High-hardness corrosion-resistant copper alloy material and preparation method thereof

Abstract

This invention discloses a high-hardness, corrosion-resistant copper alloy material and its preparation method, relating to the field of copper alloy technology. In this invention, a hyperbranched double-bond modified epoxy resin is prepared through two epoxy ring-opening reactions. Compared to ordinary epoxy resins, this resin exhibits better leveling and film-forming properties, a more regular structure, and can form a coating with higher crosslinking density and superior protective effect. Furthermore, this invention synthesizes a terminal thiol curing agent with a branched structure through the reaction of phenolic hydroxyl groups with epoxy groups and thiol groups with double bonds. Simultaneously, the presence of ether bonds in the molecular structure reduces excessive brittleness during crosslinking, and the hydrophobic and oleophobic fluorine atoms provide certain anti-corrosion properties. After mixing with the hyperbranched double-bond modified epoxy resin and additives, an anti-corrosion coating is obtained. When applied to the surface of a copper alloy substrate, a thiol-ene click reaction occurs under ultraviolet irradiation, achieving rapid curing, preventing coating cracking, and fully exerting the anti-corrosion effect.

Description

Technical Field

[0001] This invention relates to the field of copper alloy technology, specifically to a high-hardness, corrosion-resistant copper alloy material and its preparation method. Background Technology

[0002] Copper alloy materials refer to alloys made of pure copper as the base material and with the addition of one or more other elements. They are mainly produced through processes such as smelting, casting, heat treatment and powder metallurgy. They are widely used in industries such as microelectronics, transportation, metallurgy and electromechanical manufacturing. As the application industries become more and more extensive, the performance requirements for copper alloy materials are also increasing.

[0003] Patent CN110747371A discloses a high-conductivity, high-strength, and high-hardness copper alloy and its preparation method. By adding elements such as Be, Cr, and Ni to the copper matrix, the conductivity of the copper alloy is improved. Furthermore, by optimizing the process flow, the mechanical properties of the copper alloy are improved. However, the corrosion resistance of the copper alloy is not improved.

[0004] Therefore, in order to improve the overall performance of copper alloys and extend their service life, we propose a high-hardness, corrosion-resistant copper alloy material and its preparation method. By optimizing the preparation process of the copper alloy and coating the surface with a corrosion-resistant coating, we achieve the goal of improving the hardness and corrosion resistance of the copper alloy material. Summary of the Invention

[0005] The purpose of this invention is to provide a high-hardness, corrosion-resistant copper alloy material and its preparation method, so as to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a high-hardness anti-corrosion copper alloy material, comprising a copper alloy substrate and an anti-corrosion coating applied to the surface of the copper alloy substrate; The copper alloy matrix comprises the following components by mass percentage: 0.08-0.12% chromium, 1.0-2.0% titanium, 2.5-3.5% nickel, 0.01-0.15% yttrium, 0.12-0.20% cerium, 0.25-0.35% cobalt, with the remainder being copper; The anti-corrosion coating is obtained by applying an anti-corrosion paint and then curing it with ultraviolet radiation. The anti-corrosion coating comprises the following components by weight: 80-100 parts of hyperbranched double bond modified epoxy resin, 30-50 parts of end-thiol curing agent, 0.5-1.5 parts of initiator, and 1-2 parts of defoamer.

[0007] Furthermore, the defoamer is one or a mixture of BYK-052N, BYK-1790, and BYK-017; The initiator is one or a mixture of two of photoinitiator 1173 and photoinitiator 184.

[0008] A method for preparing a high-hardness, corrosion-resistant copper alloy material includes the following steps: Step 1: Take raw materials, mix them, and load them into the furnace. Then, proceed with melting, casting, homogenization, solution treatment, hot working, cooling, cold working, and aging treatment in sequence to obtain a copper alloy matrix. Step 2: Mix hyperbranched double bond modified epoxy resin, end-thiol curing agent, initiator, and defoamer, stir evenly to form an anti-corrosion coating, apply it to the surface of copper alloy substrate, and irradiate with ultraviolet light to form an anti-corrosion coating, thus obtaining a high-hardness anti-corrosion copper alloy material.

