CN105970262B - A kind of the wear-and corrosion-resistant material and its preparation process of band Ni-P-Ce-B4C@Cu composite deposites - Google Patents

Abstract

The invention discloses a wear-resistant and corrosion-resistant material with a Ni-P-Ce-B4C (Cu) composite coating and a preparation process thereof. The preparation process of the invention is simple, and the prepared product has superior performance and is suitable for industrial production. The hardness and wear resistance and corrosion resistance of the obtained material are greatly improved.

Description

A wear-resistant and corrosion-resistant material with Ni-P-Ce-B4C@Cu composite coating and its preparation craft

technical field

The invention relates to a wear-resistant and corrosion-resistant coating and a preparation method thereof, in particular to a wear-resistant and corrosion-resistant material with a Ni-P-Ce-B ₄ C@Cu composite coating and a preparation process thereof.

Background technique

Since the 1980s, people have used brush plating technology to obtain composite coatings. For the improvement of coating hardness, wear resistance and corrosion resistance, at present, the Ni-P coating is mainly mixed with second-phase particles or metals, using electroplating or The electroless plating method co-deposits metal or solid solution particles to prepare a ternary composite coating. The second phase particles mainly include SiC, WC, cubic B ₄ C, Al ₂ O ₃ , Si ₃ N ₄ and other composite particles for the purpose of improving hardness and wear resistance, as well as CuF ₂ , (CF) _n , PTFE, MoS ₂ etc. are composite particles that improve the self-lubricating properties of the coating.

In the traditional composite brush plating coating, the bond between the second-phase insoluble particles and the alloy is different, and the interface wettability is poor, which will easily produce the second-phase insoluble particles, which are easy to fall off, resulting in an increase in the surface porosity of the coating, and ultimately resulting in corrosion resistance. decrease.

Nano-B ₄ C powder is a kind of non-conductive material. In the traditional brush plating deposition process, it mainly enters the coating by mechanical capture during the growth of the matrix metal. The content of nano-powder in the obtained composite coating is low, and The distribution of nanopowder in the coating is uneven.

And in the existing preparation brush plating Ni-Cu-P coating, the brush plating bath of preparation is very complicated, in order to obtain good brush plating effect, it is difficult to grasp each component ratio in the plating bath, and operation process is also difficult to control .

The existing wear-resistant and corrosion-resistant materials containing composite coatings generally have the defects of insufficient hardness and poor wear-resistant and corrosion-resistant performance, and cannot meet the increasingly higher requirements for wear-resistant and corrosion-resistant.

Contents of the invention

The purpose of the present invention is to provide a wear-resistant and corrosion-resistant material with Ni-P-Ce-B ₄ C@Cu composite coating which has high hardness and greatly improved wear resistance and corrosion resistance.

Another object of the present invention is to provide a wear-resistant and corrosion-resistant material with a Ni-P-Ce-B ₄ C@Cu composite coating that has a simple preparation method and greatly improved hardness and wear resistance of the obtained material preparation process.

The invention provides a wear-resistant and corrosion-resistant material with a Ni-P-Ce-B ₄ C@Cu composite coating. The wear-resistant and corrosion-resistant material sequentially includes a substrate, a first Ni coating, a Ni- P-Ce coating, second Ni coating, Ni-P-Ce-B ₄ C@Cu coating.

The present invention further comprises following preferred scheme:

In a preferred solution, the thicknesses of the first Ni coating layer and the second Ni coating layer are both 0.5-1.5 μm. Preferably it is 0.5-1.0 μm, more preferably 0.5 μm.

In a preferred scheme, the thickness of the Ni-P-Ce coating is 5.0-7.0 μm, preferably 5.0-6.0 μm, more preferably 5.0 μm.

In a preferred scheme, the thickness of the Ni-P-Ce-B ₄ C@Cu coating is 6.0-8.0 μm, preferably 6.0-7.0 μm, more preferably 7.0 μm.

The present invention further relates to a preparation process of a wear-resistant and corrosion-resistant composite coating with Ni-P-Ce-B ₄ C@Cu. After the substrate surface is pretreated, the first Ni coating, Ni-P-Ce coating, and the Two Ni coatings, Ni-P-Ce-B ₄ C@Cu coatings.

