CN102400066A - A nanoparticle-reinforced metal matrix amorphous composite material and its preparation method - Google Patents

Abstract

The invention provides a nanoparticle reinforced metal matrix amorphous composite material and a preparation method thereof, wherein double-pulse electrodeposition is adopted for 1.5-6 h, and Ni-W-P/CeO with the thickness of 54-251 mu m is prepared on the surface of common carbon steel from electrolyte by utilizing the common dispersion action of ultrasonic, mechanical stirring and two surfactants₂-SiO₂An amorphous composite material. The electrolyte has the advantages of good stability, strong uniform plating capacity, high current efficiency and high deposition rate. CeO in amorphous composite material₂And SiO₂The nano-particle reinforced phase is dispersed and distributed, the size of matrix metal particles is 1-2 mu m, the tissue structure is compact, the nano-particle reinforced phase is firmly combined with a matrix, the deposition layer is thick, the plating state microhardness is high, and the nano-particle reinforced phase can be used as a surface functional plating layer of equipment parts such as metallurgy, chemical engineering, tobacco and machinery.

Description

A nanoparticle-reinforced metal matrix amorphous composite material and its preparation method

technical field

The invention relates to a method for preparing nanoparticle-reinforced metal-based amorphous composite material (Ni-WP/CeO ₂ -SiO ₂ ) by double-pulse electrodeposition, and belongs to the scientific and technical fields of metal-based composite materials, electrodeposition, and the like.

Background technique

Metallurgical, chemical, tobacco and mechanical equipment parts will wear and tear due to mutual movement during use, oxidation will occur at high operating temperatures, and corrosion will occur when exposed to high-temperature melt, gas, water and chemical media, causing damage to the surface of the parts. invalidated. The rapid development of modern industrial technology requires these equipment parts to be able to operate for a long time under high temperature, high pressure, high speed, high automation and relatively harsh working conditions. After failure, they are not simply discarded, but still remain after surface selective strengthening or modification. Continue to use, effectively increase its recycling times, and reduce production costs. Nanocomposite electrodeposition technology is based on the theory of electrocrystallization and dispersion strengthening, through the electrochemical method to make one or several kinds of insoluble solid particles with nanometer size and metal ions to co-deposit to obtain particle-reinforced metal matrix composite materials. . Utilizing the characteristics of solid particles and the synergistic effect of multi-component composite materials, high hardness and wear-resistant metal matrix composites, corrosion-resistant metal matrix composites, self-lubricating metal matrix composites, electrocatalytically active metal matrix composites, electrical contact Functional metal matrix composite materials, etc., are widely used in metallurgy, chemical industry, machinery, aerospace, automobile, tobacco, electronics, nuclear industry and other departments.

The traditional composite electrodeposition technology uses direct current, which is less effective in increasing the cathode current density, suppressing side reactions, reducing impurity content, and improving current distribution. At the same time, due to the complexity of the multi-component composite electrodeposition electrolyte system, the stability is poor and precipitation is easy to occur. The greater van der Waals attraction on the surface of the particles in the electrolyte leads to serious agglomeration. When only mechanical stirring is used to ensure the suspension of the particles, a higher stirring rate is required, which also leads to difficulties in particle deposition. Therefore, the prepared composite material has many structural defects, and it still cannot meet the requirements of use in harsh environments that require wear resistance, corrosion resistance, and high temperature oxidation resistance. Existing literature [1]: (as shown in Figure 6) Effect of the concentration of sodium tungstate and sodium hypophosphite on the microhardness and microstructure of Ni-WP-CeO ₂ -SiO ₂ nanocomposite film materials, Journal of Composite Materials, 2008 ,25(4):106-112; Literature [2]: (as shown in Figure 7) Effect of Process Parameters on the Microstructure and Properties of Ni-WP-CeO ₂ -SiO ₂ Nanocomposite Thin Film Materials, Materials Engineering, 2008, (8):17-21; Literature [3]: Preparation of Ni-WP-CeO ₂ -SiO ₂ nanocomposite thin film materials, Rare Metal Materials and Engineering, 2008,37(10):1809-1814; Literature [4] : Effect of double pulse working time on the electrodeposition of Ni-WP/CeO ₂ -SiO ₂ nanocomposites, Materials Protection, 2010,43(3):34-37; Literature [5]: Pulse electrodeposition of CeO ₂ -SiO ₂ /Ni-WP nanocomposite coating performance research, material protection, 2008, 41 (10): 37-39 and other documents, prepared Ni-WP-CeO ₂ -SiO ₂ composite materials, but the nanoparticles in the Ni-WP matrix metal The agglomeration problem is more serious, the pulse parameter range is narrow, the deposition rate of the electrolyte is low, the throwing ability and current efficiency need to be improved, the as-plated microhardness of the composite material is not high, and the deposited layer is also thin.