[0009] Furthermore, in step 1, the smelting process conditions are: heating at 8~10℃ / min to 1000~1200℃; Increase the temperature by 3~5℃ / min to 1200~1400℃ and hold for 0.5~1.0h.

[0010] Furthermore, in step 1, the homogenization process conditions are: temperature 830~880℃, time 2~6h; In step 1, the solution treatment conditions are: temperature 930~960℃, time 1~3h.

[0011] Furthermore, in step 1, the process conditions for hot working are: temperature 900~950℃, time 1~3h; In step 1, the cooling process conditions are: 25~30℃ / min to 300~350℃.

[0012] Furthermore, in step 1, the deformation during cold working is 45-65%; In step 1, the aging treatment process conditions are as follows: keep at 450~500℃ for 3~5 hours, cool to room temperature, and then keep at 420~460℃ for 1~3 hours.

[0013] Furthermore, the copper alloy substrate underwent pretreatment before being coated with the anti-corrosion coating. The specific process is as follows: Take a copper alloy substrate, immerse it in a 25-35% hydrochloric acid solution for 35-45 seconds, then wash it with deionized water and dry it at 40-50℃ for 30-50 minutes.

[0014] Furthermore, in step 2, the ultraviolet irradiation process conditions are: irradiation intensity 100~300mW / cm². 2 Irradiation time: 10-30 seconds.

[0015] Furthermore, in step 2, the thickness of the anti-corrosion coating is 50~100μm.

[0016] In the above technical solutions, chromium can be dissolved into the copper matrix through high-temperature solution treatment. After cooling and aging treatment, chromium will precipitate in the form of particles, effectively hindering dislocation movement and significantly improving the strength and hardness of the copper alloy. Titanium and chromium work together to form a precipitate phase, further enhancing the hardness of the copper alloy. Nickel can dissolve in copper in large quantities to form a continuous solid solution. Through the size difference between nickel atoms and copper atoms, a solid solution strengthening effect is generated, improving the strength of the copper alloy. Yttrium and cerium are rare earth elements with high chemical activity, which can inhibit grain growth and significantly refine the recrystallized grains. Cobalt can also dissolve in the copper matrix and work synergistically with nickel to further improve the high-temperature hardness of the alloy. Homogenization treatment, through prolonged high-temperature annealing, allows alloying elements to diffuse uniformly, ensuring that strengthening elements (chromium and titanium) can dissolve uniformly into the copper matrix during subsequent solid solution treatment. This prevents cracks from forming due to localized stress concentration during subsequent hot working processes. The aging treatment is carried out in two temperature ranges: at high temperature (450~500℃), atomic diffusion is strong, which is conducive to the uniform formation of a large number of fine nuclei in the copper matrix; at low temperature (420~460℃), atomic diffusion is moderate, which allows the fine nuclei formed at high temperature to grow slowly and stably, obtaining a structurally stable strengthening phase, which is beneficial to improving the hardness and strength of the copper matrix.

[0017] Furthermore, the hyperbranched double bond modified epoxy resin is prepared by the following process: S1: Mix pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether, heat to react, wash, and dry to obtain a carboxyl-terminated hyperbranched polyester. S2: Mix carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine, and heat to react to obtain hyperbranched double bond modified epoxy resin.

[0018] Furthermore, in S1, the ratio of pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether is 10g: (3~5)g: (130~150)mL: (20~30)g.

[0019] Furthermore, in S1, the process conditions for the heating reaction are: temperature 105~115℃, time 20~24h; In S1, the drying process conditions are: temperature 70~80℃, time 3~5h.

[0020] Furthermore, in S2, the mass ratio of carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine is 1:(15~20):(0.15~0.25).

[0021] Furthermore, in S2, the process conditions for the heating reaction are: temperature 110~120℃, time 1~3h.