In a preferred scheme, the preparation process includes the following process steps:

step one:

Under the condition of 40-50°C, the substrate with a clean surface after activation treatment is brush-plated with nickel using a nickel-containing plating solution to obtain the substrate/first Ni coating;

Step two:

The substrate/the first Ni coating sample is cleaned with water, and the brush plating of the plating solution A-1 is carried out to obtain the substrate/the first Ni coating/Ni-P-Ce coating sample, and the nickel-containing plating solution is used again after cleaning with water Carry out the brush plating of nickel, obtain substrate/the first Ni plating layer/Ni-P-Ce plating layer/the second Ni plating layer; Add Cu-coated B4C particles in the plating solution A-1, control Cu-coated B ₄ C in the plating The concentration in solution A-1 is 35-75g/L, carry out ultrasonic dispersion, stir, obtain plating solution A-2, then use plating solution A-2 to carry out brush plating, obtain substrate/the first Ni plating layer/Ni-P- Ce coating/second Ni coating/Ni-P-Ce-B ₄ C@Cu coating sample;

The nickel-containing plating solution includes the following components: 320-350 g/L of nickel sulfate hexahydrate, 60-80 g/L of citric acid, and 15-30 g/L of boric acid. During plating, the pH of the nickel-containing plating solution is 1-3;

The brush plating solution A-1 includes the following components: nickel sulfate 240g/L-280g/L, sodium hypophosphite 15-25g/L, citric acid 20-30g/L, trisodium citrate 15-25g/L , sodium sulfate 15-20g/L, glacial acetic acid 20-30ml/L, sodium lauryl sulfate 0.1-0.3g/L, cerium nitrate 25-45g/L;

During plating, the pH value of plating solution A-1 is controlled at: 3.0-5.0.

In a preferred solution, the particle size of the Cu-coated B ₄ C particles is 100-350 nm.

In a preferred solution, the Cu-coated B ₄ C particles are roughened by immersing the nano-B ₄ C powder in an NH ₄ F solution with a concentration of 8-12 wt%, and then adding 10-11g/L SnCl for solid-liquid separation ₂ and 4-5g/L HCl solution for sensitization, solid-liquid separation, adding 0.4-0.6g/L PdCl ₂ and 20-22ml/L HCl activation solution for activation, solid-liquid separation, and adding hypophosphorous acid after drying Stir in the sodium aqueous solution to form a suspension, add it to the modified solution, stir and react, and separate the solid and liquid to obtain;

Among them, the composition of the modified liquid: copper sulfate 7.5g/L-15g/L, formaldehyde 15ml/L-25ml/L, potassium sodium tartrate 20-30g/L, 2,2-bipyridine 10mg-20mg/L, nickel cyanide Potassium chloride 50mg/L-100mg/L, sodium hydroxide 6-9/L;

The pH of the modification solution is 11.5-12.5, the loading amount is 2-4g/min, and the temperature is 45-60°C.

The loading capacity refers to the capacity of the electroplating solution required for brush plating a surface area of one decimeter squared.

The above coating not only solves the problem of co-deposition and uniform distribution of powder particles in the coating, but also Cu coating can also improve the corrosion performance of the coating due to the addition of nanoparticles.

The problem of agglomeration of nano-B ₄ C particles in the solution is improved. The deposition of Cu in the coating can not only refine the cell structure of the coating in structure, but Cu also exhibits a preferential corrosion mechanism in the salt solution system, thus providing a good protection for the Ni alloy. Cathodic protection, the entire coating is an electrochemical system composed of a large number of uniform two-dimensional distribution of Ni-Cu microscopic corrosion units, which makes up for the increase in interfaces and pores caused by the addition of particles, resulting in more microscopic defects in the coating, and finally The corrosion performance decreases due to the increase in the number of localized corrosion primary cells.

In a preferred solution, when preparing the nickel layer, the brush plating time is controlled to be 50s-90s.

In a preferred scheme, when preparing the Ni-P-Ce coating, the brush plating time is controlled to be 3-4min.

In a preferred solution, when preparing the Ni-P-Ce-B ₄ C@Cu coating, the brush plating time is controlled to be 4-5 minutes.

In a preferred solution, after the brush plating is completed, the plated piece is treated at a constant temperature of 400-430° C. for 0.5h-1.5h, and then the sample is taken out and air-cooled to obtain a finished product.

In the preferred scheme, the control voltage is 11V when performing brush plating of the plating solution A-1, and the positive connection method is adopted, and the brush plating speed is 50-80mm/s.

