A nanometer rare earth nickel plated layer brass material and a preparation method thereof

Abstract

The application relates to the alloy material technical field, and discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare earth nickel plating layer brass material and preparation method thereof.The application discloses a kind of nano rare

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of alloy materials, and particularly relates to a nano-rare earth nickel plated layer brass material and a preparation method thereof. BACKGROUND

[0002] Brass has a long history of use, dating back to ancient civilizations where it was used to create decorative items and practical tools. Ancient Rome and China were pioneers in the use of brass, creating a variety of exquisite crafts and tools. With the advent of the industrial revolution, the manufacturing and application technology of brass has developed rapidly. As a historical and widely used alloy material, brass plays an important role in many fields due to its unique physical and chemical properties, such as architecture, machinery manufacturing, electronics, automobiles, and many other fields. Brass is a base alloy material composed of copper and zinc, and the proportion of its components and the addition of other elements determine the specific performance and application field of brass. The main components of brass are copper and zinc, with copper content usually above 67% and zinc content above 32%. Depending on different application requirements, elements such as lead, tin, and nickel may be added to improve its performance. During the welding process, the high temperature causes a large amount of zinc in brass to evaporate, resulting in a decrease in the corrosion resistance and mechanical properties of brass materials. The existing technology prevents the loss of zinc in brass materials by plating a nickel layer on the outer surface of brass.

[0003] For example, Chinese Patent Publication No. CN112323107 discloses a brass material with a nano-rare earth nickel plated layer and a preparation method thereof. The method includes mixing NiSO4, NiCl2, H3BO3, and nano-rare earth salt particles, dissolving them in water, and uniformly oscillating them using ultrasonic waves to prepare an electroplated rare earth nickel solution. The brass substrate is placed in the electroplated rare earth nickel solution for electroplating to obtain brass covered with a nickel rare earth plated layer. Vacuum heat treatment of the brass covered with the nickel rare earth plated layer is performed. This technical solution dopes nano-rare earth into the plated layer to inhibit the growth of brass grains during welding, resulting in refined brass grains and improved welding performance. However, nano-rare earth tends to agglomerate in the electroplating solution, causing uneven dispersion of rare earth elements in the brass plated layer, which in turn affects the inhibitory effect of rare earth elements on the volume of brass grains during welding. Therefore, the brass grains need to be further refined to improve the welding performance of brass. SUMMARY

[0004] The present application provides a nano-rare earth nickel plated layer brass material and a preparation method thereof to overcome the above problems in the prior art. The nano-rare earth nickel plated layer brass material prepared by the present application has smaller grain volume than that formed during welding according to the prior art, and has good welding performance.

[0005] To achieve the above-mentioned purposes, the present application adopts the following technical solutions:

[0006] A method for preparing a nano rare earth nickel-plated brass material comprises the following steps:

[0007] 1) polishing the surface of the brass substrate using silica sandpaper, then immersing it in deionized water for ultrasonic cleaning, and drying it in an oven to obtain a brass substrate without the oxide layer;

[0008] 2) immersing the brass substrate with the deoxidized layer in a degreasing solution, continuing ultrasonic oscillation cleaning, and drying in an oven to obtain a degreased brass substrate;

[0009] 3) soaking the degreased brass substrate in a nitric acid solution, taking it out and placing it in deionized water for ultrasonic cleaning, soaking the cleaned brass substrate in a hydrofluoric acid solution, taking it out and placing it in deionized water for ultrasonic cleaning to obtain an activated brass substrate;

[0010] 4) adding nickel chloride, nickel sulfate, boric acid, modified nano-cerium oxide, and sodium lauryl sulfate to deionized water, dispersing the mixture under ultrasonic vibration to obtain an electroplating solution, placing an activated brass substrate in the electroplating solution as a cathode, and using a pure nickel plate as an anode to perform electroplating to obtain a nano-rare earth nickel-plated brass intermediate;

[0011] 5) drying the nano rare earth nickel-plated brass intermediate in an oven, and then performing vacuum heating and baking treatment in a muffle furnace to obtain a nano rare earth nickel-plated brass material.

