A surface treatment process for zirconium-based liquid metal workpieces

Abstract

This invention discloses a surface treatment process for zirconium-based liquid metal workpieces, relating to the field of chemical mechanical polishing (CMP) technology. The surface treatment process specifically includes the following steps: S1: Rough polishing the zirconium-based liquid metal workpiece using chromium corundum in a wet polishing machine to obtain zirconium-based liquid metal workpiece A; S2: Medium polishing of zirconium-based liquid metal workpiece A using walnut shell abrasive in a dedicated partitioned polishing machine to obtain zirconium-based liquid metal workpiece B; S3: Polishing the zirconium-based liquid metal workpiece B to obtain a surface-treated zirconium-based liquid metal workpiece. This invention sequentially employs rough polishing, medium polishing, and polishing to surface treat the zirconium-based liquid metal workpiece, and provides two polishing processes based on walnut shell abrasive modification: solid-state and liquid-state. The former has higher efficiency and lower roughness (<0.1μm), while the latter can achieve both low roughness and high hardness.

Description

Technical Field

[0001] This invention relates to the field of chemical mechanical polishing technology, specifically a surface treatment process for zirconium-based liquid metal workpieces. Background Technology

[0002] Zirconium-based liquid metals typically refer to amorphous alloy systems with zirconium as the main component and containing other metallic elements (such as titanium, copper, nickel, beryllium, etc.). These materials exhibit a range of superior physicochemical properties due to their unique disordered atomic arrangement, including high strength, high hardness, corrosion resistance, and good biocompatibility. They show broad application prospects in aerospace, precision instruments, and biomedicine.

[0003] The surface quality of zirconium-based liquid metal workpieces directly determines their service performance and lifespan. Although the base material itself possesses excellent inherent properties, microscopic defects and uneven roughness on the surface can easily become stress concentration points and corrosion initiation points, leading to premature failure of the workpiece under complex working conditions. Appropriate surface treatment processes, such as chemical mechanical polishing, can significantly improve the surface properties of zirconium-based liquid metals, making them perform better in corrosive environments, friction and wear conditions, and special functional applications. However, current surface treatment processes for zirconium-based liquid metal workpieces are still immature. Conventional grinding and polishing methods suffer from long process flows, generally poor polishing quality, and further room for improvement in mechanical properties.

[0004] In summary, solving the above problems and providing a surface treatment process for zirconium-based liquid metal workpieces is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide a hydrophobic and oleophobic drag-reducing membrane and its preparation process to solve the problems mentioned in the background art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A surface treatment process for zirconium-based liquid metal workpieces includes the following steps: S1: The zirconium-based liquid metal workpiece is rough polished in a wet polishing machine using chromium corundum to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished in a special partitioned polishing machine using walnut shells to obtain zirconium-based liquid metal workpiece B; S3: Polish the zirconium-based liquid metal workpiece B to obtain a surface-treated zirconium-based liquid metal workpiece.

[0007] In step S2, the surface roughness of the metal workpiece B is 0.4~0.8μm.

[0008] Preferably, the particle size of the chromium corundum is 5-8 mm; the particle size of the walnut shell is 80-120 μm; the coarse polishing speed is 100-200 r / min and the time is 40-80 min; and the medium polishing speed is 100-180 r / min and the time is 40-60 min.

[0009] Preferably, in step S3, the specific preparation steps of the surface-treated zirconium-based liquid metal workpiece are as follows: the zirconium-based liquid metal workpiece B is polished using polishing paste in a special partitioned polishing machine to obtain the surface-treated zirconium-based liquid metal workpiece.

[0010] Preferably, the polishing treatment is performed at a speed of 50-100 rpm for a time of 80-1200 min; the polishing paste comprises the following raw materials, by mass parts: 20-30 parts modified walnut shell, 30-40 parts stearic acid, 15-25 parts waxes, 1-3 parts glycerin, and 3-4 parts polyethylene glycol.

[0011] Preferably, in step S3, the specific preparation steps of the surface-treated zirconium-based liquid metal workpiece are as follows: the zirconium-based liquid metal workpiece B is subjected to light-removing treatment in a special partitioned scintillation machine using an abrasive, and after being taken out and dried, it is subjected to nanosecond laser irradiation treatment to obtain the surface-treated zirconium-based liquid metal workpiece.

[0012] Preferably, the rotation speed of the light collection process is 50-100 rpm, and the time is 80-1200 min; during the laser irradiation process, the laser wavelength is 1064 nm, the pulse width is 7 ns, the repetition frequency is 600-800 kHz, the average power is 4-5 W, the scanning speed is 5-10 mm / s, the scanning overlap rate is 70-90%, the spot diameter is 40-45 μm, and the gas atmosphere is argon. The abrasive comprises the following raw materials, in parts by weight of 100: 15-20 parts modified walnut shells, 14-16 parts silicone-modified polyether activator, 0.4-0.6 parts benzotriazole, 0.01-0.1 parts bactericide, 0.8-1 parts triethanolamine, 0.1-0.3 parts organosilicon defoamer, and the remainder is deionized water.