In the preferred scheme, the control voltage is 12V during nickel brush plating, the positive connection method is adopted, and the brush plating speed is 40-80mm/s.

In a preferred solution, the brush plating time is controlled to be 50s-90s during brush nickel plating.

In a preferred scheme, during the stirring process of adding Cu-coated B ₄ C into the remaining plating solution B, the rotational speed is controlled to be 200-300 r/min.

In a preferred solution, when brush-plating Ni-P-Ce-B ₄ C@Cu coating, the control voltage is 11V, the positive connection method is adopted, and the brush-plating speed is 40-80mm/s.

In the preferred scheme, the process of substrate activation treatment is:

1) Manually degrease the substrate by wiping the organic solvent acetone for 20-60s.

2) Electric degreasing, using the positive connection method, adjust the voltage to 12V, use a plating pen dipped in the electro-cleaning solution to brush-plate the substrate, the brush-plating speed is 60-100mm/s, and the time is 15s-30s. After brush plating, rinse with deionized water.

3) Activation by activating solution: The activation adjustment voltage of No. 1 activating solution is 12V, the reverse connection method is adopted, the brush plating speed is 90-130mm/s, and the time is 20s-30s. When the No. 3 activation solution is activated, the voltage needs to be adjusted to 12V, and the reverse connection method is adopted. The brush plating speed is 90-130mm/s, and the time is 50s-90s.

The No. 1 activation solution consists of: 98% concentrated sulfuric acid 44.6ml/L, ammonium sulfate 110.9g/l, pH=0.4; the No. 3 activation solution consists of citric acid 94.2g/L, trisodium citrate 141.2g/L, chlorine Nickel 3g/L, pH=4.

The composition of the electrocleaning liquid is sodium hydroxide 25g/L, sodium carbonate 21.6g/L, sodium phosphate 50g/L, sodium chloride 2.4g/L, pH=13.

In a preferred scheme, the plating solution A-1 is prepared by the following scheme:

In the preferred scheme, nickel sulfate, sodium hypophosphite, citric acid, trisodium citrate are prepared according to the composition and concentration of the designed plating solution A-1 and the volume of the required plating solution A-1 in the actual production process. , glacial acetic acid, sodium sulfate, sodium lauryl sulfate, cerium nitrate; then dissolve nickel sulfate, sodium hypophosphite, citric acid, trisodium citrate, and sodium sulfate with a small amount of deionized water respectively to obtain sulfuric acid Nickel solution, sodium hypophosphite solution, citric acid solution, trisodium citrate solution, sodium sulfate solution; then mix the obtained citric acid solution, trisodium citrate solution and glacial acetic acid, and stir to obtain a complexing agent solution; Then the complexing agent solution and the nickel sulfate solution are uniformly mixed to obtain a solution A; then the cerium nitrate and sodium sulfate solutions are added to the solution A and stirred evenly to obtain a solution B. Then, under rapid stirring, sodium hypophosphite solution was added to solution B, and finally the pH value of solution B was adjusted to 3.0-4.0 with 15% dilute ammonia water to obtain plating solution A-1.

In a preferred solution, the substrate is an ink scraper, and the length of the substrate is 35.0 cm.

In the brush plating process, the time is generally controlled according to the length of the brush plating sample to finally control the thickness of the applied coating.

Beneficial effects of the present invention

The material of the invention can not only greatly improve the hardness of the plating layer, but also can greatly improve the wear resistance of the wear-resistant and corrosion-resistant materials.

The present invention has high current efficiency, accelerated alloy deposition, shortens the time from strong adsorption of inorganic particles to being captured by the mechanism, and reduces the probability of buried particles suffering from external impact and falling off, which is more conducive to inorganic particles in the alloy matrix deposition.

Defects such as grain boundaries, dislocations, and vacancies of the obtained wear-resistant and corrosion-resistant material are reduced, and the corrosion resistance and bonding strength of the coating are improved. The overall performance of the material of the present invention is greatly improved.

The invention has reasonable components and simple preparation process, effectively improves the problem of uneven dispersion of second-phase insoluble particles in the plating solution, promotes the amorphization of Ni-P alloys, and reduces defects such as grain boundaries, dislocations, and vacancies. The corrosion resistance is increased, making up for the defect that the corrosion resistance is reduced due to the addition of nanoparticles. The obtained material has excellent surface hardness and wear resistance, is suitable for industrial production, and expands its application field.

