High wear-resistant layered ni-based alloy with strong interface bonding and preparation method thereof

Abstract

The application discloses a high-wear-resistance layered Ni-based alloy with strong interface bonding and a preparation method thereof, and belongs to the technical field of metal materials. The alloy is prepared by double-slot direct current electrodeposition, and a Ni-Co-P nanocrystalline hard layer and a coarse-grained Ni soft layer are alternately deposited on a substrate, the total number of layers is 13-41, the total thickness is 200±25 microns, the thickness of a single layer is 5-25 microns, and the outermost layer is a Ni-Co-P layer. Through interface pre-activation and formula optimization, the coating is dense and defect-free, the interface bonding strength is 20.4-34.6 MPa, the bending strength is 797-1096 MPa, the wear rate is 0.7*10 ‑6 -3.8*10 ‑6 mm 3 N ‑1 m ‑1 , the wear resistance of the homogeneous coating is improved by 0.7-8.3 times, and the bonding strength and bending resistance are significantly improved. The application has the advantages of simple process and strong controllability, and is suitable for constructing a high-performance layered nickel-based alloy coating on the surface of various substrates.

Description

Technical Field

[0001] This invention relates to a highly wear-resistant layered Ni-based alloy with strong interfacial bonding and its preparation method, belonging to the field of metallic materials technology. Background Technology

[0002] Nickel-based alloys have broad application prospects in aerospace, petrochemical, marine engineering, and automotive manufacturing due to their excellent corrosion resistance, good mechanical properties, and relatively low cost. However, with the increasing demands of modern industry for material service life and reliability, traditional single-structure nickel-based alloys are struggling to meet the comprehensive requirements of high strength, high wear resistance, and good interfacial bonding under complex working conditions. Therefore, researchers have attempted to overcome these material performance bottlenecks by constructing layered heterostructures, as exemplified by Bathini et al. Ni-W multilayer coatings were prepared using reverse pulse electrodeposition. By optimizing the thickness of each layer, wear resistance was improved while maintaining thermal conductivity. However, existing layered nickel-based alloys still face two key challenges in practical applications:

[0003] First, the interfacial bonding strength is insufficient. The interfaces between different component layers in layered materials are critical areas for stress transfer and crack propagation. Currently, the interfacial bonding strength of layered nickel-based alloys prepared by electrodeposition or hot pressing is generally only 8-12 MPa. First, the interlayer bonding is weak. Under external loads or frictional stress, the interface is prone to debonding, delamination, or even spalling, severely reducing the overall mechanical properties and service life of the material. Second, wear resistance needs improvement. Although nanocrystalline nickel-based alloys have high hardness, their plasticity is poor, making them prone to microcracks and brittle spalling during friction and wear; while coarse-grained nickel layers, although possessing good plastic deformation capabilities, lack resistance to ploughing and cutting. The wear rate of conventional homogeneous nanocrystalline Ni-based alloy coatings is typically 5.0 × 10⁻⁶. -6 -8.0×10 -6 mm³N -1 m -1 Magnitude However, the wear resistance is insufficient to meet the requirements for long service life. Although existing layered structures have partially improved the above contradictions, they often come at the cost of sacrificing interfacial bonding strength, or can only achieve limited improvement in a single performance, making it difficult to achieve synergistic optimization of strong interfacial bonding and high wear resistance.

[0004] Currently, most preparation methods employ processes such as cumulative rolling, high-pressure torsion, diffusion welding combined with rolling and annealing. These methods largely rely on deformation to achieve grain refinement and interlayer bonding. However, these processes suffer from drawbacks such as poor interfacial bonding, complex processes, and difficulty in precisely controlling grain size. Electrodeposition technology offers advantages such as simple processes, mild conditions, fast deposition rates, and easy control over composition and structure. Furthermore, it allows for precise control of coating thickness by adjusting process conditions, making it a more ideal preparation method. However, for layered nickel-based alloys prepared by electrodeposition, improving the bonding strength of the soft / hard layer interface and overall wear resistance without introducing additional interfacial defects remains a pressing technical challenge.

[0005] Therefore, this invention provides a high-wear-resistant layered Ni-based alloy with strong interfacial bonding and its preparation method. Through a dual-groove DC electrodeposition process, coarse-grained nickel layers and nanocrystalline nickel-based alloy layers are alternately deposited on the substrate surface. Interfacial pre-activation treatment and multilayer structural parameter optimization significantly enhance the interlayer bonding strength. Simultaneously, the alternating soft / hard layered configuration regulates stress distribution, inhibits crack propagation, and introduces mechanisms such as work hardening and dislocation pile-up, greatly improving the material's wear resistance. This invention aims to overcome the shortcomings of existing layered nickel-based alloys, such as weak interfacial bonding and poor wear resistance, providing a simple and efficient solution for preparing high-performance nickel-based protective coatings and structural materials.

[0006] References

[0007] Summary of the Invention

[0008] The purpose of this invention is to provide a high wear-resistant layered Ni-based alloy with strong interfacial bonding, its preparation method and application. This alloy material has excellent wear resistance and good interfacial bonding strength, enabling the coating to maintain excellent stability under complex and harsh conditions.

[0009] To achieve the above-mentioned technical objectives, this invention provides a high-wear-resistant layered Ni-based alloy with strong interfacial bonding and its preparation method; the specific technical solution is as follows:

[0010] A layered Ni-based alloy with strong interfacial bonding and high wear resistance is characterized by: a coarse-grained nickel layer and a super-nano nickel-based ternary alloy layer being deposited sequentially on a substrate, with the outermost layer being a Ni-Co-P layer; the thickness of the nanocrystalline nickel alloy layer being 5-25 micrometers; the thickness of the coarse-grained nickel layer being 5-25 micrometers; the total thickness of the coating being 200±25 micrometers; and the total number of layers being 13-41, forming a layered heterogeneous nickel-based alloy.

[0011] The thickness ratio of the nanocrystalline nickel alloy layer to the coarse-crystalline nickel layer is 1:5-5:1.

[0012] This alloy was prepared by a dual-groove DC electrodeposition method and, after interface pre-activation treatment, obtained a multilayer structure with high bonding strength and clear interfaces. The resulting layered nickel-based alloy exhibits significantly higher wear resistance, bending strength, and coating bonding strength than homogeneous alloys.

[0013] The nanocrystalline nickel alloy layer is a Ni-Co-P ternary alloy with finer grain size and denser structure, and serves as the hard phase in the layered structure; the coarse-grained Ni layer has larger grain size and better toughness, and serves as the soft phase in the layered structure, aiming to deform in synergy with the hard phase to release stress.

[0014] The present invention discloses a method for preparing a highly wear-resistant layered Ni-based alloy with strong interfacial bonding, characterized by comprising the following steps:

[0015] S1. Using a nickel plate as the anode, the surface oxide layer of the nickel plate is removed by sanding with sandpaper. After covering the nickel plate with a layer of non-woven fabric, it is placed in the plating solution.

