CN115976586A - Positive and negative pulse electrolytic nickel-tungsten alloy solution, preparation method, electroplating method and nickel-tungsten alloy coating - Google Patents
Positive and negative pulse electrolytic nickel-tungsten alloy solution, preparation method, electroplating method and nickel-tungsten alloy coating Download PDFInfo
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Abstract
The invention belongs to the technical field of nickel-tungsten alloy electroplating, and particularly relates to a forward and reverse pulse electrolytic nickel-tungsten alloy solution, a preparation method, an electroplating method and a nickel-tungsten alloy coating. The nickel-tungsten alloy solution comprises: 20-150g/L of nickel salt, 30-300g/L of tungstate, 5-500g/L of organic acid salt, 3-300g/L of organic acid and 0.02-15g/L of nitrogen heterocyclic compound. The nickel-tungsten alloy plating layer separated out by electrolysis is uniform and smooth, presents the surface appearance of the amorphous alloy with the submicron structure, has very high purity and excellent compactness, can provide a nickel-tungsten alloy electroplating product with a uniformly distributed plating layer, saves the using amount of nickel-tungsten alloy of a plated part, greatly reduces the production cost, improves the product quality, and can meet the development trend of the high-tech electronic product field and high-quality and high-precision die products and the requirement on high-end nickel-tungsten amorphous alloy materials.
Description
Technical Field
The invention belongs to the technical field of nickel-tungsten alloy electroplating, and particularly relates to a forward and reverse pulse electrolytic nickel-tungsten alloy solution, a preparation method, an electroplating method and a nickel-tungsten alloy coating.
Background
The nickel-tungsten alloy coating has the characteristics of compact and bright surface, high hardness, good wear resistance, strong corrosion resistance and the like, and is widely applied to electronic products such as new energy automobiles, aerospace, communication and the like and high-precision die products. However, the non-patent literature (electroplating and coating, 1998, 17 (3): pp 22) indicates that the nickel-tungsten alloy electroplating process generally has the defects of rough and uneven coating, pocking marks and the like, and the application development of the nickel-tungsten alloy electroplating process is severely restricted.
The following patents also propose various methods for preparing nickel tungsten amorphous alloy coatings.
Patent CN 115323448A provides a nickel-tungsten alloy electrodeposition solution and an electrodeposition process, the nickel-tungsten alloy electrodeposition solution is prepared by dissolving nickel sulfate, sodium tungstate, sodium pyrophosphate, a brightener and a stabilizer in deionized water. The nickel-tungsten alloy electrodeposited by the nickel-tungsten alloy electrodeposition solution has excellent corrosion resistance and wear resistance, the service life of the electrodeposition solution is long, the production cost is reduced, and the electrodeposited nickel-tungsten alloy coating is bright and compact.
The nickel-tungsten alloy coating provided by the patent CN 115182009A is compact and bright and has high corrosion resistance, and can improve electrochemical polarization in a coating process, refine crystal grains, optimize leveling capacity of a plating solution and improve the brightness of the coating; meanwhile, the preparation process of the corrosion-resistant multilayer coating is provided under the condition of harsh requirement on corrosion resistance.
The nickel-tungsten alloy electroplating solution and the insoluble anode system provided by the patent CN 114959812A improve the current efficiency of the coating and reduce the hydrogen evolution process; can effectively reduce the stress in the coating and reduce the generation of cracks after heat treatment. The filtering membrane limits the organic matters in the plating solution to enter the anode chamber, prevents the organic matters from decomposing, and reduces the consumption of the organic matters and the aging of the plating solution.
Patent CN 112111765B provides a method for forming a nickel-tungsten alloy plating layer, which can not only prolong the service life of the plating solution, but also form a dense and bright plating layer on the workpiece.
Patent CN 105543910B provides a grain refiner using beta-cyclodextrin as nickel-tungsten alloy electroplating, the grain size of the nickel-tungsten alloy is obviously reduced in the deposition process, and the substance is stable in the preparation process, does not affect the performance of the product, and makes the plating layer have corrosion resistance.
The invention discloses CN 104032339A and relates to a method for controlling a structure of an electrodeposited nickel-tungsten alloy coating, which combines ultrasonic waves, mechanical stirring and direct current, adopts the mutual synergistic effect of the ultrasonic waves, the mechanical stirring and the direct current, and is used for controlling the structure of the electrodeposited nickel-tungsten alloy coating by adjusting and controlling the electroplating temperature and the current density. Compared with the prior art, the method has the advantages of simple and easy operation, simple structure of the required device, effective control of the structure of the nickel-tungsten alloy coating, contribution to improving the production efficiency of the nickel-tungsten alloy coating and good application prospect.
However, none of the above existing electrolytic nickel-tungsten technologies solves the defects of rough, uneven and pockmarked nickel-tungsten alloy coating, and when a high-frequency direct-current power supply and a pulse power supply are used, the current distribution in the edge area of the product is large according to the different shapes of the electrolytic product, and the edge of the nickel-tungsten alloy coating deposited by electrolysis is too thick; and the large current distribution of the specific surface occupied by the middle flat area of the product is less, so that the middle area of the nickel-tungsten alloy coating which is separated out by electrolysis is too thin. Therefore, when the nickel-tungsten alloy coating in the middle area of the product meets the technical standard requirements of the product, the nickel-tungsten alloy coating in the edge area of the product far exceeds the standard value, unnecessary waste is caused, the production cost is increased, friction damage is caused to the product assembly of the subsequent working section, and the quality of a high-end electronic product is influenced.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention provides a positive and reverse pulse electrolytic nickel-tungsten alloy solution, a preparation method, an electroplating method and a nickel-tungsten alloy coating, aiming at solving the problem of uneven coating in the prior art of electroplating nickel-tungsten alloy coatings in production and processing. According to the invention, the organic acid and the nitrogen-containing heterocyclic ring compound are added into the forward and reverse pulse electrolytic nickel-tungsten alloy solution, so that the forward and reverse pulse electrolytic nickel-tungsten alloy solution has the stable characteristic of bearing the impact of forward and reverse pulse signals and has good stability under the condition of high-speed conversion of forward and reverse pulse power signals. The nickel-tungsten alloy plating layer prepared by the method is uniform and smooth, presents the appearance of the amorphous alloy with the submicron structure, has very high purity and compactness, and has quality superior to that of the amorphous alloy with the submicron structure prepared by the traditional chemical plating method and the electrolysis method which usually adopts a high-frequency power supply and a pulse power supply. In addition, the invention can obtain the nickel-tungsten alloy electroplating product with uniformly distributed coating, saves the using amount of the nickel-tungsten alloy used by each plating part, greatly reduces the production cost, improves the product quality, and can meet the development trend of the high-tech electronic product field, the high-quality high-precision die product and the requirement of high-end nickel-tungsten amorphous alloy materials.