Description of drawings

Fig. 1 is an example of the process flow chart of multi-layer Ni-P-Ce-B ₄ C@Cu composite coating brush plating.

Detailed ways

The present invention will be described in detail below in conjunction with specific embodiments, rather than limiting the present invention, within the spirit of the present invention and the scope of claims, any amendments or changes made to the present invention will fall within the protection scope of the present invention.

Example 1

Dissolve 240g of nickel sulfate, 15g of sodium hypophosphite, 20g of citric acid, and 20g of citric acid tris in deionized water according to the composition and concentration requirements of plating solution A-1 and the volume of plating solution A-1 required in the actual production process. Sodium, 18g of sodium sulfate, 0.1g of sodium lauryl sulfate, 25g of cerium nitrate, and 20ml of glacial acetic acid were prepared; then the obtained citric acid solution, trisodium citrate solution and glacial acetic acid were stirred for 6 minutes to obtain a complexing agent solution; Then mix the complexing agent solution and nickel sulfate solution evenly for 10 minutes to obtain solution A; then add cerium nitrate and sodium sulfate solution to solution A and stir for 5 minutes to obtain solution B. Then, under rapid stirring, the sodium hypophosphite solution was slowly added to solution B, and stirred for 20 minutes. Finally, the pH of the solution was adjusted to 3.0 with a pH regulator, and the volume was adjusted to 1 L. Wherein the pH regulator is 15% dilute ammonia water, and the plating solution A-1 is prepared.

B ₄ C nanopowder (particle size is 50nm) was roughened by 10wt% NH ₄ F solution for 20min, sensitized in 10g/L SnCl ₂ and 4g/L HCl solution for 3min, and in _0.5g /L PdCl2 and 22ml/L HCl After activating in the activation solution for 3 minutes, centrifuge and dry, then put into the modification solution for Cu coating. The modification solution components are: copper sulfate 10g/L, formaldehyde 25ml/L, potassium sodium tartrate 25g/L, 2,2 Bipyridyl 10mg/L, potassium nickel cyanide 50mg/L, sodium hydroxide 7g/L, pH 12.5, loading capacity 2g/L, temperature 40°C, after stirring reaction, solid-liquid separation to obtain coated Cu B ₄ C particles; the particle size of the Cu-coated B ₄ C particles is 100 nm.

Pre-treat the surface of the workpiece on the surface of the ink scraper, first use absorbent cotton dipped in acetone to wipe the surface of the substrate to manually degrease, the time is 20s; for electric degreasing, use the positive connection method, adjust the voltage to 12V, use a plating pen to dip in the electric cleaner Wipe the substrate with liquid at a wiping speed of 60mm/s for 30s. After brushing, wash with deionized water; activation of activation solution: dip a plating pen into No. 1 activation solution to wipe the substrate, adjust the voltage to 12V, use the reverse connection method, brush plating speed of 90mm/s, and time of 30s ; When the No. 3 activation solution is activated, the voltage needs to be adjusted to 12V, the reverse connection method is adopted, the brush plating speed is 90mm/s, and the time is 90s.

Add 35g of the modified B ₄ C particles into the plating solution A-1, perform ultrasonic vibration for 10 minutes, then perform mechanical stirring for 15 minutes, and control the rotation speed at 200r/min to obtain the plating solution A-2.

After cleaning the activated substrate with deionized water, use a voltage of 12V and adopt the positive connection method to dip the plating pen into the nickel-containing plating solution to brush-plate the substrate. The speed of brush-plating is 40mm/s, and the time is 50s. Obtain the base material/the first Ni layer sample (wherein the first Ni layer thickness is 0.5 μ m), with 11V voltage, adopt positive connection method, dip in the plating solution A-1 with the plating pen and carry out brush plating to the sample, brush plating The hourly speed is 40mm/s, and the time is 3min, obtains substrate/the first Ni layer/Ni-P-Ce sample (wherein the thickness of Ni-P-Ce plating layer is 5 μm); After cleaning the sample surface with deionized water, With a voltage of 12V, using the positive connection method, use a plating pen to dip into the nickel-containing plating solution to brush-plate the substrate. The speed of brush-plating is 40mm/s, and the time is 50s to obtain the substrate/Ni/Ni-P-Ce/Ni The sample (the thickness of the special nickel sandwich layer is 0.5 μm); after cleaning the surface of the sample with deionized water, brush-plate the sample with a plating pen dipped in the plating solution A-2 at a voltage of 11V, and adopt the positive connection method , the brush-plating speed was 40mm/s, and the time was 4min to obtain the substrate/Ni/Ni-P-Ce/Ni/Ni-P-Ce-B ₄ C@Cu sample (wherein brush-plating Ni-P-Ce -B ₄ C@Cu with a thickness of 6 μm). The prepared Ni/Ni-P-Ce/Ni/Ni-P-Ce-B ₄ C@Cu multilayer composite coating was treated at 400°C for 1.5 hours at a constant temperature, and then cooled in air to obtain the final coating sample.