[0016] S2. Substrate pretreatment: The substrate is the metal or conductive material to be deposited with the coating. The substrate is subjected to surface grinding, polishing and degreasing in sequence; then it is washed with water, acid pickling, ultrasonic activation, and washed with water again.

[0017] S3. The above substrate is immersed in a nickel alloy plating solution, and a nanocrystalline nickel alloy layer is prepared by direct current electrodeposition. The nanocrystalline nickel alloy layer is a Ni-Co-P ternary alloy and serves as the hard phase in the layered structure.

[0018] S4. The substrate with nanocrystalline nickel alloy coating obtained in the above steps is washed with water, acid-washed and ultrasonically activated, then washed with water again and immersed in coarse-crystalline nickel plating solution. A coarse-crystalline nickel layer is prepared on the nanocrystalline nickel alloy layer by direct current electrodeposition as the soft phase in the layered structure.

[0019] S5. The bilayer substrate with nanocrystalline layer + coarse crystalline layer obtained by the above steps is washed with water, acid-washed and ultrasonically activated, and then washed with water again. Then the DC electrodeposition operation of steps S3 and S4 is repeated in sequence. The outermost layer is Ni-Co-P layer. This cycle is repeated to finally prepare a layered heterogeneous nickel-based alloy with a total number of 13-41 layers.

[0020] The substrate includes conventional substrates such as copper plates and stainless steel plates.

[0021] The components of the nickel alloy plating solution include nickel sulfate hexahydrate, nickel chloride hexahydrate, anhydrous citric acid, boric acid, phosphorous acid, cobalt sulfate heptahydrate, sodium dodecyl sulfate, sodium saccharin, and deionized water; the mass ratio of all the above components is as follows, based on the preparation of 1L of nickel alloy plating solution:

[0022] Nickel sulfate hexahydrate 100-300 g / L

[0023] Nickel chloride hexahydrate 10-40 g / L

[0024] Anhydrous citric acid 50-70 g / L

[0025] Boric acid 20-60 g / L

[0026] Phosphorous acid 10-30 g / L

[0027] Cobalt sulfate heptahydrate 10-30 g / L

[0028] Sodium dodecyl sulfate 0.1-0.3 g / L

[0029] Sodium saccharin 0.5-3 g / L

[0030] Deionized water balance.

[0031] The nickel alloy plating solution is prepared as follows: dissolve the raw material components in deionized water according to all the components and dosages of the designed nickel alloy plating solution, stir to dissolve, and then filter with filter paper; then, add the composite additive components to the above filtrate, stir to dissolve, and then adjust the volume to 1L to obtain the final solution.

[0032] In step S3, the DC electrodeposition process conditions are as follows: a nickel plate with a purity of 99.0 wt.% is used as the anode; magnetic stirring is employed at a speed of 500-1000 rpm, and the current density is 30-50 mA / cm². 2 The electrodeposition time for a single layer is 25-125 min; the pH and temperature of the nickel alloy plating bath are as follows:

[0033] Nanocrystalline nickel-cobalt-phosphorus alloy layers are prepared by direct current electrodeposition. The nickel alloy plating solution is a nickel-cobalt-phosphorus alloy plating solution. Before plating, the pH value of the plating solution is adjusted to 2.0-3.0 with dilute sulfuric acid solution, and the temperature of the plating solution is adjusted to 40-60℃.

[0034] In step S4, the nickel plating solution comprises nickel sulfate hexahydrate, nickel chloride hexahydrate, boric acid, sodium dodecyl sulfate, sodium saccharin, and deionized water. The raw material components are dissolved in deionized water according to the designed composition and dosage of the nickel plating solution. After stirring and dissolving, the solution is filtered through filter paper. Then, the composite additive components are added to the filtrate, stirred and dissolved, and the volume is adjusted to 1L to obtain the final product. Unlike typical watt plating solutions, this solution adds a small amount of sodium saccharin to reduce the internal stress of the plating layer and improve the interlayer adhesion. Based on a 1L coarse-grained nickel plating solution, the mass ratio of all the above components is as follows:

[0035] Nickel sulfate hexahydrate 100-300 g / L

[0036] Nickel chloride hexahydrate 10-40 g / L

[0037] Boric acid 20-60 g / L

[0038] Sodium dodecyl sulfate 0.1-0.3 g / L

[0039] Sodium saccharin 0.2-3 g / L

[0040] Deionized water balance

[0041] All components are of AR purity.

[0042] Before plating, the pH of the nickel plating bath was adjusted to 3.4-5.2 using a dilute sulfuric acid solution, and the bath temperature was adjusted to 40-60℃. The DC electrodeposition process conditions were as follows: a nickel plate with a purity of 99.0 wt.% was used as the anode; magnetic stirring was employed at a speed of 500-1000 rpm, and the current density was 30-50 mA / cm². 2 The electrodeposition time for a single layer is 10-50 min.

[0043] The beneficial effects of this invention are:

[0044] The preparation process of the Ni-Co-P / Ni alloy coating (named for its structure: consisting of alternating stacks of Ni-Co-P alloy layers and coarse-grained Ni layers) obtained by the embodiments of the present invention is as follows: Figure 1 As shown. The structural morphology was characterized using scanning electron microscopy (SEM) and light microscopy, as shown. Figure 2 , Figure 3 As shown, the layered heterogeneous nickel-based alloy prepared by this invention exhibits a dense and defect-free layered composite nanostructure nickel-based alloy coating. The coordinated deformation of the large and small grain layers imparts superior mechanical properties to the nanostructure nickel-based alloy, meeting the high mechanical performance requirements of nanostructure nickel-based alloys in engineering. In this invention, alternating different coatings are applied using a dual-groove DC electrodeposition method, which is simple, convenient, and low-cost, and can be applied to various substrate surfaces to prepare this layered nanostructure material with excellent mechanical properties.

[0045] The wear resistance, bending properties, and bonding strength of the layered nickel-based alloy obtained in the embodiments of this invention and the homogeneous nanostructured nickel-based alloy obtained in the comparative example were tested using a tribological testing machine, a universal testing machine, and a micro-scratch tester. The layered nickel-based alloy prepared in this invention exhibited superior wear resistance, bending resistance, and bonding strength compared to the homogeneous nanostructured nickel-based alloy during the experiments. See also... Figure 4 , Figure 5 , Figure 6 Compared with Table 1. From Figure 4 It can be seen that the wear rate of the homogeneous coating is approximately 6.5 x 10⁻⁶. -6 mm 3 N -1 m-1 The wear rate of the layered Ni-Co-P / Ni alloy coating is approximately 0.7 x 10⁻⁶. -6 mm 3 N -1 m -1 -3.8x10 -6 mm 3 N -1 m -1 Compared to homogeneous coatings, the wear rate is improved by nearly 0.7-8.3 times. From Figure 5 It can be observed that the bonding strength of the layered nickel-based alloy coating prepared by this invention is 20.4-34.6 MPa, and the flexural strength is 797-1096 MPa; compared with the bonding strength of 9.0 MPa and the flexural strength of 106 MPa of the homogeneous coating, the bending resistance and bonding strength of the nickel-based alloy are improved by approximately 1.3-2.8 times and 6.5-9.3 times, respectively. Figure 6 It can be clearly seen that the bonding force of Example 1, 15.2 N, is significantly higher than that of the comparative example, 5.7 N, which is nearly 1.6 times higher.

