Epoxy resin wear-resistant coating and preparation method thereof

Abstract

The invention provides an epoxy resin wear-resistant coating and a preparation method thereof, and belongs to the technical field of polymer composite materials. The epoxy resin wear-resistant coating is prepared from the following raw materials in parts by mass: 100 parts of epoxy resin, 2 to 20 parts of composite filler, 5 to 30 parts of curing agent, 0.2 to 4 parts of defoaming agent and 0.5 to 5 parts of flatting agent, the composite filler is PTFE and a modified inorganic filler; the modified inorganic filler is a compound system of modified nano SiO2, modified nano ZnO, modified MoS2 and modified nano Al2O3. According to the invention, the antifriction material and the reinforcing material are compounded, and the silane coupling agent is used for surface modification, so that firm combination of the filler and the epoxy resin matrix is realized. MoS2 and PTFE provide a continuous lubricating effect, and the friction coefficient is reduced; the hardness, the strength and the bearing capacity of the coating are remarkably improved through the nano oxide particles, and the coating has the characteristics of low friction and high wear resistance through the synergistic effect of the nano oxide particles and the coating.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer composite materials, in particular to an epoxy resin wear-resistant coating and a preparation method thereof. BACKGROUND

[0002] Surface coating technology is a key and widely used surface interface functionalization technology in modern industrial system. By constructing a functional coating on the surface of the substrate, the corrosion resistance, wear resistance and decoration of the product can be greatly improved, and the specific physical and chemical properties can be realized, the service life of the device is prolonged and the reliability of the equipment is improved. This technology is widely used in aerospace, automobile manufacturing, marine engineering, energy equipment and precision instruments and many other fields, and its performance is directly related to product quality and market competitiveness.

[0003] Among the many protective coatings, wear-resistant coatings play a crucial role. They are specially designed to withstand mechanical actions such as friction, scratching and erosion, protecting the substrate material from wear. Common wear-resistant coatings include cermet coatings, thermal spray coatings, and polymer-based coatings, etc. Among them, polymer-based coatings, especially those represented by epoxy resin and polyurethane, are favored due to their excellent adhesion, good film-forming properties, chemical resistance and convenient construction process.

[0004] However, traditional polymer-based wear-resistant coatings still face significant challenges when dealing with increasingly demanding high-load, long-time friction conditions. For example, the hardness and wear resistance of pure polymer coatings are often insufficient; and the traditional method of simply physically blending wear-resistant fillers (such as molybdenum disulfide, polytetrafluoroethylene or inorganic nanoparticles) can improve performance to some extent, but often encounters bottlenecks: filler particles tend to agglomerate, disperse unevenly in the resin matrix, and have weak interfacial bonding with the matrix. This not only limits the full play of its performance, but also may become a weak point of the material due to stress concentration, leading to premature failure of the coating.

[0005] Therefore, the development of an epoxy resin composite coating with good filler dispersion, strong interfacial bonding, and the ability to synergistically play the roles of efficient friction reduction and wear resistance, has important research value and application prospects for promoting high-end equipment manufacturing and prolonging the service life of key components. SUMMARY

[0006] Therefore, the present application aims to provide an epoxy resin wear-resistant coating and a preparation method thereof. By introducing specific solid lubricants and surface-modified nanocomposite fillers into the epoxy resin system, the present application effectively solves the problems of poor filler dispersion, weak interfacial bonding and single tribological performance in traditional wear-resistant coatings, thereby significantly improving the wear resistance and service life of the coating.

[0007] In order to achieve the above-mentioned purpose, the present application provides the following technical solutions: One of the technical solutions of the present application is an epoxy resin wear-resistant coating, wherein raw materials include 100 parts of epoxy resin, 2-20 parts of composite fillers, 5-30 parts of curing agent, 0.2-4 parts of defoaming agent and 0.5-5 parts of leveling agent by mass fraction; The composite fillers are polytetrafluoroethylene and modified inorganic fillers. The modified inorganic fillers are a complex system of modified nano-SiO2, modified nano-ZnO, modified MoS2 and modified nano-Al2O3.