[0013] Preferred method for preparing the silicon-modified polyether activator includes the following steps: (1) Under a nitrogen atmosphere, allyl polyoxyalkyl epoxy ether and Karstedt catalyst are mixed evenly at 70-75°C, heated to 95-100°C, heptamethyltrisiloxane is added dropwise, the reaction is stirred for 3-4 hours, the mixture is concentrated under reduced pressure and purified to obtain silicon-modified epoxy ether. (2) Under a nitrogen atmosphere, silicon-modified epoxy ether, 4,4-diaminodiphenyl sulfide and triethylamine are added to 80-100 parts of isopropanol and stirred at 75-85℃ for 3-4 hours. The mixture is then concentrated under reduced pressure and purified to obtain silicon-modified polyether activator.

[0014] Preferably, the silicon-modified epoxy ether comprises the following raw materials, in parts by mass: 8-10 parts allyl polyoxyalkyl epoxy ether, 5-10 ppm Karstedt catalyst, and 3.3-3.5 parts heptamethyltrisiloxane; The silicon-modified polyether activator comprises the following raw materials, in parts by mass: 8-10 parts silicon-modified epoxy ether, 6.2-6.6 parts 4,4-diaminodiphenyl sulfide, 0.05-0.07 parts triethylamine, and 80-100 parts isopropanol.

[0015] Preferred method for preparing modified walnut shells includes the following steps: (1) dispersing walnut shells in an aqueous ethanol solution, adding 3-aminopropyltriethoxysilane, stirring at 40-50°C for 3-5 hours, centrifuging, washing, and drying to obtain amino-modified walnut shells; (2) dispersing amino-modified walnut shells in isopropanol under a nitrogen atmosphere, adding silicon-modified epoxy ether and triethylamine, stirring at 75-85°C for 3-5 hours, centrifuging, washing, and drying to obtain modified walnut shells.

[0016] Preferably, the raw materials for the amino-modified walnut shell include walnut shell and 3-aminopropyltriethoxysilane in a mass ratio of 0.4~0.6:1; the particle size of the walnut shell is 5~20μm; and the raw materials for the modified walnut shell include amino-modified walnut shell, silicon-modified epoxy ether, and triethylamine in a mass ratio of 1:4~4.2:0.01~0.02.

[0017] The dedicated partitioned polishing machine features an independent housing design, with each workpiece placed individually in a separate abrasive tank. This avoids surface scratches caused by traditional clamping and prevents cross-contamination of abrasives. The machine consists of four independent polishing units with adjustable speeds from 0-180 rpm. Each unit is equipped with an independent drive motor with adjustable speed (0-180 rpm). Each polishing unit comprises multiple independent polishing units, and each unit has a built-in replaceable abrasive tank, supporting liquid (abrasive suspension) or solid (abrasive paste) polishing.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: The present invention uses rough polishing, medium polishing and finishing to perform surface treatment on zirconium-based liquid metal workpieces in sequence, and provides two finishing processes based on walnut shell modification: solid and liquid. The former has higher efficiency and smaller roughness (<0.1μm), while the latter can have both low roughness and high hardness.

[0019] This invention employs chromium corundum for rough polishing, as its moderate hardness allows for efficient material removal while avoiding over-cutting. It then uses walnut shell powder (processed walnut shell powder) for medium polishing, a low-cost natural abrasive with relatively soft hardness that reduces scratches. Finally, it uses finer walnut shell powder (80-120μm) for finishing, effectively filling defects and achieving a mirror finish. A separate polishing machine enables clamp-free polishing, improving yield. Each workpiece is processed individually using independent polishing units, preventing collisions. Furthermore, it supports rapid replacement of different abrasives (liquid / solid), and automated control adjusts speed and pressure to ensure process consistency.

[0020] The preparation method of the silicon-modified polyether activator is as follows: the allyl group in the allyl polyoxyalkyl epoxy ether and the silanol group in the heptamethyltrisiloxane undergo a hydrosilylation reaction under the catalysis of Karstedt catalyst to obtain a silicon-modified epoxy ether containing epoxy groups; further, under the catalysis of triethylamine, the epoxy groups in the two molecular weight silicon-modified epoxy ether and the one molecular weight 4,4-diaminodiphenyl sulfide undergo a ring-opening reaction to obtain a silicon-modified polyether activator with a symmetrical structure.

[0021] The modified walnut shell is prepared by grafting 3-aminopropyltriethoxysilane onto the surface of walnut shell in an aqueous ethanol solution to obtain amino-modified walnut shell, which then undergoes a ring-opening reaction with the aforementioned silicon-modified epoxy ether containing epoxy groups to obtain modified walnut shell.

[0022] In the solid-state finishing process, a grinding paste containing modified walnut shells is used. The modified walnut shells significantly improve compatibility with the grinding paste matrix, enhance dispersibility, and reduce the problem of low grinding efficiency due to instability. This invention successfully introduces amphiphilic segments onto the surface of the walnut shells, with one end being a long siloxane chain (hydrophobic structure) and the other end being a polyether (hydrophilic structure). These segments exhibit excellent compatibility in both water and organic matter. During the grinding process, both the polyether and siloxane segments act as auxiliary lubricants, reducing and repairing surface scratches, and significantly lowering the roughness of the substrate.