The invention is realized by the following technical scheme:
the invention provides a forward and reverse pulse electrolytic nickel-tungsten alloy solution, which comprises the following components:
20-150g/L of nickel salt, 30-300g/L of tungstate, 5-500g/L of organic acid salt, 3-300g/L of organic acid and 0.02-15g/L of nitrogen heterocyclic compound.
Preferably, the components used in the invention are high-grade pure, which is beneficial to improving the purity of the electrolytic nickel-tungsten alloy solution and the performance of a plating layer.
Preferably, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel sulfamate, nickel citrate, nickel carbonate, nickel bromide, nickel phosphate, nickel borate, nickel benzenesulfonate, nickel hypophosphite and nickel 4-toluenesulfonate; the tungstate is one or more of sodium tungstate, potassium tungstate, ammonium metatungstate and ammonium metatungstate; the organic acid salt is one or more of salts of monocarboxylic acid to hexacarboxylic acid; the organic acid is one or more of monocarboxylic acid to hexacarboxylic acid; the nitrogen-containing heterocyclic compound is one or more of pyrrole, pyrazole, oxazole, thiazole, imidazole, pyridine, pyrimidine, azaindole and pyrazine.
Preferably, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel sulfamate, nickel citrate, nickel carbonate, nickel bromide, nickel phosphate, nickel borate, nickel benzenesulfonate, nickel hypophosphite and nickel 4-toluenesulfonate; the tungstate is one or more of sodium tungstate, potassium tungstate, ammonium metatungstate and ammonium metatungstate; the organic acid salt is one or more of salts of monocarboxylic acid to hexacarboxylic acid; the organic acid is one or more of monocarboxylic acid to hexacarboxylic acid; the nitrogen-containing heterocyclic compound is one or more of pyrrole, pyrazole, oxazole, thiazole, imidazole, pyridine, pyrimidine, azaindole and pyrazine.
Preferably, the organic acid salt is one or more of sodium formate, ammonium formate, sodium acetate, ammonium acetate, sodium propionate, ammonium ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate monohydrate, tetrasodium ethylenediaminetetraacetate dihydrate, triammonium ethylenediaminetetraacetate, potassium ethylenediaminetetraacetate, tripotassium ethylenediaminetetraacetate, dipotassium ethylenediaminetetraacetate, ammonium isethionate, dimethylamine 2-isethionate, ammonium dihydrogen citrate, potassium dihydrogen citrate, diammonium hydrogen citrate, disodium citrate, trisodium citrate hydrate, triammonium citrate, choline dihydrogen citrate, choline citrate, ammonium oxalate, ammonium succinate, pentasodium diethylenetriaminepentaacetate, and alkyl-phosphonic polybasic carboxylic acid salt; wherein the phosphonate alkyl polycarboxylic acid salts are one or more of 2-phosphonate butane-1,2,4-tricarboxylic acid sodium salt, 2-phosphonate butane-1,2,4-tricarboxylic acid tetrasodium salt, 2-phosphonobutane-1,2,4-tricarboxylic acid potassium salt, diethylenetriamine pentamethylene phosphonic acid heptasodium salt and diethylenetriamine pentamethylene phosphonic acid sodium salt;
the organic acid is one or more of formic acid, acetic acid, malonic acid, ethylene diamine tetraacetic acid, 3-hydroxy-3-carboxyglutaric acid, tricarballylic acid, propane tricarboxylic acid, 3-amino-1,1,3-propane tricarboxylic acid, 1,2,4-butane tricarboxylic acid, 2-phosphonic butane-1,2,4-tricarboxylic acid, water dwarf acid, butane tetracarboxylic acid, diethylene triamine pentaacetic acid, triethylene tetramine hexaacetic acid and phosphonic alkyl polybasic carboxylic acid; wherein the phosphonic acid alkyl polycarboxylic acids are one or more of diethylenetriamine pentamethylene phosphonic acid and triethylene tetramine hexa (methyl phosphonic acid).
Preferably, the pyrrole is one or more of 5- (pyrrolidin-3-yl) -2H-1,2,3,4-tetrazole hydrochloride, 3-methyl-5-pyrrole-1,2,4-oxadiazole, 2- (pyrrolidin-3-yl) ethane-1-alkoxide, 4-pyrrolidinyl-1-pyridine-2-carboxylic acid hydrochloride, 4- (pyrrolidin-3-yl) pyridine hydrochloride, 1- (2-chlorobenzyl) -pyrrolidin-3-amine dihydrochloride, 1- (4-chlorobenzyl) -pyrrolidin-3-amine dihydrochloride;
the pyrazole is one or more of 5-amino-1- (2-hydroxyethyl) pyrazole, 5-amino-1-ethylpyrazole, 2- (4-bromo-1H-pyrazol-1-yl) ethanol, 2- (4-bromo-1H-pyrazol-1-yl) acetamide, 2- (4-bromo-1H-pyrazol-1-yl) propionamide, 4-amino-1-methyl-3-propylpyrazole-5-carboxamide hydrochloride, 5-amino-1-ethylpyrazole-4-carboxylic acid and 5-amino- (2-hydroxyethyl) -4-pyrazolecarboxylic acid;
the oxazole is one or more of 5-nitro-1,2 benzisoxazole, 3-amino-5-nitro-1,2-benzisoxazole, 3-chloro-7-nitro-1,2-benzisoxazole, 3-methyl-5-nitro-1,2-benzisoxazole, 5-fluoro-3- (4-piperidinyl) -1,2-benzisoxazole, 6-nitro-1,2-benzisoxazole, 6-nitro-1,2-benzisoxazole-3-methanol, 6-nitro-1,2-benzisoxazole-3-carboxylic acid;
the thiazole is one or more of 2-methyl-5-nitrothiazole, 3-amino-5-nitrobenzoisothiazole, 2-methyl-5-nitrobenzothiazole, 2-methyl-5-phenyl-thiazole-4-carboxylic acid, 4-methyl-5-nitrothiazole, 2-amino-5-nitrothiazole and 2-methyl-5-thiazolamine;
the imidazoles are one or more of 2- (difluoromethyl) -1-phenyl-4,5-dihydro-1H-imidazole, 2-methyl-5-nitroimidazole, 1- (2,3-dihydroxypropyl) -2-methyl-5-nitroimidazole, 1-propyl-2,3-methylimidazole tetrafluoroborate, 1- (2-iodoethyl) -2-methyl-5-nitro-1H-imidazole, 2-methyl-5-nitrobenzimidazole, 1-benzyl-2-methyl-5-nitro-1H-1,3-benzimidazole and 2-mercapto-5-nitrobenzimidazole;