[0022] In the above technical solution, pyromellitic acid provides multiple carboxyl branching sites, and itaconic acid provides double bonds and carboxyl groups. The carboxyl groups of both react with the epoxy groups of bisphenol A diglycidyl ether to undergo ring-opening reactions, and can also react with the hydroxyl groups of isobutanol to undergo esterification reactions, forming a highly branched end-carboxyl hyperbranched polyester. The end-carboxyl groups on it then react with epoxy resin to undergo another ring-opening reaction, resulting in a hyperbranched double-bond modified epoxy resin. The hyperbranched structure reduces intermolecular chain entanglement, resulting in better leveling and film-forming properties, forming a continuous, non-porous coating on the surface of the copper alloy substrate. Moreover, the hyperbranched structure is more regular than the linear structure, and can form a coating with higher crosslinking density and better protective effect.

[0023] Furthermore, the preparation process of the terminal thiol curing agent is as follows: Step A: Mix 4-fluorocatechol and acetone, stir to dissolve, add allyl glycidyl ether and KOH aqueous solution, heat to react, filter, wash and dry to obtain a compound containing double bonds; Step B: Pentaerythritol tetrakis(3-mercaptopropionic acid) ester, a compound containing double bonds, ethyl acetate, and triethylamine are mixed and heated and stirred under a nitrogen atmosphere. The mixture is then rotary evaporated to obtain a mercapto-terminated curing agent.

[0024] Furthermore, in step A, the mass ratio of 4-fluorocatechol, acetone, allyl glycidyl ether, and KOH aqueous solution is 10:(50~70):(25~35):(18~22). The mass fraction of the KOH aqueous solution is 20-25%.

[0025] Furthermore, in step A, the process conditions for the heating reaction are: temperature 75~85℃, time 1.0~1.5h.

[0026] Furthermore, in step A, the drying process conditions are: temperature 55~60℃, time 10~12h.

[0027] Furthermore, in step B, the ratio of pentaerythritol tetrakis(3-mercaptopropionic acid), the compound containing double bonds, ethyl acetate, and triethylamine is (45~50) g ​​: (10~15) g : (60~70) mL : (0.13~0.18) g.

[0028] Furthermore, in step B, the process conditions for heating and stirring the reaction are: temperature 75~85℃, time 11~13h, and rotation speed 350~450r / min.

[0029] Furthermore, in step B, the rotary evaporation process conditions are: temperature 35~45℃, vacuum degree -0.08~-0.09MPa, and time 10~15min.

[0030] In the above technical solution, firstly, under alkaline conditions (KOH aqueous solution), the phenolic hydroxyl group of 4-fluorocatechol undergoes ring-opening with the epoxy group of allyl glycidyl ether to obtain a compound containing ether bonds and fluorine. Then, the thiol group of pentaerythritol tetrakis(3-mercaptopropionic acid) reacts with the double bond of the compound containing double bonds. Triethylamine acts as a weak alkaline catalyst to promote the reaction. Since pentaerythritol tetrakis(3-mercaptopropionic acid) contains multiple thiol groups and is used in excess, a thiol-terminated curing agent is obtained. After being mixed with hyperbranched double bond modified epoxy resin, a thiol-olefin click reaction occurs under ultraviolet irradiation to achieve rapid curing and avoid coating cracking. In addition, the terminal thiol curing agent also has a branched structure, which has good compatibility with hyperbranched double bond modified epoxy resin. It is not easy to volatilize and separate into phases. During the reaction, it can form a more uniform and dense three-dimensional network. At the same time, the molecular structure contains ether bonds, which reduces the excessive brittleness during crosslinking. The fluorine atoms are hydrophobic and oleophobic, which has certain anti-corrosion properties, further improving the performance of the anti-corrosion coating.

[0031] Compared with the prior art, the beneficial effects of the present invention are: 1. In this application, copper is blended with chromium, titanium, nickel, yttrium, cerium, and cobalt to prepare a copper alloy matrix. Rare earth elements (yttrium and cerium) can inhibit grain growth, significantly refine the recrystallized grains, and greatly improve the strength and hardness of the copper alloy. Homogenization treatment can make the alloying elements diffuse evenly, avoiding cracks caused by local stress concentration during hot working. The aging treatment is carried out in two temperature ranges. At high temperature (450~500℃), the atomic diffusion ability is strong, which is conducive to the uniform formation of a large number of fine nuclei in the copper matrix. At low temperature (420~460℃), the atomic diffusion ability is moderate, which allows the fine nuclei formed at high temperature to grow slowly and stably, obtaining a structurally stable strengthening phase, which is beneficial to improving the hardness and strength of the copper matrix.