[0012] By adding rare earth nano-cerium oxide to the electroplating solution, the present invention can inhibit the enlargement of brass grains during the welding process, thereby refining the brass grains and improving welding performance and mechanical strength. Simultaneously, a nickel-copper-zinc rare earth diffusion alloy layer is formed between the surface of the brass substrate and the nickel rare earth coating. This nickel-copper-zinc rare earth diffusion alloy layer enhances the bonding strength between the nickel rare earth coating and the brass and prevents zinc from diffusing into the nickel rare earth coating. Compared to conventional nickel coatings, this layer exhibits better zinc retention and further enhances the corrosion resistance and mechanical strength of the material.

[0013] Preferably, in step 2), the degreasing liquid comprises sodium hydroxide, sodium carbonate and sodium silicate.

[0014] Preferably, in step 3), the volume concentration of the nitric acid solution is 3-5%.

[0015] Preferably, in step 3), the volume concentration of the hydrofluoric acid solution is 10-20%.

[0016] Preferably, in step 4), the mass volume concentration of the modified nano-cerium oxide is 1-8 g / L.

[0017] Preferably, in the step 4), the plating temperature is 40-50℃, the current density is 4-5A / dm 2 , the plating solution pH is kept at 4-5, and the plating time is 1.5-3h.

[0018] Preferably, in the step 4), the preparation method of the modified nano ceria comprises the following steps:

[0019] The epoxy silane coupling agent is added into the aqueous ethanol solution and heated and stirred to obtain an epoxy silane coupling agent solution;

[0020] The nano ceria is added into the epoxy silane coupling agent solution and heated and stirred to react, and then centrifugal separation, washing and drying are performed to obtain the silane coupling agent grafted modified nano ceria.

[0021] The sodium alginate is added into the deionized water and stirred to dissolve, to obtain a sodium alginate solution, and the silane coupling agent grafted modified nano ceria is added into the sodium alginate solution, SnCl4 and HCl are added, and heated and stirred to react, and then filtration separation, washing and drying are performed to obtain the modified nano ceria.

[0022] In the prior art, nano rare earth is doped into the plating layer to inhibit the brass grain from becoming large during welding, so that the brass grain is refined and the welding performance is improved. However, the nano rare earth is prone to agglomeration in the plating solution, which causes uneven dispersion of the rare earth element in the brass plating layer, and further affects the inhibition of the rare earth element on the volume of the brass grain during welding. To solve the above technical problems, the nano ceria is modified by grafting an epoxy silane coupling agent on the surface of the nano ceria to load an epoxy functional group on the surface of the nano ceria, and then the sodium alginate is grafted onto the surface of the nano ceria by the reaction between the epoxy silane coupling agent and the sodium alginate. The sodium alginate is negatively charged in the aqueous solution, so that the surface of the nano ceria is negatively charged, and the agglomeration of the nano ceria is prevented under the action of the electrostatic repulsion force. Therefore, the dispersion performance of the nano ceria in the aqueous solution is improved, the inhibition of the rare earth element on the volume of the brass grain is improved, the function of further refining the brass grain is achieved, and the welding performance of the brass material is improved.

[0023] Preferably, the mass ratio of the nano ceria to the epoxy silane coupling agent is 1:0.2-0.8.

[0024] Preferably, the mass ratio of the silane coupling agent grafted modified nano ceria to the sodium alginate is 1:0.4-0.7.

[0025] The surface of the nanometer cerium oxide must be loaded with a sufficient amount of sodium alginate to fully disperse the nanometer cerium oxide and avoid agglomeration thereof. Through experiments, it is obtained that the mass ratio of the silane coupling agent grafted modified nanometer cerium oxide to sodium alginate should be less than 1:0.4. However, the team of the present application accidentally finds that when the mass ratio of the silane coupling agent grafted modified nanometer cerium oxide to sodium alginate should be less than 1:0.7, the thickness of the nickel-copper-zinc-rare earth diffusion alloy layer formed between the surface of the brass matrix and the nickel-rare earth plating layer is greatly reduced, resulting in the decrease of the zinc retention performance of the brass material, which is unexpected by the team of the present application. This may be because the amount of the grafted sodium alginate on the nanometer cerium oxide is too large, and the surface thereof has a strong negative electricity, and the repulsive force therebetween prevents the diffusion of the nanometer cerium oxide into the nickel plating layer, the rare earth elements in the nickel plating layer are reduced, the rare earth elements in the nickel-copper-zinc-rare earth diffusion alloy layer are reduced, and then the thickness of the nickel-copper-zinc-rare earth diffusion alloy layer is reduced. Therefore, the present application strictly controls the mass ratio of the silane coupling agent grafted modified nanometer cerium oxide to sodium alginate to be greater than 1:0.7.