the pyridine is one or more of 2- (4-bromo-1H-pyrazol-1-yl) -5-fluoropyridine, 2-bromo-6- (1H-pyrazol-1-yl) pyridine, 2- (pyrrolidin-1-yl) pyridine-3-boronic acid, 2- (4-bromopyrazol-1-yl) pyridine, 2- ((4-iodo-1H-pyrazol-1-yl) methyl) pyridine, 2- (4-bromo-3-methyl-5- (trifluoromethyl) pyrazol-1-yl) -6-chloropyridine, 5- (chloromethyl) -2- (1H-pyrazol-1-yl) pyridine, 2- (4-bromo-1H-imidazol-1-yl) pyridine, 1-benzenesulfonyl-3-iodo-1H-pyrrole [2,3-B ] pyridine;
the pyrimidines are one or more of 2- (4-bromo-1H-pyrazol-1-yl) pyrimidine, 2- (1H-pyrazol-1-yl) -5- (trifluoromethyl) pyrimidine, 2- (4-fluoro-1H-pyrazol-1-yl) pyrimidine-5-carboxylic acid, (9 CI) -4- (1H-pyrazol-1-yl) -pyrimidine, 2,4-dichloro-5- (1H-pyrazolyl) pyrimidine, 2- (1H-pyrazol-1-yl) -5- (trifluoromethyl) pyrimidine, 4- (4-bromo-1H-pyrazol-1-yl) -6-chloropyrimidine, 4-chloro-6- (1H-pyrazol-1-yl) pyrimidine;
the azaindoles are one or more of 4-bromo-2-iodo-N-p-toluenesulfonyl-7-azaindole, 4-bromo-1-p-toluenesulfonyl-7-azaindole, 2-difluoromethyl-1-benzenesulfonyl-7-azaindole, 4-bromo-2-iodo-7-azaindole, N-toluenesulfonyl-5-bromo-4,7-diazaindole, 1-benzenesulfonyl-4-chloro-2-iodo-7-azaindole, 2-iodo-1-benzenesulfonyl-7-azaindole, 2-methyl-1- (benzenesulfonyl) -7-azaindole, 2-difluoromethyl-1-benzenesulfonyl-7-azaindole, 4-bromo-pyrrolo [2,3-F ] -7-azaindole;
the pyrazine is one or more of 2- (4-bromo-1H-pyrazol-1-yl) pyrazine, pyrazine-2-boric acid, 2- (4-bromo-1H-pyrazol-1-yl) pyrazine, 3- (4-bromo-1H-pyrazol-1-yl) -6-chloropyrazine e, 3-chloro-6- (4-iodo-1H-pyrazol-1-yl) pyrazine, 5- (1H-pyrazol-1-yl) pyrazine-2-carboxylic acid and 2-bromo-5- (1H-pyrrol-1-yl) pyrazine.
The nickel-tungsten electrolyte in the prior art has the following problems when a positive and reverse pulse method is applied to electroplating a nickel-tungsten coating: (1) Although a nickel-tungsten alloy product can be obtained by electrolysis, a nickel-tungsten alloy solution is turbid and unstable, and cannot be applied to continuous electrolysis production; (2) In the electrolytic process, the nickel-tungsten alloy solution generates suspended particles which are co-precipitated with nickel and tungsten to cause the obtained nickel-tungsten alloy coating to contain impurities; and (3) obtaining no nickel-tungsten alloy coating after electrolysis.
Aiming at the problems, the invention adds the monocarboxylic acid to the hexacarboxylic acid compound, the p-pi conjugation effect in the carboxyl is favorable for reducing the electron cloud density on the hydroxyl oxygen atom, the stability of the compound is enhanced, the more the carboxyl is, the stronger the p-pi conjugation effect is, the better the thermal stability is, and meanwhile, the forward and reverse pulse electrolytic nickel-tungsten alloy solution has the performances of acid resistance, alkali resistance, oxidant resistance and the like, and can meet the strong impact of the instantaneous pulse of the reverse pulse power supply. Especially, the phosphonic acid alkyl polycarboxylic acid has the characteristics of polycarboxylic acid, and the stability is further enhanced through the supporting action of phosphonic acid alkyl, so that the stability of the nickel-tungsten alloy solution is improved.
According to the invention, by adding the monocarboxylic acid to the hexacarboxylate compound, the monocarboxylic acid to hexacarboxylate compound not only has the characteristics of polycarboxylic acid, but also can form a very stable buffer solution system with the carboxylic acid compound, so that the pH value of the solution is maintained between 7 and 8, and the stability of the nickel-tungsten alloy solution is very facilitated. Especially phosphonic acid alkyl polycarboxylic acid salts, is more favorable for forming a very stable buffer solution system and improving the stability of the nickel-tungsten alloy during electrolysis.
The five-membered ring and the six-membered ring of the nitrogen heterocyclic compound of the invention form compound salts with nitrogen and acids, so that the electron cloud density of the heterocyclic ring is reduced, the induction effect of electron absorption is enhanced, the compound has the characteristics of difficult oxidation and strong electromagnetic field resistance, and the effect of positive and reverse pulse plating of nickel-tungsten alloy is further improved.
The invention also provides a preparation method of the forward and reverse pulse electrolytic nickel-tungsten alloy solution, which comprises the following steps:
s1, adding a small amount of nickel sulfate into a part of pure water for multiple times under the conditions of heating and stirring;
s2, after the nickel sulfate is completely dissolved, adding a small amount of organic acid for multiple times;
s3, after the organic acid is completely dissolved, adding a small amount of organic acid salt for multiple times;
s4, after the organic acid salt is completely dissolved, testing the pH value of the solution, and controlling the pH value to be in the range of 7.0-8.0;
s5, adding tungstate for multiple times in a small amount, and adding a nitrogen-containing heterocyclic compound for multiple times in a small amount after the tungstate is completely dissolved;
and S6, after the nitrogenous heterocyclic compounds are completely dissolved, uniformly stirring, and adding part of pure water to obtain the forward and reverse pulse electrolytic nickel-tungsten alloy solution.
