A lubricating coating for alloy wire surfaces and a method for producing same

Abstract

The application belongs to the technical field of lubricating coating and specifically relates to a lubricating coating for alloy wire surfaces and a preparation method thereof. The lubricating coating for alloy wire surfaces is composed of the following raw materials in percentage by weight: 13-17% modified silicone resin, 5-8% molybdenum disulfide, 2-4% NiFe2O4, 5-8% anticorrosive filler, 2-3% thixotropic agent, 1.5-2% dispersant, 0.5-1% leveling agent, and the rest solvent. The modified silicone resin prepared by the organic silicon-boron nitride hybrid crosslinking network has excellent high-temperature resistance (>800 DEG C), can significantly improve the wear resistance and mechanical properties of the coating, and the addition of Mo-Si-B-Sm-based anticorrosive filler can improve the high-temperature oxidation corrosion resistance of the coating.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of lubricating coating and specifically relates to a lubricating coating for alloy wire surfaces and a preparation method thereof. BACKGROUND

[0002] In the hot upsetting process of high-temperature alloy fasteners, since the processing temperature is as high as 600-1000 DEG C and is accompanied by great upsetting pressure, the protective coating of the fastener needs not only to have excellent high-temperature resistance but also to meet good impact resistance and toughness and corrosion resistance. The existing lubricating coating faces the following technical problems: the traditional polymer matrix is easy to decompose and carbonize at high temperatures, leading to the destruction of the coating structure; the interface bonding force between the inorganic filler and the matrix is weak, and brittle fracture is easy to occur under dynamic load; the commonly used solid lubricants such as molybdenum disulfide and graphite will be oxidized and fail at high temperature and high pressure, losing the lubricating function; more importantly, the decrease in the compactness of the coating at high temperatures will accelerate the oxidation and corrosion of the matrix, and the traditional corrosion-resistant filler is difficult to maintain structural stability at extreme temperatures. The superposition of these problems not only causes serious adhesion of the product and the mold, affecting the demolding effect and production continuity, but also leads to rapid wear of the mold and damage to the material surface, directly affecting the product quality and production efficiency. Therefore, developing a lubricating coating capable of meeting the requirements of high-temperature resistance and corrosion resistance simultaneously has become a key technical breakthrough for improving the hot upsetting process quality of high-temperature alloy fasteners. SUMMARY

[0003] The first object of the application is to provide a lubricating coating for alloy wire surfaces, which has excellent mechanical properties and excellent high-temperature corrosion resistance.

[0004] The second object of the application is to provide a preparation method of the above-mentioned silicon-carbon composite negative electrode material.

[0005] In order to achieve the above object, the technical scheme adopted by the application is:

[0006] A lubricating coating for alloy wire surfaces is composed of the following raw materials by weight percentage: 13-17% modified silicone resin, 5-8% molybdenum disulfide, 2-4% NiFe2O4, 5-8% corrosion-resistant filler, 2-3% thixotropic agent, 1.5-2% dispersing agent, 0.5-1% leveling agent, and the balance is solvent.

[0007] The modified silicone resin is prepared by the following preparation process:

[0008] (1) 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane and hydroxylated boron nitride are added to an ethanol aqueous solution, stirred and reacted, filtered, washed, and dried to obtain intermediate 1;

[0009] (2) under inert gas atmosphere, the polymethylsilane, intermediate 1 is added to anhydrous toluene, heated reaction, after reaction is finished, the modified silicone resin is obtained by distillation under reduced pressure.

[0010] Further, the structural formula of intermediate 1 in step (1) is .

[0011] Further, the mass ratio of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane and boron nitride hydroxide in step (1) is 1: (6-8); the stirring reaction temperature is 60-80℃, and the time is 4-6h.

[0012] Further, the use amount ratio of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane and ethanol aqueous solution in step (1) is 1g: (200-250) mL; the volume ratio of ethanol and water in the ethanol aqueous solution is 9:1.

[0013] Further, the mass ratio of intermediate 1 and polymethylsilane in step (2) is 1: (1.5-2); the heating reaction temperature is 110-130℃, and the time is 2-4h.