Contents of the invention

The present invention aims at the above-mentioned deficiencies _existing in _the prior art, and provides a nanoparticle-reinforced metal-based amorphous composite material and a preparation method thereof. High microhardness and thick deposition layer. The electrolyte used has good stability, strong throwing ability, high current efficiency and fast deposition rate.

The technical scheme of the present invention is: the nanoparticle reinforced metal-based amorphous composite material is Ni-WP/CeO ₂ -SiO ₂ amorphous composite material, and the CeO ₂ and SiO ₂ nanoparticles in the composite material are evenly distributed in the Ni-WP matrix metal Dispersion, the matrix metal particle size is 1-2μm.

The thickness of the Ni-WP/CeO ₂ -SiO ₂ amorphous composite material is 54-251 μm. The composition of the Ni-WP/CeO ₂ -SiO ₂ amorphous composite material is: Ni 66.04～73.24wt%, W 5.23～7.43wt%, P 9.96～11.97wt%, CeO ₂ 8.41～11.84wt%, SiO ₂ 3.16 ~4.38wt%, and its microhardness in the as-plated state is between 739 and 797HV.

The specific preparation steps of the preparation method of the present nanoparticle-reinforced metal matrix amorphous composite material are as follows:

(1) Use the electrolytic nickel plate as the anode material of the electrodeposition process, clean it with water, then immerse it in the electrolyte, and connect it with the anode wire of the double pulse power supply;

(2) Ordinary carbon steel is used as the cathode (substrate) material of the electrodeposition process, which is mechanically polished and cleaned with water, then immersed in the electrolyte, and connected with the cathode wire of the double pulse power supply.

(3) Turn on the ultrasonic and mechanical stirring and dispersing device and the double-pulse power supply, electrodeposit for 1.5-6 hours under the double-pulse parameters, take it out, wash it with cold water and dry it, and obtain Ni-WP with a thickness of 54-251 μm on the surface of ordinary carbon steel /CeO ₂ -SiO ₂ amorphous composite material.

The electrolyte solution in the steps (1) and (2) is: nickel chloride, nickel sulfate, sodium tungstate, sodium hypophosphite as the main salt, glycolic acid and citric acid as complex complexing agent, CeO ₂ And SiO ₂ nanoparticles were deposited reinforcement phase particles, and polyethylene glycol 10000 and hexadecyl trimethyl amine were used as nanoparticle surfactants.

The composition of the electrolyte in the steps (1) and (2) is: the concentration of nickel chloride is 10-30g/L, the concentration of nickel sulfate is 30-70g/L, the concentration of sodium tungstate is 80-120g/L, The concentration of sodium hypophosphite is 10~14g/L, the concentration of glycolic acid is 30~60g/L, the concentration of citric acid is 60~90g/L, the concentration of _CeO2 is 10~15g/L, the average particle size is 30nm, the concentration of _SiO2 The concentration is 30-40g/L, the average particle size is 30nm, the concentration of polyethylene glycol 10000 is 25-35mg/L, and the concentration of hexadecyltrimethylamine is 10-12mg/L.

The electrolyte temperature: 45-60° C., and the pH value of the electrolyte: 4.0-6.5.

The parameters of the double-pulse electrodeposition in the step (3) are: forward pulse parameters: pulse width: 200-400 μs, off-time: 600-800 μs, working time: 300-500 ms, pulse average current density: 15-20 A/ dm ² ; reverse pulse parameters are pulse width: 100~300μs, off time: 700~900μs, working time: 30~50ms, pulse average current density: 1~3A/dm ² .

The ultrasonic dispersion current in the step (3) is 2-4A, and the mechanical stirring rate is 100-300rpm.