[0046] This invention utilizes anhydrous citric acid and phosphorous acid in a nickel alloy plating bath to synergistically refine grains, and precisely proportions sodium dodecyl sulfate and sodium saccharin to achieve nanocrystal densification and high hardness. A small amount of sodium saccharin is added to the nickel plating bath to reduce internal stress in the coating while simultaneously improving interlayer adhesion.

[0047] The preparation method of this invention is based on a dual-groove direct current electrodeposition method, which produces a layered nickel-based alloy with alternating grain sizes along the cross-section, such as... Figure 2 and Figure 3 As shown, the prepared layered nickel-based alloy has high bonding strength and excellent wear resistance, and can be used as a reinforcing coating for metallic materials or as a high-performance structural material. Attached Figure Description

[0048] Figure 1 This is a flowchart illustrating the preparation of the Ni-Co-P / Ni alloy coating according to an embodiment of the present invention.

[0049] Figure 2 This is a cross-sectional SEM image of the Ni-Co-P / Ni alloy coating prepared according to an embodiment of the present invention.

[0050] Figure 3 This is a cross-sectional OM diagram of the Ni-Co-P / Ni alloy coating prepared according to an embodiment of the present invention.

[0051] Figure 4 The friction coefficients and wear rates are those of the examples and comparative examples.

[0052] Figure 5The diagram shows the bending stress-strain curves of the three-point bending in the examples and comparative examples.

[0053] Figure 6 These are the OM diagrams of scratch tests for the embodiments and comparative examples. Detailed Implementation

[0054] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. 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.

[0055] To further understand the features and beneficial effects of the present invention, the following is a detailed description of several preferred embodiments of the present invention.

[0056] The comparative examples and embodiments of the present invention include the following steps.

[0057] The preparation of the comparative homogeneous nanostructured nickel-cobalt-phosphorus alloy was carried out according to the following steps: (This comparative example was prepared according to the plating solution formulation of Zhang, Yin, et al. “Study on the Wear and Seawater Corrosion Resistance of Ni-Co-P Alloy Coatings with Jet Electrodeposition in Different Jet Voltages and Temperatures of Plating Solution.” Coatings, vol. 10, no. 7, 2020, p.639, https: / / doi.org / 10.3390 / coatings10070639.)

[0058] (1) Select copper plate as the base metal and pretreat it:

[0059] The surface of the copper plate was polished sequentially with 400#, 800#, and 1500# sandpaper. It was then rinsed with deionized water to remove residual substrate wear and abrasive particles. Next, it was polished with 0.5# diamond polishing paste. Afterward, it was soaked in a 20% sodium hydroxide aqueous solution at 75°C for 10 minutes to degrease and remove oil. Then, it was rinsed with tap water and deionized water sequentially to obtain a smooth, uncontaminated surface. Finally, it was acid-washed with a 10% hydrochloric acid aqueous solution for 45 seconds to activate the surface. The acid solution was then rinsed off with tap water and deionized water sequentially. The treated copper plate was then soaked in deionized water for later use.

[0060] (2) Preparation of nickel-cobalt-phosphorus alloy electroplating solution:

[0061] The electroplating solution, calculated per liter, comprises 200g nickel sulfate, 30g nickel chloride, 60g anhydrous citric acid, 20g phosphorous acid, 20g cobalt sulfate, 3g sodium saccharin, 0.2g sodium dodecyl sulfate, and the remainder deionized water. Nickel sulfate, nickel chloride, boric acid, anhydrous citric acid, phosphorous acid, cobalt sulfate, and composite additives are sequentially dissolved in deionized water. Then, under stirring, the pH of the plating solution is adjusted to 2.3 with dilute sulfuric acid solution, resulting in a homogeneous nanostructured nickel-cobalt-phosphorus alloy electroplating solution.

[0062] (3) Electrodeposition preparation of homogeneous nanostructured nickel-cobalt-phosphorus alloy:

[0063] The copper plate treated in step (1) was used as the cathode and the pure nickel material was used as the anode. These were then placed in the nickel-cobalt-phosphorus electroplating solution prepared in step (2) and connected to the negative and positive terminals of a DC regulated power supply, respectively. The electroplating solution was heated to 60°C with continuous mechanical stirring, and the solution was heated to 40 mA / cm². 2 Electrodeposition was performed for 16.7 hours, resulting in a homogeneous nanostructured nickel-cobalt-phosphorus coating with a thickness of approximately 200 micrometers on the copper plate, denoted as Sample 1.

[0064] Example 1: Preparation of a layered Ni-Co-P / Ni alloy coating, the steps are as follows:

[0065] (1) Prepare two anodes, using a nickel plate as the anode. Polish the nickel plate (5×50×140 mm) with sandpaper. 3 Remove the surface oxide layer, wrap a layer of non-woven fabric around the nickel plate, and then place it in the plating solution.

[0066] (2) Select a copper plate as the cathode (i.e., substrate), and polish the pre-cut copper plate (1×30×30mm) with 400#, 800#, and 2000# sandpaper in sequence. 3The copper plate was immersed in acetone and ultrasonically degreased. It was then soldered to a long wire using solder rods, and the soldered surface was sealed with cold mounting liquid (CM1, Naibo Testing Technology Co., Ltd.). After drying, it was wet-ground and mechanically polished with 400#, 1000# and 2000# sandpaper until there were no visible scratches. Then, it was cleaned with concentrated hydrochloric acid and dilute hydrochloric acid for 5 minutes in sequence. After each cleaning, it was rinsed with deionized water. Finally, the copper plate was immersed in anhydrous ethanol for later use.

[0067] (3) Two plating solutions were prepared, including a 500 mL nickel-cobalt-phosphorus alloy plating solution and a pure nickel plating solution:

[0068] A 500 mL nickel-cobalt-phosphorus alloy plating bath was prepared, comprising 100 g nickel sulfate, 15 g nickel chloride, 30 g anhydrous citric acid, 10 g phosphorous acid, 10 g cobalt sulfate, 0.9 g sodium saccharin, 0.1 g sodium dodecyl sulfate, and the balance deionized water. The nickel sulfate, nickel chloride, boric acid, sodium citrate, and composite additives were dissolved in the deionized water. Then, under stirring at 500 rpm, the pH was adjusted to 2.5 with dilute sulfuric acid solution.

[0069] A 500 mL coarse-grained nickel plating solution was prepared, comprising 150 g nickel sulfate, 15 g nickel chloride, 20 g boric acid, 0.5 g sodium saccharin, 0.1 g sodium dodecyl sulfate, and the remainder deionized water. The nickel sulfate, nickel chloride, boric acid, and composite additives were dissolved in the deionized water. Then, under stirring at 500 rpm, the pH was adjusted to 3.8 with dilute sulfuric acid solution.