Wherein the heating temperature is 40-60 deg.C, and organic acid salt is added in S4 if pH is lower than 7.0, and organic acid is added if pH is higher than 8.0.
The invention also provides a method for electroplating nickel-tungsten alloy by using forward and reverse pulses, which comprises the following steps:
(1) Putting the nickel-tungsten alloy electrolyte into an electrolytic cell, and heating to 40-60 ℃;
(2) Connecting a nickel plate to the positive electrode of a pulse reverse power supply through a positive electrode conductive connecting rod, and connecting a plated part to the negative electrode of the pulse reverse power supply through a negative electrode conductive connecting rod;
(3) Electroplating by adopting forward and reverse pulses: impressed with a positive pulse current I 1 Time t of forward pulse 1 Then applying a reverse pulse current I 2 Time t of reverse pulse 2 Completing one cycle of positive and reverse pulse plating;
(4) And (4) repeating the positive and reverse pulse circulation of the step (3) until the set electroplating time is finished.
It should be noted that, when the nickel-tungsten alloy plating layer is electroplated by performing the forward and reverse pulse circulation of the present invention, in a cycle period, when the forward pulse is firstly applied, the current distribution of the edge region of the plated part is large, which results in a thicker edge plating layer, and when the reverse pulse is applied, the plated part will be anodized and dissolved, and also the current distribution of the edge region of the plated part is large, which makes the dissolution speed of the edge plating layer faster than that of the middle region, and finally makes the thickness of the whole plating layer product uniform, and the anodic dissolution occurs during the reverse pulse, which greatly reduces the impurity inclusion in the plating layer, and improves the purity and density of the plating layer.
Further, the current density of the forward pulse current in the step (3) is in the range of 0.5-30.0A/dm 2 The current density of the reverse pulse current is in the range of 5.0-100.0A/dm 2 。
As can be seen from the above, the pulse current and pulse time settings during each cycle of positive and negative pulses affect the quality of the overall coating, and as a priority, t 1 And t 2 The ratio of (10-100) to (1); I.C. A 1 And I 2 The ratio range of (1) to (2-5). The control is effectively carried out by setting the magnitudes and pulse time of the forward pulse current and the reverse pulse currentThe deposition speed and the dissolution speed of the edge and the middle area of the nickel-tungsten coating are controlled, so that the thickness of the edge area and the middle area of the nickel-tungsten alloy coating obtained by final electroplating is uniform.
Preferably, the electroplating time is 1-100min, and the thickness of the nickel-tungsten alloy coating obtained by electroplating is 0.5-100 μm.
Preferably, the method is used for barrel plating, rack plating and continuous production lines of nickel-tungsten amorphous alloy materials, and more preferably, the method is used for surface electrolytic machining of through holes, inner walls of blind holes and inner walls of tiny precise products.
The invention also provides a nickel-tungsten alloy coating obtained by electroplating with the method, wherein the nickel-tungsten alloy coating contains Ni 100-m W m M is the percentage of tungsten atoms, and m is more than or equal to 43.43 percent and less than or equal to 53.52 percent.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, organic acids, organic acid salts and nitrogen-containing heterocyclic compounds are added into the forward and reverse pulse electrolytic nickel-tungsten alloy solution, so that the nickel-tungsten alloy plating solution has the stable characteristic of bearing the impact of forward and reverse pulse signals, has good stability under the condition of high-speed conversion of forward and reverse pulse power signals, and avoids the problems that the nickel-tungsten alloy solution is turbid, and suspended particles are generated in the nickel-tungsten alloy solution and are co-precipitated with nickel-tungsten alloy to cause impurities in the obtained nickel-tungsten alloy plating layer, thereby ensuring that the subsequent electroplated product has good quality.
(2) In the process of electroplating the nickel-tungsten alloy coating by the forward pulse and the reverse pulse, the nickel-tungsten alloy coating with uniform thickness is obtained by circularly printing the forward pulse and the reverse pulse.
(3) The electroplating process is formed by the optimized nickel-tungsten alloy solution and the forward and reverse pulse parameters, the prepared nickel-tungsten alloy coating is uniform and smooth, presents the appearance of the amorphous alloy with the submicron structure, has very high purity and compactness, and has quality superior to that of the amorphous alloy with the submicron structure prepared by the traditional chemical plating method and the electrolysis method which usually adopts a high-frequency power supply and a pulse power supply; in particular, the surface electrolytic machining of products with inner walls of through holes and blind holes and inner walls of tiny precise various shapes is provided with a very effective preparation method.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic diagram of an apparatus for electroplating nickel-tungsten alloy by forward and reverse pulse according to the present invention, wherein (a) is a schematic diagram of applying a forward pulse current, and (b) is a schematic diagram of applying a reverse pulse current;
FIG. 2 is a schematic diagram of the electrolysis of a pulsed reverse power supply according to the present invention;
FIG. 3 is a schematic diagram of test point distribution;
FIG. 4 is an enlarged schematic view of a test point A;
FIG. 5 is an external view of embodiment 3;
FIG. 6 is an external view of example 9;
FIG. 7 is a rough appearance of comparative example 3;
FIG. 8 is a rough appearance diagram of comparative example 9;
FIG. 9 is a diagram of a pocked outer tube of comparative example 6;
FIG. 10 is an appearance of pockmarks of comparative example 7;
FIG. 11 is a graph showing the results of the nitric acid vapor test of example 3;
FIG. 12 is a graph showing the results of the nitric acid vapor test of example 9;
FIG. 13 is a graph of the results of the frictional wear test of example 3;
FIG. 14 is a graph showing a result of a frictional wear test of comparative example 9;
FIG. 15 is a graph showing the results of the surface roughness test of example 3;
FIG. 16 is a graph showing the results of the surface roughness test of comparative example 9;
FIG. 17 is a graph of a nitric acid vapor test of a sample of copper sheet from example 11;
FIG. 18 is a nitric acid vapor test chart of a sample of copper sheet of example 13;
FIG. 19 is a nitric acid vapor test pattern for the terminal sample of example 11;
FIG. 20 is a nitric acid vapor test pattern for the terminal sample of example 13;
FIG. 21 is an X-ray diffraction pattern of example 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The embodiment provides a forward and reverse pulse electrolytic nickel-tungsten alloy solution, which comprises: 28g/L of nickel sulfate, 165g/L of sodium tungstate, 83g/L of 1,2,4-butane tricarboxylic acid, 320g/L of 2-phosphonic acid butane-1,2,4-sodium tricarboxylate and 0.7g/L of 2- (pyrrolidine-3-yl) ethane-1-alkoxide.