The performance test value of the finished product is as follows:

The cross-sectional microhardness is 1053HV, the self-corrosion current density is 3.85μA, and the self-corrosion potential is -213mV.

Example 2

Dissolve 260g of nickel sulfate, 20g of sodium hypophosphite, 20g of citric acid, and 20g of citric acid tris in deionized water according to the composition and concentration requirements of plating solution A-1 and the volume of plating solution A-1 required in the actual production process. Sodium, 18g of sodium sulfate, 0.1g of sodium lauryl sulfate, 35g of cerium nitrate, and 20ml of glacial acetic acid were prepared; then the obtained citric acid solution, trisodium citrate solution and glacial acetic acid were stirred for 6 minutes to obtain a complexing agent solution; Then mix the complexing agent solution and nickel sulfate solution evenly for 10 minutes to obtain solution A; then add cerium nitrate and sodium sulfate solution to solution A and stir for 5 minutes to obtain solution B. Then, under rapid stirring, the sodium hypophosphite solution was slowly added to solution B, and stirred for 20 minutes. Finally, the pH of the solution was adjusted to 4.0 with a pH regulator, and the volume was adjusted to 1 L. Wherein the pH adjuster is 15% dilute ammonia water, and the preparation of plating solution A-1 is completed at this time.

After B ₄ C powder was coarsened with 0wt% NH ₄ F solution for 25min, sensitized in 10g/L SnCl ₂ and 4g/L HCl solution for 5min, and activated in 0.5g/L PdC ₁₂ and 22ml/L HCl activation solution for 5min Centrifugal separation and drying, put into the modification solution for copper coating, the modification solution components are: copper sulfate 12g/L, formaldehyde 20ml/L, potassium sodium tartrate 25g/L, 2,2-bipyridine 15mg/L, Nickel potassium cyanide 75mg/L, sodium hydroxide 7g/L, pH 11, loading capacity 3g/L, temperature 50°C, after stirring reaction, solid-liquid separation, to obtain B ₄ C particles coated with Cu; The particle size of the Cu-coated B ₄ C particles is 200 nm.

55g of the modified B ₄ C particles were added into the plating solution A-1, subjected to ultrasonic vibration for 10 minutes, then mechanically stirred for 15 minutes, and the rotational speed was controlled at 250r/min to obtain the plating solution A-2.

Pre-treat the surface of the workpiece on the surface of the ink scraper, first use absorbent cotton dipped in acetone to wipe the surface of the substrate and manually degrease for 40 seconds; for electric degreasing, use the positive connection method, adjust the voltage to 12V, and use a plating pen dipped in electro-cleaning liquid to clean the substrate. Wipe the material, the wiping speed is 80mm/s, and the time is 25s. After brushing, wash with deionized water; activation of activation solution: dip a plating pen into No. 1 activation solution to wipe the substrate, adjust the voltage to 12V, use the reverse connection method, brush plating speed is 110mm/s, and the time is 25s ; When the No. 3 activation solution is activated, the voltage needs to be adjusted to 12V, the reverse connection method is adopted, the brush plating speed is 110mm/s, and the time is 70s.