[0032] 2. In this application, hyperbranched double bond modified epoxy resin is prepared through two epoxy ring-opening reactions. Compared with ordinary epoxy resin, it has better leveling and film-forming properties, more regular structure, and can form a coating with higher crosslinking density and better protective effect. In addition, the introduction of double bonds facilitates subsequent reactions.

[0033] 3. In this application, a terminal thiol curing agent with a branched structure is synthesized by reacting phenolic hydroxyl groups with epoxy groups and thiol groups with double bonds. It has good compatibility with hyperbranched double bond modified epoxy resin. At the same time, the presence of ether bonds in the molecular structure reduces excessive brittleness during crosslinking. The fluorine atoms are hydrophobic and oleophobic, providing certain anti-corrosion properties. After being mixed with hyperbranched double bond modified epoxy resin, a thiol-alkene click reaction occurs under ultraviolet irradiation, achieving rapid curing, avoiding coating cracking, and fully exerting the anti-corrosion effect. Detailed Implementation

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] In the following specific implementation; The defoamer is BYK-052N; The initiator is photoinitiator 1173; Epoxy resin, grade E44.

[0036] Example 1: A method for preparing a high-hardness, corrosion-resistant copper alloy material, comprising the following steps: (1) Preparation of hyperbranched double bond modified epoxy resin: S1: Pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether are mixed, heated, washed, and dried to obtain carboxyl-terminated hyperbranched polyester; S2: Carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine are mixed, heated, and reacted to obtain hyperbranched double-bond modified epoxy resin; In S1, the ratio of pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether is 10g:5g:150mL:30g; In S1, the heating reaction conditions are: temperature 115℃, time 24h; In S1, the drying conditions are: temperature 80℃, time 5h; In S2, the mass ratio of carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine is 1:20:0.25; In S2, the heating reaction conditions are: temperature 120℃, time 3h. (2) Preparation of end-thiol curing agent: Step A: 4-fluorocatechol and acetone are mixed and stirred to dissolve. Allyl glycidyl ether and KOH aqueous solution are added, and the mixture is heated to react. After filtration, washing, and drying, a compound containing double bonds is obtained. Step B: Pentaerythritol tetrakis(3-mercaptopropionic acid) ester, the compound containing double bonds, ethyl acetate, and triethylamine are mixed and heated and stirred under a nitrogen atmosphere. The mixture is then rotary evaporated to obtain a mercapto-terminated curing agent. In Step A, the mass ratio of 4-fluorocatechol, acetone, allyl glycidyl ether, and KOH aqueous solution is 10:70:35:22; the mass fraction of KOH aqueous solution is 25%. In step A, the heating reaction conditions are: temperature 85℃, time 1.5h; in step A, the drying reaction conditions are: temperature 60℃, time 12h; in step B, the ratio of pentaerythritol tetrakis(3-mercaptopropionic acid), double bond-containing compound, ethyl acetate, and triethylamine is 50g:15g:70mL:0.18g; in step B, the heating and stirring reaction conditions are: temperature 85℃, time 13h, rotation speed 450r / min; in step B, the rotary evaporation conditions are: temperature 45℃, vacuum degree -0.09MPa, time 15min. (3) Preparation of high-hardness corrosion-resistant copper alloy materials: Step 1: The raw materials are mixed and loaded into the furnace, and then sequentially subjected to melting, casting, homogenization, solution treatment, hot working, cooling, cold working, and aging treatment to obtain a copper alloy matrix. The copper alloy matrix is ​​immersed in a 35% hydrochloric acid solution for 45 seconds, then rinsed with deionized water and dried at 50°C for 50 minutes. Step 2: 100 parts of hyperbranched double-bond modified epoxy resin, 50 parts of end-thiol curing agent, 1.5 parts of initiator, and 2 parts of defoamer are mixed and stirred evenly to form an anti-corrosion coating. This coating is applied to the surface of the copper alloy matrix and subjected to ultraviolet irradiation to form an anti-corrosion coating, resulting in a high-hardness anti-corrosion copper alloy material. The copper alloy matrix comprises the following components by mass percentage: 0.12% chromium, 2.0% titanium, 3.5% nickel, 0.15% yttrium, 0.20% cerium, and 0.35% cobalt. The remainder is copper; in step 1, the smelting process conditions are: heating at 10℃ / min to 1200℃; heating at 5℃ / min to 1400℃, holding for 1.0h; in step 1, the homogenization process conditions are: temperature 880℃, time 6h; in step 1, the solution treatment process conditions are: temperature 960℃, time 3h; in step 1, the hot working process conditions are: temperature 950℃, time 3h; in step 1, the cooling process conditions are: cooling at 30℃ / min to 350℃; in step 1, the cold working deformation is 65%; in step 1, the aging treatment process conditions are: holding at 500℃ for 5h, cooling to room temperature, and then holding at 460℃ for 3h; in step 2, the ultraviolet irradiation process conditions are: irradiation intensity 300mW / cm². 2 The irradiation time is 30s; in step 2, the thickness of the anti-corrosion coating is 100μm.