[0026] A nanometer rare earth nickel plating layer brass material is prepared by the above method.

[0027] The present application has the following beneficial effects:

[0028] 1) By adding the rare earth nanometer cerium oxide in the electroplating solution, the brass crystal grains can be inhibited from becoming large during welding, so that the brass crystal grains are refined, and the welding performance and the mechanical strength are improved. Meanwhile, a nickel-copper-zinc-rare earth diffusion alloy layer is formed between the surface of the brass matrix and the nickel-rare earth plating layer, the nickel-copper-zinc-rare earth diffusion alloy layer can improve the bonding strength between the nickel-rare earth plating layer and the brass, and can also prevent the diffusion of zinc elements into the nickel-rare earth plating layer. Compared with the ordinary nickel plating layer, the present application has better zinc retention performance, and further improves the corrosion resistance and the mechanical strength of the material.

[0029] 2) The nanometer cerium oxide is modified to have a negative electricity on the surface thereof, and the electrostatic repulsive force prevents the agglomeration of the nanometer cerium oxide, so as to improve the dispersion performance of the nanometer cerium oxide in the aqueous solution, improve the inhibition of the rare earth elements on the volume of the brass crystal grains, and further refine the brass crystal grains, so as to improve the welding performance and the mechanical performance of the brass material. DETAILED DESCRIPTION

[0030] The present application will be further described in detail with specific examples. Based on these descriptions, the ordinary skilled in the art will be able to implement the present application. In addition, the examples of the present application involved in the following description are generally only a part of the examples of the present application, but not all the examples. Therefore, based on the examples in the present application, all the other examples obtained by the ordinary skilled in the art without making creative efforts shall belong to the protection scope of the present application.

[0031] The raw materials used in the embodiments of the present application are all commercially available or available to those skilled in the art, unless otherwise specified; the methods used in the embodiments of the present application are all mastered by those skilled in the art, unless otherwise specified.

[0032] The brass matrix used in the embodiment of the present application is Cu 57 Zn 41.2 Fe 0.3 Pb 0.5 , and the impurity content is 1%.

[0033] Example 1

[0034] A preparation method of a nano-rare earth nickel plated brass material, comprising the following steps:

[0035] 1) The surface of the brass matrix is polished using silica sandpaper, and then immersed in deionized water for ultrasonic oscillation cleaning for 20 min, and dried in an oven to obtain a deoxidized brass matrix;

[0036] 2) The deoxidized brass matrix is immersed in an oil removal liquid for ultrasonic oscillation cleaning for 30 min, and dried in an oven to obtain an oil-removed brass matrix, wherein the oil removal liquid comprises sodium hydroxide, sodium carbonate and sodium silicate, and the mass concentration of sodium hydroxide is 15 g / L, the mass concentration of sodium carbonate is 20 g / L, and the mass concentration of sodium silicate is 25 g / L;

[0037] 3) The oil-removed brass matrix is first immersed in a 4% volume concentration nitric acid solution for 10 min, and then placed in deionized water for ultrasonic oscillation cleaning for 5 min, and then immersed in a 15% volume concentration hydrofluoric acid solution for 10 min, and then placed in deionized water for ultrasonic oscillation cleaning for 5 min to obtain an activated brass matrix;

[0038] 4) Nickel chloride, nickel sulfate, boric acid, modified nano cerium oxide and sodium dodecyl sulfate are added to deionized water, and ultrasonic oscillation is dispersed for 20 min to obtain an electroplating solution;

[0039] The nickel chloride in the electroplating solution is 25 g / L, the nickel sulfate is 250 g / L, the boric acid is 20 g / L, the modified nano cerium oxide is 7 g / L, and the sodium dodecyl sulfate is 0.03 g / L;

[0040] The activated brass matrix is placed in the electroplating solution as a cathode, and a pure nickel plate is used as an anode for electroplating treatment, the electroplating temperature is 45℃, the current density is 4.5 A / dm 2 , the pH of the electroplating solution is maintained at 4.5, and the electroplating time is 2.5 h to obtain a nano-rare earth nickel plated brass intermediate;

[0041] 5) The nano rare earth nickel-plated brass intermediate was placed in an oven and dried at 60° C., and then placed in a muffle furnace and vacuum-heated and baked at 500° C. for 3 h to obtain a nano rare earth nickel-plated brass material.