[0023] In liquid polishing processes, abrasives are difficult to disperse evenly in water, and the low viscosity of water hinders effective and uniform polishing. This invention first treats the substrate with an abrasive containing modified walnut shell powder and a silicon-modified polyether activator, followed by nanosecond laser irradiation, significantly improving the surface hardness while maintaining low roughness. The modified polyether activator and the modified walnut shell powder have similar modified chain ends, resulting in better compatibility. Furthermore, the silicon-modified polyether activator contains a diphenyl sulfide group, a rigid, flat structure that readily adsorbs onto the metal workpiece surface, effectively anchoring the amphiphilic chain segments and promoting contact between the abrasive and the metal workpiece, thus enhancing polishing performance. Additionally, the sulfide bond possesses flexibility and electron enrichment, allowing for slight twisting under deformation, thus providing toughness and adapting to localized stress changes during polishing, acting as a micro-damping mechanism and maintaining performance over extended polishing periods. Following liquid laser absorption, this invention further employs nanosecond laser irradiation. Rapid melting and solidification of the workpiece surface effectively reduces roughness. During laser irradiation, the silicon-modified polyether activator and modified walnut shell residue remaining on the workpiece surface decompose to produce carbon and silicon elements. These elements form strong chemical bonds with zirconium, generating a hard phase that significantly improves the surface hardness of the alloy workpiece. Simultaneously, the decomposition of the sulfide bonds facilitates dehydrogenation and deoxidation, reducing the impact on the alloy workpiece's hardness. Furthermore, the zirconium sulfide formed with zirconium possesses high hardness and a layered structure, further reducing surface roughness and increasing hardness. However, the laser power for nanosecond laser irradiation needs to be limited to 4-5W. Excessive power can cause over-melting of the alloy matrix, potentially leading to the dissolution and diffusion of sulfur into the molten matrix. This sulfur can then form low-melting-point eutectic phases with other elements in the zirconium-based liquid metal, such as iron and nickel, causing segregation at grain boundaries and severely affecting the matrix's hardness. Detailed Implementation

[0024] 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.

[0025] It should be noted that the following quantities are by weight. There are no special restrictions on the suppliers of any of the raw materials involved in this invention. Exemplary examples include: allyl polyoxyalkylene epoxy ether, molecular weight 600; Karstedt catalyst, brand name M58817, provided by Shanghai Mairui Biochemical Technology Co., Ltd.; heptamethyltrisiloxane CAS number: 1873-88-7; 4,4-diaminodiphenyl sulfide CAS number: 139-65-1; 3-aminopropyltriethoxysilane CAS number: 919-30-2; stearic acid CAS number: 57-11-4; waxes: microcrystalline wax, provided by Wuhan Jiyesheng Chemical Co., Ltd.; polyethylene glycol, molecular weight 2000; and sodium benzoate as a bactericide.

[0026] In the following examples, parts refer to parts by weight, and all raw materials mentioned above and others not mentioned are commercially available.

[0027] Example 1: A surface treatment process for a zirconium-based liquid metal workpiece includes the following steps: Step 1: Preparation of silicon-modified epoxy ether: (1) Under a nitrogen atmosphere, 9 parts of allyl polyoxyalkyl epoxy ether and 7 ppm Karstedt catalyst were mixed evenly at 70°C, heated to 100°C, and 3.4 parts of heptamethyltrisiloxane were added dropwise. The mixture was stirred and reacted for 4 hours. The mixture was concentrated under reduced pressure and purified to obtain silicon-modified epoxy ether. Step 2: Preparation of modified walnut shell: (1) Disperse walnut shell in an ethanol aqueous solution, add 3-aminopropyltriethoxysilane, stir at 45°C for 4 hours, centrifuge, wash, and dry to obtain amino-modified walnut shell; (2) Under a nitrogen atmosphere, disperse amino-modified walnut shell in isopropanol, add silicon-modified epoxy ether and triethylamine, stir at 80°C for 4 hours, centrifuge, wash, and dry to obtain modified walnut shell; wherein, the raw materials of the amino-modified walnut shell include walnut shell and 3-aminopropyltriethoxysilane in a mass ratio of 0.5:1; the particle size of the walnut shell is 10 μm; the raw materials of the modified walnut shell include amino-modified walnut shell, silicon-modified epoxy ether, and triethylamine in a mass ratio of 1:4.1:0.01; Step 3: Surface treatment process for zirconium-based liquid metal workpieces: S1: The zirconium-based liquid metal workpiece is rough polished for 60 minutes in a wet polishing machine using chromium corundum (6mm particle size) at a speed of 150r / min to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished with walnut shells (particle size of 100μm) in a special partitioned polishing machine for 50 minutes at a speed of 120r / min to obtain the zirconium-based liquid metal workpiece B. S3: The zirconium-based liquid metal workpiece B is polished for 180 minutes in a special partitioned polishing machine at a speed of 75 r / min using polishing paste to obtain a surface-treated zirconium-based liquid metal workpiece; wherein, the polishing paste includes the following raw materials, by mass parts: 25 parts modified walnut shell powder, 35 parts stearic acid, 20 parts wax, 2 parts glycerin, and 3 parts polyethylene glycol.