Compared with prior art, the present invention has following advantage or positive effect:

1. Replace the single citric acid complexing agent with glycolic acid and citric acid complexing agent, which further prevents the precipitation of nickel hydroxide or nickel phosphite in the electrolyte, increases the stability of the electrolyte, and prolongs the service life . At the same time, the deposition rate of the system is also improved.

2. Adopt polyethylene glycol 10000 (nonionic surfactant) and cetyl trimethyl amine (cationic surfactant) composite surfactant to replace single cetyl trimethyl amine, And the simultaneous use of ultrasonic dispersion and mechanical stirring during double-pulse electrodeposition reduces the rate of mechanical stirring, increases the amount of nanoparticles added in the electrolyte and the amount of nanoparticles deposited in the nanocomposite material, and significantly improves the agglomeration of nanoparticles .

3. The use of electrolytic nickel plate instead of 316L stainless steel as the anode and double pulse electrodeposition improves the pulse average current density, increases the deposition rate as much as possible, and shortens the deposition time. At the same time, the high forward instantaneous current density is used to achieve grain refinement, and the reverse current density is used to dissolve the microscopic protrusions on the surface of the deposited layer, which further improves the flatness of the deposited layer surface.

4. The stability of the electroplating solution is good, the current efficiency is higher than 80%, the throwing ability is higher than 95%, and the deposition rate is higher than 36% m/h, thick deposition layer, good batch production stability; the prepared composite material has an amorphous structure, the particles are dispersed and evenly distributed, the crystallization is fine, the tissue structure is compact, and it is firmly combined with the matrix without peeling, peeling and peeling , High microhardness.

Description of drawings

Fig. 1 is the technological process schematic diagram that the present invention adopts;

Figure 2 is the surface microstructure of the Ni-WP/CeO ₂ -SiO ₂ amorphous composite material prepared in Example 1 of the present invention under 10000 times;

Fig. 3 is the surface microstructure of the Ni-WP/CeO ₂ -SiO ₂ amorphous composite material prepared in Example 2 of the present invention under 10000 times;

Figure 4 is the surface microstructure of the Ni-WP/CeO ₂ -SiO ₂ amorphous composite material prepared in Example 3 of the present invention under 10000 times;

Figure 5 is the surface microstructure of the Ni-WP/CeO ₂ -SiO ₂ amorphous composite material prepared in Example 4 of the present invention under 10000 times;

Figure 6 is the surface microstructure of the Ni-WP/CeO ₂ -SiO ₂ composite material prepared under the conditions of literature [1] under 10000 times;

Fig. 7 is the surface microstructure of the Ni-WP/CeO ₂ -SiO ₂ composite material prepared under the conditions of literature [2] under 10000 times.

Detailed ways

The present invention will be further described below in conjunction with drawings and embodiments.

Embodiment 1: Referring to Fig. 1, the specific preparation steps of the preparation method of the nanoparticle-reinforced metal-based amorphous composite material are as follows:

(1) Use the electrolytic nickel plate as the anode material of the electrodeposition process, clean it with water, then immerse it in the electrolyte, and connect it with the anode wire of the double pulse power supply;

(2) Ordinary carbon steel is used as the cathode (substrate) material of the electrodeposition process, which is mechanically polished and cleaned with water, then immersed in the electrolyte, and connected with the cathode wire of the double pulse power supply.

(3) Turn on the ultrasonic and mechanical stirring and dispersing device and double pulse power supply, electrodeposit 1.5 under the double pulse parameters, take it out, wash it with water and dry it, and then get Ni-WP/CeO ₂ -SiO ₂ amorphous composite on the surface of ordinary carbon steel Material.

The electrolyte in steps (1) and (2) is: nickel chloride, nickel sulfate, sodium tungstate, sodium hypophosphite as the main salt, glycolic acid and citric acid as complex complexing agent, cerium oxide ( CeO ₂ ) and silicon dioxide (SiO ₂ ) nanoparticles are deposited particles, with polyethylene glycol 10000 (nonionic surfactant) and hexadecyl trimethyl amine (cationic surfactant) as nanometer Granular surfactant. The specific ingredients are: the concentration of nickel chloride is 10g/L, the concentration of nickel sulfate is 30g/L, the concentration of sodium tungstate is 80g/L, the concentration of sodium hypophosphite is 10g/L, the concentration of glycolic acid is 30g/L, and the concentration of citric acid The concentration of _CeO2 is 10g/L, the average particle size is 30nm, the concentration of _SiO2 is 30g/L, the average particle size is 30nm, the concentration of polyethylene glycol 10000 is 25mg/L, cetyl trimethyl The concentration of oxaline is 10mg/L.