After the activated substrate is cleaned with deionized water, use a voltage of 12V and adopt the positive connection method to dip the plating pen into the nickel-containing plating solution to perform brush plating on the substrate. The speed of brush plating is 50mm/s, and the time is 50s. Obtain base material/Ni layer sample (wherein special nickel thickness is 1.0 μ m); With 11V voltage, adopt positive connection method, dip in plating solution A-1 with plating pen and dip in plating solution A-1 sample is carried out brush-plating, speed during brush-plating is 60mm/s, the time is 3.5min, to obtain the substrate/Ni/Ni-P-Ce sample (the Ni-P-Ce coating thickness is 6μm); after cleaning the sample surface with deionized water, with 12V voltage, use In the positive connection method, the base material is brush-plated with a plating pen dipped in the nickel-containing plating solution. The brush-plating speed is 60mm/s and the time is 70s to obtain the base material/Ni/Ni-P-Ce/Ni sample (including special The thickness of the nickel sandwich layer is 1.0 μm); after the surface of the sample is cleaned with deionized water, the sample is brush-plated with a plating pen dipped in the plating solution A-2 with a voltage of 11V, and the positive connection method is adopted. is 60mm/s, and the time is 4.5min, to obtain substrate/Ni/Ni-P-Ce/Ni/Ni-P-Ce-B ₄ C@Cu sample (where Ni-P-Ce-B ₄ C @Cu thickness is 7.0 μm). The prepared Ni/Ni-P-Ce/Ni/Ni-P-Ce-B ₄ C@Cu multilayer composite coating was treated at 415°C for 1.0 h at a constant temperature, and then cooled in air to obtain the final coating sample.

The performance test value of the finished product is as follows:

The cross-sectional microhardness is 1052HV, the self-corrosion current density is 3.79μA, and the self-corrosion potential is -214mV.

Example 3

Dissolve 280g nickel sulfate, 25g sodium hypophosphite, 20g citric acid, 20g trisodium citrate, 18g of sodium sulfate, 0.1g of sodium lauryl sulfate, 45g of cerium nitrate, and 20ml of glacial acetic acid; then the obtained citric acid solution, trisodium citrate solution and glacial acetic acid were stirred for 6 minutes to obtain a complexing agent solution; The complexing agent solution and nickel sulfate solution were mixed evenly for 10 minutes to obtain solution A; then cerium nitrate and sodium sulfate solutions were added to solution A and stirred for 5 minutes to obtain solution B. Then, under rapid stirring, the sodium hypophosphite solution was slowly added to solution B, and stirred for 20 minutes. Finally, the pH of the solution was adjusted to 5.0 with a pH regulator, and the volume was adjusted to 1 L. The regulator is 15% dilute ammonia water, and the plating solution A-1 is prepared at this time.

B ₄ C powder was roughened with 10% NH4F solution for 30min, sensitized in 10g/L SnCl2 and 4g/L HCl solution for 8min, and activated in 0.5g/L PdCl2 and 22ml/L HCl activation solution for 8min, then centrifuged and dried Dry, put into the modification solution for copper coating, the modification solution components are: copper sulfate 10g/L, formaldehyde 15ml/L, potassium sodium tartrate 25g/L, 2,2-bipyridine 20mg/L, nickel cyanide Potassium 100mg/L, sodium hydroxide 7g/L, pH 11, loading capacity 4g/min, temperature 60°C, after stirring reaction, solid-liquid separation, to obtain B ₄ C particles coated with Cu; The particle size of the B ₄ C particles is 200nm.

Add 75g of the modified B ₄ C particles into the plating solution A-1, perform ultrasonic vibration for 10 minutes, then perform mechanical stirring for 15 minutes, and control the rotation speed at 300r/min to obtain the plating solution A-2.

Pre-treat the surface of the workpiece on the surface of the ink scraper, first use absorbent cotton dipped in acetone to wipe the surface of the substrate and manually degrease for 60 seconds; for electric degreasing, use the positive connection method, adjust the voltage to 12V, and use a plating pen dipped in electro-cleaning liquid to clean the substrate. Wipe the material, the wiping speed is 100mm/s, and the time is 20s. After brushing, wash with deionized water; activation of activation solution: dip a plating pen into No. 1 activation solution to wipe the substrate, adjust the voltage to 12V, use the reverse connection method, brush plating speed of 130mm/s, and time of 20s ; When the No. 3 activation solution is activated, the voltage needs to be adjusted to 12V, the reverse connection method is adopted, the brush plating speed is 130mm/s, and the time is 50s.

