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CN-116103711-B - Forward and reverse pulse electrolytic nickel-phosphorus alloy solution, preparation method, electroplating method and nickel-phosphorus alloy coating

CN116103711BCN 116103711 BCN116103711 BCN 116103711BCN-116103711-B

Abstract

The invention belongs to the technical field of nickel-phosphorus alloy electroplating, and particularly relates to a nickel-phosphorus alloy solution for forward and reverse pulse electrolysis, a preparation method, an electroplating method and a nickel-phosphorus alloy coating. The nickel-phosphorus alloy solution comprises 20-500g/L of nickel salt, 30-300g/L of phosphorous acid compound, 5-30g/L of boric acid, 0.5-50g/L of organic acid and 0.2-35g/L of pyridinium compound. The invention adopts the forward and backward pulse circulation electroplating method, can obtain nickel-phosphorus alloy electroplating products with uniform plating layer distribution, saves the use quantity of nickel-phosphorus alloy used by each plating piece, reduces the production cost, improves the quality of the products, and can meet the trend of high-end development of nickel-phosphorus alloy plating layers in electroplating manufacture in the field of electronic product manufacture.

Inventors

  • Door pine Pearl
  • ZHOU AIHE

Assignees

  • 安徽智备工业科技有限公司

Dates

Publication Date
20260508
Application Date
20221229

Claims (10)

  1. 1. The positive and negative pulse electrolytic nickel-phosphorus alloy solution is characterized by comprising the following components: 20-500g/L of nickel salt, 30-300g/L of phosphorous acid compound, 5-30g/L of boric acid, 0.5-50g/L of organic acid and 0.2-35g/L of pyridinium compound; Wherein the organic acid is one or more of carboxylic acid, sulfonic acid, lactic acid and citric acid; The pyridinium compound is 1- (carboxymethyl) pyridinium, 1- (2-oxo-2-phenethyl) pyridinium, 1-butyl-4-methylpyridinium, 1-methyl-2-carboxypyridinium, 1-methyl-2-methoxycarbonylpyridinium, 1-methyl-2-phenylpyridinium, 1-methyl-2-cyanopyridinium, 1-ethyl-2-aminopyridinium, 1-ethyl-2-carboxypyridinium, 1-ethyl-2-methoxycarbonylpyridinium, 1-propyl-2-aminopyridinium, 1-propyl-2-carboxypyridinium, 1-propyl-2-methoxycarbonylpyridinium, 1-propyl-2-phenylpyridinium, 1-propyl-2-cyanopyridinium, 1-butyl-2-methylpyridinium, 1-butyl-2-ethylpyridinium, 1-butyl-2-butylpyridinium, 1-butyl-2-sulfopyridinium, 1-butyl-2-methoxysulfonylpyridinium, 1-butyl-2-aminopyridinium, 1-butyl-4-carboxypyridinium, 1-propyl-2-methoxypyridinium, 1-propyl-2-aminopyridinium, 1-propyl-2-methoxypyridinium, 1-propyl-2-methylpyridinium, 1-butyl-2-methylpyridinium, 1-butyl-2-methylpyridinium, or 1-methylpyridinium, one or more of 2, 3-dimethylbenzothiazolium and 5,10,15, 20-tetra (N-methyl-4-pyridinium) porphine.
  2. 2. The nickel-phosphorus alloy solution for forward and reverse pulse electrolysis according to claim 1, wherein the nickel salt is one or more of nickel sulfate, nickel sulfamate, nickel chloride and nickel carbonate; The phosphite compound is one or more of phosphorous acid, sodium phosphite, potassium phosphite, monopotassium phosphite and sodium dihydrogen phosphite.
  3. 3. The forward and reverse pulse electrolytic nickel-phosphorus alloy solution according to claim 1, wherein the carboxylic acid is one or more of 4-hydroxybenzoic acid, 2-amino-4-hydroxybenzoic acid, 3-amino-4-hydroxybenzoic acid, 2-amino-5-hydroxybenzoic acid, 3-amino-5-hydroxybenzoic acid, 4-amino-2-hydroxybenzoic acid, 2-amino-1, 3, 5-benzenetricarboxylic acid, 5-amino isophthalic acid, 3-hydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, 2, 6-dihydroxybenzoic acid, 2, 3-dihydroxybenzoic acid, and 3,4, 5-trihydroxybenzoic acid; The sulfonic acid is one or more of benzenesulfonic acid, p-toluenesulfonic acid, 2-toluenesulfonic acid, 3-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-1, 3-diphenylsulfonic acid, 4- (dimethylamino) benzenesulfonic acid, 3, 4-diaminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 4-methoxybenzenesulfonic acid, 3-amino-4-methoxybenzenesulfonic acid, 4-fluorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, 3-sodium nitrobenzenesulfonate, 2-amino-5-nitrobenzenesulfonate, 2-iodobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-iodobenzenesulfonic acid, 3-bromobenzenesulfonic acid and 4-mercaptobenzenesulfonic acid.
  4. 4. A method for preparing the positive and negative pulse electrolytic nickel-phosphorus alloy solution according to any one of claims 1-3, which comprises the following steps: s1, adding boric acid into a part of pure water for a small amount for many times under the heating and stirring conditions; S2, adding a small amount of nickel salt for many times after the boric acid is completely dissolved; S3, adding the phosphorous acid compound after the nickel salt is completely dissolved, and uniformly stirring; And S4, sequentially adding the organic acid and the pyridinium compound, uniformly stirring, and adding the rest of pure water to obtain the forward and reverse pulse electrolytic nickel-phosphorus alloy solution.
  5. 5. The formulation process according to claim 4, wherein the heating temperature is 40-60 ℃.
  6. 6. A method for electroplating nickel-phosphorus alloy by using forward and reverse pulse, which is characterized by comprising the following steps: (1) Placing the nickel-phosphorus alloy electrolyte (10) according to any one of claims 1-3 into an electrolytic cell (50), and heating to a temperature of 40-60 ℃; (2) The nickel plate (20) is connected to the positive electrode of the pulse reverse power supply (100) through the positive electrode conductive connecting rod (21), and the plating piece (30) is connected to the negative electrode of the pulse reverse power supply (100) through the negative electrode conductive connecting rod (31); (3) Electroplating by adopting forward and reverse pulse, namely applying forward pulse current I 1 and forward pulse time t 1 within the current density range of 0.5-8.0A/dm 2 , and then applying reverse pulse current I 2 and reverse pulse time t 2 to finish one cycle of forward and reverse pulse electroplating; (4) Repeating the positive and negative pulse cycle of the step (3) until the set electroplating time is over.
  7. 7. The method of electroplating a nickel-phosphorus alloy according to claim 6, wherein the ratio of t 1 to t 2 is in the range of (10-100): 1.
  8. 8. The method of electroplating a nickel-phosphorus alloy according to claim 6, wherein the ratio of I 1 to I 2 is in the range of 1 (2-5).
  9. 9. The method for electroplating a nickel-phosphorus alloy by using forward and reverse pulse according to claim 6, wherein the electroplating time is 1-60min, and the thickness of the electroplated nickel-phosphorus alloy layer is 0.5-100 μm.
  10. 10. A nickel-phosphorus alloy plating layer obtained by electroplating according to any one of claims 6-9, wherein the nickel-phosphorus alloy plating layer has a composition of Ni 100-m P m , m is a percentage of phosphorus atoms, and m is 10% or more and 16% or less.