[0037] Example 2: A method for preparing a high-hardness, corrosion-resistant copper alloy material, comprising the following steps: (1) Preparation of hyperbranched double bond modified epoxy resin: S1: Pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether are mixed, heated, washed, and dried to obtain carboxyl-terminated hyperbranched polyester; S2: Carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine are mixed, heated, and reacted to obtain hyperbranched double bond modified epoxy resin; In S1, the ratio of pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether is 10g:4g:140mL:25g; In S1, the heating reaction conditions are: temperature 110℃, time 22h; In S1, the drying conditions are: temperature 75℃, time 4h; In S2, the mass ratio of carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine is 1:18:0.20; In S2, the heating reaction conditions are: temperature 115℃, time 2h. (2) Preparation of end-thiol curing agent: Step A: 4-fluorocatechol and acetone are mixed and stirred to dissolve. Allyl glycidyl ether and KOH aqueous solution are added, and the mixture is heated to react. After filtration, washing, and drying, a compound containing double bonds is obtained. Step B: Pentaerythritol tetrakis(3-mercaptopropionic acid) ester, the compound containing double bonds, ethyl acetate, and triethylamine are mixed and heated and stirred under a nitrogen atmosphere. The mixture is then rotary evaporated to obtain a mercapto-terminated curing agent. In Step A, the mass ratio of 4-fluorocatechol, acetone, allyl glycidyl ether, and KOH aqueous solution is 10:60:30:20; the mass fraction of KOH aqueous solution is 22%. In step A, the heating reaction conditions are: temperature 80℃, time 1.3h; in step A, the drying reaction conditions are: temperature 58℃, time 11h; in step B, the ratio of pentaerythritol tetrakis(3-mercaptopropionic acid), double bond-containing compound, ethyl acetate, and triethylamine is 48g:13g:65mL:0.15g; in step B, the heating and stirring reaction conditions are: temperature 80℃, time 12h, rotation speed 400r / min; in step B, the rotary evaporation conditions are: temperature 40℃, vacuum degree -0.08MPa, time 13min. (3) Preparation of high-hardness corrosion-resistant copper alloy materials: Step 1: Raw materials are mixed and loaded into a furnace, then sequentially subjected to melting, casting, homogenization, solution treatment, hot working, cooling, cold working, and aging treatment to obtain a copper alloy matrix. The copper alloy matrix is ​​immersed in a 30% hydrochloric acid solution for 40 seconds, then rinsed with deionized water and dried at 45°C for 40 minutes. Step 2: 90 parts of hyperbranched double-bond modified epoxy resin, 40 parts of end-thiol curing agent, 1.0 part of initiator, and 1 part of defoamer are mixed and stirred evenly to form an anti-corrosion coating. This coating is applied to the surface of the copper alloy matrix and subjected to ultraviolet irradiation to form an anti-corrosion coating, resulting in a high-hardness, anti-corrosion copper alloy material. The copper alloy matrix comprises the following components by mass percentage: 0.10% chromium, 1.5% titanium, 3.0% nickel, 0.10% yttrium, 0.16% cerium, and 0.30% cobalt. The remainder is copper; in step 1, the smelting process conditions are: heating at 9℃ / min to 1100℃; heating at 4℃ / min to 1300℃, holding for 0.8h; in step 1, the homogenization process conditions are: temperature 850℃, time 4h; in step 1, the solution treatment process conditions are: temperature 940℃, time 2h; in step 1, the hot working process conditions are: temperature 930℃, time 2h; in step 1, the cooling process conditions are: cooling at 27℃ / min to 330℃; in step 1, the cold working deformation is 55%; in step 1, the aging treatment process conditions are: holding at 470℃ for 4h, cooling to room temperature, and then holding at 440℃ for 2h; in step 2, the ultraviolet irradiation process conditions are: irradiation intensity 200mW / cm². 2 The irradiation time is 20s; in step 2, the thickness of the anti-corrosion coating is 80μm.