[0070] (4) After preparing the above two plating solutions, a dual-tank DC electrodeposition method is used to electroplate the ultra-nano nickel-cobalt-phosphorus alloy and the coarse-grained nickel layer. The main process is as follows: Two plating tanks are selected and labeled as plating tank 1 and plating tank 2, respectively. An anode is placed in plating tank 1 and plating tank 2, and the cathode is placed in plating tank 1 containing the ultra-nano nickel-cobalt-phosphorus alloy plating solution to begin plating the Ni-Co-P stage. After the Ni-Co-P layer is plating, the cathode is transferred to plating tank 2 containing the Ni plating solution. This process of alternating plating tanks is repeated until a layered Ni-Co-P / Ni alloy coating is finally obtained on the substrate. The specific process is as follows:

[0071] The copper plate processed in step (2) is placed as the cathode in plating tank 1, and the two nickel plates processed in step (1) are placed as the anodes in plating tank 1 containing ultra-nano nickel-cobalt-phosphorus alloy plating solution and plating tank 2 containing coarse-grained Ni plating solution, respectively. For plating tank 1, the cathode and anode are connected to the negative and positive terminals of a DC regulated power supply, respectively. Under the conditions of plating solution temperature of 50℃ and continuous mechanical stirring in plating tank 1, the temperature is 40 mA / cm². 2Electrodeposition was performed for 25 minutes. After the Ni-Co-P layer was deposited, the cathode was transferred to plating tank 2. The cathode and anode were connected to the negative and positive terminals of a DC regulated power supply, respectively. The plating bath in tank 2 was maintained at 50°C with continuous mechanical stirring, and the electroplating rate was 40 mA / cm². 2 Electrodeposition was performed for 50 minutes. The cathode sample was repeatedly transferred between plating tank 1 and plating tank 2 for DC electrodeposition. After a total electrodeposition time of 7.9 hours, a total of 13 layers of layered Ni-Co-P / Ni alloy with a total thickness of 205 micrometers were obtained on the copper substrate, designated as Sample 2. In Example 1, the mass percentage of cobalt was 15.0-17.0%, the mass percentage of phosphorus was 2.0-3.0%, and the balance was nickel and unavoidable impurities. Figure 1 The cross-sectional SEM image of sample 2 is shown. Figure 1 As can be seen, alternating light and dark layers can be observed, and there are no obvious transition features between the layers, indicating that the bonding between the layers is good and that they have obvious layered features.

[0072] Example 2: Preparation of a layered composite Ni-Co-P / Ni alloy coating, the preparation steps are as follows:

[0073] (1) Prepare two anodes, using a nickel plate as the anode. Polish the nickel plate (5×50×140 mm) with sandpaper. 3 Remove the surface oxide layer, wrap a layer of non-woven fabric around the nickel plate, and then place it in the plating solution.

[0074] (2) Select a copper plate as the cathode (i.e., substrate), and polish the pre-cut copper plate (1×30×30mm) with 400#, 800#, and 2000# sandpaper in sequence. 3 The copper plate was immersed in acetone and ultrasonically degreased. It was then soldered to a long wire using solder rods, and the soldered surface was sealed with cold mounting liquid (CM1, Naibo Testing Technology Co., Ltd.). After drying, it was wet-ground and mechanically polished with 400#, 1000# and 2000# sandpaper until there were no visible scratches. Then, it was cleaned with concentrated hydrochloric acid and dilute hydrochloric acid for 5 minutes in sequence. After each cleaning, it was rinsed with deionized water. Finally, the copper plate was immersed in anhydrous ethanol for later use.

[0075] (3) Two plating solutions were prepared, including a 500 mL nickel-cobalt-phosphorus alloy plating solution and a pure nickel plating solution:

[0076] A 500 mL nickel-cobalt-phosphorus alloy plating bath was prepared, comprising 150 g nickel sulfate, 20 g nickel chloride, 35 g anhydrous citric acid, 15 g phosphorous acid, 15 g cobalt sulfate, 1.5 g sodium saccharin, 0.15 g sodium dodecyl sulfate, and the balance deionized water. The nickel sulfate, nickel chloride, boric acid, sodium citrate, and composite additives were dissolved in the deionized water. Then, under stirring at 1000 rpm, the pH was adjusted to 2.0 with dilute sulfuric acid solution.

[0077] A 500 mL coarse-grained nickel plating solution was prepared, comprising 100 g nickel sulfate, 15 g nickel chloride, 20 g boric acid, 0.5 g sodium saccharin, 0.1 g sodium dodecyl sulfate, and the remainder deionized water. The nickel sulfate, nickel chloride, boric acid, and composite additives were dissolved in the deionized water. Then, under stirring at 500 rpm, the pH was adjusted to 3.8 with dilute sulfuric acid solution.

[0078] (4) After preparing the above two plating solutions, a dual-tank DC electrodeposition method is used to electroplate the ultra-nano nickel-cobalt-phosphorus alloy and the coarse-grained nickel layer. The main process is as follows: Two plating tanks are selected and labeled as plating tank 1 and plating tank 2, respectively. An anode is placed in plating tank 1 and plating tank 2, and the cathode is placed in plating tank 1 containing the ultra-nano nickel-cobalt-phosphorus alloy plating solution to begin plating the Ni-Co-P stage. After the Ni-Co-P layer is plating, the cathode is transferred to plating tank 2 containing the Ni plating solution. This process of alternating plating tanks is repeated until a layered Ni-Co-P / Ni alloy coating is finally obtained on the substrate. The specific process is as follows:

[0079] The copper plate processed in step (2) is placed in plating tank 1 as the cathode, and the two nickel plates processed in step (1) are placed in plating tank 1 containing ultra-nano nickel-cobalt-phosphorus alloy plating solution and plating tank 2 containing coarse-grained Ni plating solution, respectively, as anodes. For plating tank 1, the cathode and anode are connected to the negative and positive terminals of a DC regulated power supply, respectively. Under the conditions of plating solution temperature of 60℃ and continuous mechanical stirring in plating tank 1, the temperature is 30 mA / cm². 2 Electrodeposition was performed for 25 minutes. After the Ni-Co-P layer was deposited, the cathode was transferred to plating tank 2. The cathode and anode were connected to the negative and positive terminals of a DC regulated power supply, respectively. The plating bath in tank 2 was maintained at 50°C with continuous mechanical stirring, and the electroplating rate was 40 mA / cm². 2 Electrodeposition was performed for 30 minutes. The cathode sample was repeatedly transferred between plating tank 1 and plating tank 2 and DC electrodeposition was performed. After a total electrodeposition time of 9.6 hours, a total of 21 layers of Ni-Co-P / Ni alloy with a total thickness of 197 micrometers were obtained on the copper substrate, which was designated as sample 3.

[0080] Example 3: Preparation of a layered composite Ni-Co-P / Ni alloy coating, the preparation steps are as follows:

[0081] (1) Prepare two anodes, using a nickel plate as the anode. Polish the nickel plate (5×50×140 mm) with sandpaper. 3 Remove the surface oxide layer, wrap a layer of non-woven fabric around the nickel plate, and then place it in the plating solution.