The preparation method of the nickel-tungsten alloy electrolyte comprises the following steps:
s0, adding 10 liters of pure water into a cleaned 20-liter electrolytic tank 50, starting an internal circulation pumping power supply, and starting a heating system to heat under the stirring of the pure water in a circulating flow manner;
s1, when the temperature of pure water in an electrolytic bath reaches 50 ℃, adding 420 g of nickel sulfate into the electrolytic bath 50 in small amount for multiple times;
s2, after the nickel sulfate in the electrolytic cell 50 is completely dissolved, dividing 1,2,4-butane tricarboxylic acid 1245 g into a plurality of times to be added into the electrolytic cell 50;
s3, when 1,2,4-butane tricarboxylic acid in the electrolytic cell 50 is completely dissolved, 4800 g of 2-phosphonic acid butane-1,2,4-sodium tricarboxylate is added into the electrolytic cell 50 in multiple times;
s4, testing the solution prepared in the electrolytic cell 50 by using a pH meter after 2-phosphonic acid butane-1,2,4-sodium tricarboxylate in the electrolytic cell 50 is uniformly stirred, and controlling the pH value to be in the range of 7.0-8.0; adding organic acid salt if the pH is lower than 7.0, and adding organic acid for adjusting if the pH is higher than 8.0;
s5, adding 2475 g of sodium tungstate into the electrolytic bath 50 for a plurality of times in a small amount;
s6, when the sodium tungstate in the electrolytic bath 50 is uniformly stirred, adding a small amount of 10.5 g of 2- (pyrrolidine-3-yl) ethyl-1-alkoxide into the electrolytic bath 50 for many times;
and S7, when the 2- (pyrrolidine-3-yl) ethyl-1-alkoxide is completely dissolved, adding pure water to enable the volume of the solution in the electrolytic bath 50 to reach 15 liters, and obtaining the nickel-tungsten alloy electrolyte 10 for later use.
In this example, the plating material selected was copper alloy, the size was 100 × 70mm, the thickness was 0.3mm, after degreasing, acid activation and drying, the sample was precisely weighed with an HR-120 electronic balance, the sample weight was 18.7263 g, and electrolytic treatment was performed according to the following procedure.
As shown in fig. 1, the method for electroplating nickel-tungsten alloy by using forward and reverse pulses, when the forward pulse runs, the nickel plate 20 is printed with a positive electrode, and the plating piece 30 is printed with a negative electrode (shown in (a) in fig. 1), when the reverse pulse runs, the nickel plate 20 is printed with a negative electrode, and the plating piece 30 Yin Jia is printed with a positive electrode (shown in (b) in fig. 1), and electroplating nickel-tungsten alloy plating is performed, wherein the plating thickness is required to be 1 μm, and the method specifically comprises the following steps:
(1) Directly utilizing the nickel-tungsten alloy electrolyte 10 prepared in the electrolytic bath 50, and heating to 55 ℃;
(2) A copper plate with the size of 100 multiplied by 70mm and the thickness of 0.3mm is taken as a plating piece 30, one surface of the plating piece 30 is bonded and shielded by a special protective film, and only the other surface is exposed and arranged opposite to the nickel plate 20;
(3) Carrying out ultrasonic degreasing treatment on the shielded plating piece 30 for 15 seconds, and then cleaning with pure water; the cleaned plating piece 30 is subjected to cathodic electrolysis for 10 seconds and cleaned by pure water; then carrying out acid activation treatment for 20 seconds, and carrying out pure water treatment;
(4) The nickel plate 20 is connected to the anode of the pulse reverse power supply 100 through the anode conductive connecting rod 21, and the plating piece 30 is connected to the cathode of the pulse reverse power supply 100 through the cathode conductive connecting rod 31;
(5) Electroplating with positive and reverse pulse, and applying positive pulse current I as shown in FIG. 2 1 5A, forward pulse time t 1 20 ms, 1 ms intermission, then applying a reverse pulse current I 2 15A, reverse pulse time t 2 Completing one cycle of forward and reverse pulse plating within 2 milliseconds;
(6) And (5) repeating the forward and reverse pulse circulation in the step (5), finishing after the total electroplating time is 1-3 minutes, and tearing off the special protective film to obtain the nickel-tungsten alloy coating.
Example 1 was tested against A, B, C, D, E in fig. 3, each testing point tested 1-5 data in fig. 4 (zero at the top left of fig. 4, coordinate No. 1 (2,2), coordinate No. 2 (2,6), coordinate No. 3 (6,6), coordinate No. 4 (6,2), coordinate No. 5 (4,4)) and the results are shown in table 1:
table 1 example 1 nickel tungsten alloy plating test results (μm)
| 1 | 2 | 3 | 4 | 5 | Ave. | |
| A | 1.213 | 1.196 | 1.165 | 1.184 | 1.174 | 1.186 |
| B | 1.193 | 1.186 | 1.156 | 1.195 | 1.165 | 1.179 |
| C | 1.202 | 1.194 | 1.167 | 1.186 | 1.173 | 1.184 |
| D | 1.211 | 1.195 | 1.163 | 1.183 | 1.166 | 1.183 |
| E | 1.154 | 1.166 | 1.145 | 1.154 | 1.136 | 1.151 |
| Ave. | 1.194 | 1.187 | 1.159 | 1.180 | 1.163 | 1.177 |
In this example, the thickness of the coating is 1 μm, the standard test point is the center E5, and the thickness of nickel-tungsten is 1.136 μm as detected by a high-precision XRF analyzer FISCOPE X-RAY XDV-SDD. The result of detection by an S-4800 scanning electron microscope/X-ray energy spectrometer shows that the tungsten content is 53.52%. Precisely weighing by using an electronic balance, wherein the weight of the nickel-tungsten alloy product is 18.9676 g; namely the weight of the nickel-tungsten alloy coating is 18.9676-18.7263 = 0.2413 g.
As can be seen from Table 1, the average plating thickness of the five test points A to E of example 1 was 1.177. Mu.m.