[0028] Example 2: A surface treatment process for a zirconium-based liquid metal workpiece includes the following steps: Step 1: Silicon-modified epoxy ether: (1) Under a nitrogen atmosphere, 9 parts of allyl polyoxyalkyl epoxy ether and 7 ppm of Karstedt catalyst were mixed evenly at 70°C, heated to 100°C, and 3.4 parts of heptamethyltrisiloxane were added dropwise. The mixture was stirred and reacted for 4 hours. The mixture was concentrated under reduced pressure and purified to obtain silicon-modified epoxy ether. Step 2: Preparation of modified walnut shell: (1) Disperse walnut shell in an ethanol aqueous solution, add 3-aminopropyltriethoxysilane, stir at 45°C for 4 hours, centrifuge, wash, and dry to obtain amino-modified walnut shell; (2) Under a nitrogen atmosphere, disperse amino-modified walnut shell in isopropanol, add silicon-modified epoxy ether and triethylamine, stir at 80°C for 4 hours, centrifuge, wash, and dry to obtain modified walnut shell; wherein, the raw materials of the amino-modified walnut shell include walnut shell and 3-aminopropyltriethoxysilane in a mass ratio of 0.5:1; the particle size of the walnut shell is 10 μm; the raw materials of the modified walnut shell include amino-modified walnut shell, silicon-modified epoxy ether, and triethylamine in a mass ratio of 1:4.1:0.01; Step 3: Surface treatment process for zirconium-based liquid metal workpieces: S1: The zirconium-based liquid metal workpiece is rough polished for 60 minutes in a wet polishing machine using chromium corundum (6mm particle size) at a speed of 150r / min to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished with walnut shells (particle size of 100μm) in a special partitioned polishing machine for 50 minutes at a speed of 120r / min to obtain the zirconium-based liquid metal workpiece B. S3: The zirconium-based liquid metal workpiece B is polished for 120 minutes in a special partitioned polishing machine at a speed of 80 r / min using polishing paste to obtain a surface-treated zirconium-based liquid metal workpiece; wherein, the polishing paste includes the following raw materials, by mass parts: 25 parts modified walnut shell powder, 35 parts stearic acid, 20 parts wax, 2 parts glycerin, and 3 parts polyethylene glycol.

[0029] Example 3: A surface treatment process for a zirconium-based liquid metal workpiece includes the following steps: Step 1: Preparation of silicon-modified polyether activator: (1) Under a nitrogen atmosphere, 9 parts of allyl polyoxyalkyl epoxy ether and 7 ppm Karstedt catalyst were mixed evenly at 70°C, heated to 100°C, and 3.4 parts of heptamethyltrisiloxane were added dropwise. The mixture was stirred and reacted for 4 hours. The mixture was concentrated under reduced pressure and purified to obtain silicon-modified epoxy ether. (2) Under a nitrogen atmosphere, 9 parts of silicone-modified epoxy ether, 6.4 parts of 4,4-diaminodiphenyl sulfide, and 0.06 parts of triethylamine were added to 100 parts of isopropanol. The mixture was stirred at 80°C for 3 hours, concentrated under reduced pressure, and purified to obtain a silicone-modified polyether activator. Step 2: Preparation of modified walnut shell: (1) Disperse walnut shell in an ethanol aqueous solution, add 3-aminopropyltriethoxysilane, stir at 45°C for 4 hours, centrifuge, wash, and dry to obtain amino-modified walnut shell; (2) Under a nitrogen atmosphere, disperse amino-modified walnut shell in isopropanol, add silicon-modified epoxy ether and triethylamine, stir at 80°C for 4 hours, centrifuge, wash, and dry to obtain modified walnut shell; wherein, the raw materials of the amino-modified walnut shell include walnut shell and 3-aminopropyltriethoxysilane in a mass ratio of 0.5:1; the particle size of the walnut shell is 10 μm; the raw materials of the modified walnut shell include amino-modified walnut shell, silicon-modified epoxy ether, and triethylamine in a mass ratio of 1:4.1:0.01; Step 3: Surface treatment process for zirconium-based liquid metal workpieces: S1: The zirconium-based liquid metal workpiece is rough polished for 60 minutes in a wet polishing machine using chromium corundum (6mm particle size) at a speed of 150r / min to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished with walnut shells (particle size of 100μm) in a special partitioned polishing machine for 50 minutes at a speed of 120r / min to obtain the zirconium-based liquid metal workpiece B. S3: The zirconium-based liquid metal workpiece B is treated with an abrasive in a dedicated partitioned polishing machine at a speed of 75 r / min for 900 min. After drying, it is treated with nanosecond laser irradiation. The specific process parameters are as follows: During the laser irradiation treatment, the laser wavelength is 1064 nm, the pulse width is 7 ns, the repetition frequency is 600 kHz, the average power is 4.5 W, the scanning speed is 10 mm / s, the scanning overlap rate is 80%, the spot diameter is 40 μm, and the gas atmosphere is argon. The surface-treated zirconium-based liquid metal workpiece is obtained. The abrasive includes the following raw materials, in 100 parts by weight: 18 parts modified walnut shell powder, 15 parts silicon-modified polyether activator, 0.5 parts benzotriazole, 0.05 parts bactericide, 0.9 parts triethanolamine, 0.2 parts organosilicon defoamer, and the remainder is deionized water.