[0042] The preparation method of modified nano-cerium oxide comprises the following steps:

[0043] Add 2 g of epoxy silane coupling agent KH-560 to 150 mL of 60% ethanol aqueous solution, heat to 50°C and stir for 1 hour to obtain an epoxy silane coupling agent solution;

[0044] The nano-cerium oxide was added to the epoxy silane coupling agent solution at a mass ratio of 1:0.7, and the mixture was heated to 60° C. and stirred for 2 h. After centrifugation, washing and drying, the silane coupling agent-grafted modified nano-cerium oxide was obtained.

[0045] 1.5 g of sodium alginate was added to 200 mL of deionized water and stirred to dissolve to obtain a sodium alginate solution. Nano-cerium oxide grafted with a silane coupling agent was added to the sodium alginate solution. The mass ratio of nano-cerium oxide grafted with a silane coupling agent to sodium alginate was 1:0.6. 0.01 g of SnCl4 and 0.1 g of a 15% HCl solution were added. The mixture was heated to 80° C. and stirred for reaction for 3 h. The mixture was filtered, separated, washed, and dried to obtain modified nano-cerium oxide.

[0046] Example 2

[0047] A method for preparing a nano rare earth nickel-plated brass material comprises the following steps:

[0048] 1) polishing the surface of the brass substrate using silica sandpaper, then immersing it in deionized water for ultrasonic cleaning for 20 minutes, and drying it in an oven to obtain a brass substrate without the oxide layer;

[0049] 2) immersing the brass substrate with the oxide layer removed in a degreasing solution, continuing ultrasonic oscillation cleaning for 30 minutes, and drying in an oven to obtain a degreasing brass substrate, wherein the degreasing solution comprises sodium hydroxide, sodium carbonate, and sodium silicate, wherein the mass concentration of sodium hydroxide is 15 g / L, the mass concentration of sodium carbonate is 20 g / L, and the mass concentration of sodium silicate is 25 g / L;

[0050] 3) soaking the degreased brass substrate in a 4% nitric acid solution for 10 minutes, removing it and ultrasonically cleaning it in deionized water for 5 minutes. Then, soaking the cleaned brass substrate in a 15% hydrofluoric acid solution for 10 minutes, removing it and ultrasonically cleaning it in deionized water for 5 minutes to obtain an activated brass substrate;

[0051] 4) adding nickel chloride, nickel sulfate, boric acid, modified nano cerium oxide and sodium dodecyl sulfate into deionized water, ultrasonic oscillation dispersion for 20 min to obtain an electroplating solution;

[0052] The electroplating solution contains 25 g / L of nickel chloride, 250 g / L of nickel sulfate, 20 g / L of boric acid, 2 g / L of modified nano cerium oxide and 0.03 g / L of sodium dodecyl sulfate;

[0053] The activated brass substrate is placed in the electroplating solution as a cathode, and a pure nickel plate is used as an anode to perform electroplating treatment, with an electroplating temperature of 45℃, an electroplating current density of 4.5 A / dm 2 , an electroplating solution pH of 4.5, and an electroplating time of 1.8 h, to obtain a nano rare earth nickel plated brass intermediate;

[0054] 5) The nano rare earth nickel plated brass intermediate is placed in an oven for drying at 60℃, and then placed in a muffle furnace for vacuum heating and baking treatment at 500℃ for 3 h to obtain a nano rare earth nickel plated brass material.