According to the results, under the condition that the tungsten content of the coating is 53.52%, the coating weight is 0.2040 g theoretically calculated when the product specification coating is 1 mu m;
example 1 nickel tungsten 0.2413-standard nickel tungsten 0.2040 = 0.0373 grams;
that is, the weight of the plating layer in example 1 is 0.0373 g more than that of the plating layer in the product specification, and accounts for 18.3%.
The nickel-tungsten alloy plating layer of example 3 was examined by Ultima IV using a physical X-ray diffractometer, and the results are shown in fig. 21.
As shown in fig. 21, when the incident angle of X-ray is 15 °, the diffraction peak of copper, which is a material of the plated article, is still relatively distinct, in addition to the broad and short diffraction peak of nickel-tungsten; when the incident angle of X-ray is reduced to 5 degrees, the diffraction peak of the copper of the plated part material almost disappears; when the incident angle of X-ray is reduced to 2 deg., it only presents a broad and short diffraction peak, indicating that the nickel-tungsten alloy coating layer is in amorphous structure.
Examples 2 to 10
The compositions of the forward and reverse pulse electrolytic nickel-tungsten alloy solutions provided in examples 2 to 10 are shown in table 2. The preparation method of the nickel tungsten alloy electrolyte of examples 2 to 10 was the same as that of example 1. The nickel tungsten alloy plating tests of examples 2-10 were the same as example 1 and the test data are given in table 5. The method of electroplating nickel tungsten alloy plating layers of examples 2 to 10 is substantially the same as that of example 1, except that:
the total electroplating time of the embodiment 2 is 3-9 minutes, the thickness of the coating is 3.0 μm, and the tungsten content is 45.72%;
the total electroplating time of the embodiment 3 is 5 to 11 minutes, the thickness of the coating is 5.0 mu m, and the tungsten content is 48.63 percent;
the total electroplating time of the embodiment 4 is 13 to 21 minutes, the thickness of the coating is 10.0 mu m, and the tungsten content is 49.18 percent;
the total electroplating time of the embodiment 5 is 30 to 45 minutes, the thickness of the coating is 30.0 mu m, and the tungsten content is 43.52 percent;
the total electroplating time of the embodiment 6 is 50 to 65 minutes, the thickness of the coating is 50.0 mu m, and the tungsten content is 47.91 percent;
the total electroplating time of the embodiment 7 is 5 to 11 minutes, the thickness of the plating layer is 5.0 mu m, and the tungsten content is 45.75 percent;
the total electroplating time of the embodiment 8 is 13 to 21 minutes, the thickness of the coating is 10.0 mu m, and the tungsten content is 48.47 percent;
the total electroplating time of the embodiment 9 is 30 to 45 minutes, the thickness of the plating layer is 30.0 mu m, and the tungsten content is 46.25 percent;
the total plating time of example 10 was 50 to 65 minutes, the plating thickness was 50.0 μm, and the tungsten content was 43.43%.
TABLE 2 compositions (g/L) of the nickel-tungsten alloy solutions of examples 1 to 10
Comparative examples 1 to 12
The compositions of the forward and reverse pulse electrolytic nickel-tungsten alloy solutions provided in comparative examples 1 to 12 are shown in Table 3. The preparation method of the nickel tungsten alloy electrolyte of comparative examples 1 to 12 was the same as that of example 1. The nickel tungsten alloy plating tests of comparative examples 1 to 12 were the same as in example 1, and the test data are shown in table 5. The method of electroplating nickel-tungsten alloy plating layers of comparative examples 1 to 12 was substantially the same as in example 1 except that:
comparative examples 1 to 4 and comparative examples 9 to 12 used high frequency power sources, and comparative examples 5 to 8 used reverse pulse power sources;
comparative example 2 has a total plating time of 2 to 6 minutes, a plating thickness of 5.0 μm, a tungsten content of 37.27%;
the total electroplating time of the comparative example 3 is 3 to 9 minutes, the thickness of the coating is 10.0 mu m, and the tungsten content is 35.56 percent;
comparative example 4 has a total plating time of 37 to 48 minutes, a plating thickness of 50.0 μm, and a tungsten content of 38.73%;
comparative example 6 has a total plating time of 3 to 9 minutes, a plating thickness of 3.0 μm, a tungsten content of 37.61%;
the total plating time of comparative example 9 was 1 to 3 minutes, the plating thickness was 1.0 μm, and the tungsten content was 35.32%;
comparative example 10 has a total plating time of 2 to 6 minutes, a plating thickness of 5.0 μm, a tungsten content of 37.65%;
comparative example 11 has a total plating time of 3 to 9 minutes, a plating thickness of 10.0 μm, a tungsten content of 36.27%;
comparative example 12 total plating time was 37 to 48 minutes, plating thickness was 50.0 μm, tungsten content was 39.71%;
TABLE 3 composition (g/L) of Ni-W alloy solutions of comparative examples 1 to 12
TABLE 4 COMPARATIVE EXAMPLE 1 Nickel-tungsten alloy coating test results (. Mu.m)
| 1 | 2 | 3 | 4 | 5 | Ave. | |
| A | 1.935 | 1.935 | 1.874 | 1.815 | 1.154 | 1.743 |
| B | 1.917 | 1.914 | 1.853 | 1.794 | 1.146 | 1.725 |
| C | 2.014 | 1.954 | 1.892 | 1.888 | 1.162 | 1.782 |
| D | 1.975 | 1.976 | 1.865 | 1.876 | 1.153 | 1.769 |
| E | 1.193 | 1.202 | 1.194 | 1.190 | 1.194 | 1.194 |
| Ave. | 1.807 | 1.796 | 1.735 | 1.712 | 1.162 | 1.642 |
Comparative example 1 requires a plating thickness of 1 μm, a standard test point at the center E5, and a sample weight of 18.4713 g before plating; the nickel tungsten thickness at the center E5 of comparative example 1 was 1.194 μm.
The result of detection by an S-4800 scanning electron microscope/X-ray energy spectrometer shows that the tungsten content is 36.41 percent.
Precisely weighing by using an electronic balance, wherein the weight of the nickel-tungsten alloy product is 18.7642 g; namely the weight of the nickel-tungsten alloy coating is = 18.7642-18.4713= 0.2929 g;
as can be seen from Table 4, the five test points A to E of comparative example 1 had an average plating of 1.642 μm.
