CN112981500B - High-brightness composite nickel-plated layer - Google Patents

High-brightness composite nickel-plated layer Download PDF

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CN112981500B
CN112981500B CN202110247092.3A CN202110247092A CN112981500B CN 112981500 B CN112981500 B CN 112981500B CN 202110247092 A CN202110247092 A CN 202110247092A CN 112981500 B CN112981500 B CN 112981500B
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赵琳琳
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Shenzhen Kangheng Electronics Co ltd
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Abstract

The utility model provides a high-brightness composite nickel-plated layer, wherein the plating solution comprises highly dispersed inorganic nano particles, the particles are molybdenum sulfide coated with silicon oxide, the hardness of the plating layer is effectively improved and the friction coefficient is reduced due to the addition of lubricating inorganic particles, and the brightness of the plating layer is effectively maintained through a composite brightener.

Description

High-brightness composite nickel-plated layer
Technical Field
The utility model belongs to the field of electroplating, and relates to an inorganic modified particle composite bright nickel plating layer.
Background
Wear and corrosion are the primary forms of material failure. The friction wear is one of the main reasons of the failure of mechanical equipment, about 80 percent of the failure of parts is caused by various types of wear, the wear not only consumes energy and materials, but also accelerates the scrapping of the equipment, causes frequent part replacement, causes great loss to economy, causes resource, energy waste and economic loss due to corrosion and rusting, and even endangers the personal safety in severe cases, statistics show that about 1/3 of energy in the mechanical manufacturing is directly or indirectly consumed by the loss caused by the wear and the corrosion. To improve the high temperature corrosion resistance and wear resistance of metal surfaces, many methods for strengthening the surfaces have been developed. The electrodeposition technology is very important in improving the wear resistance, lubricity and the like of the metal surface. At present, a better electrodeposition method for improving the high-temperature corrosion resistance and wear resistance of a metal surface is to deposit metallic nickel or chromium and the like on the metal surface by electrodeposition to form a self-lubricating resistant composite coating and a highly wear-resistant composite coating.
The self-lubricating composite coating is accompanied with friction and abrasion in mechanical motion, and the loss caused by the mechanical motion is huge every year. Two methods of case hardening and reducing the coefficient of friction are commonly used to improve the wear resistance of materials. The self-lubricating composite coating is a composite coating with an antifriction effect, and the added composite particles are so-called solid lubricating particles with a self-lubricating effect, such as: MoS2BN, graphite, polytetrafluoroethylene and other matrix metals form various composite coatings with higher hardness and excellent wear resistance.
High wear-resistant composite coating: the high wear-resistant composite coating has attracted more and more attention due to its good wear resistance. The high wear resistance of the composite coating comes from the strength of the composite particles themselves, the refinement of the matrix metal crystals, and also the dispersion strengthening of sufficiently small particles (usually of the order of nanometers). The hard particles added in the high-wear-resistance composite coating are the most widely applied and important composite coatings. The application of highly wear resistant composite coatings to internal combustion engine blocks is the most successful example. The cylinder block is the heart of the internal combustion engine and its life determines to a large extent the life of the internal combustion engine. The sliding surface of the cylinder body of the internal combustion engine is required to have the performances of wear resistance, heat resistance, mechanical scratch resistance, corrosion resistance and the like, and the common gray cast iron cylinder is difficult to meet the requirements. Efforts are constantly being made to improve the wear and corrosion resistance of the cylinder block and to extend the service life thereof.
For example, CN20091025571A discloses an electroplated nickel-based-graphite self-lubricating material and a coating treatment method thereof, wherein the material is prepared by using nickel sulfate as a base material, adding graphite, boric acid, sodium chloride, sodium sulfate, magnesium sulfate and sodium dodecyl sulfate, and then directly electroplating the surface of a metal part by an electroplating technology. The utility model can obviously improve the wear-resisting strength of the surface of the metal part and has the obvious advantages of simple process, convenient operation and low production cost.