[0082] (2) Select a copper plate as the cathode (i.e., substrate), and polish the pre-cut copper plate (1×30×30mm) with 400#, 800#, and 2000# sandpaper in sequence. 3 The copper plate was immersed in acetone and ultrasonically degreased. It was then soldered to a long wire using solder rods, and the soldered surface was sealed with cold mounting liquid (CM1, Naibo Testing Technology Co., Ltd.). After drying, it was wet-ground and mechanically polished with 400#, 1000# and 2000# sandpaper until there were no visible scratches. Then, it was cleaned with concentrated hydrochloric acid and dilute hydrochloric acid for 5 minutes in sequence. After each cleaning, it was rinsed with deionized water. Finally, the copper plate was immersed in anhydrous ethanol for later use.

[0083] (3) Two plating solutions were prepared, including a 500 mL nickel-cobalt-phosphorus alloy plating solution and a pure nickel plating solution:

[0084] A 500 mL nickel-cobalt-phosphorus alloy plating bath was prepared, comprising 100 g nickel sulfate, 15 g nickel chloride, 30 g anhydrous citric acid, 10 g phosphorous acid, 10 g cobalt sulfate, 0.9 g sodium saccharin, 0.1 g sodium dodecyl sulfate, and the balance deionized water. The nickel sulfate, nickel chloride, boric acid, sodium citrate, and composite additives were dissolved in the deionized water. Then, under stirring at 750 rpm, the pH was adjusted to 2.5 with dilute sulfuric acid solution.

[0085] A 500 mL coarse-grained nickel plating solution was prepared, comprising 150 g nickel sulfate, 20 g nickel chloride, 30 g boric acid, 1.5 g sodium saccharin, 0.15 g sodium dodecyl sulfate, and the remainder deionized water. The nickel sulfate, nickel chloride, boric acid, and composite additives were dissolved in the deionized water. Then, under stirring at 500 rpm, the pH was adjusted to 3.4 with dilute sulfuric acid solution.

[0086] (4) After preparing the above two plating solutions, a dual-tank DC electrodeposition method is used to electroplate the ultra-nano nickel-cobalt-phosphorus alloy and the coarse-grained nickel layer. The main process is as follows: Two plating tanks are selected and labeled as plating tank 1 and plating tank 2, respectively. An anode is placed in plating tank 1 and plating tank 2, and the cathode is placed in plating tank 1 containing the ultra-nano nickel-cobalt-phosphorus alloy plating solution to begin plating the Ni-Co-P stage. After the Ni-Co-P layer is plating, the cathode is transferred to plating tank 2 containing the Ni plating solution. This process of alternating plating tanks is repeated until a layered Ni-Co-P / Ni alloy coating is finally obtained on the substrate. The specific process is as follows:

[0087] The copper plate processed in step (2) is placed as the cathode in plating tank 1, and the two nickel plates processed in step (1) are placed as the anodes in plating tank 1 containing ultra-nano nickel-cobalt-phosphorus alloy plating solution and plating tank 2 containing coarse-grained Ni plating solution, respectively. For plating tank 1, the cathode and anode are connected to the negative and positive terminals of a DC regulated power supply, respectively. Under the conditions of plating solution temperature of 40℃ and continuous mechanical stirring in plating tank 1, the temperature is 50 mA / cm². 2 Electrodeposition was performed for 25 minutes. After the Ni-Co-P layer was deposited, the cathode was transferred to plating tank 2. The cathode and anode were connected to the negative and positive terminals of a DC regulated power supply, respectively. The plating bath in tank 2 was maintained at 50°C with continuous mechanical stirring, and the electroplating rate was 40 mA / cm². 2 Electrodeposition was performed for 10 minutes. The cathode sample was repeatedly transferred between plating tank 1 and plating tank 2 and DC electrodeposition was performed. After a total electrodeposition time of 12 hours, a total of 41 layers of layered Ni-Co-P / Ni alloy with a total thickness of 204 micrometers were obtained on the copper substrate, which was designated as sample 4.

[0088] Example 4: Preparation of a layered composite Ni-Co-P / Ni alloy coating, the preparation steps are as follows:

[0089] (1) Prepare two anodes, using a nickel plate as the anode. Polish the nickel plate (5×50×140 mm) with sandpaper. 3 Remove the surface oxide layer, wrap a layer of non-woven fabric around the nickel plate, and then place it in the plating solution.

[0090] (2) Select a copper plate as the cathode (i.e., substrate), and polish the pre-cut copper plate (1×30×30mm) with 400#, 800#, and 2000# sandpaper in sequence. 3The copper plate was immersed in acetone and ultrasonically degreased. It was then soldered to a long wire using solder rods, and the soldered surface was sealed with cold mounting liquid (CM1, Naibo Testing Technology Co., Ltd.). After drying, it was wet-ground and mechanically polished with 400#, 1000# and 2000# sandpaper until there were no visible scratches. Then, it was cleaned with concentrated hydrochloric acid and dilute hydrochloric acid for 5 minutes in sequence. After each cleaning, it was rinsed with deionized water. Finally, the copper plate was immersed in anhydrous ethanol for later use.

[0091] (3) Two plating solutions were prepared, including a 500 mL nickel-cobalt-phosphorus alloy plating solution and a pure nickel plating solution:

[0092] A 500 mL nickel-cobalt-phosphorus alloy plating bath was prepared, comprising 50 g nickel sulfate, 10 g nickel chloride, 25 g anhydrous citric acid, 5 g phosphorous acid, 5 g cobalt sulfate, 0.25 g sodium saccharin, 0.05 g sodium dodecyl sulfate, and the balance deionized water. The nickel sulfate, nickel chloride, boric acid, sodium citrate, and composite additives were dissolved in the deionized water. Then, under stirring at 750 rpm, the pH was adjusted to 3.0 with dilute sulfuric acid solution.

[0093] A 500 mL coarse-grained nickel plating solution was prepared, comprising 150 g nickel sulfate, 15 g nickel chloride, 20 g boric acid, 0.5 g sodium saccharin, 0.1 g sodium dodecyl sulfate, and the remainder deionized water. The nickel sulfate, nickel chloride, boric acid, and composite additives were dissolved in the deionized water. Then, under stirring at 750 rpm, the pH was adjusted to 3.8 with dilute sulfuric acid solution.