According to the above results, the theoretical calculated coating weight is 0.1789 g for a product specification coating of 1.0 μm under the condition of the tungsten content of 36.41% in comparative example 1;
comparative example 1 nickel tungsten 0.2929-standard nickel tungsten 0.1789 = 0.1140 grams;
that is, the weight of the coating of the comparative example 1 is larger than that of the coating of the product specification by 0.1140 g, which accounts for 63.7%.
Comparing the results of the example 1 in table 1 with the results of the comparative example 1 in table 3, it can be seen that, when the same nickel-tungsten alloy solution is used and the reverse pulse power supply of the example 1 is replaced by the high-frequency power supply of the comparative example 1, the nickel-tungsten alloy plating layer of the comparative example 1 has a great difference in thickness according to the difference in position, and the edge part of the product is much higher than the middle part, and from the plating layer test result and the weight difference data before and after plating, it is verified that the reverse pulse electroplating method of the present invention is favorable for improving the uniformity of the nickel-tungsten alloy plating layer, and meanwhile, the usage amount of the nickel-tungsten alloy of the plated part can be greatly saved, thereby reducing the production cost.
TABLE 5 examination results of the nickel-phosphorus alloy plating layers obtained in examples 1 to 10 and comparative examples 1 to 12
From the results in table 5, it can be seen that the nickel-tungsten alloy plating products with tungsten content of 43.43% -53.52% obtained by the nickel-tungsten alloy solutions of the present invention of examples 1-10 by using the reverse pulse electrolysis technique, the plating range of 1.0 μm-50.0 μm required by the product specification, and the actual test plating range of 1.183 μm-59.656 μm; the weight range of the nickel-tungsten alloy added before and after the electrolysis is 0.2413 g-11.5995 g.
The nickel-tungsten alloy solution of the invention of comparative example 1 to comparative example 4 and the nickel-tungsten alloy solution of the prior art of comparative example 9 to comparative example 12 are electrolyzed by a high-frequency power supply to obtain a nickel-tungsten alloy coating product with the tungsten content of 35.56-38.73%, and the product with the coating range of 1.0-50.0 μm is also required to the product specification, and the actual test coating range is 1.586 μm-83.051 μm; the weight of the nickel-tungsten alloy added before and after the electrolysis is 0.2812 g-15.2602 g.
In the prior art nickel-tungsten alloy solutions of comparative examples 5 to 8, when the reverse pulse power supply was used for electrolysis, only comparative example 6 could obtain the test data, and the following problems existed: electrolyzing to obtain nickel-tungsten alloy; (2) In the electrolytic process, the nickel-tungsten alloy solution is turbid, and the nickel-tungsten coating has pits; (3) the nickel-tungsten alloy plating layer obtained by electrolysis is rough and matt; (4) The nickel-tungsten alloy product can be obtained in the initial stage of electrolysis, and after the nickel-tungsten alloy product is used for several hours, the solution is turbid and foreign matters are attached to the surface of the nickel-tungsten coating.
Further, the actually measured weight of the nickel-tungsten alloy coating in the embodiments 1 to 10 is increased by 17.2 to 19.5 percent compared with the weight of the standard nickel-tungsten alloy coating of the coating required by the product specification; while comparative examples 1 to 12 increased the weight percent range from 58.6% to 66.1%.
From the above data, it can be seen that the nickel-tungsten alloy coatings obtained by the method have the problem of uneven distribution no matter the nickel-tungsten alloy solution in the prior art is compared with the nickel-tungsten alloy solution in comparative examples 9-12 or the nickel-tungsten alloy solution in the invention is compared with the nickel-tungsten alloy solution in comparative examples 1-4, and no matter the common high-frequency power supply or the single pulse power supply is adopted; all the problems existing in the prior art can be completely solved by the nickel-tungsten alloy solution and the reverse pulse electrolysis process technology.
Further, the appearances of the plating layers of examples 1 to 10 and comparative examples 1 to 12 were measured by optical microscope, and the results are shown in Table 6.
And (3) measuring the porosity of the nickel-tungsten alloy plating layer, wherein the nitric acid steam test is carried out according to the national standard GB/T19351-2003/ISO 14647:2000 implementation; the sample was cut into 3mm × 3mm, the periphery and the back were bonded with a 3M plating protective tape, and the single side was exposed to 2mm × 2mm for the test, the test time was 2 hours, and the test results are shown in table 6.
The high-temperature service life test of the nickel-tungsten alloy coating is carried out according to the national standard GJB360A-96, the high temperature is 300 ℃, the experimental time is 2 hours, and the experimental results are listed in Table 6.
The nickel-tungsten alloy coating sliding friction wear test is implemented according to the national standard GB-T12444-2006, and is tested by CSM ball friction wear test equipment; the larger the frictional wear value is, the larger the surface roughness of the nickel-tungsten alloy is, or the lower the hardness of the nickel-tungsten alloy coating is, and the experimental results are shown in table 6.
The surface roughness of the nickel-tungsten alloy coating is implemented according to the national standard GB3505-83, the surface roughness is detected by a 3D profilometer VR-5000 manufactured by Kenyishi, and the experimental results are listed in Table 6.
TABLE 6 examination results of the nickel-phosphorus alloy plating layers obtained in examples 1 to 10 and comparative examples 1 to 12
* And (3) excellent: no corrosion spots; good: a small spot; slight corrosion: two small spots; there is corrosion: 3 and more spots.
As seen from table 6, the plating appearances of examples 1 to 10 were half-bright, bright and smooth-bright, and those of comparative examples 1 to 12 were half-bright, bright and smooth-bright;
from the nitric acid steam test result measured by the porosity of the nickel-tungsten alloy plating layer, the samples of the examples 1 to 10 are excellent and good, and the samples of the comparative examples 1 to 12 are good, slightly corroded and corroded;
from the high-temperature test results of the nickel-tungsten alloy coating, the nickel-tungsten alloy coating is excellent and good in the examples 1 to 10, and good, skinned and pocked in the comparative examples 1 to 12;
from the results of the sliding frictional wear test of the nickel-tungsten alloy plated ball, the frictional wear amounts of examples 1 to 10 were 0.7mg to 1.7mg, and the range was 0.7mg to 1.1mg except for 1.7mg of example 1; and the frictional wear amounts of comparative examples 1 to 12 were 2.1mg to 2.9mg;
from the surface roughness test results of the copper alloy materials of the plated parts, the average arithmetic roughness of the copper alloy materials of the examples 1 to 10 is 0.431 to 0.438 μm; the average arithmetic roughness of comparative examples 1 to 12 is 0.432 to 0.439. Mu.m;
from the test result of the surface roughness of the nickel-tungsten alloy plating, the roughness of the nickel-tungsten alloy plating is 0.443 to 0.449 μm in examples 1 to 10; the average arithmetic roughness of the comparative examples 1 to 12 is 0.631 μm to 0.647 μm;
from the results in tables 5 and 6, it is seen that the tungsten content of the nickel-tungsten alloy coating is not less than 50% in example 1, which is not ideal, and the tungsten content of examples 2 to 10 is 43.43% to 49.18%, all the experimental results are excellent; while the tungsten content of the comparative examples 1 to 12 is 35.56 to 39.71 percent, the comprehensive experiment results are not ideal, and the defects of rough and uneven nickel-tungsten alloy coating, pocking marks and the like still exist.