The parameters of the double-pulse electrodeposition in step (3) are: the forward pulse parameter is pulse width: 200μs, the off time is 800μs, the working time is 300ms, and the pulse average current density is 15A/dm ² ; the reverse pulse parameter is pulse width : 100μs, off time: 900μs, working time: 30ms, pulse average current density: 15A/dm ² . Electrolyte temperature: 45°C, electrolyte pH: 4. The ultrasonic dispersion current is 2A, and the mechanical stirring rate is 300rpm.

The throwing power of the electrolyte in this embodiment is higher than 95%, the current efficiency is 80-85%, the deposition rate is 36.49 μm/h, and the thickness of the obtained deposited layer is 54 μm.

The structure of the Ni-WP/CeO ₂ -SiO ₂ composite material obtained by this method is amorphous, consisting of: Ni 73.24wt%, W 5.23wt%, P 9.96wt%, CeO ₂ 8.41wt%, SiO ₂ 3.16wt% ; CeO ₂ and SiO ₂ nanoparticles are uniformly dispersed in the Ni-WP matrix metal, and the matrix metal particle size is 1-2 μm (as shown in Figure 2); the as-plated microhardness of the composite material is 739HV, and it is firmly combined with the matrix. No peeling, flaking and peeling. However, the nanoparticles of Ni-WP/CeO ₂ -SiO ₂ composite materials prepared under the conditions of the existing literature [1] (as shown in Figure 6) and literature [2] (as shown in Figure 7) are seriously agglomerated, and the matrix metal particles The distribution is uneven, and its size is 2 to 4 μm. The as-plated microhardness of the composite material is between 649 and 673HV. According to the conditions described in the existing literature [1] and literature [2], the throwing ability of the electrolyte is between 85-88%, the current efficiency is between 74-77%, and the deposition rate is between 25.03-28.78μm/h between.

Embodiment 2: Referring to Fig. 1, the specific preparation steps of the preparation method of the nanoparticle-reinforced metal-based amorphous composite material are as follows:

(1) Use the electrolytic nickel plate as the anode material of the electrodeposition process, clean it with water, then immerse it in the electrolyte, and connect it with the anode wire of the double pulse power supply.

(2) Ordinary carbon steel is used as the cathode material of the electrodeposition process, which is mechanically polished and cleaned with water, then immersed in the electrolyte, and connected with the cathode wire of the double pulse power supply.

(3) Turn on the ultrasonic and mechanical stirring and dispersing device and the double-pulse power supply, electrodeposit for 3 hours under the double-pulse parameters, take it out, wash it with cold water and dry it, and get Ni-WP/CeO ₂ -SiO ₂ amorphous on the surface of ordinary carbon steel composite material.

The electrolyte in steps (1) and (2) is: nickel chloride, nickel sulfate, sodium tungstate, sodium hypophosphite as the main salt, glycolic acid and citric acid as complex complexing agent, _CeO2 and SiO2 ₂ Nanoparticles are deposited reinforcement phase particles, and polyethylene glycol 10000 and cetyl trimethylamine are used as nanoparticle surfactants. The specific ingredients are: the concentration of nickel chloride is 20g/L, the concentration of nickel sulfate is 50g/L, the concentration of sodium tungstate is 100g/L, the concentration of sodium hypophosphite is 12g/L, the concentration of glycolic acid is 40g/L, and the concentration of citric acid 70g/L, CeO ₂ concentration 13g/L, average particle size 30nm, SiO ₂ concentration 35g/L, average particle size 30nm, polyethylene glycol 10000 concentration 30mg/L, hexadecyl trimethyl Glycerin: 11mg/L.

The parameters of double-pulse electrodeposition in step (3) are: forward pulse parameter: pulse width: 300μs, off time: 700μs, working time: 400ms, pulse average current density: 16A/dm ² ; reverse pulse parameter: pulse width : 200μs, off time: 800μs, working time: 40ms, pulse average current density: 18A/dm ² . Electrolyte temperature: 50°C, electrolyte pH: 5. The ultrasonic dispersion current is 3A, and the mechanical stirring rate is 200rpm.