[0008] The second technical solution of the present application is a preparation method of the above-mentioned epoxy resin wear-resistant coating, comprising the following steps: The epoxy resin is dissolved in solvent 1, then the composite fillers are added and uniformly mixed to obtain component A; The curing agent is dissolved in solvent 2, then the defoaming agent and the leveling agent are added and uniformly mixed to obtain component B; Components A and B are uniformly mixed, then coated on the surface of a metal substrate and cured to obtain the epoxy resin wear-resistant coating.

[0009] The present application discloses the following technical effects: The present application realizes the firm combination of fillers and epoxy resin matrix by compounding friction-reducing materials (MoS2, PTFE) with reinforcing materials (nano-SiO2, ZnO, Al2O3) and surface modification by using silane coupling agent. MoS2 and PTFE provide continuous lubrication effect and reduce the friction coefficient; nano-oxide particles significantly improve the hardness, strength and load capacity of the coating, and the synergistic effect of the two makes the coating have the characteristics of low friction and high wear resistance.

[0010] The present application uses silane coupling agent to modify the surface of nano-fillers, effectively improves the dispersibility of fillers in the organic resin matrix, prevents agglomeration and enhances the interfacial bonding force between fillers and resin. This avoids stress concentration caused by interfacial defects, thereby delaying the wear and peeling of the coating and greatly prolonging the service life of the coating. BRIEF DESCRIPTION OF DRAWINGS

[0011] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0012] Fig. 1 The friction coefficient of the composite coating in Examples 1-2 and Comparative Examples 1-11 of the present application; Fig. 2The average friction coefficient of the composite coating in the examples 1-2 and comparative examples 1-11 of the present application; Fig. 3 The average wear rate of the composite coating in the examples 1-2 and comparative examples 1-11 of the present application. DETAILED DESCRIPTION

[0013] Various exemplary embodiments of the present application will now be described in detail, which should be considered to be illustrative of the application and not restrictive of the application. It should be understood that many changes and modifications to the preferred embodiments described herein can be made by those skilled in the art without departing from the scope or spirit of the application.

[0014] It should be understood that the terms used in the present application merely describe particular embodiments and are not intended to limit the present application. In addition, for numerical ranges in the present application, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Each smaller range between any stated value or stated range, and any other stated value or stated range within the stated range is also encompassed within the present application. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0015] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, preferred methods and materials are described. All documents mentioned herein are incorporated by reference to disclose and describe in full the methods and / or materials which are described therein. In the case of conflict between the present specification and any document incorporated herein by reference, the present specification will control.

[0016] Various modifications and changes can be made to the specific embodiments of the present application described herein without departing from the scope or spirit of the application. Other embodiments of the application will be apparent to those of ordinary skill in the art from the description and examples that follow. The description and examples are illustrative of the application and are not intended to limit the scope of the application.

[0017] As used herein, the terms "comprise", "comprising", "include", "including", "have", "having" and the like are open-ended terms that are intended to mean including, but not limited to.

[0018] The first aspect of the present application provides an epoxy wear-resistant coating, characterized in that the raw materials include 100 parts of epoxy resin, 2-20 parts of composite filler, 5-30 parts of curing agent, 0.2-4 parts of defoaming agent and 0.5-5 parts of leveling agent by mass fraction; The composite filler is polytetrafluoroethylene and modified inorganic filler; The modified inorganic filler is a complex system of modified nano-SiO2, modified nano-ZnO, modified MoS2 and modified nano-Al2O3.

[0019] In the preferred embodiment of the present application, the raw materials of the epoxy resin wear-resistant coating include 100 parts of epoxy resin, 2-10 parts of composite filler, 15-25 parts of curing agent, 0.2-1 part of defoaming agent and 0.5-2 parts of leveling agent by mass fraction.

[0020] In the preferred embodiment of the present application, the raw materials of the epoxy resin wear-resistant coating include 100 parts of epoxy resin, 8-10 parts of composite filler, 20 parts of curing agent, 0.5 parts of defoaming agent and 1 part of leveling agent by mass fraction.

[0021] In the preferred embodiment of the present application, the mass ratio of polytetrafluoroethylene (PTFE) and modified inorganic filler is 5: (3-5); The mass ratio of modified nano-SiO2, modified nano-ZnO, modified MoS2 and modified nano-Al2O3 is (1-3):(1-2):(1-3):(1-2).