[0014] Further, the use amount ratio of intermediate 1 and anhydrous toluene in step (2) is 1g: (100-120) mL.

[0015] Further, the anticorrosive filler is prepared by the following preparation process:

[0016] (a) under inert gas atmosphere, molybdenum powder, silicon powder, boron powder and samarium powder are ball-mixed to obtain alloy powder, and the alloy powder is pressure sintered under vacuum condition, pressure reduction and heat preservation, and cooled to obtain Mo-Si-B-Sm alloy powder;

[0017] (b) the surface of the Mo-Si-B-Sm alloy powder is polished, sandblasted, ultrasonically cleaned and dried to obtain treated Mo-Si-B-Sm alloy powder;

[0018] (c) dopamine hydrochloride and Al2O3 nanosheet are added to Tris-HCl buffer solution, ultrasonically dispersed to obtain a mixed solution, the treated Mo-Si-B-Sm alloy powder is immersed in the mixed solution, stirred, centrifuged, washed and dried, and then annealed in argon atmosphere to obtain the anticorrosive filler.

[0019] Further, the mass ratio of the molybdenum powder, the silicon powder, the boron powder and the samarium powder in step (a) is (90-97):(2-5):(0.5-2):(0.5-3); the temperature of the pressure sintering is 1400-1600℃, the pressure is 30-50MPa, and the time is 2-5h; the temperature of the pressure reduction and heat preservation is 1700-1800℃, the pressure is 10-20MPa, and the time is 2-3h.

[0020] Further, the air flow pressure of the sand blasting treatment in step (b) is 0.5-0.8MPa, and the time is 10-15s; the mass ratio of the Al2O3 nanosheet and the hydrochloric acid dopamine in step (c) is 1:(1-1.2); the dosage ratio of the Mo-Si-B-Sm alloy powder after the treatment and the mixed solution is 1g:100-150mL; the temperature of the annealing is 300-350℃, and the time is 1-1.5h.

[0021] Further, the concentration of the Tris-HCl buffer solution is 0.2mol / L; the dosage ratio of the Al2O3 nanosheet and the Tris-HCl buffer solution is 1g:(2-2.5)mL.

[0022] Further, the thixotropic agent is any one of wax paste, bentonite or BYK320; the leveling agent is BYK354 or BYK300; the dispersing agent is BYK110; and the solvent is a mixed solution of ethanol and isopropyl alcohol.

[0023] Further, the solvent is a mixed solution of ethanol and isopropyl alcohol in a volume ratio of 7:3.

[0024] The preparation method of the lubricating coating for the surface of the alloy wire material comprises the following steps:

[0025] According to the weight percentage, the modified organic silicon resin is added into 50-60% of the solvent mass for stirring to form a resin solution, then the molybdenum disulfide, the NiFe2O4 and the corrosion-resistant filler are sequentially added, the thixotropic agent, the dispersing agent BYK110 and the remaining solvent are added after stirring, and finally the leveling agent is added for stirring to obtain the lubricating coating.

[0026] The beneficial technical effects of the present application are:

[0027] 1. The modified silicone resin prepared by the organic silicon-boron nitride hybrid crosslinking network has excellent high temperature resistance (>800℃) and can significantly improve the wear resistance and mechanical properties of the coating. The present application uses high-temperature-resistant hydroxylated boron nitride as raw material, utilizes the condensation reaction of the surface hydroxyl group with 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane to form stable Si-O-B covalent bond and introduce active double bond, so that h-BN is uniformly dispersed and anchored in the polymer network, which endows the resin with high temperature resistance and avoids the interface defects caused by filler agglomeration; then through the silicon hydrogen addition reaction of the introduced double bond with the Si-H bond in polymethylsilane, a network structure with high crosslinking density is constructed, and the generated flexible Si-CH2-CH2-Si segment cooperates with Si-O-Si chain to improve the mechanical properties and wear resistance of the coating. Under the action of dynamic load, the flexible segment absorbs friction energy through conformation change, and the interlayer slip effect of h-BN nanosheet further dissipates stress, effectively inhibiting crack initiation and propagation.