After cleaning the activated substrate with deionized water, use a voltage of 12V and adopt the positive connection method to dip the plating pen into the nickel-containing plating solution to brush-plate the substrate. The speed of brush-plating is 50mm/s, and the time is 90s. Obtain base material/Ni layer sample (wherein special nickel thickness is 1.5 μ m); With 11V voltage, adopt positive connection method, dip in plating solution A-1 with plating pen and dip in plating solution A-1 sample is carried out brush-plating, speed during brush-plating is 80mm/s, the time is 4min, to obtain the substrate/Ni/Ni-P-Ce sample (the Ni-P-Ce coating thickness is 7.0μm); after cleaning the sample surface with deionized water, with 12V voltage, use In the positive connection method, the substrate is brush-plated with a plating pen dipped in a nickel-containing plating solution. The brush-plating speed is 80mm/s and the time is 90s to obtain the substrate/Ni/Ni-P-Ce/Ni sample (including special The thickness of the nickel sandwich layer is 1.5 μm); after cleaning the surface of the sample with deionized water, with a voltage of 11V, use a plating pen dipped in the plating solution A-2 to brush-plate the sample, adopt the positive connection method, and the speed of brush-plating is 80mm/s, and the time is 5min, the substrate/Ni/Ni-P-Ce/Ni/Ni-P-Ce-B ₄ C@Cu sample (wherein Ni-P-Ce-B ₄ C@ Cu thickness is 8.0 μm). The prepared Ni/Ni-P-Ce/Ni/Ni-P-Ce-B ₄ C@Cu multilayer composite coating was treated at 430° C. for 0.5 h at a constant temperature, and then air-cooled to obtain the final coating sample.

The performance test value of the product is as follows:

The cross-sectional microhardness is 1033HV, the self-corrosion current density is 3.87μA, and the self-corrosion potential is -201mV.

Comparative example 1

Dissolve 280g of nickel sulfate, 25g of sodium hypophosphite, 20g of citric acid, 20g of trisodium citrate, 18g of sodium sulfate, 0.1g of sodium lauryl sulfate, and 45g of cerium nitrate in deionized water, and prepare 20ml of glacial acetic acid; The obtained citric acid solution, trisodium citrate solution and glacial acetic acid were stirred for 6 minutes to obtain a complexing agent solution; then the complexing agent solution and nickel sulfate solution were mixed uniformly for 10 minutes to obtain solution A; Sodium phosphate solution was slowly added to solution B and stirred for 20 min. Finally, adjust the pH of the solution to 5.0 with a pH meter, and set the volume to 1 L. The regulator is 15% dilute ammonia water, and the plating solution A is prepared at this time.

Pre-treat the surface of the workpiece on the surface of the ink scraper, first use absorbent cotton dipped in acetone to wipe the surface of the substrate and manually degrease for 60 seconds; for degreasing by electric cleaning, use the positive connection method, adjust the voltage to 12V, use a plating pen dipped in the electro-cleaning liquid to clean the substrate Wipe the material, the wiping speed is 100mm/s, and the time is 20s. After brushing, wash with deionized water; activation of activation solution: dip a plating pen into No. 1 activation solution to wipe the substrate, adjust the voltage to 12V, use the reverse connection method, brush plating speed of 130mm/s, and time of 20s ; When the No. 3 activation solution is activated, the voltage needs to be adjusted to 12V, the reverse connection method is adopted, the brush plating speed is 130mm/s, and the time is 50s. After cleaning the activated substrate with deionized water, use a voltage of 12V and adopt the positive connection method to dip the plating pen into the nickel-containing plating solution to brush-plate the substrate. The speed of brush-plating is 50mm/s, and the time is 90s. Obtain base material/Ni layer sample (wherein special nickel thickness is 1.5 μ m); With 11V voltage, adopt positive connection method, dip in plating solution A with plating pen and dip in plating solution A and carry out brush plating to sample, speed during brush plating is 80mm/ s, the time is 4min, and the substrate/Ni/Ni-P sample is obtained. Treat the prepared Ni/Ni-P composite coating at 400°C for 0.5h at a constant temperature, take it out and cool it in air to obtain the final coating sample.

The performance test value of the finished product is as follows:

The cross-sectional microhardness is 780HV, the self-corrosion current density is 7.81μA, and the self-corrosion potential is -311.8mV.