[0022] In the preferred embodiment of the present application, the mass ratio of polytetrafluoroethylene (PTFE) and modified inorganic filler is 5:5; the mass ratio of modified nano-SiO2, modified nano-ZnO, modified MoS2 and modified nano-Al2O3 is 2:1:2:1.

[0023] In the preferred embodiment of the present application, the modified nano-SiO2 is silane coupling agent modified nano-SiO2; the modified nano-ZnO is silane coupling agent modified nano-ZnO; the modified MoS2 is silane coupling agent modified MoS2; the modified nano-Al2O3 is silane coupling agent modified nano-Al2O3; and the silane coupling agent is KH550.

[0024] In the preferred embodiment of the present application, the preparation method of the silane coupling agent modified nano-SiO2 is as follows: uniformly dispersing nano-SiO2 in an ethanol aqueous solution, then adding a silane coupling agent, stirring and reacting at room temperature, solid-liquid separation, collecting the solid and drying and grinding the obtained solid; the volume content of ethanol in the ethanol aqueous solution is 66%; the amount of the silane coupling agent is 1%-10% of the mass of nano-SiO2; and the stirring and reaction time at room temperature is 1-10 h. The preparation methods of the silane coupling agent modified nano-ZnO, the silane coupling agent modified MoS2 and the silane coupling agent modified nano-Al2O3 are the same as that of the silane coupling agent modified nano-SiO2, and the corresponding raw materials are used instead of nano-SiO2, which will not be described herein.

[0025] In the present application, the modified inorganic filler can be obtained by mixing modified nano-SiO2, modified nano-ZnO, modified MoS2 and modified nano-Al2O3 uniformly, or by mixing nano-SiO2, nano-ZnO, MoS2 and nano-Al2O3 uniformly and then modifying them according to the preparation method of the silane coupling agent modified nano-SiO2.

[0026] In the preferred embodiment of the present application, the epoxy resin is epoxy resin CYD-011, epoxy resin E44 or epoxy resin E51.

[0027] In the preferred embodiment of the present application, the curing agent is polyamide curing agent 650, phenolic amine curing agent T-31 or polyether amine curing agent D230.

[0028] In the preferred embodiment of the present application, the defoaming agent is Germany BYK-066N.

[0029] In the preferred embodiment of the present application, the leveling agent is DiGo TEGO Glide 410.

[0030] The second aspect of the present application provides a preparation method of the above-mentioned epoxy resin wear-resistant coating, comprising the following steps: The epoxy resin is dissolved in solvent 1, then the composite filler is added and mixed uniformly to obtain component A; The curing agent is dissolved in solvent 2, then the defoaming agent and the leveling agent are added and mixed uniformly to obtain component B; Components A and B are mixed uniformly, then coated on the surface of the metal substrate and cured to obtain the epoxy resin wear-resistant coating.

[0031] In the preferred embodiment of the present application, the solvent 1 is at least one of butyl acetate, propylene glycol methyl ether acetate and butanone; the solvent 1 is the same as the solvent 2; the curing temperature is 50-60℃ and the curing time is 10-14h.

[0032] In the preferred embodiment of the present application, the solvent 1 is butyl acetate and propylene glycol methyl ether acetate with a mass ratio of 1: (1-3).

[0033] The technical solutions of the present application are conventional solutions in the art, unless otherwise specified, and the reagents or raw materials used are purchased from commercial channels or are already disclosed, unless otherwise specified.

[0034] In the following examples and comparative examples: The modified inorganic filler SZMA is prepared as follows: nano-SiO2, nano-ZnO, MoS2 and nano-Al2O3 are dispersed in 300 mL of 66 vol% ethanol aqueous solution at a mass ratio of 2:1:2:1 (where nano-SiO2 is 10 g), 0.9 g KH550 is added, the mixture is stirred at room temperature for 5 h, filtered, dried under vacuum at 60℃, and ground for later use.

[0035] The preparation method of modified inorganic filler (M) is the same as that of modified inorganic filler SZMA, except that nano-SiO2, nano-ZnO and nano-Al2O3 are omitted.