[0028] 2. The present application also adds Mo-Si-B-Sm based corrosion resistant filler, which can improve the high temperature oxidation corrosion resistance of the coating. The present application adds rare earth element Sm in Mo-Si-B alloy, which further refines the grain size and improves the material density, and Sm generates Sm2O3 when oxidized at high temperature, which forms Sm-Si-B-O composite glass phase with SiO2 / B2O3, which can effectively block oxygen diffusion. After multi-stage grinding and sand blasting treatment of Mo-Si-B-Sm alloy powder, a uniform rough surface is formed on the surface, which significantly increases the specific surface area and the number of active sites, and then through in-situ polymerization reaction of polydopamine, Al2O3 nanosheet is adhered to form a continuous layer of dense accumulation, which can effectively block the penetration of corrosive medium and delay the chemical corrosion of the matrix.

[0029] 3. The present application selects molybdenum disulfide and NiFe2O4 as lubricating filler, molybdenum disulfide has lubricating property at low temperature (<300℃), NiFe2O4 has excellent oxidation stability, which can replace the lubricating effect after the failure of molybdenum disulfide, and at high temperature, the metal ions in the spinel crystal structure will undergo reversible displacement, and this crystal slip phenomenon can form a lubricating transfer film on the contact surface. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 The infrared characterization graph of the intermediate 1 and the modified silicone resin in the embodiment 1 of the present application. DETAILED DESCRIPTION

[0031] The following further describes the present application in connection with specific preferred embodiments, which should not be construed as limiting the present application to these specific embodiments. Those skilled in the art of the present application will be able to make numerous simple substitutions or replacements without departing from the spirit of the present application, which should be considered as falling within the scope of the present application. The specific conditions not mentioned in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are conventional products available in the market, unless otherwise specified.

[0032] The preparation process of the polymethylsilane of the present application is as follows: sodium metal block is cut into sodium particles with a particle size <2 mm in dry THF, 10 g of sodium particles are added to 250 mL of toluene under a dry nitrogen atmosphere, and then 22 mL of monomer dichloromethylsilane is added dropwise, and the reaction is refluxed for 10-12 h; after the reaction is completed, it is cooled to room temperature, filtered, and toluene in the filtrate is removed by distillation under reduced pressure to obtain the polymethylsilane; the weight average molecular weight of the polymethylsilane is 1820.

[0033] The preparation process of the hydroxylated boron nitride of the present application is as follows: 1 g of hexagonal boron nitride (specification: 100 nm) is added to 30 mL of sodium hydroxide solution (1 mol / L), stirred at 110°C for 10 h, suction filtered, washed with deionized water, and dried to obtain the hydroxylated boron nitride.

[0034] (I) Examples

[0035] Example 1: Example 1 provides a lubricating coating for the surface of alloy wire, which is composed of the following raw materials by weight percentage: 15% modified silicone resin, 6% molybdenum disulfide, 3% NiFe2O4, 6% anticorrosive filler, 2% wax paste, 1.5% BYK110, 0.8% BYK354, and the balance is solvent prepared by mixing ethanol and isopropanol at a volume ratio of 7:3;

[0036] The modified silicone resin is prepared by the following process:

[0037] (1) According to the use amount ratio of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane, hydroxylated boron nitride and ethanol aqueous solution 1 g:7 g:200 mL, 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane and hydroxylated boron nitride are added to an ethanol aqueous solution with a volume ratio of 9:1, stirred at 70°C for 5 h, filtered, washed, and dried to obtain intermediate 1;

[0038]

[0039] (2) Under a nitrogen atmosphere, intermediate 1 and polymethylsilane were added to anhydrous toluene in a ratio of 1g:1.8g:100mL. The mixture was reacted at 120°C for 3 hours. After the reaction was completed, the modified organosilicon resin was obtained by vacuum distillation.