[0038] Example 3: A method for preparing a high-hardness, corrosion-resistant copper alloy material, comprising the following steps: (1) Preparation of hyperbranched double bond modified epoxy resin: S1: Pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether are mixed, heated, washed, and dried to obtain carboxyl-terminated hyperbranched polyester; S2: Carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine are mixed, heated, and reacted to obtain hyperbranched double bond modified epoxy resin; In S1, the ratio of pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether is 10g:3g:130mL:20g; In S1, the heating reaction conditions are: temperature 105℃, time 20h; In S1, the drying conditions are: temperature 70℃, time 3h; In S2, the mass ratio of carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine is 1:15:0.15; In S2, the heating reaction conditions are: temperature 110℃, time 1h. (2) Preparation of end-thiol curing agent: Step A: 4-fluorocatechol and acetone are mixed and stirred to dissolve. Allyl glycidyl ether and KOH aqueous solution are added, and the mixture is heated to react. After filtration, washing, and drying, a compound containing double bonds is obtained. Step B: Pentaerythritol tetrakis(3-mercaptopropionic acid) ester, the compound containing double bonds, ethyl acetate, and triethylamine are mixed and heated and stirred under a nitrogen atmosphere. The mixture is then rotary evaporated to obtain a mercapto-terminated curing agent. In Step A, the mass ratio of 4-fluorocatechol, acetone, allyl glycidyl ether, and KOH aqueous solution is 10:50:25:18; the mass fraction of KOH aqueous solution is 20%. In step A, the heating reaction conditions are: temperature 75℃, time 1.0 h; in step A, the drying reaction conditions are: temperature 55℃, time 10 h; in step B, the ratio of pentaerythritol tetrakis(3-mercaptopropionic acid), double bond-containing compound, ethyl acetate, and triethylamine is 45 g: 10 g: 60 mL: 0.13 g; in step B, the heating and stirring reaction conditions are: temperature 75℃, time 11 h, rotation speed 350 r / min; in step B, the rotary evaporation conditions are: temperature 35℃, vacuum degree -0.08 MPa, time 10 min. (3) Preparation of high-hardness corrosion-resistant copper alloy materials: Step 1: Raw materials are mixed and loaded into a furnace, then sequentially subjected to melting, casting, homogenization, solution treatment, hot working, cooling, cold working, and aging treatment to obtain a copper alloy matrix. The copper alloy matrix is ​​immersed in a 25% hydrochloric acid solution for 35 seconds, then rinsed with deionized water and dried at 40°C for 30 minutes. Step 2: 80 parts of hyperbranched double-bond modified epoxy resin, 30 parts of end-thiol curing agent, 0.5 parts of initiator, and 1 part of defoamer are mixed and stirred evenly to form an anti-corrosion coating. This coating is applied to the surface of the copper alloy matrix and subjected to ultraviolet irradiation to form an anti-corrosion coating, resulting in a high-hardness, anti-corrosion copper alloy material. The copper alloy matrix comprises the following components by mass percentage: 0.08% chromium, 1.0% titanium, 2.5% nickel, 0.01% yttrium, 0.12% cerium, and 0.25% cobalt. The remainder is copper; in step 1, the smelting process conditions are: heating at 8℃ / min to 1000℃; heating at 3℃ / min to 1200℃, holding for 0.5h; in step 1, the homogenization process conditions are: temperature 830℃, time 2h; in step 1, the solution treatment process conditions are: temperature 930℃, time 1h; in step 1, the hot working process conditions are: temperature 900℃, time 1h; in step 1, the cooling process conditions are: cooling at 25℃ / min to 300℃; in step 1, the cold working deformation is 45%; in step 1, the aging treatment process conditions are: holding at 450℃ for 3h, cooling to room temperature, and then holding at 420℃ for 1h; in step 2, the ultraviolet irradiation process conditions are: irradiation intensity 100mW / cm². 2 The irradiation time is 10s; in step 2, the thickness of the anti-corrosion coating is 50μm.