[0094] (4) After preparing the above two plating solutions, a dual-tank DC electrodeposition method is used to electroplate the ultra-nano nickel-cobalt-phosphorus alloy and the coarse-grained nickel layer. The main process is as follows: Two plating tanks are selected and labeled as plating tank 1 and plating tank 2, respectively. An anode is placed in plating tank 1 and plating tank 2, and the cathode is placed in plating tank 1 containing the ultra-nano nickel-cobalt-phosphorus alloy plating solution to begin plating the Ni-Co-P stage. After the Ni-Co-P layer is plating, the cathode is transferred to plating tank 2 containing the Ni plating solution. This process of alternating plating tanks is repeated until a layered Ni-Co-P / Ni alloy coating is finally obtained on the substrate. The specific process is as follows:

[0095] The copper plate processed in step (2) is placed as the cathode in plating tank 1, and the two nickel plates processed in step (1) are placed as the anodes in plating tank 1 containing ultra-nano nickel-cobalt-phosphorus alloy plating solution and plating tank 2 containing coarse-grained Ni plating solution, respectively. For plating tank 1, the cathode and anode are connected to the negative and positive terminals of a DC regulated power supply, respectively. Under the conditions of plating solution temperature of 50℃ and continuous mechanical stirring in plating tank 1, the temperature is 40 mA / cm². 2Electrodeposition was performed for 75 minutes. After the Ni-Co-P layer was deposited, the cathode was transferred to plating tank 2. The cathode and anode were connected to the negative and positive terminals of a DC regulated power supply, respectively. The plating bath in tank 2 was maintained at 60°C with continuous mechanical stirring, and the electroplating rate was 30 mA / cm². 2 Electrodeposition was performed for 10 minutes. The cathode sample was repeatedly transferred between plating tank 1 and plating tank 2 and DC electrodeposition was performed. After a total electrodeposition time of 15.4 hours, a total of 21 layers of layered Ni-Co-P / Ni alloy with a total thickness of 209 micrometers were obtained on the copper substrate, which was designated as sample 5.

[0096] Example 5: Preparation of a layered composite Ni-Co-P / Ni alloy coating, the preparation steps are as follows:

[0097] (1) Prepare two anodes, using a nickel plate as the anode. Polish the nickel plate (5×50×140 mm) with sandpaper. 3 Remove the surface oxide layer, wrap a layer of non-woven fabric around the nickel plate, and then place it in the plating solution.

[0098] (2) Select a copper plate as the cathode (i.e., substrate), and polish the pre-cut copper plate (1×30×30mm) with 400#, 800#, and 2000# sandpaper in sequence. 3 The copper plate was immersed in acetone and ultrasonically degreased. It was then soldered to a long wire using solder rods, and the soldered surface was sealed with cold mounting liquid (CM1, Naibo Testing Technology Co., Ltd.). After drying, it was wet-ground and mechanically polished with 400#, 1000# and 2000# sandpaper until there were no visible scratches. Then, it was cleaned with concentrated hydrochloric acid and dilute hydrochloric acid for 5 minutes in sequence. After each cleaning, it was rinsed with deionized water. Finally, the copper plate was immersed in anhydrous ethanol for later use.

[0099] (3) Two plating solutions were prepared, including a 500 mL nickel-cobalt-phosphorus alloy plating solution and a pure nickel plating solution:

[0100] A 500 mL nickel-cobalt-phosphorus alloy plating bath was prepared, comprising 150 g nickel sulfate, 20 g nickel chloride, 35 g anhydrous citric acid, 15 g phosphorous acid, 15 g cobalt sulfate, 1.5 g sodium saccharin, 0.15 g sodium dodecyl sulfate, and the balance deionized water. The nickel sulfate, nickel chloride, boric acid, sodium citrate, and composite additives were dissolved in the deionized water. Then, under stirring at 750 rpm, the pH was adjusted to 2.0 with dilute sulfuric acid solution.

[0101] A 500 mL coarse-grained nickel plating solution was prepared, comprising 150 g nickel sulfate, 20 g nickel chloride, 30 g boric acid, 1.5 g sodium saccharin, 0.15 g sodium dodecyl sulfate, and the remainder deionized water. The nickel sulfate, nickel chloride, boric acid, and composite additives were dissolved in the deionized water. Then, under stirring at 1000 rpm, the pH was adjusted to 3.4 with dilute sulfuric acid solution.

[0102] (4) After preparing the above two plating solutions, a dual-tank DC electrodeposition method is used to electroplate the ultra-nano nickel-cobalt-phosphorus alloy and the coarse-grained nickel layer. The main process is as follows: Two plating tanks are selected and labeled as plating tank 1 and plating tank 2, respectively. An anode is placed in plating tank 1 and plating tank 2, and the cathode is placed in plating tank 1 containing the ultra-nano nickel-cobalt-phosphorus alloy plating solution to begin plating the Ni-Co-P stage. After the Ni-Co-P layer is plating, the cathode is transferred to plating tank 2 containing the Ni plating solution. This process of alternating plating tanks is repeated until a layered Ni-Co-P / Ni alloy coating is finally obtained on the substrate. The specific process is as follows:

[0103] The copper plate processed in step (2) is placed as the cathode in plating tank 1, and the two nickel plates processed in step (1) are placed as the anodes in plating tank 1 containing ultra-nano nickel-cobalt-phosphorus alloy plating solution and plating tank 2 containing coarse-grained Ni plating solution, respectively. For plating tank 1, the cathode and anode are connected to the negative and positive terminals of a DC regulated power supply, respectively. Under the conditions of plating solution temperature of 50℃ and continuous mechanical stirring in plating tank 1, the temperature is 40 mA / cm². 2 Electrodeposition was performed for 125 minutes. After the Ni-Co-P layer was deposited, the cathode was transferred to plating tank 2. The cathode and anode were connected to the negative and positive terminals of a DC regulated power supply, respectively. The plating bath in tank 2 was maintained at 40°C with continuous mechanical stirring, and the electrochemical flux was increased to 50 mA / cm². 2 Electrodeposition was performed for 10 minutes. The cathode sample was repeatedly transferred between plating tank 1 and plating tank 2 and DC electrodeposition was performed. After a total electrodeposition time of 15.6 hours, a total of 13 layers of layered Ni-Co-P / Ni alloy with a total thickness of 218 micrometers were obtained on the copper substrate, which was designated as sample 6.

[0104] Example 6: Preparation of a layered composite Ni-Co-P / Ni alloy coating, the preparation steps are as follows:

[0105] (1) Prepare two anodes, using a nickel plate as the anode. Polish the nickel plate (5×50×140 mm) with sandpaper. 3 Remove the surface oxide layer, wrap a layer of non-woven fabric around the nickel plate, and then place it in the plating solution.

[0106] (2) Select a copper plate as the cathode (i.e., substrate), and polish the pre-cut copper plate (1×30×30mm) with 400#, 800#, and 2000# sandpaper in sequence. 3 The copper plate was immersed in acetone and ultrasonically degreased. It was then soldered to a long wire using solder rods, and the soldered surface was sealed with cold mounting liquid (CM1, Naibo Testing Technology Co., Ltd.). After drying, it was wet-ground and mechanically polished with 400#, 1000# and 2000# sandpaper until there were no visible scratches. Then, it was cleaned with concentrated hydrochloric acid and dilute hydrochloric acid for 5 minutes in sequence. After each cleaning, it was rinsed with deionized water. Finally, the copper plate was immersed in anhydrous ethanol for later use.

[0107] (3) Two plating solutions were prepared, including a 500 mL nickel-cobalt-phosphorus alloy plating solution and a pure nickel plating solution:

[0108] A 500 mL nickel-cobalt-phosphorus alloy plating bath was prepared, comprising 50 g nickel sulfate, 10 g nickel chloride, 25 g anhydrous citric acid, 5 g phosphorous acid, 5 g cobalt sulfate, 0.3 g composite additive, and the balance deionized water. The composite additive consisted of sodium saccharin and sodium dodecyl sulfate in a mass ratio of 0.5:0.1. The nickel sulfate, nickel chloride, boric acid, sodium citrate, and composite additive were dissolved in the deionized water. Then, under stirring at 750 rpm, the pH was adjusted to 3.0 with dilute sulfuric acid solution.