[0040] Infrared characterization of the above intermediate 1 and modified organosilicon resin is as follows: Figure 1 As shown, by Figure 1 It can be seen that, compared to hydroxylated boron nitride, intermediate 1 has a lower concentration of 3060-3020 cm⁻¹. -1 1600cm -1 The characteristic peak of -CH=CH2 appears at 1010-950 cm⁻¹. -1 The location corresponds to SiCH=CH2, 1410 cm. -1 The location corresponds to Si-CH3, 1260 cm. -1 1080cm -1 The peaks are for Si-C and Si-O, respectively; the 3060-3020 cm⁻¹ peaks in the modified organosilicon resin curve. -1 1600cm -1 The characteristic peak of -CH=CH2 disappears at 2110 cm⁻¹. -1 The presence of Si-H characteristic peaks indicates the successful preparation of the modified organosilicon resin.

[0041] The corrosion-resistant filler is prepared by the following process:

[0042] (a) Molybdenum powder, silicon powder, boron powder and samarium powder were weighed in a mass percentage ratio of 95:4:1:1 and mixed and ball-milled for 24 hours in a nitrogen atmosphere at a ball-to-material ratio of 15:1 to obtain alloy powder. The alloy powder was heated to 1500°C at a rate of 5 / min under a vacuum of 0.010 Pa and sintered under a pressure of 40 MPa for 3 hours. Then the temperature was increased to 1700°C and the pressure was reduced to 15 MPa and held for 3 hours. After cooling in the furnace, Mo-Si-B-Sm alloy powder was obtained.

[0043] (b) The surface of the Mo-Si-B-Sm alloy powder was polished sequentially with 800#, 1500# and 2000# sandpaper. The polished alloy surface was then sandblasted with 36-mesh brown corundum shot using compressed air at a pressure of 0.6MPa for 12s. After the sandblasting, the surface was ultrasonically cleaned with acetone and distilled water to obtain the treated Mo-Si-B-Sm alloy powder.

[0044] (c) Al2O3nanosheet, dopamine hydrochloride and Tris-HCl buffer solution (0.2 mol / L) with pH of 8.5 were mixed according to the usage ratio of 1 mg: 1 mg: 2 mL, and a mixed solution was obtained after ultrasonic treatment for 30 min. The treated Mo-Si-B-Sm alloy powder was added into the mixed solution according to the usage ratio of 1 g: 100 mL, and stirred for 10 h. After centrifugation, the solid product was washed with deionized water and ethanol, dried at 60°C, and then annealed at 300°C in an argon atmosphere for 1 h to obtain the above-mentioned corrosion-resistant filler.

[0045] The embodiment also provides a preparation method of the above-mentioned lubricating coating for the surface of alloy wire, and the specific steps are as follows: the modified silicone resin is added into 50% of the solvent according to the above-mentioned weight percentage, stirred at 600 rpm for 12 min to form a uniform resin solution, then the molybdenum disulfide, NiFe2O4 and corrosion-resistant filler are sequentially added, the wax paste, BYK110 and the remaining solvent are added after stirring, and the system is stirred at 1000 rpm for 18 min to reach a uniform viscous state; finally, BYK354 is added, and low-speed stirring is performed at 500 rpm for 8 min to obtain the above-mentioned lubricating coating for the surface of alloy wire.

[0046] Example 2 provides a lubricating coating for the surface of alloy wire, which is composed of the following raw materials with the weight percentage: 13% of modified silicone resin, 5% of molybdenum disulfide, 2% of NiFe2O4, 5% of corrosion-resistant filler, 2% of bentonite, 1.5% of BYK110, 1% of BYK300, and the rest is a solvent prepared by mixing ethanol and isopropanol according to the volume ratio of 7:3;

[0047] The modified silicone resin is prepared by the following preparation process:

[0048] (1) 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane, hydroxylated boron nitride and an ethanol aqueous solution are added into an ethanol aqueous solution with a volume ratio of 9:1 according to the usage ratio of 1 g: 6 g: 200 mL, and stirred at 60°C for 4 h. After filtration, washing and drying, intermediate 1 is obtained.

[0049] (2) Under a nitrogen atmosphere, intermediate 1, polymethylsilane and anhydrous toluene are added into anhydrous toluene according to the usage ratio of 1 g: 1.5 g: 100 mL, and reacted at 110°C for 2 h. After the reaction, the above-mentioned modified silicone resin is obtained by reduced pressure distillation.