[0030] Example 4: A surface treatment process for a zirconium-based liquid metal workpiece includes the following steps: Step 1: Preparation of silicon-modified polyether activator: (1) Under a nitrogen atmosphere, 9 parts of allyl polyoxyalkyl epoxy ether and 7 ppm Karstedt catalyst were mixed evenly at 70°C, heated to 100°C, and 3.4 parts of heptamethyltrisiloxane were added dropwise. The mixture was stirred and reacted for 4 hours. The mixture was concentrated under reduced pressure and purified to obtain silicon-modified epoxy ether. (2) Under a nitrogen atmosphere, 9 parts of silicone-modified epoxy ether, 6.4 parts of 4,4-diaminodiphenyl sulfide, and 0.06 parts of triethylamine were added to 100 parts of isopropanol. The mixture was stirred at 80°C for 3 hours, concentrated under reduced pressure, and purified to obtain a silicone-modified polyether activator. Step 2: Preparation of modified walnut shell: (1) Disperse walnut shell in an ethanol aqueous solution, add 3-aminopropyltriethoxysilane, stir at 45°C for 4 hours, centrifuge, wash, and dry to obtain amino-modified walnut shell; (2) Under a nitrogen atmosphere, disperse amino-modified walnut shell in isopropanol, add silicon-modified epoxy ether and triethylamine, stir at 80°C for 4 hours, centrifuge, wash, and dry to obtain modified walnut shell; wherein, the raw materials of the amino-modified walnut shell include walnut shell and 3-aminopropyltriethoxysilane in a mass ratio of 0.5:1; the particle size of the walnut shell is 10 μm; the raw materials of the modified walnut shell include amino-modified walnut shell, silicon-modified epoxy ether, and triethylamine in a mass ratio of 1:4.1:0.01; Step 3: Surface treatment process for zirconium-based liquid metal workpieces: S1: The zirconium-based liquid metal workpiece is rough polished for 60 minutes in a wet polishing machine using chromium corundum (6mm particle size) at a speed of 150r / min to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished with walnut shells (particle size of 100μm) in a special partitioned polishing machine for 50 minutes at a speed of 120r / min to obtain the zirconium-based liquid metal workpiece B. S3: The zirconium-based liquid metal workpiece B is treated with an abrasive in a dedicated partitioned polishing machine at a speed of 75 r / min for 600 min. After drying, it is treated with nanosecond laser irradiation. The specific process parameters are as follows: During the laser irradiation treatment, the laser wavelength is 1064 nm, the pulse width is 7 ns, the repetition frequency is 600 kHz, the average power is 4 W, the scanning speed is 10 mm / s, the scanning overlap rate is 80%, the spot diameter is 40 μm, and the gas atmosphere is argon. The surface-treated zirconium-based liquid metal workpiece is obtained. The abrasive includes the following raw materials, in 100 parts by weight: 18 parts modified walnut shell powder, 15 parts silicon-modified polyether activator, 0.5 parts benzotriazole, 0.05 parts bactericide, 0.9 parts triethanolamine, 0.2 parts organosilicon defoamer, and the remainder is deionized water.

[0031] Comparative Example 1, based on Example 1, involves unmodified walnut shell extract with the remaining processes unchanged, as follows: Step 1: Surface treatment process for zirconium-based liquid metal workpieces: S1: The zirconium-based liquid metal workpiece is rough polished for 60 minutes in a wet polishing machine using chromium corundum (6mm particle size) at a speed of 150r / min to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished with walnut shells (particle size of 100μm) in a special partitioned polishing machine for 50 minutes at a speed of 120r / min to obtain the zirconium-based liquid metal workpiece B. S3: The zirconium-based liquid metal workpiece B is polished in a special partitioned polishing machine at a speed of 75 r / min for 180 min using polishing paste to obtain a surface-treated zirconium-based liquid metal workpiece; wherein, the polishing paste includes the following raw materials, by mass parts: 25 parts walnut shell powder, 35 parts stearic acid, 20 parts wax, 2 parts glycerin, and 3 parts polyethylene glycol.