Description

Forward and reverse pulse electrolytic nickel-phosphorus alloy solution, preparation method, electroplating method and nickel-phosphorus alloy coating Technical Field The invention belongs to the technical field of nickel-phosphorus alloy electroplating, and particularly relates to a nickel-phosphorus alloy solution for forward and reverse pulse electrolysis, a preparation method, an electroplating method and a nickel-phosphorus alloy coating. Background The nickel-phosphorus alloy coating has the characteristics of compact surface, high hardness, corrosion resistance, excellent magnetism and the like, and is widely applied to electronic products such as new energy automobiles, aerospace, communication and the like. The common mode of preparing the nickel-phosphorus alloy coating by chemical plating has high production cost due to long processing time, low productivity, low yield and frequent re-cylinder opening. Therefore, in recent years, in the field of electronic product manufacturing, the development trend of high-end electrolytic manufacturing of nickel-phosphorus alloy plating layers is not blocked. The nickel-phosphorus alloy electroplating solution provided by the patent CN114232040A has the characteristics of small internal stress of a plating layer, high electroplating deposition speed and the like during electroplating, can be applicable to various base materials, has simple electroplating process, and has obvious cost advantage compared with the existing commonly used nickel-tungsten electroplating solution. The electroplating solution provided by the patent CN112853415B adopts a nickel-phosphorus alloy process to replace a semi-gloss nickel process and is used in combination with a gloss nickel electroplating process, so that the corrosion resistance of an electroplating protection system is ensured under the condition that the use amount of the whole metal nickel is obviously reduced, and the effects of reducing the use amount of the metal nickel, saving resources and saving production cost can be achieved. However, in the prior electrolytic nickel-phosphorus technology, when a high-frequency direct current power supply and a pulse power supply are used, according to different shapes of electrolytic products, the current distribution of the edge area of the product is more, the edge of the electrolytic deposited nickel-phosphorus alloy coating is too thick, and the large current distribution of the specific surface occupied by the flat area in the middle of the product is less, so that the middle area of the electrolytic deposited nickel-phosphorus alloy coating is too thin. Therefore, when the nickel-phosphorus alloy coating in the middle area of the product meets the technical standard requirement of the product, the nickel-phosphorus alloy coating in the edge area of the product far exceeds the standard value, so that unnecessary waste is caused, the production cost is increased, friction damage is caused to product assembly in the subsequent working section, and the quality of high-end electronic products is affected. In view of this, the present invention has been made. Disclosure of Invention In order to solve the problems in production and processing caused by uneven plating of a nickel-phosphorus alloy plating layer in the prior art, the invention provides a nickel-phosphorus alloy solution for forward and reverse pulse electrolysis, a preparation method, an electroplating method and a nickel-phosphorus alloy plating layer. The nickel-phosphorus alloy solution for forward and reverse pulse electrolysis has stable characteristics of bearing forward and reverse pulse signal impact by adding the organic acid and the pyridinium compound, and has good stability under the condition of high-speed conversion of forward and reverse pulse power supply signals. In addition, the invention adopts a forward and backward pulse circulation electroplating method, can obtain nickel-phosphorus alloy electroplating products with uniform plating layer distribution, saves the use quantity of nickel-phosphorus alloy used by each plating piece, and improves the quality of the products. The invention is realized by the following technical scheme: the invention provides a forward and backward pulse electrolytic nickel-phosphorus alloy solution, which comprises the following components: 20-500g/L of nickel salt, 30-300g/L of phosphorous acid compound, 5-30g/L of boric acid, 0.5-50g/L of organic acid and 0.2-35g/L of pyridinium compound. Preferably, the nickel salt is one or more of nickel sulfate, nickel sulfamate, nickel chloride and nickel carbonate; the phosphorous acid compound is one or more of phosphorous acid, sodium phosphite, potassium phosphite, monopotassium phosphite and sodium dihydrogen phosphite; the organic acid is one or more of carboxylic acid, sulfonic acid, lactic acid and citric acid; the nickel-phosphorus electrolyte in the prior art has the problems that (1) although nickel-phosphorus all