[0055] The preparation method of the modified nano cerium oxide comprises the following steps:

[0056] 2 g of epoxy silane coupling agent KH-560 is added into 150 mL of 60% mass concentration ethanol aqueous solution, heated to 50℃ and stirred for 1 h to obtain an epoxy silane coupling agent solution;

[0057] The nano cerium oxide is added into the epoxy silane coupling agent solution, with a mass ratio of nano cerium oxide to epoxy silane coupling agent being 1:0.3, heated to 60℃ and stirred for 2 h, and then centrifuged, washed and dried to obtain silane coupling agent grafted modified nano cerium oxide;

[0058] 1.5 g of sodium alginate is added into 200 mL of deionized water and stirred to dissolve, to obtain a sodium alginate solution, and the silane coupling agent grafted modified nano cerium oxide is added into the sodium alginate solution, with a mass ratio of silane coupling agent grafted modified nano cerium oxide to sodium alginate being 1:0.45, 0.01 g of SnCl4 and 0.1 g of 15% concentration HCl solution are added, heated to 80℃ and stirred for 3 h, and then filtered, washed and dried to obtain modified nano cerium oxide.

[0059] Example 3

[0060] A preparation method of a nano rare earth nickel plated brass material comprises the following steps:

[0061] 1) The surface of a brass substrate is polished using silica sandpaper, and then immersed in deionized water for ultrasonic oscillation cleaning for 20 min, and placed in an oven for drying to obtain an oxygen layer removed brass substrate;

[0062] 2) the oxide layer removal brass matrix is soaked in an oil removal liquid and ultrasonic oscillation cleaning is continued for 30 min, and the oxide layer removal brass matrix is dried in an oven to obtain an oil removal brass matrix, wherein the oil removal liquid comprises sodium hydroxide, sodium carbonate and sodium silicate, the mass concentration of the sodium hydroxide is 15 g / L, the mass concentration of the sodium carbonate is 20 g / L, and the mass concentration of the sodium silicate is 25 g / L;

[0063] 3) the oil removal brass matrix is first soaked in a 4% nitric acid solution for 10 min, and then placed in deionized water for ultrasonic oscillation cleaning for 5 min, the cleaned brass matrix is soaked in a 15% hydrofluoric acid solution for 10 min, and then placed in deionized water for ultrasonic oscillation cleaning for 5 min to obtain an activated brass matrix;

[0064] 4) nickel chloride, nickel sulfate, boric acid, modified nano cerium oxide and sodium dodecyl sulfate are added to deionized water, and ultrasonic oscillation dispersion is performed for 20 min to obtain an electroplating solution;

[0065] The mass concentrations of the nickel chloride, the nickel sulfate, the boric acid, the modified nano cerium oxide and the sodium dodecyl sulfate in the electroplating solution are 25 g / L, 250 g / L, 20 g / L, 4 g / L and 0.03 g / L, respectively;

[0066] The activated brass matrix is placed in the electroplating solution as a cathode, and a pure nickel plate is used as an anode to perform electroplating treatment, the electroplating temperature is 45°C, the current density is 4.5 A / dm 2 , the pH of the electroplating solution is maintained at 4.5, and the electroplating time is 2 h to obtain a nano rare earth nickel plated brass intermediate;

[0067] 5) the nano rare earth nickel plated brass intermediate is dried in an oven at 60°C, and then vacuum heating baking treatment is performed in a muffle furnace at 500°C for 3 h to obtain a nano rare earth nickel plated brass material.

[0068] The preparation method of the modified nano cerium oxide comprises the following steps:

[0069] 2g of an epoxy silane coupling agent KH-560 is added to 150 mL of an ethanol aqueous solution with a mass concentration of 60%, heated to 50°C and stirred for 1 h to obtain an epoxy silane coupling agent solution;

[0070] Nano cerium oxide is added to the epoxy silane coupling agent solution, the mass ratio of the nano cerium oxide to the epoxy silane coupling agent is 1:0.5, heated to 60°C and stirred for 2 h of reaction, and then centrifugal separation, washing and drying are performed to obtain silane coupling agent grafted modified nano cerium oxide;

[0071] 1.5 g of sodium alginate was added into 200 mL of deionized water and stirred to dissolve, to obtain a sodium alginate solution, and the silane coupling agent grafted modified nanometer cerium oxide was added into the sodium alginate solution, the mass ratio of the silane coupling agent grafted modified nanometer cerium oxide to the sodium alginate being 1:0.5, 0.01 g of SnCl4 and 0.1 g of a 15% HCl solution were added, and the mixture was heated to 80°C and stirred to react for 3 h, and then filtered, washed and dried to obtain the modified nanometer cerium oxide.