[0032] Comparative Example 2, based on Example 3, does not include the silicone-modified polyether activator, but the remaining processes remain unchanged, as follows: Step 1: Preparation of silicon-modified epoxy ether: (1) Under a nitrogen atmosphere, 9 parts of allyl polyoxyalkyl epoxy ether and 7 ppm Karstedt catalyst were mixed evenly at 70°C, heated to 100°C, and 3.4 parts of heptamethyltrisiloxane were added dropwise. The mixture was stirred and reacted for 4 hours. The mixture was concentrated under reduced pressure and purified to obtain silicon-modified epoxy ether. Step 2: Preparation of modified walnut shell: (1) Disperse walnut shell in an ethanol aqueous solution, add 3-aminopropyltriethoxysilane, stir at 45°C for 4 hours, centrifuge, wash, and dry to obtain amino-modified walnut shell; (2) Under a nitrogen atmosphere, disperse amino-modified walnut shell in isopropanol, add silicon-modified epoxy ether and triethylamine, stir at 80°C for 4 hours, centrifuge, wash, and dry to obtain modified walnut shell; wherein, the raw materials of the amino-modified walnut shell include walnut shell and 3-aminopropyltriethoxysilane in a mass ratio of 0.5:1; the particle size of the walnut shell is 10 μm; the raw materials of the modified walnut shell include amino-modified walnut shell, silicon-modified epoxy ether, and triethylamine in a mass ratio of 1:4.1:0.01; Step 3: Surface treatment process for zirconium-based liquid metal workpieces: S1: The zirconium-based liquid metal workpiece is rough polished for 60 minutes in a wet polishing machine using chromium corundum (6mm particle size) at a speed of 150r / min to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished with walnut shells (particle size of 100μm) in a special partitioned polishing machine for 50 minutes at a speed of 120r / min to obtain the zirconium-based liquid metal workpiece B. S3: The zirconium-based liquid metal workpiece B is treated with an abrasive in a dedicated partitioned polishing machine at a speed of 75 r / min for 900 min. After drying, it is treated with nanosecond laser irradiation. The specific process parameters are as follows: During the laser irradiation treatment, the laser wavelength is 1064 nm, the pulse width is 7 ns, the repetition frequency is 600 kHz, the average power is 4.5 W, the scanning speed is 10 mm / s, the scanning overlap rate is 80%, the spot diameter is 40 μm, and the gas atmosphere is argon. The surface-treated zirconium-based liquid metal workpiece is obtained. The abrasive includes the following raw materials, in 100 parts by weight: 18 parts modified walnut shell powder, 15 parts polyethylene glycol, 0.5 parts benzotriazole, 0.05 parts bactericide, 0.9 parts triethanolamine, 0.2 parts organosilicon defoamer, and the remainder is deionized water.

[0033] Comparative Example 3, based on Example 3, does not involve nanosecond laser irradiation, but the remaining processes remain unchanged, as follows: Step 1: Preparation of silicon-modified polyether activator: (1) Under a nitrogen atmosphere, 9 parts of allyl polyoxyalkyl epoxy ether and 7 ppm Karstedt catalyst were mixed evenly at 70°C, heated to 100°C, and 3.4 parts of heptamethyltrisiloxane were added dropwise. The mixture was stirred and reacted for 4 hours. The mixture was concentrated under reduced pressure and purified to obtain silicon-modified epoxy ether. (2) Under a nitrogen atmosphere, 9 parts of silicone-modified epoxy ether, 6.4 parts of 4,4-diaminodiphenyl sulfide, and 0.06 parts of triethylamine were added to 100 parts of isopropanol. The mixture was stirred at 80°C for 3 hours, concentrated under reduced pressure, and purified to obtain a silicone-modified polyether activator. Step 2: Preparation of modified walnut shell: (1) Disperse walnut shell in an ethanol aqueous solution, add 3-aminopropyltriethoxysilane, stir at 45°C for 4 hours, centrifuge, wash, and dry to obtain amino-modified walnut shell; (2) Under a nitrogen atmosphere, disperse amino-modified walnut shell in isopropanol, add silicon-modified epoxy ether and triethylamine, stir at 80°C for 4 hours, centrifuge, wash, and dry to obtain modified walnut shell; wherein, the raw materials of the amino-modified walnut shell include walnut shell and 3-aminopropyltriethoxysilane in a mass ratio of 0.5:1; the particle size of the walnut shell is 10 μm; the raw materials of the modified walnut shell include amino-modified walnut shell, silicon-modified epoxy ether, and triethylamine in a mass ratio of 1:4.1:0.01; Step 3: Surface treatment process for zirconium-based liquid metal workpieces: S1: The zirconium-based liquid metal workpiece is rough polished for 60 minutes in a wet polishing machine using chromium corundum (6mm particle size) at a speed of 150r / min to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished with walnut shells (particle size of 100μm) in a special partitioned polishing machine for 50 minutes at a speed of 120r / min to obtain the zirconium-based liquid metal workpiece B. S3: The zirconium-based liquid metal workpiece B is polished for 900 minutes in a dedicated partitioned polishing machine at a speed of 75 r / min using an abrasive. After drying, the surface-treated zirconium-based liquid metal workpiece is obtained. The abrasive comprises the following raw materials, in 100 parts by weight: 18 parts modified walnut shell powder, 15 parts silicone-modified polyether activator, 0.5 parts benzotriazole, 0.05 parts bactericide, 0.9 parts triethanolamine, 0.2 parts organosilicon defoamer, and the remainder is deionized water.