The throwing power of the electrolyte in this example is higher than 95%, the current efficiency is 80-85%, the deposition rate is 39.14 μm/h, and the thickness of the deposited layer obtained under double-pulse electrodeposition for 3 hours is 117.42 μm.

The structure of the Ni-WP/CeO ₂ -SiO ₂ composite material obtained by this method is amorphous, and the composition is: 70.15wt% Ni, 5.42wt% W, 10.41wt% P, 10.21wt% CeO ₂ , 3.81wt% SiO ₂ ; CeO ₂ and SiO ₂ nanoparticles are uniformly dispersed in the Ni-WP matrix metal, and the matrix metal particle size is 1-2 μm (as shown in Figure 3); the as-plated microhardness of the composite material is 758HV, and it is firmly combined with the matrix. No peeling, flaking and peeling. However, the nanoparticles of Ni-WP/CeO ₂ -SiO ₂ composite materials prepared under the conditions of the existing literature [1] (as shown in Figure 6) and literature [2] (as shown in Figure 7) are seriously agglomerated, and the matrix metal particles The distribution is uneven, and its size is 2 to 4 μm. The as-plated microhardness of the composite material is between 649 and 673HV. According to the conditions described in the existing literature [1] and literature [2], the throwing ability of the electrolyte is between 85-88%, the current efficiency is between 74-77%, and the deposition rate is between 25.03-28.78μm/h between.

Embodiment 3: Referring to Fig. 1, the specific preparation steps of the preparation method of the nanoparticle-reinforced metal-based amorphous composite material are as follows:

(1) Use the electrolytic nickel plate as the anode material of the electrodeposition process, clean it with water, then immerse it in the electrolyte, and connect it with the anode wire of the double pulse power supply.

(2) Ordinary carbon steel is used as the cathode material of the electrodeposition process, which is mechanically polished and cleaned with water, then immersed in the electrolyte, and connected with the cathode wire of the double pulse power supply.

(3) Turn on the ultrasonic and mechanical stirring and dispersing device and the double pulse power supply, electrodeposit for 6 hours under the double pulse parameters, take it out, wash it with cold water and dry it, and get Ni-WP/CeO ₂ -SiO ₂ amorphous on the surface of ordinary carbon steel composite material.

The electrolyte in steps (1) and (2) is: nickel chloride, nickel sulfate, sodium tungstate, sodium hypophosphite as the main salt, glycolic acid and citric acid as complex complexing agent, _CeO2 and SiO2 ₂ Nanoparticles are deposited reinforcement phase particles, and polyethylene glycol 10000 and cetyl trimethylamine are used as nanoparticle surfactants. The specific composition of the electrolyte is: the concentration of nickel chloride is 30g/L, the concentration of nickel sulfate is 70g/L, the concentration of sodium tungstate is 120g/L, the concentration of sodium hypophosphite is 14g/L, and the concentration of glycolic acid is 60g/L. The concentration of citric acid is 90g/L, the concentration of _CeO2 is 15g/L, the average particle size is 30nm, the concentration of _SiO2 is 40g/L, the average particle size is 30nm, the concentration of polyethylene glycol 10000 is 35mg/L, hexadecane The concentration of trimethyl amine is 12mg/L.

The parameters of double-pulse electrodeposition in step (3) are: forward pulse parameter is pulse width: 400μs, off time is 600μs, working time: 500ms, pulse average current density: 20A/dm ² ; reverse pulse parameter is pulse width : 200μs, off time: 700μs, working time: 50ms, pulse average current density: 20A/dm ² . Electrolyte temperature: 60°C, electrolyte pH: 5.5. The ultrasonic dispersion current is 4A, and the mechanical stirring rate is 100rpm.

The throwing power of the electrolyte in this example is higher than 95%, the current efficiency is 80-85%, the deposition rate is 43.07 μm/h, and the thickness of the deposited layer obtained under double-pulse electrodeposition for 4.5 hours is 193.82 μm.