For example, CN201710481903A discloses a nickel-plated silicon carbide copper-based alloy material and a preparation method thereof, and the material comprises the following components by volume percent: 88-93.5% of copper alloy ZCuAl10Fe3Mn2 and 6.5-12% of nickel-plated silicon carbide, and further improvement of the performance of the copper alloy material is realized by utilizing the high hardness, high wear resistance, good self-lubrication and high-temperature strength of the nano-scale silicon carbide, so that the nickel-plated silicon carbide copper-based alloy obtained according to the utility model has higher strength, hardness, wear resistance and corrosion resistance, thereby prolonging the service life of aerospace high-strength pressure-resistant products, petroleum engineering wear-resistant part products and ocean engineering equipment corrosion-resistant product accessories.
At present, the most critical limiting factor of composite plating is the hydrophilicity of the doped particles, and those skilled in the art know that the hydrophilicity of particles such as molybdenum sulfide, tungsten sulfide, boron nitride and the like is very poor, so that the particles are dispersed in a liquid phase, and the primary problem is that the particles can be wetted by liquid and can enter the liquid phase, so that the surface modification of the particles is needed to realize uniform composite plating of the particles.
Disclosure of Invention
Based on the defects of the prior art, the utility model provides the high-brightness composite nickel-plated layer, the plating solution comprises highly dispersed inorganic nano particles, the particles are molybdenum sulfide coated with silicon oxide, the hardness of the plated layer is effectively improved and the friction coefficient is reduced by adding the lubricating inorganic particles, and the brightness of the plated layer is effectively maintained by using the composite brightener.
The high-brightness composite nickel-plated layer is characterized in that the brightness GU value of the nickel-plated layer is 249 +/-15, the hardness 923HV +/-50 Hv and the friction coefficient is 0.27-0.35, the area rate of inorganic nano modified particles in a cross section with a vertical surface of a plating layer is 1-15%, the inorganic nano modified particles are molybdenum sulfide materials coated with silicon oxide, and the preparation method of the inorganic nano modified particles is as follows:
(1) putting 1.5-2.5 g of molybdenum sulfide into a three-neck flask, and adding 45-50 mL of 98% H by mass fraction2SO4And 10-15mL of HNO with the mass fraction of 65% -67%3Sealing, magnetically stirring for 15-20 min, heating in water bath to 100%oC refluxing for 4-6 h, washing with deionized water to neutrality, and air-drying in an air furnace for 60-70 hoC, drying for 12-18h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment;
(2) weighing 1-1.5g of molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 1-2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, weighing 50-75ml of 5-15mmol/L azo grafting agent solution, and adding N2And (2) protecting, stirring for 18-24h at room temperature, washing with methanol for multiple times, and preparing 2-5wt.% of a grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2-3);
(3) placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, emptying by using pure oxygen, and pressurizing by using pure oxygenSo that the pressure of the hydrothermal reaction kettle is 1-1.1Mpa, the pure oxygen inlet valve is closed, the hydrothermal reaction kettle is sealed, and the hydrothermal reaction kettle is heated to 180-oAnd C, continuously reacting for 24-36h under the stirring condition, and naturally cooling.
(4) Washing with deionized water, and roasting to obtain the silicon oxide coated molybdenum sulfide modified particles.
Furthermore, the area ratio of the inorganic nano modified particles in the cross section vertical to the surface of the coating is 2-10%.
Furthermore, the area ratio of the inorganic nano modified particles in the cross section vertical to the surface of the coating is 3-5%.
Further, the plating solution used in the preparation process of the plating layer comprises the following components: 240g/L of nickel sulfate 230-.
Further, the primary brightening agent is sodium dodecyl diphenyl ether disulfonate, the secondary brightening agent is o-chlorobenzaldehyde, and the auxiliary brightening agent is sodium methylene dinaphthalene sulfonate.
Further, the technological parameters of the plating layer are pH value 4-6, and the electroplating parameters are as follows: cathode current density of 2.5-3A/dm2Stirring at 5-15rpm for 30-50min at 40-50 deg.CoC。
Further, the azo grafting agent has the following structure:
Figure 377270DEST_PATH_IMAGE002
。
further, the temperature of the roasting is 200-300-oAnd C, the atmosphere is air.
Furthermore, the particle size of the molybdenum sulfide is 50-150nm, and the purity is more than 99.8%.