[0050] The corrosion-resistant filler is prepared by the following preparation process:

[0051] (a) Molybdenum powder, silicon powder, boron powder and samarium powder are weighed according to a mass ratio of 90:5:2:3, mixed and ball milled under a nitrogen atmosphere according to a ball-to-material ratio of 10:1 for 20 h to obtain alloy powder, the alloy powder is sintered at 5 / min to 1400℃ under a vacuum of 0.008 Pa, a pressure of 30 MPa is applied for 2 h, then the temperature is continuously increased to 1700℃, the pressure is reduced to 10 MPa for 3 h, and the alloy powder is cooled in the furnace to obtain Mo-Si-B-Sm alloy powder;

[0052] (b) The surface of the Mo-Si-B-Sm alloy powder is polished by using 800#, 1500# and 2000# sandpaper in sequence, and the polished surface of the alloy is subjected to sandblasting treatment by using brown corundum sand with a mesh number of 36 for 10 s under a gas flow pressure of 0.5 MPa, and then the sandblasted surface is cleaned by using acetone and distilled water through ultrasonic cleaning to obtain treated Mo-Si-B-Sm alloy powder;

[0053] (c) Al2O3nanosheets, dopamine hydrochloride and Tris-HCl buffer solution (0.2 mol / L) with a pH of 8.5 are mixed according to a use amount ratio of 1 mg:1.2 mg:2 mL, and a mixed solution is obtained after ultrasonic treatment for 30 min, the treated Mo-Si-B-Sm alloy powder is put into the mixed solution according to a use amount ratio of 1 g:120 mL, and stirring is performed for 10 h, then the solid product is washed with deionized water and ethanol, dried at 60℃, and then annealed in an argon atmosphere at 320℃ for 1 h to obtain the above-mentioned corrosion-resistant filler.

[0054] The embodiment also provides a preparation method of the above-mentioned lubricating coating for the surface of alloy wire, and the specific steps are as follows: the modified silicone resin is added into 50% of the solvent according to the above-mentioned weight percentage, stirred at 500 rpm for 10 min to form a uniform resin solution, then the molybdenum disulfide, NiFe2O4 and corrosion-resistant filler are sequentially added, the mixture is stirred, then the bentonite, BYK110 and the remaining solvent are added, the system is stirred at 800 rpm for 15 min until it reaches a uniform viscous state, and finally the BYK300 is added, and the mixture is stirred at 400 rpm for 5 min to obtain the above-mentioned lubricating coating for the surface of alloy wire.

[0055] Example 3 provides a lubricating coating for the surface of alloy wire, which is composed of the following raw materials with the following weight percentages: 17% modified silicone resin, 8% molybdenum disulfide, 4% NiFe2O4, 8% corrosion-resistant filler, 3% BYK320, 2% BYK110, 1% BYK354, and the rest is a solvent prepared by mixing ethanol and isopropanol in a volume ratio of 7:3.

[0056] The modified silicone resin is prepared by the following process:

[0057] (1) According to the use amount ratio of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane, hydroxylated boron nitride and aqueous ethanol of 1 g:8 g:250 mL, 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane and hydroxylated boron nitride are added to an aqueous ethanol solution with a volume ratio of ethanol to water of 9:1, and stirred at 80°C for 6h, and after filtration, washing and drying, intermediate 1 is obtained;

[0058] (2) Under a nitrogen atmosphere, according to the use amount ratio of intermediate 1, polymethylsilane and anhydrous toluene of 1 g:2 g:120 mL, intermediate 1 and polymethylsilane are added to anhydrous toluene, and reacted at 130°C for 4h, and after the reaction is completed, the above modified silicone resin is obtained by reduced pressure distillation.