The structure of the Ni-WP/CeO ₂ -SiO ₂ composite material obtained by this method is amorphous, and the composition is: 66.04wt% Ni, 6.22wt% W, 11.97wt% P, 11.39wt% CeO ₂ , 4.38wt% SiO ₂ ; CeO ₂ and SiO ₂ nanoparticles are uniformly dispersed in the Ni-WP matrix metal, and the matrix metal particle size is 1-2 μm (as shown in Figure 4); the as-plated microhardness of the composite material is 781HV, and it is firmly combined with the matrix. No peeling, flaking and peeling. However, the nanoparticles of Ni-WP/CeO ₂ -SiO ₂ composite materials prepared under the conditions of the existing literature [1] (as shown in Figure 6) and literature [2] (as shown in Figure 7) are seriously agglomerated, and the matrix metal particles The distribution is uneven, and its size is 2 to 4 μm. The as-plated microhardness of the composite material is between 649 and 673HV. According to the conditions described in the existing literature [1] and literature [2], the throwing ability of the electrolyte is between 85-88%, the current efficiency is between 74-77%, and the deposition rate is between 25.03-28.78μm/h between.

Embodiment 4: Referring to Fig. 1, the specific preparation steps of the preparation method of the nanoparticle-reinforced metal-based amorphous composite material are as follows:

(1) Use the electrolytic nickel plate as the anode material in the electrodeposition process, clean it with cold water, then immerse it in the electrolyte, and connect it with the anode wire of the double pulse power supply.

(2) Ordinary carbon steel is used as the cathode (substrate) material of the electrodeposition process, which is mechanically polished and cleaned with cold water, then immersed in the electrolyte, and connected to the cathode wire of the double pulse power supply.

(3) Turn on the ultrasonic and mechanical stirring and dispersing device and the double pulse power supply, electrodeposit for 6 hours under the double pulse parameters, then take it out, wash it with cold water and dry it, and get Ni-WP/CeO ₂ -SiO ₂ non- crystal composites.

The electrolyte in steps (1) and (2) is: nickel chloride, nickel sulfate, sodium tungstate, sodium hypophosphite as the main salt, glycolic acid and citric acid as complex complexing agent, _CeO2 and SiO2 ₂ Nanoparticles are deposited reinforcement phase particles, and polyethylene glycol 10000 and cetyl trimethylamine are used as nanoparticle surfactants. The specific ingredients are: the concentration of nickel chloride is 20g/L, the concentration of nickel sulfate is 60g/L, the concentration of sodium tungstate is 120g/L, the concentration of sodium hypophosphite is 14g/L, the concentration of glycolic acid is 45g/L, and the concentration of citric acid The concentration of _CeO2 is 15g/L, the average particle size is 30nm, the concentration of _SiO2 is 35g/L, the average particle size is 30nm, the concentration of polyethylene glycol 10000 is 35mg/L, cetyl trimethyl The concentration of acetoamine is 12mg/L.

The parameters of double-pulse electrodeposition in step (3) are: forward pulse parameter: pulse width: 300μs, off time: 700μs, working time: 400ms, pulse average current density: 18A/dm ² ; reverse pulse parameter: pulse width : 300μs, off time: 700μs, working time: 40ms, pulse average current density: 18A/dm ² . Electrolyte temperature: 60°C, electrolyte pH: 6.5. The ultrasonic dispersion current is 4A, and the mechanical stirring rate is 300rpm.

The throwing power of the electrolyte in this example is higher than 95%, the current efficiency is 85-88%, the deposition rate is 41.68 μm/h, and the thickness of the deposited layer obtained under double-pulse electrodeposition for 6 hours is 251 μm.

The structure of the Ni-WP/CeO ₂ -SiO ₂ composite material obtained by this method is amorphous, consisting of: 65.60wt%Ni, 7.43wt%W, 10.92wt%P, 11.84wt%CeO ₂ , 4.21SiO ₂ ; CeO ₂ and SiO ₂ nanoparticles are uniformly dispersed in the Ni-WP matrix metal, and the matrix metal particle size is 1-2 μm (as shown in Figure 5); the as-plated microhardness of the composite material is 797HV, and it is firmly combined with the matrix without cracking. Peeling, desquamation and peeling. However, the nanoparticles of Ni-WP/CeO ₂ -SiO ₂ composite materials prepared under the conditions of the existing literature [1] (as shown in Figure 6) and literature [2] (as shown in Figure 7) are seriously agglomerated, and the matrix metal particles The distribution is uneven, and its size is 2 to 4 μm. The as-plated microhardness of the composite material is between 649 and 673HV. According to the conditions described in the existing literature [1] and literature [2], the throwing ability of the electrolyte is between 85-88%, the current efficiency is between 74-77%, and the deposition rate is between 25.03-28.78μm/h between.