Furthermore, the hydrothermal process is temperature programming, and the temperature is 5-6 ℃ from the normal temperatureoC/min is raised to 180-oC。
With respect to the present invention:
(1) the brightness nickel liquid of the utility model is composed of 240g/L of nickel sulfate 230-,
wherein, the nickel sulfate and the nickel chloride are main salts, the dosage of the nickel sulfate is almost 6 to 8 times of that of the nickel chloride, and the nickel sulfate is mainly used for maintaining the conductivity of the plating solution and simultaneously effectively reducing the internal stress of the plating layer.
Wherein, the boric acid is used as a buffering agent, so that the stability of the pH value of 4-6 is effectively maintained, and the generation of pinholes due to over-low pH value and the generation of hydroxide precipitate due to over-low pH value are avoided.
The wetting agent is sodium dodecyl benzene sulfonate which can be used as a brightening agent and a surface wetting agent simultaneously, can effectively reduce the consumption of the primary brightening agent, and can be used as a surfactant to further improve the wettability of the inorganic particles and improve the dispersibility of the inorganic composite plating particles in a plating layer.
Primary brightening agent: sodium dodecyl diphenyl oxide disulfonate, an unsaturated organic compound, can be used alone to obtain a semi-bright coating.
Secondary brightener: the secondary brightener is o-chlorobenzaldehyde, and can obviously improve the brightness and leveling property of the plating layer.
Auxiliary brightening agent: the auxiliary brightener is sodium methylene dinaphthalene sulfonate, so that the brightness and the evenness of the plating layer are further improved, the plating layer contains inorganic particles, the inorganic particles have great influence on the evenness of the surface of the plating layer in the composite plating process, and if the auxiliary brightener is not added, the brightness and the evenness of the plating layer are required to be improved.
Inorganic particle suspension solvent: sulfide particles coated with silicon oxide, wherein the silicon oxide is used for improving the water solubility of the sulfide, the sulfide is molybdenum sulfide, and the sulfide is conventional lubricating particles for composite plating and is mainly used for reducing the friction coefficient of a plating layer.
(2) Preparing inorganic composite plating particles: putting 1.5-2.5 g of molybdenum sulfide into a three-neck flask, and adding 45-50 mL of 98% H by mass fraction2SO4And 10-15mL of HNO with the mass fraction of 65% -67%3Sealing, magnetically stirring for 15-20 min, heating in water bath to 100%oC refluxing for 4-6 h, washing with deionized water to neutrality, and air-drying in an air furnace for 60-70 hoC, drying for 12-18h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment;
as known to those skilled in the art, the molybdenum sulfide surface does not contain any water-soluble bonds or functional groups, making it extremely poorly water-soluble, via H2SO4And HNO3Mixed acid, heating and refluxing the molybdenum sulfide, aiming at improving the solubility and the dispersibility of the molybdenum sulfide in the solution, and the mixed acid treatment has the following effects: (1) can remove the pollutants and impurities on the surface, such as grease, dust and the like; (2) the roughness of the surface is improved; (3) hydrophilic functional groups are introduced, and infrared tests show that the molybdenum sulfide is acidified and at least contains strong active groups such as-COOH, -CHO, C = O and the like on the surface.
Weighing 1-1.5g of molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 1-2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, weighing 50-75ml of 5-15mmol/L azo grafting agent solution, and adding N2Protecting, stirring for 18-24h at room temperature, washing for multiple times by using methanol, preparing 2-5wt.% of grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1- (2-3), and under the initiated catalysis condition of triethylamine, performing chemical reaction on the silicon-containing azo grafting agent solution and the molybdenum sulfide surface to directly graft the molybdenum sulfide surface to form Si-O-MoS2。
Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, evacuating by using pure oxygen, pressurizing by using pure oxygen to ensure that the pressure of the hydrothermal reaction kettle is 1-1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating and placing in a 180-phase 200-phase reactoroC, continuously reacting for 24-36h under the stirring condition, naturally cooling, performing hydrothermal treatment,under the conditions of high temperature and high pressure, the azo reagent is dissociated, silicon adsorbed on the surface of the sulfide is oxidized to form silicon sol or silicon oxide under the conditions of alkaline price adjustment and pure oxygen price adjustment, and finally, the silicon oxide-coated molybdenum sulfide nano particles are obtained through drying, wherein the particles have extremely strong hydrophilicity.