[0072] Example 4

[0073] A preparation method of a nanometer rare earth nickel plated brass material comprises the following steps:

[0074] 1) The surface of a brass substrate is polished using silica sandpaper, and then immersed in deionized water for ultrasonic oscillation cleaning for 20 min, and dried in an oven to obtain an oxygen layer-removed brass substrate;

[0075] 2) The oxygen layer-removed brass substrate is immersed in a degreasing solution and ultrasonic oscillation cleaned for 30 min, and then dried in an oven to obtain a degreased brass substrate, wherein the degreasing solution comprises sodium hydroxide, sodium carbonate and sodium silicate, and the mass concentration of the sodium hydroxide is 15 g / L, the mass concentration of the sodium carbonate is 20 g / L, and the mass concentration of the sodium silicate is 25 g / L;

[0076] 3) The degreased brass substrate is first immersed in a 5% nitric acid solution for 10 min, and then taken out and ultrasonic oscillation cleaned in deionized water for 5 min, and then immersed in a 20% hydrofluoric acid solution for 10 min, and then taken out and ultrasonic oscillation cleaned in deionized water for 5 min to obtain an activated brass substrate;

[0077] 4) Nickel chloride, nickel sulfate, boric acid, modified nanometer cerium oxide and sodium dodecyl sulfate are added into deionized water and ultrasonic oscillation dispersed for 20 min to obtain an electroplating solution;

[0078] The nickel chloride in the electroplating solution is 25 g / L, the nickel sulfate is 250 g / L, the boric acid is 20 g / L, the modified nanometer cerium oxide is 8 g / L, and the sodium dodecyl sulfate is 0.03 g / L;

[0079] The activated brass substrate is placed in the electroplating solution as a cathode, and a pure nickel plate is used as an anode to perform electroplating treatment, the electroplating temperature is 50°C, the current density is 5 A / dm 2 , the pH of the electroplating solution is maintained at 5, and the electroplating time is 3 h to obtain a nanometer rare earth nickel plated brass intermediate;

[0080] 5) The nanometer rare earth nickel plated brass intermediate is dried in an oven at 60°C, and then vacuum heated and baked in a muffle furnace at 500°C for 3 h to obtain a nanometer rare earth nickel plated brass material.

[0081] The preparation method of the modified nanometer cerium oxide comprises the following steps:

[0082] 2g of epoxy silane coupling agent KH-560 is added into 150mL of 60% mass concentration ethanol aqueous solution, heated to 50℃ and stirred for 1h to obtain an epoxy silane coupling agent solution;

[0083] The nanometer cerium oxide is added into the epoxy silane coupling agent solution, the mass ratio of the nanometer cerium oxide to the epoxy silane coupling agent is 1:0.8, heated to 60℃ and stirred for 2h, and then centrifugal separation, washing and drying are performed to obtain the silane coupling agent grafted modified nanometer cerium oxide;

[0084] 1.5g of sodium alginate is added into 200mL of deionized water and stirred to be dissolved to obtain a sodium alginate solution, the silane coupling agent grafted modified nanometer cerium oxide is added into the sodium alginate solution, the mass ratio of the silane coupling agent grafted modified nanometer cerium oxide to the sodium alginate is 1:0.7, 0.01g of SnCl4 and 0.1g of 15% concentration HCl solution are added, heated to 80℃ and stirred for 3h, and then filtration separation, washing and drying are performed to obtain the modified nanometer cerium oxide.

[0085] Example 5

[0086] A preparation method of a nanometer rare earth nickel plating layer brass material comprises the following steps:

[0087] 1) The surface of the brass substrate is polished using silica sandpaper, then immersed in deionized water for ultrasonic oscillation cleaning for 20min, and placed in an oven for drying to obtain an oxygen layer-removed brass substrate;

[0088] 2) The oxygen layer-removed brass substrate is immersed in an oil removal liquid and continues to be ultrasonic oscillation cleaned for 30min, and then placed in an oven for drying to obtain an oil-removed brass substrate, wherein the oil removal liquid comprises sodium hydroxide, sodium carbonate and sodium silicate, the mass concentration of the sodium hydroxide is 15g / L, the mass concentration of the sodium carbonate is 20g / L, and the mass concentration of the sodium silicate is 25g / L;