[0059] The corrosion-resistant filler is prepared by the following preparation process:

[0060] (a) According to the mass ratio of molybdenum powder, silicon powder, boron powder and samarium powder of 97:2:0.5:0.5, the powders are mixed and ball milled under a nitrogen atmosphere for 30h with a ball-to-material ratio of 20:1, to obtain alloy powder, and the alloy powder is sintered under a vacuum of 0.015 Pa by increasing the temperature to 1600°C at a rate of 5 / min, applying a pressure of 50 MPa for 5h, and then continuously increasing the temperature to 1800°C, reducing the pressure to 20 MPa for 3h, and cooling in the furnace to obtain Mo-Si-B-Sm alloy powder;

[0061] (b) The surface of the Mo-Si-B-Sm alloy powder is polished by sequentially polishing with 800#, 1500# and 2000# sandpaper, and the polished surface of the alloy is sandblasted by using brown corundum sand with a mesh size of 36 under a gas flow pressure of 0.8 MPa for 15s, and then cleaned with acetone and distilled water by ultrasonic cleaning to obtain treated Mo-Si-B-Sm alloy powder;

[0062] (c) Al2O3nanosheets, dopamine hydrochloride and Tris-HCl buffer solution (0.2 mol / L) with a pH of 8.5 are mixed according to the use amount ratio of 1 mg:1.2 mg:2.5 mL, and a mixed solution is obtained after ultrasonic treatment for 30 min, and the treated Mo-Si-B-Sm alloy powder is added to the mixed solution according to the use amount ratio of 1 g:150 mL, and stirred for 12h, and then centrifuged, and the solid product is washed with deionized water and ethanol, and dried at 60°C, and then annealed at 350°C in an argon atmosphere for 1.5h to obtain the above corrosion-resistant filler.

[0063] The embodiment also provides a preparation method of the lubricating coating for the surface of an alloy wire rod, and the specific steps are as follows: the modified silicone resin is added into 60% of the solvent by weight percentage, stirred at 800 rpm for 15 min to form a uniform resin solution, then the molybdenum disulfide, the NiFe2O4 and the corrosion-resistant filler are sequentially added, the BYK320, the BYK110 and the remaining solvent are added after stirring, the system is stirred at 1000 rpm for 20 min to reach a uniform viscous state, finally the BYK354 is added, and low-speed stirring is performed at 600 rpm for 10 min to obtain the lubricating coating for the surface of an alloy wire rod.

[0064] (II) Comparative Examples

[0065] Comparative Example 1

[0066] Comparative Example 1 is basically the same as Example 1, except that the modified silicone resin is replaced by a physical mixture of polymethylsilane and hydroxylated boron nitride.

[0067] Comparative Example 2

[0068] Comparative Example 2 is basically the same as Example 1, except that the step (c) of preparing the corrosion-resistant filler is omitted, that is, the corrosion-resistant filler is replaced by the Mo-Si-B-Sm alloy powder after treatment.

[0069] Comparative Example 3

[0070] Comparative Example 3 is basically the same as Example 1, except that the samarium powder in the step (a) of preparing the corrosion-resistant filler is replaced by yttrium powder, that is, the Mo-Si-B-Sm alloy powder in the step (b) is replaced by a Mo-Si-B-Y alloy powder.

[0071] Comparative Example 4

[0072] Comparative Example 4 is basically the same as Example 1, except that the step (c) of preparing the corrosion-resistant filler is omitted, and the Mo-Si-B-Sm alloy powder and the Al2O3 nanosheet are directly physically mixed, that is, the corrosion-resistant filler is replaced by a physical mixture of the Mo-Si-B-Sm alloy powder and the aluminum oxide.

[0073] (III) Test Examples

[0074] The lubricating coating of the above Examples 1-3 and Comparative Examples 1-4 is respectively sprayed on the surface of a GH2909 alloy test piece, the spraying thickness is 50 μm, and after heating and curing at 200 ℃ for 2 h, a lubricating coating protective coating is formed.

[0075] Impact resistance: The impact resistance of the lubricating coatings of Examples 1-3 and Comparative Examples 1-4 was tested according to GB / T 1732-2020 "Determination of impact resistance of paint films", and the results are shown in Table 1.

[0076] Wear resistance: The wear resistance of the lubricating coatings of Examples 1-3 and Comparative Examples 1-4 was tested according to GB / T 12444-2006 "Metallic materials - Wear testing - Ring - Block on block sliding wear test", with a load of 20 N, a reciprocating frequency of 5 Hz, a friction length of 4 mm, and a wear time of 30 min, and the results are shown in Table 1.