Advantageous technical effects
(1) The preparation method comprises the steps of introducing a multifunctional functional group through acidification pretreatment on the surface of molybdenum sulfide, then grafting a silicon-containing azo grafting agent on the functional group, regulating the pH value through hydrothermal treatment, and oxidizing with pure oxygen to obtain silicon oxide-coated molybdenum sulfide nanoparticles, wherein silicon oxide is a shell, molybdenum sulfide is a core, and the coating rate is 100%.
(2) The molybdenum sulfide particles coated with the silicon oxide have extremely high dispersibility in water, under a sealed condition, the complete settling time of 20wt.% of the suspension solution is 140h, obvious precipitation can be seen at the bottom of the solution within 80-90h, the complete settling time is more than 160h under a 5wt.% suspension test, obvious precipitation can be seen at the bottom of the solution within 120-130h, and the suspension time is increased along with the reduction of the concentration of the molybdenum sulfide particles coated with the silicon oxide.
(3) The silicon oxide-coated molybdenum sulfide particle high-dispersion particles are used for composite nickel plating and can be uniformly dispersed on the surface of a plating layer.
(4) The obtained nickel coating effectively ensures the brightness and the flatness of the coating under the synergistic action of the primary brightener, the secondary brightener and the auxiliary brightener.
(5) In the composite plating process, the inorganic modified nano particles are added into the plating solution, so that the hardness of the plating layer is effectively improved, and the friction coefficient of the plating layer is reduced.
The attached drawings of the specification:
FIG. 1 is a TEM image of molybdenum sulfide of the present invention after acidification treatment.
FIG. 2 is a TEM image of molybdenum sulfide coated with silicon oxide according to the present invention.
FIG. 3 is an SEM image (with ultrasonic oscillation) of a molybdenum sulfide coated with silicon oxide according to the present invention.
FIG. 4 is a sedimentation test of the modified inorganic particles of the present invention.
FIG. 5 is a SEM image of a cross-sectional view of a composite coating of the present invention.
FIG. 6 is an SEM image of the surface of the composite coating of the present invention.
The specific implementation mode is as follows:
examples 1 to 3 and comparative examples 1 to 3 are methods for preparing inorganic modified particles, examples 4 to 6 and comparative examples 4 to 7 are methods for compositely plating a bright nickel plating solution to obtain a plated layer, and the inorganic particle suspension solvent used in examples 4 to 6 is prepared by the method of example 2.
Example 1
A preparation method of modified particles for composite electroplating is provided, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method is as follows.
(1) 1.5g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 45 mL of H with the mass fraction of 98 percent is added2SO4And 10 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 15 min, heating in water bath to 100%oC refluxing for 4h, washing to neutrality with deionized water, and heating in an air furnace for 60%oAnd C, drying for 12 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1g of molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, and then measuring 50ml of 5mmol/L azo grafting agent solution, N2Protection, stirring for 18h at room temperature, washing with methanol for multiple times, and preparing a 2wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2-3).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5, evacuating with pure oxygen for 3min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 5MpaoThe rate of C/min is increased to 180oAnd C, continuously reacting for 24 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 200oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting atmosphere is air.
Example 2
A preparation method of modified particles for composite electroplating is provided, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method is as follows.
(1) 2g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, 47.5mL of H with the mass fraction of 98 percent is added2SO4And 12.5 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 17.5min, heating in water bath to 100%oC refluxing for 5 h, washing to neutrality with deionized water, and air drying in an air oven 65oAnd C, drying for 15 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1.25g of the molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1.5ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 62.5ml of 10mmol/L azo grafting agent solution, and measuring N2Protection, stirring for 21 hours at room temperature, washing with methanol for multiple times, and preparing a 3.5wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.75, evacuating with pure oxygen for 4min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 5.5 MpaoThe rate of C/min is increased to 190oAnd C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 250oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting atmosphere is air.
Example 3
A preparation method of modified particles for composite electroplating is provided, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method is as follows.
(1) 2.5g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 50mL of H with the mass fraction of 98 percent is added2SO4And 15mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 20min, heating in water bath to 100%oC refluxing for 6h, washing to neutrality with deionized water, and air-oven drying for 70%oAnd C, drying for 18h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1-1.5g of molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 75ml of 15mmol/L azo grafting agent solution, and N2Protection, stirring for 24 hours at room temperature, washing with methanol for multiple times, and preparing a 5wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: 3.