[0039] Comparative Example 1: Compared with Example 1, pyromellitic acid was replaced with an equal mass of terephthalic acid to prepare a carboxyl-terminated polyester, and the other conditions remained unchanged as in Example 1.

[0040] Comparative Example 2: Compared with Example 1, 4-fluorocatechol was replaced with an equal mass of catechol, and all other conditions remained the same as in Example 1.

[0041] Comparative Example 3: Compared with Example 1, pentaerythritol tetrakis(3-mercaptopropionic acid) was replaced with an equal mass of 1,3-propanedithiol, and all other conditions remained the same as in Example 1.

[0042] Comparative Example 4: Compared with Example 1, pyromellitic acid was replaced with an equal mass of terephthalic acid, 4-fluorocatechol was replaced with an equal mass of catechol, and pentaerythritol tetrakis(3-mercaptopropionic acid) was replaced with an equal mass of 1,3-propanedithiol. All other conditions remained the same as in Example 1.

[0043] Comparative Example 5: Compared with Example 1, the hyperbranched double bond modified epoxy resin was replaced with an equal mass of epoxy resin, the terminal mercapto curing agent was replaced with an equal mass of ethylenediamine, no initiator was added, and the curing process was set as follows: temperature 80°C, time 4h, and other conditions remained unchanged, the same as in Example 1.

[0044] Comparative Example 6: Compared with Example 1, no anti-corrosion coating was applied to the surface of the copper alloy substrate, and all other conditions remained the same as in Example 1.

[0045] Experiment: The high-hardness, corrosion-resistant copper alloy materials obtained in the examples and comparative examples were tested for various properties, as detailed below: Hardness test: The Rockwell hardness of the products of the examples and comparative examples was tested according to GB / T 230.1-2018; Tensile strength test: Refer to GB / T 228.1-2021 for the tensile strength of the test examples and comparative products; Salt spray resistance test: The salt spray resistance of the examples and comparative products was tested according to ASTM B117; Based on the data in the table above, the following conclusions can be drawn: Compared with Example 1, the coatings of Comparative Examples 1 to 3 showed slight cracking, but no corrosion was observed on the surface of the copper alloy substrate. It can be seen that the use of raw materials with branched structures in this application can promote the formation of coatings with higher crosslinking density and better protective effect. Compared with Example 1, the coating in Comparative Example 4 cracked and slight corrosion appeared on the surface of the copper alloy substrate, indicating that the coating composition in this application can promote the improvement of the anti-corrosion coating performance through the synergistic effect between the components. Compared with Example 1, the coating in Comparative Example 5 cracked and multiple corrosions appeared on the surface of the copper alloy substrate, indicating that the hyperbranched double bond modified epoxy resin and end-thiol curing agent prepared in this application have better anti-corrosion performance than ordinary epoxy resin and amine curing agent. Compared with Example 1, the copper alloy substrate surface in Comparative Example 6 showed corrosion in multiple places, indicating that the anti-corrosion coating in this application can promote the improvement of the anti-corrosion performance of the prepared copper alloy material.

[0046] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A high-hardness, corrosion-resistant copper alloy material, characterized in that: Includes a copper alloy substrate and an anti-corrosion coating applied to the surface of the copper alloy substrate; The copper alloy matrix comprises the following components by mass percentage: 0.08-0.12% chromium, 1.0-2.0% titanium, 2.5-3.5% nickel, 0.01-0.15% yttrium, 0.12-0.20% cerium, 0.25-0.35% cobalt, with the remainder being copper; The copper alloy matrix is ​​obtained by melting and casting raw materials, followed by homogenization, solution treatment, hot working, cooling, cold working and aging treatment. The aging process is divided into a higher temperature range and a lower temperature range.