[0077] Flexibility: The flexibility of the lubricating coatings of Examples 1-3 and Comparative Examples 1-4 was tested according to GB / T 1731-2020 "Determination of flexibility of paint films and putty films", and the results are shown in Table 1.

[0078] High temperature corrosion resistance: The oxidation resistance of Examples 1-3 and Comparative Examples 1-4 was tested at an experimental temperature of 800°C according to HB 5258-2000 "Determination of oxidation resistance of steel and high temperature alloy", and the results are shown in Table 1.

[0079] Table 1 Wear resistance, flexibility, and high temperature corrosion test results of lubricating coatings

[0080] Group Impact resistance (cm) wear rate (mm 3 / N·m) Flexibility (mm) Oxidation rate (g / m 2 • h) Example 1 50 3.12 x 10 -7 ]]> 1 0.06 Example 2 50 3.83 x 10 -7 ]] 1 0.07 Example 3 50 4.02 x 10 -7 ]]> 1 0.09 Comparative Example 1 45 9.55 x 10 -7 ]] 2 0.14 Comparative Example 2 50 6.58 x 10 -7 ]]> 1 0.29 Comparative Example 3 50 6.81 x 10 -7 ]] 1 0.17 Comparative Example 4 50 5.34 x 10 -7 ]]> 1 0.23

[0081] As shown in Table 1, the lubricating coating prepared by the application examples 1-3 has excellent mechanical properties and excellent chemical corrosion resistance. Compared with the example 1, the comparative example 1 replaces the modified silicone resin with a physical mixture of polymethylsilane and hydroxylated boron nitride, the comparative example 2 replaces the corrosion-resistant filler with the Mo-Si-B-Sm alloy powder after treatment, the comparative example 3 replaces the Mo-Si-B-Sm alloy powder in step (b) with Mo-Si-B-Y alloy powder, and the comparative example 4 replaces the corrosion-resistant filler with a physical mixture of Mo-Si-B-Sm alloy powder and alumina. The wear resistance, flexibility and high temperature corrosion resistance of the comparative examples 1-4 all decrease. Specific analysis shows that: on the one hand, the modified silicone resin prepared by the organic silicon-boron nitride hybrid crosslinking network has excellent high temperature resistance (>800℃), which can significantly improve the wear resistance and mechanical properties of the coating. In the application, the hydroxylated boron nitride with high temperature resistance is used as raw material, the condensation reaction of the surface hydroxyl group and 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane is used to form stable Si-O-B covalent bond and introduce active double bond, so that the h-BN is uniformly dispersed and anchored in the polymer network, which gives the resin high temperature resistance and avoids the interface defects caused by the agglomeration of the filler; then the silicon-hydrogen addition reaction of the introduced double bond and Si-H bond in polymethylsilane is used to build a network structure with high crosslinking density, and the generated flexible Si-CH2-CH2-Si segment cooperates with Si-O-Si chain to improve the mechanical properties and wear resistance of the coating. Under the action of dynamic load, the flexible segment absorbs friction energy through conformation change, and the interlayer slip effect of h-BN nanosheet further dissipates stress, effectively inhibiting crack initiation and propagation. On the other hand, the application also adds Mo-Si-B-Sm based corrosion-resistant filler, which can improve the high temperature oxidation corrosion resistance of the coating. The application adds rare earth element Sm in Mo-Si-B alloy, which further refines the grain size and improves the material density. Sm generates Sm2O3 when oxidized at high temperature, which forms Sm-Si-B-O composite glass phase with SiO2 / B2O3, effectively blocking oxygen diffusion. After multi-stage grinding and sand blasting treatment of the Mo-Si-B-Sm alloy powder, a uniform rough surface is formed on the surface, which significantly increases the specific surface area and the number of active sites. Through in-situ polymerization reaction of polydopamine, Al2O3 nanosheet is adhered to form a continuous layer of dense accumulation, which can effectively block the penetration of corrosive medium and delay the chemical corrosion of the matrix.

[0082] Finally, it should be pointed out that the above examples are only used to illustrate the technical solutions of the application, but not to limit it. The basic principles and main features of the application have been described in the above specific embodiments, and some modifications or replacements can be made on the basis of the application, but these modifications or replacements do not make the corresponding technical solutions deviate from the scope of the application.