(3) placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 8, evacuating with pure oxygen for 5min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 6 MPaoThe rate of C/min is increased to 200oAnd C, continuously reacting for 36 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 300oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting atmosphere is air.
As shown in fig. 1, by subjecting molybdenum sulfide to a strong acid acidification treatment, the particles are relatively dispersed, but are left to partially agglomerate.
As shown in fig. 2, the dispersion degree of particles is effectively improved by coating the surface of the molybdenum sulfide with the silicon oxide film, and the molybdenum sulfide can be separated in the solution.
Ultrasonic oscillation is carried out on the molybdenum sulfide particles coated with the silicon oxide, so that a part of the silicon oxide film is stripped, and an obvious core-shell structure exists as shown in SEM of attached figure 3.
As shown in fig. 4, the molybdenum sulfide particles coated with silicon oxide obtained by the treatment method of example 2 were prepared into 5-20wt.% suspension solution, and the suspension solution was magnetically stirred at 500-800rpm for 5min, and the suspension time test was performed, so that it is obvious that the suspension solution of fig. 4 was 20wt.% suspension solution, the complete settling time was 140h, and obvious precipitation was observed at the bottom of the solution in 80-90 h.
The time to complete settling was > 160h, with a significant precipitation at the bottom of the solution seen at 120-130h, by testing for 5wt.% suspension.
Comparative example 1
Commercial molybdenum sulphide particles, passing the water solubility test at 5wt.%, have a time to complete sedimentation of less than 3 min.
Comparative example 2
The preparation method is as follows.
(1) 2g of molybdenum sulfide deionized water with the particle size of 75nm and the purity of more than 99.8 percent and ethanol are alternately washed.
(2) Weighing 1.25g of the molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1.5ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 62.5ml of 10mmol/L azo grafting agent solution, and measuring N2Protection, stirring for 21 hours at room temperature, washing with methanol for multiple times, and preparing a 3.5wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.75, evacuating with pure oxygen for 4min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 5.5 MpaoThe rate of C/min is increased to 190oAnd C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 250oAnd C, air roasting.
The complete settling time is less than 1h through a water solubility test of 5wt.%, the main reason is that no strong acid treatment is used for introducing active groups on the surface of the inert molybdenum sulfide, namely, the grafting effect cannot be exerted, the water solubility is improved through partial coating of hydrothermal ethyl orthosilicate, the coating is disordered coating, silicon effectively performs self-aggregation due to the fact that the surface of the molybdenum sulfide is inert, and a small amount of partially physically coated molybdenum sulfide can be formed under the stirring condition.
Comparative example 3
The preparation method is as follows.
(1) 2g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 47.5mL of H with the mass fraction of 98 percent is added2SO4And 12.5 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 17.5min, heating in water bath to 100%oC refluxing for 5 h, washing to neutrality with deionized water, and air-drying in an air furnace 65oAnd C, drying for 15 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1.25g of the molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1.5ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 62.5ml of 10mmol/L azo grafting agent solution, and measuring N2Protection, stirring for 21 hours at room temperature, washing with methanol for multiple times, and preparing a 3.5wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, pressurizing by using air to ensure that the pressure of the hydrothermal reaction kettle is 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle by 5.5oThe rate of C/min is increased to 190oAnd C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 250oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting atmosphere is air.
The time for complete settling was less than 3h by testing the water solubility of 5wt.%, mainly because the grafted silicon was directly oxidized in a hydrothermal process under hydrothermal conditions without using ammonia and pure oxygen, and the silicon oxide was fixed by means of subsequent calcination, so that the silicon oxide was easily separated from the molybdenum sulfide and it was easy to separate, and if the 5wt.% suspension obtained in comparative example 3 was subjected to ultrasonic vibration treatment, the time for complete settling was less than 20 min.