[0034] Comparative Example 4, based on Example 3, increases the power of nanosecond laser irradiation processing while keeping the other processes unchanged, as follows: Step 1: Preparation of silicon-modified polyether activator: (1) Under a nitrogen atmosphere, 9 parts of allyl polyoxyalkyl epoxy ether and 7 ppm Karstedt catalyst were mixed evenly at 70°C, heated to 100°C, and 3.4 parts of heptamethyltrisiloxane were added dropwise. The mixture was stirred and reacted for 4 hours. The mixture was concentrated under reduced pressure and purified to obtain silicon-modified epoxy ether. (2) Under a nitrogen atmosphere, 9 parts of silicone-modified epoxy ether, 6.4 parts of 4,4-diaminodiphenyl sulfide, and 0.06 parts of triethylamine were added to 100 parts of isopropanol. The mixture was stirred at 80°C for 3 hours, concentrated under reduced pressure, and purified to obtain a silicone-modified polyether activator. Step 2: Preparation of modified walnut shell: (1) Disperse walnut shell in an ethanol aqueous solution, add 3-aminopropyltriethoxysilane, stir at 45°C for 4 hours, centrifuge, wash, and dry to obtain amino-modified walnut shell; (2) Under a nitrogen atmosphere, disperse amino-modified walnut shell in isopropanol, add silicon-modified epoxy ether and triethylamine, stir at 80°C for 4 hours, centrifuge, wash, and dry to obtain modified walnut shell; wherein, the raw materials of the amino-modified walnut shell include walnut shell and 3-aminopropyltriethoxysilane in a mass ratio of 0.5:1; the particle size of the walnut shell is 10 μm; the raw materials of the modified walnut shell include amino-modified walnut shell, silicon-modified epoxy ether, and triethylamine in a mass ratio of 1:4.1:0.01; Step 3: Surface treatment process for zirconium-based liquid metal workpieces: S1: The zirconium-based liquid metal workpiece is rough polished for 60 minutes in a wet polishing machine using chromium corundum (6mm particle size) at a speed of 150r / min to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished with walnut shells (particle size of 100μm) in a special partitioned polishing machine for 50 minutes at a speed of 120r / min to obtain the zirconium-based liquid metal workpiece B. S3: The zirconium-based liquid metal workpiece B is treated with an abrasive in a dedicated partitioned polishing machine at a speed of 75 r / min for 900 min. After drying, it is treated with nanosecond laser irradiation. The specific process parameters are as follows: During the laser irradiation treatment, the laser wavelength is 1064 nm, the pulse width is 7 ns, the repetition frequency is 600 kHz, the average power is 8 W, the scanning speed is 10 mm / s, the scanning overlap rate is 80%, the spot diameter is 40 μm, and the gas atmosphere is argon. The surface-treated zirconium-based liquid metal workpiece is obtained. The abrasive includes the following raw materials, in 100 parts by weight: 18 parts modified walnut shell powder, 15 parts silicon-modified polyether activator, 0.5 parts benzotriazole, 0.05 parts bactericide, 0.9 parts triethanolamine, 0.2 parts organosilicon defoamer, and the remainder is deionized water.

[0035] Performance testing: (1) The surface roughness of each embodiment and comparative example was measured by laser confocal microscopy; (2) The hardness of each embodiment and comparative example was tested by a nanoindenter with a load of 200 mN and a loading speed of 10 mN / s; the experimental data are shown in the table below.

[0036] Example 1 0.071 6.4 Example 2 0.076 6.5 Example 3 0.051 22.1 Example 4 0.055 20.2 Comparative Example 1 0.279 6.4 Comparative Example 2 0.128 13.1 Comparative Example 3 0.097 6.5 Comparative Example 4 0.085 8.7 Conclusion: As shown in Table 1, the grinding time of Examples 1 and 2 within 120-180 min was sufficient to reduce the roughness to less than 0.1 μm, indicating high production efficiency and low roughness. In Comparative Example 1, the unmodified walnut sand had poor dispersibility, poor grinding effect, and was prone to scratches, resulting in a significant increase in roughness. In contrast, Examples 3 and 4 could maintain low roughness while significantly improving hardness. In Comparative Example 2, without the addition of silicon-modified polyether activator, the grinding effect was poor due to the lack of its special rivet and micro-damping effects, and it could not play a series of effects in subsequent laser treatment. The coefficient of friction and hardness were obviously not as good as in Example 3, but the hardness was improved to a certain extent compared with Example 1. This may be because the modified walnut shell residue on the workpiece surface had a limited effect on increasing hardness. In Comparative Example 3, without nanosecond laser irradiation treatment, the hardness could not be improved, and the roughness increased. In Comparative Example 4, increasing the power of nanosecond laser irradiation treatment caused the alloy matrix to over-melt, and a large amount of sulfur dissolved and diffused into the molten matrix, resulting in increased roughness and a significant decrease in hardness.

[0037] In summary, this invention employs rough polishing, medium polishing, and finishing processes sequentially to treat the surface of zirconium-based liquid metal workpieces. Based on walnut shell modification, it provides two finishing processes: solid and liquid. The former has higher efficiency and lower roughness (<0.1μm), while the latter can have both low roughness and high hardness.