[0089] 3) The oil-removed brass substrate is first immersed in a 3% volume concentration nitric acid solution for 10min, then taken out and placed in deionized water for ultrasonic oscillation cleaning for 5min, then immersed in a 10% volume concentration hydrofluoric acid solution for 10min, then taken out and placed in deionized water for ultrasonic oscillation cleaning for 5min to obtain an activated brass substrate;

[0090] 4) Nickel chloride, nickel sulfate, boric acid, modified nanometer cerium oxide and sodium dodecyl sulfate are added into deionized water and ultrasonic oscillation dispersed for 20min to obtain an electroplating solution;

[0091] Nickel chloride 25 g / L, nickel sulfate 250 g / L, boric acid 20 g / L, modified nano cerium oxide 1 g / L, sodium dodecyl sulfate 0.03 g / L in the electroplating solution;

[0092] The activated brass substrate is placed in the electroplating solution as a cathode, and a pure nickel plate is used as an anode to perform electroplating treatment, with an electroplating temperature of 40 DEG C and a current density of 4 A / dm 2 The pH of the electroplating solution is maintained at 4, and the electroplating time is 1.5 h to obtain a nano rare earth nickel plated brass intermediate;

[0093] 5) The nano rare earth nickel plated brass intermediate is dried in an oven at 60 DEG C and then subjected to vacuum heating and baking treatment in a muffle furnace at 500 DEG C for 3 h to obtain a nano rare earth nickel plated brass material.

[0094] The preparation method of the modified nano cerium oxide comprises the following steps:

[0095] 2 g of epoxy silane coupling agent KH-560 is added to 150 mL of an ethanol aqueous solution with a mass concentration of 60%, heated to 50 DEG C and stirred for 1 h to obtain an epoxy silane coupling agent solution;

[0096] Nano cerium oxide is added to the epoxy silane coupling agent solution, and the mass ratio of the nano cerium oxide to the epoxy silane coupling agent is 1:0.2, heated to 60 DEG C and stirred for 2 h of reaction, followed by centrifugal separation, washing and drying to obtain silane coupling agent grafted modified nano cerium oxide;

[0097] 1.5 g of sodium alginate is added to 200 mL of deionized water and stirred to dissolve to obtain a sodium alginate solution, and the silane coupling agent grafted modified nano cerium oxide is added to the sodium alginate solution, with a mass ratio of the silane coupling agent grafted modified nano cerium oxide to the sodium alginate of 1:0.4, 0.01 g of SnCl4 and 0.1 g of a 15% HCl solution are added, heated to 80 DEG C and stirred for 3 h of reaction, followed by filtration separation, washing and drying to obtain modified nano cerium oxide.

[0098] Comparative Example 1

[0099] The difference between Comparative Example 1 and Example 1 is that:

[0100] The nano cerium oxide is not subjected to modification treatment,

[0101] and the remaining operation steps are the same as those of Example 1.

[0102] Comparative Example 2

[0103] The difference between Comparative Example 2 and Example 5 is that:

[0104] In the preparation process of the modified nano cerium oxide,

[0105] The mass ratio of the silane coupling agent grafted modified nano cerium oxide to sodium alginate is 1:0.3,

[0106] The remaining operation steps are the same as those of Example 5.

[0107] Comparative Example 3

[0108] The difference between Comparative Example 3 and Example 4 is that:

[0109] The mass ratio of the silane coupling agent grafted modified nano cerium oxide to sodium alginate is 1:0.8,

[0110] The remaining operation steps are the same as those of Example 4.

[0111] Comparative Example 4

[0112] The difference between Comparative Example 4 and Example 4 is that:

[0113] The mass ratio of the silane coupling agent grafted modified nano cerium oxide to sodium alginate is 1:0.9,

[0114] The remaining operation steps are the same as those of Example 4.

[0115] Comparative Example 5

[0116] The difference between Comparative Example 5 and Example 4 is that:

[0117] The mass ratio of the silane coupling agent grafted modified nano cerium oxide to sodium alginate is 1:1,

[0118] The remaining operation steps are the same as those of Example 4.

[0119] Comparative Example 6

[0120] The difference between Comparative Example 5 and Example 4 is that:

[0121] The mass ratio of the silane coupling agent grafted modified nano cerium oxide to sodium alginate is 1:1.5,

[0122] The remaining operation steps are the same as those of Example 4.