In addition, the contact angle test was performed on example 2 and comparative example 1, and the silicon oxide-coated molybdenum sulfide of example 2 and the molybdenum sulfide particles of comparative example 1 were tabletted for 90s under a powder tabletting machine of 40MPa with a thickness of about 1-2mm, and the contact angle of the tabletted sheets of example 2 was tested to be 9-12 using deionized water as a solution probeoContact angles 83-87 of comparative example 1o。
Example 4
The preparation method of the high-brightness composite nickel-plated layer comprises the following steps:
2300g/L of nickel sulfate;
30g/L of nickel chloride;
30g/L of boric acid;
0.02g/L sodium dodecyl benzene sulfonate wetting agent;
0.6g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.2g/L of o-chlorobenzaldehyde secondary brightener;
0.15g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 2.5A/dm2Stirring at 5rpm for 30min at 40 deg.CoC。
Example 5
The preparation method of the high-brightness composite nickel-plated layer comprises the following steps:
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.035g/L sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.3g/L of o-chlorobenzaldehyde secondary brightener;
0.2g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
Example 6
The preparation method of the high-brightness composite nickel-plated layer comprises the following steps:
240g/L of nickel sulfate;
40g/L of nickel chloride;
35g/L of boric acid;
0.05g/L of sodium dodecyl benzene sulfonate wetting agent;
0.8g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.4g/L of o-chlorobenzaldehyde secondary brightener;
0.25g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 3A/dm2Stirring at 15rpm for 50min at 50 deg.CoC。
Comparative example 4
The preparation method of the nickel-plated layer comprises the following steps:
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.035g/L sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.3g/L of o-chlorobenzaldehyde secondary brightener;
0.2g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% aqueous molybdenum sulfide;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
Is named D-4.
Comparative example 5
The preparation method of the nickel-plated layer comprises the following steps:
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
Is named D-5.
Comparative example 6
The preparation method of the nickel-plated layer comprises the following steps:
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.035g/L sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.3g/L of o-chlorobenzaldehyde secondary brightener;
0.2g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
The preparation process of the inorganic particles is as follows:
(1) 2g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 47.5mL of H with the mass fraction of 98 percent is added2SO4And 12.5 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 17.5min, heating in water bath to 100%oC refluxing for 5 h, washing to neutrality with deionized water, and air-drying in an air furnace 65oAnd C, drying for 15 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
Is named D-6.
Comparative example 7
The preparation method of the nickel-plated layer comprises the following steps:
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.035g/L sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.3g/L of o-chlorobenzaldehyde secondary brightener;
0.2g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
Was designated as D-7.
Figure 763252DEST_PATH_IMAGE004
As is apparent from the above table and fig. 5 and fig. 6, the surface smoothness, brightness and hardness of the plating layer can be effectively improved by the composite plating of the inorganic modified particles and the brightener with synergistic effect, and the friction coefficient is extremely low, wherein the brightness GU value is 249, the hardness is 923HV, and the friction coefficient is 0.27-0.32, compared with D-7, the hardness and the friction coefficient of the plating layer are both significantly improved, but the brightness is lost, the main reason is that the introduction of the inorganic particles usually generates an obvious plating layer unevenness phenomenon, as shown in D-4, when the pure molybdenum sulfide without modification is added into the plating solution, the surface brightness of the plating layer is only 117 due to the unevenness of the plating layer surface.
It should be noted here that the bath settling time of example 5 is significantly reduced compared to examples 1-3, mainly because the bath is acidic and can significantly corrode the silica coating on the sulfide surface, resulting in a reduction in the suspension settling time of the bath.
Furthermore, it is further demonstrated by comparative examples 5 and D-5 that only a semi-bright nickel coating can be obtained using the primary brightener alone, and further that the brightness is inferior to D-6 due to the influence of the inorganic particles, and further that the flatness of the coating is affected due to the absence of the secondary and secondary brighteners in the bath, resulting in no significant difference in the coefficient of friction from D-7.
In conclusion, the composite plating inorganic modified particles and the synergistic brightener can effectively improve the surface smoothness, brightness and hardness of the nickel plating layer and reduce the friction coefficient of the nickel plating layer.
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.

