosion-resistance hydrophobic sealing agent as claimed in claim 1, which is characterized by comprising the following components in parts by weight: 30 parts of water-based resin, 10 parts of silane coupling agent, 5 parts of silicon-containing agent, 20 parts of alkaline compound and the balance of water.
3. The magnesium alloy high-corrosion-resistance hydrophobic sealing agent as claimed in claim 1, which is characterized by comprising the following components in parts by weight: 60 parts of water-based resin, 20 parts of silane coupling agent, 10 parts of silicon-containing agent, 40 parts of alkaline compound and the balance of water.
4. The magnesium alloy high-corrosion-resistance hydrophobic sealing agent as claimed in claim 1, which is characterized by comprising the following components in parts by weight: 50 parts of water-based resin, 15 parts of silane coupling agent, 8 parts of silicon-containing agent, 35 parts of alkaline compound and the balance of water.
5. The magnesium alloy high-corrosion-resistance hydrophobic sealing agent as claimed in claim 1, wherein the silane coupling agent is one or more selected from gamma-aminopropyltriethoxysilane, gamma- (2,3-glycidoxy) propyltrimethoxysilane and N-aminoethyl-gamma-aminopropyltrimethoxysilane.
6. The magnesium alloy high-corrosion-resistance hydrophobic sealing agent as claimed in claim 1, wherein the silicon-containing agent is selected from one or more of nano silica sol, water-based silicone oil and water-based nano silica.
7. The magnesium alloy high-corrosion-resistance hydrophobic sealing agent as claimed in claim 1, wherein the alkaline compound is selected from one or more of triethanolamine, monoethanolamine, and ammonia monohydrate.
8. The magnesium alloy high-corrosion-resistance hydrophobic sealing agent as claimed in claim 2, which comprises the following components in parts by weight: 30 parts of water-based organic silicon resin, 10 parts of gamma- (2,3-glycidoxy) propyl trimethoxy silane, 5 parts of water-based silicone oil, 20 parts of triethanolamine and the balance of water.
9. The use method of the magnesium alloy high-corrosion-resistance hydrophobic sealing agent according to any one of claims 1 to 8, characterized by soaking a magnesium alloy product in a soaking solution for 6 to 10 minutes; the soaking solution is prepared by adding water into the magnesium alloy high-corrosion-resistance hydrophobic sealing agent, and the mass percentage of the magnesium alloy high-corrosion-resistance hydrophobic sealing agent in the soaking solution is 10% -20%.
10. The use method of claim 9, wherein after the magnesium alloy product is placed into the soaking solution for soaking, the magnesium alloy product is placed into an oven to be baked for 15-20 minutes at a constant temperature of 150 ℃.
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| CN115558915B (en) | 2023-06-09 |
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