Claims

1. A lubricating coating for the surface of an alloy wire, characterized in that Composed of the following raw materials by weight percentage: 13-17% modified silicone resin, 5-8% molybdenum disulfide, 2-4% NiFe2O4, 5-8% corrosion-resistant filler, 2-3% thixotropic agent, 1.5-2% dispersing agent, 0.5-1% leveling agent, and the balance solvent; The modified silicone resin is prepared by the following process: (1) 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane and hydroxylated boron nitride are added to an aqueous ethanol solution, stirred and reacted, filtered, washed, and dried to obtain intermediate 1; (2) In an inert gas atmosphere, polymethylsilane and intermediate 1 are added to anhydrous toluene, heated and reacted, and after the reaction is completed, the modified silicone resin is obtained by reduced pressure distillation; The corrosion-resistant filler is prepared by the following process: (a) Molybdenum powder, silicon powder, boron powder, and samarium powder are ball-mixed under an inert gas atmosphere to obtain alloy powder, which is pressure-sintered under vacuum, pressure-reduced and heat-treated, and cooled to obtain Mo-Si-B-Sm alloy powder; (b) The surface of the Mo-Si-B-Sm alloy powder is polished, sandblasted, ultrasonically cleaned, and dried to obtain treated Mo-Si-B-Sm alloy powder; (c) Dopamine hydrochloride and Al2O3 nanosheets are added to Tris-HCl buffer solution, ultrasonically dispersed to obtain a mixed solution, the treated Mo-Si-B-Sm alloy powder is immersed in the mixed solution, stirred, centrifuged, washed, and dried, and then annealed in an argon atmosphere to obtain the corrosion-resistant filler.

2. The lubricating coating for alloy wire surfaces according to claim 1, characterized in that, The structure of the intermediate 1 in step (1) is .

3. The lubricating coating for alloy wire surfaces according to claim 1, characterized in that, In step (1), the mass ratio of 1,3-dimethoxy-1,3-dimethyl-1,3-divinyl disiloxane to hydroxylated boron nitride is 1:(6-8); the stirring reaction temperature is 60-80°C, and the time is 4-6h.

4. The lubricating coating for alloy wire surfaces according to claim 1, characterized by In step (2), the mass ratio of intermediate 1 to polymethylsilane is 1:(1.5-2); the heating reaction temperature is 110-130°C, and the time is 2-4h.

5. The lubricating coating for alloy wire surfaces according to claim 1, characterized in that, In step (a), the mass ratio of molybdenum powder to silicon powder to boron powder to samarium powder is (90-97):(2-5):(0.5-2):(0.5-3); the pressure-sintering temperature is 1400-1600°C, the pressure is 30-50MPa, and the time is 2-5h; the pressure-reducing and heat-treating temperature is 1700-1800°C, the pressure is 10-20MPa, and the time is 2-3h.

6. The lubricating coating for alloy wire surfaces according to claim 1, characterized in that, In step (b), the air flow pressure of sandblasting treatment is 0.5-0.8MPa, and the time is 10-15s; in step (c), the mass ratio of Al2O3 nanosheets to dopamine hydrochloride is 1:(1-1.2); the dosage ratio of treated Mo-Si-B-Sm alloy powder to mixed solution is 1g:100-150mL; the annealing temperature is 300-350°C, and the time is 1-1.5h.

7. The lubricating coating for alloy wire surfaces according to claim 1, characterized in that, The thixotropic agent is any one of wax paste, bentonite, or BYK320; the leveling agent is BYK354 or BYK300; the dispersing agent is BYK110; and the solvent is a mixed solution of ethanol and isopropyl alcohol.

8. The method of producing a lubricating coating for the surface of an alloy wire according to any one of claims 1 to 7, characterized in that, The method comprises the following steps: According to the weight percentage, the modified silicone resin is added into 50-60% of the solvent mass to form a resin solution, then the molybdenum disulfide, NiFe2O4 and anticorrosive filler are added in sequence, after stirring, the thixotropic agent, dispersant and the remaining solvent are added, and finally the leveling agent is added to prepare the lubricating coating.

Images