Claims (9)

1. A wear-resistant and corrosion-resistant material with Ni-P-Ce-B ₄ C@Cu composite coating, it is characterized in that, described wear-resistant and corrosion-resistant material comprises base material, first Ni coating, Ni-P-Ce coating, second Ni coating, Ni-P-Ce-B ₄ C@Cu coating; The preparation process of the wear-resistant and corrosion-resistant material with Ni-P-Ce-B ₄ C@Cu composite coating is as follows: after the substrate surface is pretreated, the first Ni coating, Ni-P-Ce coating, and the second coating are sequentially brushed. Two Ni coatings, Ni-P-Ce-B ₄ C@Cu coatings. 2 . The wear-resistant and corrosion-resistant material according to claim 1 , wherein the thicknesses of the first Ni coating and the second Ni coating are both 0.5-1.5 μm. 3. The wear-resistant and corrosion-resistant material according to claim 1 or 2, characterized in that, the thickness of the Ni-P-Ce coating is 5.0-7.0 μm. 4 . The wear-resistant and corrosion-resistant material according to claim 3 , wherein the thickness of the Ni-P-Ce-B ₄ C@Cu coating is 6.0-8.0 μm. 5. A preparation process of a wear-resistant and corrosion-resistant material with Ni-P-Ce-B ₄ C@Cu wear-resistant and corrosion-resistant composite coating, characterized in that it comprises the following process steps: step one: Under the condition of 40-50°C, the substrate with a clean surface after activation treatment is brush-plated with nickel using a nickel-containing plating solution to obtain the substrate/first Ni coating; Step two: The substrate/the first Ni coating sample is cleaned with water, and the brush plating of the plating solution A-1 is carried out to obtain the substrate/the first Ni coating/Ni-P-Ce coating sample, and the nickel-containing plating solution is used again after cleaning with water Perform nickel brush plating to obtain substrate/first Ni coating/Ni-P-Ce coating/second Ni coating; add Cu-coated B ₄ C particles to plating solution A-1 to control Cu-coated B ₄ C In the plating solution A-1, the concentration is 35-75g/L, ultrasonically dispersed and stirred to obtain the plating solution A-2, and then use the plating solution A-2 to perform brush plating to obtain the substrate/the first Ni coating layer/Ni- P-Ce coating/second Ni coating/Ni-P-Ce-B ₄ C@Cu coating sample; The nickel-containing plating solution includes the following components: 320-350 g/L of nickel sulfate hexahydrate, 60-80 g/L of citric acid, and 15-30 g/L of boric acid. During plating, the pH of the nickel-containing plating solution is 1-3; The brush plating solution A-1 includes the following components: nickel sulfate 240g/L-280g/L, sodium hypophosphite 15-25g/L, citric acid 20-30g/L, trisodium citrate 15-25g/L , sodium sulfate 15-20g/L, glacial acetic acid 20-30ml/L, sodium lauryl sulfate 0.1-0.3g/L, cerium nitrate 25-45g/L; During plating, the pH value of plating solution A-1 is controlled at: 3.0-5.0. 6 . The preparation process according to claim 5 , wherein the particle size of the Cu-coated B ₄ C particles is 100-350 nm. 7. The preparation process according to claim 5 or 6, characterized in that the Cu-coated _B4C particles are roughened by immersing nano _-B4C powder in an _NH4F solution with a concentration of 8-12wt% After solid-liquid separation, add 10-11g/L SnCl ₂ and 4-5g/L HCl solution for sensitization, solid-liquid separation, add 0.4-0.6g/L PdCl ₂ and 20-22ml/L HCl activation solution for activation , solid-liquid separation, and after drying, add it to the sodium hypophosphite aqueous solution and stir to form a suspension, add it to the modified liquid, and after stirring and reacting, the solid-liquid separation is obtained; Among them, the composition of the modified liquid: copper sulfate 7.5g/L-15g/L, formaldehyde 15ml/L-25ml/L, potassium sodium tartrate 20-30g/L, 2,2-bipyridine 10mg-20mg/L, nickel cyanide Potassium chloride 50mg/L-100mg/L, sodium hydroxide 6-9/L; The pH of the modification solution is 11.5-12.5, the loading amount is 2-4 g/L, and the temperature is 45-60°C. 8. The preparation process according to claim 7, characterized in that, when preparing the nickel layer, the control brush plating time is 50s-90s; When preparing the Ni-P-Ce coating, control the brush plating time to 3-4min; When preparing the Ni-P-Ce-B ₄ C@Cu coating, the brush plating time is controlled to be 4-5 min. 9 . The preparation process according to claim 5 or 8 , characterized in that, after the brush-plating is completed, the plated piece is treated at 400-430° C. for 0.5h-1.5h at a constant temperature, and then air-cooled to obtain the finished product.