Claims (8)

1. A nanoparticle-reinforced metal matrix amorphous composite material, characterized in that: it is Ni-WP/CeO ₂ -SiO ₂ amorphous composite material, CeO ₂ and SiO ₂ nanoparticles in the Ni-WP matrix metal in the composite material Evenly dispersed, the matrix metal particle size is 1-2 μm. 2. The nanoparticle-reinforced metal matrix amorphous composite material according to claim 1, characterized in that the thickness of the Ni-WP/CeO ₂ -SiO ₂ amorphous composite material is 54-251 μm. 3. The nanoparticle-reinforced metal-based amorphous composite material according to claim 1, characterized in that the composition of the Ni-WP/CeO ₂ -SiO ₂ amorphous composite material is: Ni 66.04-73.24wt%, W 5.23 ~7.43wt%, P 9.96~11.97wt%, CeO ₂ 8.41~11.84wt%, SiO ₂ 3.16~4.38wt%. 4. A method for preparing a nanoparticle-reinforced metal-based amorphous composite material, characterized in that the specific preparation steps are as follows: (1) Use the electrolytic nickel plate as the anode material of the electrodeposition process, clean it with water, then immerse it in the electrolyte, and connect it with the anode wire of the double pulse power supply; (2) Ordinary carbon steel is used as the cathode material of the electrodeposition process, which is mechanically polished and cleaned with water, then immersed in the electrolyte, and connected with the cathode wire of the double pulse power supply; (3) Turn on the ultrasonic and mechanical stirring and dispersing device and double pulse power supply, electrodeposit under the double pulse parameters for 1.5~6h, take it out, wash it with cold water and dry it, and get Ni-WP/CeO ₂ -SiO ₂ on the surface of ordinary carbon steel Amorphous composite materials. 5. The method for preparing nanoparticle-reinforced metal-based amorphous composites according to claim 4, wherein the electrolytic solution is based on nickel chloride, nickel sulfate, sodium tungstate, and sodium hypophosphite as the main salt , using glycolic acid and citric acid as composite complexing agents, CeO ₂ and SiO ₂ nanoparticles as the reinforced phase particles deposited, and polyethylene glycol 10000 and cetyl trimethylamine as the nanoparticle surface active agent. 6. The method for preparing nanoparticle-reinforced metal-based amorphous composites according to claim 4 or 5, characterized in that: the composition of the electrolyte is: the concentration of nickel chloride is 10-30g/L, nickel sulfate The concentration is 30-70g/L, the concentration of sodium tungstate is 80-120g/L, the concentration of sodium hypophosphite is 10-14g/L, the concentration of glycolic acid is 30-60g/L, and the concentration of citric acid is 60-90g/L. The concentration of CeO ₂ is 10-15g/L, the average particle size is 30nm, the concentration of SiO ₂ is 30-40g/L, the average particle size is 30nm, the concentration of polyethylene glycol 10000 is 25-35mg/L, hexadecyl tri The concentration of methyl amine is 10-12mg/L, the temperature of the electrolyte is 45-60°C, and the pH value of the electrolyte is 4.0-6.5. 7. The preparation method of nanoparticle-reinforced metal matrix amorphous composite material according to claim 4, characterized in that: the parameters of the double-pulse electrodeposition in the step (3) are: the forward pulse parameter is the pulse width: 200～400μs, off time 600～800μs, working time: 300～500ms, pulse average current density: 15～20A/dm ² ; reverse pulse parameters are pulse width: 100～300μs, off time: 700～900μs, Working time: 30~50ms, pulse average current density: 1~3A/dm ² . 8. The method for preparing nanoparticle-reinforced metal matrix amorphous composite material according to claim 4, characterized in that: the ultrasonic dispersion current is 2-4A, and the mechanical stirring rate is 100-300rpm.

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