[0038] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A surface treatment process for a zirconium-based liquid metal workpiece, characterized in that: Includes the following steps: S1: The zirconium-based liquid metal workpiece is rough polished in a wet polishing machine using chromium corundum to obtain zirconium-based liquid metal workpiece A; S2: The zirconium-based liquid metal workpiece A is polished in a special partitioned polishing machine using walnut shells to obtain zirconium-based liquid metal workpiece B; S3: Polish the zirconium-based liquid metal workpiece B to obtain a surface-treated zirconium-based liquid metal workpiece; In step S3, the specific preparation steps of the surface-treated zirconium-based liquid metal workpiece are as follows: the zirconium-based liquid metal workpiece B is polished using polishing paste in a special partitioned polishing machine to obtain the surface-treated zirconium-based liquid metal workpiece. The grinding paste comprises the following raw materials, by weight: 20-30 parts modified walnut shell, 30-40 parts stearic acid, 15-25 parts waxes, 1-3 parts glycerin, and 3-4 parts polyethylene glycol; The light-collecting process is performed at a rotation speed of 50-100 rpm for a duration of 80-1200 min. The preparation method of the modified walnut shell includes the following steps: (1) Disperse walnut shell in an ethanol aqueous solution, add 3-aminopropyltriethoxysilane, stir and react at 40~50℃ for 3~5h, centrifuge, wash, and dry to obtain amino-modified walnut shell; (2) Under a nitrogen atmosphere, disperse amino-modified walnut shell in isopropanol, add silicon-modified epoxy ether and triethylamine, stir at 75~85℃ for 3~5h, centrifuge, wash, and dry to obtain modified walnut shell; The raw materials for the amino-modified walnut shell include walnut shell and 3-aminopropyltriethoxysilane in a mass ratio of 0.4~0.6:1; the particle size of the walnut shell is 5~20μm; the raw materials for the modified walnut shell include amino-modified walnut shell, silicon-modified epoxy ether, and triethylamine in a mass ratio of 1:4~4.2:0.01~0.

02.

2. A surface treatment process for a zirconium-based liquid metal workpiece as claimed in claim 1, characterized in that: The particle size of the chromium corundum is 5-8 mm; the particle size of the walnut shell is 80-120 μm; the coarse polishing speed is 100-200 r / min and the time is 40-80 min; the medium polishing speed is 100-180 r / min and the time is 40-60 min.

3. The surface treatment process of a zirconium-based liquid metal workpiece according to claim 1, wherein, Alternatively: In step S3, the specific preparation steps of the surface-treated zirconium-based liquid metal workpiece are as follows: the zirconium-based liquid metal workpiece B is subjected to light-removing treatment in a special partitioned scintillation machine using an abrasive, and after being taken out and dried, it is subjected to nanosecond laser irradiation treatment to obtain the surface-treated zirconium-based liquid metal workpiece.

4. The surface treatment process for a zirconium-based liquid metal workpiece according to claim 3, characterized in that: The light collection process involves a rotation speed of 50-100 rpm and a duration of 80-1200 min. During the laser irradiation process, the laser wavelength is 1064 nm, the pulse width is 7 ns, the repetition frequency is 600-800 kHz, the average power is 4-5 W, the scanning speed is 5-10 mm / s, the scanning overlap rate is 70-90%, the spot diameter is 40-45 μm, and the gas atmosphere is argon. The abrasive comprises the following raw materials, in parts by weight of 100: 15-20 parts modified walnut shells, 14-16 parts silicone-modified polyether activator, 0.4-0.6 parts benzotriazole, 0.01-0.1 parts bactericide, 0.8-1 parts triethanolamine, 0.1-0.3 parts organosilicon defoamer, and the remainder is deionized water.

5. A surface treatment process for a zirconium-based liquid metal workpiece as claimed in claim 4, characterized in that: The preparation method of the silicon-modified polyether activator includes the following steps: (1) Under a nitrogen atmosphere, allyl polyoxyalkyl epoxy ether and Karstedt catalyst are mixed evenly at 70~75℃, heated to 95~100℃, heptamethyltrisiloxane is added dropwise, the reaction is stirred for 3~4h, the mixture is concentrated under reduced pressure and purified to obtain silicon-modified epoxy ether. (2) Under a nitrogen atmosphere, silicon-modified epoxy ether, 4,4-diaminodiphenyl sulfide and triethylamine are added to 80-100 parts of isopropanol and stirred at 75-85℃ for 3-4 hours. The mixture is then concentrated under reduced pressure and purified to obtain silicon-modified polyether activator.

6. A surface treatment process for a zirconium-based liquid metal workpiece as claimed in claim 5, characterized in that: The silicon-modified epoxy ether comprises the following raw materials, in parts by mass: 8-10 parts allyl polyoxyalkyl epoxy ether, 5-10 ppm Karstedt catalyst, and 3.3-3.5 parts heptamethyltrisiloxane; The silicon-modified polyether activator comprises the following raw materials, in parts by mass: 8-10 parts silicon-modified epoxy ether, 6.2-6.6 parts 4,4-diaminodiphenyl sulfide, 0.05-0.07 parts triethylamine, and 80-100 parts isopropanol.