[0036] The preparation method of modified inorganic filler SZ is the same as that of modified inorganic filler SZMA, the only difference being that nano MoS2 and nano Al2O3 are omitted.

[0037] The preparation method of modified inorganic filler SZA is the same as that of modified inorganic filler SZMA, the only difference being that nano MoS2 is omitted.

[0038] The preparation method of modified inorganic filler SZM is the same as that of modified inorganic filler SZMA, the only difference being that nano Al2O3 is omitted.

[0039] In the examples, the defoamer was BYK-066N purchased from Germany, and the leveling agent was TEGO Glide410 purchased from Germany.

[0040] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0041] Example 1 This embodiment provides an epoxy resin wear-resistant coating, and the preparation steps are as follows: S1. Weigh 24 g of butyl acetate and 56 g of propylene glycol methyl ether acetate, place them in a 250 mL clean beaker, sonicate in a water bath for half an hour, then stir with a magnetic stirrer at 300 rpm for 4 hours. After mixing evenly, seal and set aside for later use. S2. Take 40 g of the mixed solvent prepared by S1, add 100 g of epoxy resin CYD-011, stir to dissolve, then add 5 g of PTFE and 3 g of modified inorganic filler SZMA and stir at high speed for 20 minutes to mix evenly to obtain component A. S3. Take 10g of the mixed solvent obtained from S1, add 20g of polyamide curing agent 650, and stir to dissolve. Then add 0.5g of defoamer and 1g of leveling agent, and continue stirring for 30 minutes until the mixture is uniform, to obtain component B; S4, the A component and the B component were mixed uniformly, and then the excess gas in the resin was removed by vacuum assistance, and finally the resin was coated on the pre-cleaned stainless steel sheet, and after curing at 50 °C for 12 h, a 5PTFE-3SZMA epoxy resin coating was obtained.

[0042] Example 2 The difference from Example 1 is only that 3 g of modified inorganic filler SZMA is replaced by 5 g of modified inorganic filler SZMA, and the other steps and parameters are the same as those of Example 1. A 5PTFE-5SZMA epoxy resin coating is obtained.

[0043] Comparative Example 1 Pure epoxy resin coating: The difference from Example 1 is only that PTFE and modified inorganic filler SZMA are omitted, and the other steps and parameters are the same as those of Example 1. A CYD-011 coating is obtained.

[0044] Comparative Example 2 The difference from Example 1 is only that the addition of modified inorganic filler SZMA is omitted, and the other steps and parameters are the same as those of Example 1. A 5PTFE composite coating is obtained.

[0045] Comparative Example 3 The difference from Example 1 is only that 5 g of PTFE and 3 g of modified inorganic filler SZMA are replaced by 10 g of unmodified MoS2, and the other steps and parameters are the same as those of Example 1. A 10MoS2 composite coating is obtained.

[0046] Comparative Example 4 The difference from Example 1 is only that 3 g of modified inorganic filler SZMA is replaced by 10 g of unmodified MoS2, and the other steps and parameters are the same as those of Example 1. A 5PTFE-10MoS2 composite coating is obtained.

[0047] Comparative Example 5 The difference from Example 1 is only that 3 g of modified inorganic filler SZMA is replaced by 3 g of modified inorganic filler SZ, and the other steps and parameters are the same as those of Example 1. A 5PTFE-3SZ composite coating is obtained.

[0048] Comparative Example 6 The difference from Example 1 is only that 3 g of modified inorganic filler SZMA is replaced by 3 g of modified inorganic filler SZ and 2 g of modified inorganic filler M, and the other steps and parameters are the same as those of Example 1. A 5PTFE-3SZ-2M composite coating is obtained.

[0049] Comparative Example 7 The difference between Example 1 and Comparative Example 1 is that 5 g of PTFE and 3 g of modified inorganic filler SZMA are replaced by 5 g of modified inorganic filler M, and other steps and parameters are the same as those of Example 1. A 5M composite coating is obtained.

[0050] Comparative Example 8 The difference between Example 1 and Comparative Example 8 is that 3 g of modified inorganic filler SZMA is replaced by 3 g of modified inorganic filler SZA, and other steps and parameters are the same as those of Example 1. A 5PTFE-3SZA composite coating is obtained.