[0109] A 500 mL coarse-grained nickel plating solution was prepared, comprising 50 g nickel sulfate, 10 g nickel chloride, 10 g boric acid, 0.15 g composite additive, and the remainder deionized water. The composite additive consisted of sodium saccharin and sodium dodecyl sulfate in a mass ratio of 0.2:0.1. The nickel sulfate, nickel chloride, boric acid, and composite additive were dissolved in the deionized water. Then, under stirring at 500 rpm, the pH was adjusted to 5.2 with dilute sulfuric acid solution.

[0110] (4) After preparing the above two plating solutions, a dual-tank DC electrodeposition method is used to electroplate the ultra-nano nickel-cobalt-phosphorus alloy and the coarse-grained nickel layer. The main process is as follows: Two plating tanks are selected and labeled as plating tank 1 and plating tank 2, respectively. An anode is placed in plating tank 1 and plating tank 2, and the cathode is placed in plating tank 1 containing the ultra-nano nickel-cobalt-phosphorus alloy plating solution to begin plating the Ni-Co-P stage. After the Ni-Co-P layer is plating, the cathode is transferred to plating tank 2 containing the Ni plating solution. This process of alternating plating tanks is repeated until a layered Ni-Co-P / Ni alloy coating is finally obtained on the substrate. The specific process is as follows:

[0111] The copper plate processed in step (2) is placed in plating tank 1 as the cathode, and the two nickel plates processed in step (1) are placed in plating tank 1 containing ultra-nano nickel-cobalt-phosphorus alloy plating solution and plating tank 2 containing coarse-grained Ni plating solution, respectively, as anodes. For plating tank 1, the cathode and anode are connected to the negative and positive terminals of a DC regulated power supply, respectively. Under the conditions of plating solution temperature of 60℃ and continuous mechanical stirring in plating tank 1, the temperature is 30 mA / cm². 2 Electrodeposition was performed for 75 minutes. After the Ni-Co-P layer was deposited, the cathode was transferred to plating tank 2. The cathode and anode were connected to the negative and positive terminals of a DC regulated power supply, respectively. The plating bath in plating tank 2 was maintained at 50°C with continuous mechanical stirring, and the deposition rate was 40 mA / cm². 2 Electrodeposition was performed for 30 minutes. The cathode sample was repeatedly transferred between plating tank 1 and plating tank 2 and DC electrodeposition was performed. After a total electrodeposition time of 11.7 hours, a total of 13 layers of layered Ni-Co-P / Ni alloy with a total thickness of 194 micrometers were obtained on the copper substrate, which was designated as sample 7. Figure 3 A cross-sectional SEM image of sample 7 is shown. Figure 3 As can be seen, alternating light and dark layers can be observed, and there are no obvious transition features between the layers, indicating that the bonding force between the layers is good and that they have obvious layered features.

[0112] The wear resistance and bonding strength of samples 1-6 were tested.

[0113] In this invention, a multi-functional friction and wear testing machine (RTEC BMT-5000, Rtec Instruments, USA) was used to conduct friction and wear tests on the samples. The samples were cut into 8×8×0.5 mm pieces. 3 The sample was a cuboid and ultrasonically cleaned in acetone and alcohol for 10 minutes each to remove surface oil. After cleaning and drying, the sample was glued to the center of a cylindrical base plate with 502 glue to fix the small sample. WC-Co microspheres were selected as the friction and wear pair. The specific experimental parameters were: frequency 2 Hz, load 10 N, rotation radius 3 mm, and time 1 h. During the friction and wear experiment, the friction coefficient was recorded in real time by the testing machine's sensing system. The wear morphology was captured using the three-dimensional white light interferometry module of the friction and wear testing machine, and the wear rate was calculated based on the obtained data. The calculation formula is as follows:

[0114]

[0115] In the formula, F is the load (N); L is the total distance of the friction test (m); V is the wear amount (mm). 3 The wear amount V is expressed as the average wear cross-sectional area S (mm²). 2It is calculated using the wear mark perimeter C (m).

[0116] The obtained friction coefficient and wear rate are as follows Figure 4 As shown. From Figure 4 As can be seen from the comparative electrodeposition, the wear rate of the homogeneous nano-nickel-cobalt-phosphorus alloy sample 1 is approximately 6.5 x 10⁻⁶. -6 mm 3 N -1 m -1 The coefficient of friction is approximately 0.63. The wear rate of the layered Ni-Co-P / Ni alloy coating in Sample 2, obtained by dual-tank electrodeposition in Example 1, is approximately 0.7 x 10⁻⁶. -6 mm 3 N -1 m -1 The coefficient of friction is approximately 0.54. The wear rate of the layered Ni-Co-P / Ni alloy coating obtained by dual-tank electrodeposition in Example 2 is approximately 1.2 x 10⁻⁶. -6 mm 3 N - 1 m -1 The coefficient of friction is approximately 0.58. The wear rate of the layered Ni-Co-P / Ni alloy coating in sample 4, obtained by dual-tank electrodeposition in Example 3, is approximately 1.5 x 10⁻⁶. -6 mm 3 N -1 m -1 The coefficient of friction is approximately 0.57. The wear rate of the layered Ni-Co-P / Ni alloy coating obtained by dual-tank electrodeposition in Example 4 is approximately 3.3 x 10⁻⁶. -6 mm 3 N -1 m -1 The coefficient of friction is approximately 0.58. The wear rate of the layered Ni-Co-P / Ni alloy coating obtained by dual-tank electrodeposition in Example 5 is approximately 3.8 x 10⁻⁶. -6 mm 3 N -1 m -1 The coefficient of friction is approximately 0.59. This indicates that the layered nickel-based alloy prepared in this invention has superior wear resistance.

[0117] Figure 5 The bond strength and flexural strength of samples 1-6 were tested using an INSTRON 68TM-500,000 strength testing machine. The test conditions were a loading speed of 0.18 mm / min and a sample size of 12 × 4 × 0.2 mm. 3 The span dimension is 8mm. Based on the obtained data, the bond strength, flexural strength, and plasticity were calculated using the following formulas:

[0118]

[0119] In the formula, P is the bending load (N); b is the specimen width (mm); and h is the specimen thickness (mm).

[0120]

[0121]

[0122] In the formula, b and h are the width and thickness of the specimen (mm), respectively; F is the bending force (N) applied to the specimen; L is the span between the two support points, L=8 mm, which remains constant in the experiment.

[0123] in accordance with Figure 5 The calculated bending strength, plasticity, and bond strength are shown in Table 1.