Claims (9)

1. The high-brightness composite nickel-plated layer is characterized in that the brightness GU value of the nickel-plated layer is 249 +/-15, the hardness 923HV +/-50 Hv and the friction coefficient is 0.27-0.35, the area rate of inorganic nano modified particles in a cross section of the nickel-plated layer vertical to the surface is 1-15%, the inorganic nano modified particles are molybdenum sulfide materials coated with silicon oxide, and the preparation method of the inorganic nano modified particles is as follows:
(1) putting 1.5-2.5 g of molybdenum sulfide into a three-neck flask, and adding 45-50 mL of 98% H by mass fraction2SO4And 10-15mL of HNO with the mass fraction of 65% -67%3Sealing and magnetically stirring for 15-20 min, heating in water bath at 100 deg.C for reflux treatment for 4-6 h, washing with deionized water to neutrality, and drying in air furnace at 60-70 deg.C for 12-18h to obtain molybdenum sulfide particles treated by mixed acid oxidation;
(2) weighing 1-1.5g of molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 1-2ml of triethylamine into the three-necked bottle, and slowly dropwise adding 50-75ml of 5-15mmol/L azo grafting agent solution and N2And (2) protecting, stirring for 18-24h at room temperature, washing with methanol for multiple times, and preparing 2-5wt.% of aqueous solution of grafted molybdenum sulfide particles by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2-3);
the azo grafting agent has the following structure:
Figure DEST_PATH_IMAGE002
；
(3) placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, evacuating by using pure oxygen, pressurizing by using pure oxygen to ensure that the pressure of the hydrothermal reaction kettle is 1-1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating to 180 ℃ and 200 ℃, continuously reacting for 24-36h under the stirring condition, and naturally cooling;
(4) washing with deionized water, and roasting to obtain the silicon oxide coated molybdenum sulfide modified particles.
2. The high-brightness composite nickel-plated layer according to claim 1, wherein the area ratio of the inorganic nano-modified particles in the cross section perpendicular to the surface of the nickel-plated layer is 2-10%.
3. The high-brightness composite nickel-plated layer according to claim 1, wherein the area ratio of the inorganic nano-modified particles in the vertical cross section of the surface of the nickel-plated layer is 3-5%.
4. The high-brightness composite nickel-plated layer according to claim 1, wherein the plating solution used in the preparation of said nickel-plated layer has the following composition: 240g/L of nickel sulfate 230-.
5. The high gloss composite nickel plating layer of claim 4, wherein the primary brightener is sodium dodecyl diphenyl ether disulfonate, the secondary brightener is o-chlorobenzaldehyde, and the secondary brightener is sodium methylene dinaphthalene sulfonate.
6. The high-brightness composite nickel-plated layer according to claim 4, wherein the process parameters in the preparation process of the nickel-plated layer are pH 4-6, and the electroplating parameters are as follows: the cathode current density is 2.5-3A/dm2, the stirring speed is 5-15rpm, the time is 30-50min, and the temperature is 40-50 ℃.
7. The high-brightness composite nickel-plating layer as claimed in claim 1, wherein the baking temperature is 200-300 ℃, and the atmosphere is air.
8. The high brightness composite nickel plating layer according to claim 1, wherein the molybdenum sulfide has a particle size of 50 to 150nm and a purity of more than 99.8%.
9. The high-brightness composite nickel-plated layer as claimed in claim 1, wherein the hydrothermal process is temperature programming from 5-6 ℃/min to 180-200 ℃.
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CN112981502A (en) * 2021-03-05 2021-06-18 赵琳琳 High-dispersion suspending agent for composite electroplating
CN112981501A (en) * 2021-03-05 2021-06-18 赵琳琳 Composite bright nickel plating solution

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CN106400065A (en) * 2016-06-03 2017-02-15 安徽长青电子机械（集团）有限公司 Composite electroplate liquid capable of forming molybdenum disilicide-nickel coating

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106400065A (en) * 2016-06-03 2017-02-15 安徽长青电子机械（集团）有限公司 Composite electroplate liquid capable of forming molybdenum disilicide-nickel coating

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112981502A (en) * 2021-03-05 2021-06-18 赵琳琳 High-dispersion suspending agent for composite electroplating
CN112981501A (en) * 2021-03-05 2021-06-18 赵琳琳 Composite bright nickel plating solution
CN112981501B (en) * 2021-03-05 2024-03-01 惠州市荣安达化工有限公司 Composite bright nickel plating solution
CN112981502B (en) * 2021-03-05 2024-04-12 东莞市金稻田化工有限公司 Suspending agent for high-dispersion composite electroplating

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