[0051] Comparative Example 9 The difference between Example 1 and Comparative Example 9 is that 3 g of modified inorganic filler SZMA is replaced by 5 g of modified inorganic filler SZA, and other steps and parameters are the same as those of Example 1. A 5PTFE-5SZA composite coating is obtained.

[0052] Comparative Example 10 The difference between Example 1 and Comparative Example 10 is that 3 g of modified inorganic filler SZMA is replaced by 3 g of modified inorganic filler SZM, and other steps and parameters are the same as those of Example 1. A 5PTFE-3SZM composite coating is obtained.

[0053] Comparative Example 11 The difference between Example 1 and Comparative Example 11 is that 3 g of modified inorganic filler SZMA is replaced by 5 g of modified inorganic filler SZM, and other steps and parameters are the same as those of Example 1. A 5PTFE-5SZM composite coating is obtained.

[0054] The friction coefficient, average friction coefficient, and average wear rate of the coatings obtained in Examples 1-2 and Comparative Examples 1-11 are shown in Table 1. Figs. 1-3 As can be seen, the friction coefficient of CYD-011 alone (Comparative Example 1) is high and fluctuates greatly. When PTFE and different inorganic fillers are added (Comparative Examples 2-11), the friction coefficient and wear rate are reduced, but the fluctuation of the friction coefficient is still relatively large. Examples 1 and 2, which contain both PTFE and surface-modified inorganic filler SZMA, have low and stable friction coefficients and relatively small wear rates, and have the best comprehensive effect of friction reduction and wear resistance.

[0055] The above is only a preferred embodiment of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the scope of protection of the present application.

Claims

1. An epoxy resin wear-resistant coating, characterized in that, By weight, the raw materials include 100 parts epoxy resin, 2-20 parts composite filler, 5-30 parts curing agent, 0.2-4 parts defoamer and 0.5-5 parts leveling agent; The composite filler is polytetrafluoroethylene and modified inorganic filler; The modified inorganic filler is a composite system of modified nano-SiO2, modified nano-ZnO, modified MoS2 and modified nano-Al2O3.

2. The epoxy resin wear-resistant coating according to claim 1, characterized in that, The mass ratio of the polytetrafluoroethylene to the modified inorganic filler is 5:(3~5). The mass ratio of the modified nano-SiO2, modified nano-ZnO, modified MoS2 and modified nano-Al2O3 is (1-3):(1-2):(1-3):(1-2).

3. The epoxy resin wear-resistant coating according to claim 1, characterized in that, The modified nano-SiO2 is silane coupling agent modified nano-SiO2; the modified nano-ZnO is silane coupling agent modified nano-ZnO; the modified MoS2 is silane coupling agent modified MoS2; the modified nano-Al2O3 is silane coupling agent modified nano-Al2O3; and the silane coupling agent is KH550.

4. The epoxy resin wear-resistant coating according to claim 1, characterized in that, The epoxy resin is epoxy resin CYD-011, epoxy resin E44, or epoxy resin E51.

5. The epoxy resin wear-resistant coating according to claim 1, characterized in that, The curing agent is polyamide curing agent 650, phenolic amine curing agent T-31, or polyether amine curing agent D230.

6. The epoxy resin wear-resistant coating according to claim 1, characterized in that, The defoamer is BYK-066N from Germany.

7. The epoxy resin wear-resistant coating according to claim 1, characterized in that, The leveling agent is TEGOGlide 410.

8. The method for preparing the epoxy resin wear-resistant coating as described in claim 1, characterized in that, Includes the following steps: Epoxy resin was dissolved in solvent 1, and then composite filler was added and mixed evenly to obtain component A. The curing agent is dissolved in solvent 2, then the defoamer and leveling agent are added and mixed evenly to obtain component B; Components A and B are mixed evenly, then coated onto the surface of a metal substrate and cured to obtain the epoxy resin wear-resistant coating.

9. The preparation method according to claim 8, characterized in that, Solvent 1 is at least one of butyl acetate, propylene glycol methyl ether acetate, and butanone; solvent 1 is the same as solvent 2; the curing temperature is 50~60℃ and the time is 10~14h.

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