[0124] Table 1

[0125] Sample number Instance number Bending strength (MPa) Plasticity (%) Bond strength (MPa) 1 Comparative Example 106 1.9 9.0 2 Example 1 854 8.6 34.6 3 Example 2 797 5.7 33.7 4 Example 3 1078 6.2 22.4 5 Example 4 1096 4.3 20.4 6 Example 5 796 2.3 21.3

[0126] Summary Table 1 and Figure 5 Data shows that the layered composite nanostructure nickel-based alloy coating prepared using this invention has a bonding strength of 20.4-34.6 MPa, a bending strength of 797-1096 MPa, and a plasticity of 2.3%-8.6%. Compared with the homogeneous coating, which has a bonding strength of 9.0 MPa, a bending strength of 106 MPa, and a plasticity of 1.9%, the bending resistance and bonding strength of the nickel-based alloy are significantly improved. Figure 6 The adhesion between the coating and the substrate was measured using a Swiss CSM-MCT micrometer under a load of 0–30 N and a speed of 5 mm / min. Figure 6 It is evident that the bonding strength of Example 1, at 15.2 N, is significantly higher than that of the comparative example, at 5.7 N. This indicates that constructing a layered structure endows the nickel-based alloy with superior overall mechanical properties, meeting the engineering requirements for the comprehensive mechanical properties of nickel-based alloy metal coatings and nanostructured metal components.

[0127] The technical solutions disclosed and proposed in this invention can be implemented by those skilled in the art by appropriately modifying the conditions and routes, etc. Although the methods and preparation techniques of this invention have been described through preferred embodiments, those skilled in the art can obviously modify or recombine the methods and technical routes described herein without departing from the content, spirit, and scope of this invention to achieve the final preparation technique. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included within the spirit, scope, and content of this invention.

Claims

1. A highly wear-resistant layered Ni-based alloy with strong interfacial bonding, characterized in that, A coarse-grained nickel layer and a super-nano nickel-based ternary alloy layer are sequentially deposited on a substrate, with the outermost layer being a Ni-Co-P layer; the thickness of the nanocrystalline nickel alloy layer is 5-25 micrometers; the thickness of the coarse-grained nickel layer is 5-25 micrometers; the total thickness of the coating is 200±25 micrometers, and the total number of layers is 13-41 layers of layered heterogeneous nickel-based alloy.

2. The high-wear-resistant layered Ni-based alloy with strong interfacial bonding as described in claim 1, characterized in that, The thickness ratio of the nanocrystalline nickel alloy layer to the coarse-crystalline nickel layer is 1:5-5:

1.

3. The method for preparing a high-wear-resistant layered Ni-based alloy with strong interfacial bonding as described in claim 1, characterized in that, Includes the following steps: S1. Using a nickel plate as the anode, the surface oxide layer of the nickel plate is removed by sanding with sandpaper. After covering the nickel plate with a layer of non-woven fabric, it is placed in the plating solution. S2. Substrate pretreatment: The substrate is the metal or conductive material to be deposited with the coating. The substrate is subjected to surface grinding, polishing and degreasing in sequence; then it is washed with water, acid pickling, ultrasonic activation, and washed with water again. S3. The above substrate is immersed in a nickel alloy plating solution, and a nanocrystalline nickel alloy layer is prepared by direct current electrodeposition. The nanocrystalline nickel alloy layer is a Ni-Co-P ternary alloy and serves as the hard phase in the layered structure. S4. The substrate with nanocrystalline nickel alloy coating obtained in the above steps is washed with water, acid-washed and ultrasonically activated, then washed with water again and immersed in coarse-crystalline nickel plating solution. A coarse-crystalline nickel layer is prepared on the nanocrystalline nickel alloy layer by direct current electrodeposition as the soft phase in the layered structure. S5. The bilayer substrate with nanocrystalline layer + coarse crystalline layer obtained by the above steps is washed with water, acid-washed and ultrasonically activated, and then washed with water again. Then the DC electrodeposition operation of steps S3 and S4 is repeated in sequence. The outermost layer is Ni-Co-P layer. This cycle is repeated to finally prepare a layered heterogeneous nickel-based alloy with a total number of 13-41 layers.

4. The method for preparing a high-wear-resistant layered Ni-based alloy with strong interfacial bonding as described in claim 3, characterized in that, The components of the nickel alloy plating solution include nickel sulfate hexahydrate, nickel chloride hexahydrate, anhydrous citric acid, boric acid, phosphorous acid, cobalt sulfate heptahydrate, sodium dodecyl sulfate, sodium saccharin, and deionized water. Based on the preparation of 1L of nickel alloy plating solution, the mass ratio of all the above components is as follows: Nickel sulfate hexahydrate 100-300 g / L Nickel chloride hexahydrate 10-40 g / L Anhydrous citric acid 50-70 g / L Boric acid 20-60 g / L Phosphorous acid 10-30 g / L Cobalt sulfate heptahydrate 10-30 g / L Sodium dodecyl sulfate 0.1-0.3 g / L Sodium saccharin 0.5-3 g / L Deionized water balance.

5. The method for preparing a high-wear-resistant layered Ni-based alloy with strong interfacial bonding as described in claim 3, characterized in that, The nickel alloy plating solution is a nickel-cobalt-phosphorus alloy plating solution. Before plating, the pH value of the plating solution is adjusted to 2.0-3.0 with a dilute sulfuric acid solution, and the temperature of the plating solution is adjusted to 40-60℃.

6. The method for preparing a high-wear-resistant layered Ni-based alloy with strong interfacial bonding as described in claim 3, characterized in that, In step S3, the DC electrodeposition process conditions are as follows: a nickel plate with a purity of 99.0 wt.% is used as the anode; magnetic stirring is employed at a speed of 500-1000 rpm, and the current density is 30-50 mA / cm². 2 The electrodeposition time for a single layer of coating is 25-125 min.

7. The method for preparing a high-wear-resistant layered Ni-based alloy with strong interfacial bonding as described in claim 3, characterized in that, The components of the nickel plating solution include nickel sulfate hexahydrate, nickel chloride hexahydrate, boric acid, sodium dodecyl sulfate, sodium saccharin, and deionized water; based on the preparation of 1L of coarse-grained nickel plating solution, the mass ratio of all the above components is as follows: Nickel sulfate hexahydrate 100-300 g / L Nickel chloride hexahydrate 10-40 g / L Boric acid 20-60 g / L Sodium dodecyl sulfate 0.1-0.3 g / L Sodium saccharin 0.2-3 g / L Deionized water balance.

8. The method for preparing a high-wear-resistant layered Ni-based alloy with strong interfacial bonding as described in claim 3, characterized in that, Before plating, the pH value of the nickel plating solution is adjusted to 3.4-5.2 using a dilute sulfuric acid solution, and the temperature of the plating solution is adjusted to 40-60℃.

9. The method for preparing a high-wear-resistant layered Ni-based alloy with strong interfacial bonding as described in claim 3, characterized in that, In step S4, the process conditions for direct current electrodeposition are as follows: a nickel plate with a purity of 99.0 wt.% is used as the anode; magnetic stirring is employed at a speed of 500-1000 rpm, and the current density is 30-50 mA / cm². 2 The electrodeposition time for a single layer is 10-50 min.

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