2. The high-hardness, corrosion-resistant copper alloy material according to claim 1, characterized in that: The anti-corrosion coating is obtained by applying an anti-corrosion paint and then curing it with ultraviolet radiation. The anti-corrosion coating comprises the following components by weight: 80-100 parts of hyperbranched double bond modified epoxy resin, 30-50 parts of end-thiol curing agent, 0.5-1.5 parts of initiator, and 1-2 parts of defoamer; The hyperbranched double bond modified epoxy resin is obtained by modifying epoxy resin with carboxyl-terminated hyperbranched polyester. The terminal thiol curing agent is prepared by reacting a compound containing double bonds with pentaerythritol tetrakis(3-mercaptopropionic acid) ester.

3. A method for preparing a high-hardness, corrosion-resistant copper alloy material, characterized in that: Includes the following steps: Step 1: Take raw materials, mix them, and load them into the furnace. Then, proceed with melting, casting, homogenization, solution treatment, hot working, cooling, cold working, and aging treatment in sequence to obtain a copper alloy matrix. Step 2: Mix hyperbranched double bond modified epoxy resin, end-thiol curing agent, initiator, and defoamer, stir evenly to form an anti-corrosion coating, apply it to the surface of copper alloy substrate, and irradiate with ultraviolet light to form an anti-corrosion coating, thus obtaining a high-hardness anti-corrosion copper alloy material.

4. The method for preparing a high-hardness, corrosion-resistant copper alloy material according to claim 3, characterized in that: The hyperbranched double bond modified epoxy resin is prepared by the following process: S1: Mix pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether, heat to react, wash, and dry to obtain a carboxyl-terminated hyperbranched polyester. S2: Mix carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine, and heat to react to obtain hyperbranched double bond modified epoxy resin.

5. The method for preparing a high-hardness, corrosion-resistant copper alloy material according to claim 3, characterized in that: The preparation process of the terminal thiol curing agent is as follows: Step A: Mix 4-fluorocatechol and acetone, stir to dissolve, add allyl glycidyl ether and KOH aqueous solution, heat to react, filter, wash and dry to obtain a compound containing double bonds; Step B: Pentaerythritol tetrakis(3-mercaptopropionic acid) ester, a compound containing double bonds, ethyl acetate, and triethylamine are mixed and heated and stirred under a nitrogen atmosphere. The mixture is then rotary evaporated to obtain a mercapto-terminated curing agent.

6. The method for preparing a high-hardness, corrosion-resistant copper alloy material according to claim 4, characterized in that: In S1, the ratio of pyromellitic acid, itaconic acid, isobutanol, and bisphenol A diglycidyl ether is 10g: (3~5)g: (130~150)mL: (20~30)g.

7. The method for preparing a high-hardness, corrosion-resistant copper alloy material according to claim 4, characterized in that: In S2, the mass ratio of carboxyl-terminated hyperbranched polyester, epoxy resin, and triphenylphosphine is 1:(15~20):(0.15~0.25).

8. The method for preparing a high-hardness, corrosion-resistant copper alloy material according to claim 5, characterized in that: In step A, the mass ratio of 4-fluorocatechol, acetone, allyl glycidyl ether and KOH aqueous solution is 10:(50~70):(25~35):(18~22).

9. The method for preparing a high-hardness, corrosion-resistant copper alloy material according to claim 5, characterized in that: In step B, the ratio of pentaerythritol tetrakis(3-mercaptopropionic acid), double bond-containing compound, ethyl acetate, and triethylamine is (45~50) g ​​: (10~15) g : (60~70) mL : (0.13~0.18) g.

10. The method for preparing a high-hardness, corrosion-resistant copper alloy material according to claim 3, characterized in that: In step 1, the aging treatment process conditions are as follows: keep at 450~500℃ for 3~5 hours, cool to room temperature, and then keep at 420~460℃ for 1~3 hours.

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