[0123] Performance test

[0124] The nano rare earth nickel plated layer brass materials obtained by the examples and comparative examples are reflow soldered at 200℃ for 15s, and then soldered with a PCB board to obtain a soldered part. The thicknesses of the plating layer and the diffusion layer are tested by GB / T6462-2005 Metal and Oxide Coating Thickness Measurement Microscopy Method, and the grain size of the brass substrate after soldering is measured according to ASTM E112-2013 Standard Test Method for Determining Average Grain Size, and the zinc content in the brass substrate is tested and confirmed by GB-T15074-2008 General Method for Quantitative Analysis by Electron Probe.

[0125]

[0126] The above merely preferred embodiments of the present application should not be considered as limiting the present application, and the protection scope of the present application should be defined by the scope of the claims. For those skilled in the art, several improvements and refinements can be made without departing from the spirit and scope of the present application, and these improvements and refinements should also be considered as falling within the protection scope of the present application.

Claims

1. A method for preparing a nano rare earth nickel plated brass material, characterized in that: The following steps are involved: 1) polishing the surface of the brass substrate using silica sandpaper, then immersing it in deionized water for ultrasonic cleaning, and drying it in an oven to obtain a brass substrate without the oxide layer; 2) immersing the brass substrate with the deoxidized layer in a degreasing solution, continuing ultrasonic oscillation cleaning, and drying in an oven to obtain a degreased brass substrate; 3) soaking the degreased brass substrate in a nitric acid solution, taking it out and placing it in deionized water for ultrasonic cleaning, soaking the cleaned brass substrate in a hydrofluoric acid solution, taking it out and placing it in deionized water for ultrasonic cleaning to obtain an activated brass substrate; 4) adding nickel chloride, nickel sulfate, boric acid, modified nano-cerium oxide, and sodium lauryl sulfate to deionized water, dispersing the mixture under ultrasonic vibration to obtain an electroplating solution, placing an activated brass substrate in the electroplating solution as a cathode, and using a pure nickel plate as an anode to perform electroplating to obtain a nano-rare earth nickel-plated brass intermediate; The preparation method of modified nano-cerium oxide comprises the following steps: adding an epoxy silane coupling agent to an ethanol aqueous solution, heating and stirring, to obtain an epoxy silane coupling agent solution; adding nano-cerium oxide to an epoxy silane coupling agent solution in a mass ratio of nano-cerium oxide to epoxy silane coupling agent of 1:0.2-0.8, heating and stirring for reaction, and performing centrifugal separation, washing and drying to obtain silane coupling agent grafted modified nano-cerium oxide; Sodium alginate is added to deionized water and stirred to dissolve to obtain a sodium alginate solution, nano-cerium oxide grafted with a silane coupling agent is added to the sodium alginate solution, wherein the mass ratio of nano-cerium oxide grafted with a silane coupling agent to sodium alginate is 1:0.4-0.7, SnCl4 and HCl are added, heated and stirred to react, and filtered, washed, and dried to obtain modified nano-cerium oxide; 5) drying the nano rare earth nickel-plated brass intermediate in an oven, and then performing vacuum heating and baking treatment in a muffle furnace to obtain a nano rare earth nickel-plated brass material.

2. The method for preparing a nano rare earth nickel plated brass material according to claim 1, wherein: In the step 2), the degreasing liquid includes sodium hydroxide, sodium carbonate and sodium silicate.

3. The method for preparing a nano rare earth nickel plated brass material according to claim 1, wherein: In step 3), the volume concentration of the nitric acid solution is 3-5%.

4. The method for preparing a nano rare earth nickel plated brass material according to claim 1, wherein: In step 3), the volume concentration of the hydrofluoric acid solution is 10-20%.

5. The method for preparing a nano rare earth nickel plated brass material according to claim 1, wherein: In the step 4), the mass volume concentration of the modified nano-cerium oxide is 1-8 g / L.

6. The method for preparing a nano rare earth nickel plated brass material according to claim 1, wherein: In step 4), the electroplating temperature is 40-50°C and the current density is 4-5A / dm 2 , the pH of the electroplating solution is maintained at 4-5, and the electroplating time is 1.5-3h.

7. A nano rare earth nickel plated brass material, characterized in that: The method is prepared by any one of claims 1 to 6.

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