In conclusion, the process technology provided by the invention solves the defects of roughness, non-uniformity, pocking mark and the like of the nickel-tungsten alloy coating in the prior art.
Example 11
The formula of the nickel-tungsten alloy solution is the same as that of the embodiment 3, the materials adopt a copper alloy terminal consisting of 5 metal needles and a copper sheet with the thickness of 30mm multiplied by 30mm and 0.2mm, the nickel-tungsten alloy plating layer is 1.5 mu m, and then the gold is plated for 0.1 mu m.
Comparative example 13
The formula of the nickel-tungsten alloy solution is the same as that of the comparative example 9, the material adopts a copper alloy terminal consisting of 5 metal needles, a copper sheet with the thickness of 30mm multiplied by 30mm and 0.2mm, a nickel-tungsten alloy coating layer is 1.5 mu m, and then gold is plated for 0.1 mu m.
And (3) measuring the porosity of the nickel-tungsten alloy coating, wherein the nitric acid steam test is carried out according to the national standard GB/T19351-2003/ISO 14647:2000 implementation; the copper sheet sample is bonded on the periphery and the back by using a 3M special electroplating protective adhesive tape, the exposed single surface is 20mm multiplied by 20mm for testing, and the terminal sample is bonded on the periphery and the back by using the 3M special electroplating protective adhesive tape, and the exposed single surface is 20mm multiplied by the testing time for 7 hours. The results are shown in Table 7.
Table 7 nitric acid vapor test results of example 11 and comparative example 13
From the results of the nitric acid vapor test of the connector terminal plating material shown in table 7, the nickel-tungsten alloy plating/gold-plated composite material of the present invention was not corroded under a long-term strong nitric acid vapor test and had very excellent corrosion resistance, as compared with the composite material of the prior art.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined by the scope of the claims.
Claims (14)
1. The forward and reverse pulse electrolytic nickel-tungsten alloy solution is characterized by comprising the following components:
20-150g/L of nickel salt, 30-300g/L of tungstate, 5-500g/L of organic acid salt, 3-300g/L of organic acid and 0.02-15g/L of nitrogen heterocyclic compound.
2. The forward and reverse pulse electrolytic nickel-tungsten alloy solution according to claim 1, wherein the nickel salt is one or more of nickel sulfate, nickel chloride, nickel nitrate, nickel sulfamate, nickel citrate, nickel carbonate, nickel bromide, nickel phosphate, nickel borate, nickel benzenesulfonate, nickel hypophosphite, and nickel 4-toluenesulfonate;
the tungstate is one or more of sodium tungstate, potassium tungstate, ammonium metatungstate and ammonium metatungstate;
the organic acid salt is one or more of salts of monocarboxylic acid to hexacarboxylic acid;
the organic acid is one or more of monocarboxylic acid to hexacarboxylic acid;
the nitrogen-containing heterocyclic compound is one or more of pyrrole, pyrazole, oxazole, thiazole, imidazole, pyridine, pyrimidine, azaindole and pyrazine.
3. The positive and reverse pulse electrolytic nickel-tungsten alloy solution according to claim 2, wherein the organic acid salt is one or more selected from sodium formate, ammonium formate, sodium acetate, ammonium acetate, sodium propionate, ammonium ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate monohydrate, tetrasodium ethylenediaminetetraacetate dihydrate, triammonium ethylenediaminetetraacetate, potassium ethylenediaminetetraacetate, tripotassium ethylenediaminetetraacetate, dipotassium ethylenediaminetetraacetate, ammonium isethionate, dimethylamine 2-isethionate, ammonium dihydrogen citrate, potassium dihydrogen citrate, diammonium hydrogen citrate, disodium citrate, trisodium citrate hydrate, triammonium citrate, choline dihydrogen citrate, choline citrate, ammonium oxalate, ammonium succinate, butane-2-phosphonate-1,2,4-trisodium carboxylate, butane-2-phosphonate-1,2,4-tetrasodium tricarboxylate, butane-2-phosphonobutane-1,2,4-potassium tricarboxylate, pentasodium diethylenetriaminepentaacetate, heptasodium diethylenetriaminepentamethylenephosphonate, and sodium diethylenetriamine pentamethylenephosphonate;
the organic acid is one or more of formic acid, acetic acid, malonic acid, ethylene diamine tetraacetic acid, 3-hydroxy-3-carboxyl glutaric acid, tricarballylic acid, propane tricarboxylic acid, 3-amino-1,1,3-propane tricarboxylic acid, 1,2,4-butane tricarboxylic acid, 2-phosphonic butane-1,2,4-tricarboxylic acid, water malted acid, butane tetracarboxylic acid, diethylenetriamine pentaacetic acid, triethylenetetramine hexaacetic acid, diethylenetriamine penta methylene phosphonic acid and triethylenetetramine hexa (methyl phosphonic acid).
4. The forward-reverse pulse electrolytic nickel-tungsten alloy solution according to claim 2, wherein the pyrrole is one or more of 5- (pyrrolidin-3-yl) -2H-1,2,3,4-tetrazole hydrochloride, 3-methyl-5-pyrrole-1,2,4-oxadiazole, 2- (pyrrolidin-3-yl) ethane-1-alkoxide, 4-pyrrolidinyl-1-pyridine-2-carboxylic acid hydrochloride, 4- (pyrrolidin-3-yl) pyridine hydrochloride, 1- (2-chlorobenzyl) -pyrrolidin-3-amine dihydrochloride, 1- (4-chlorobenzyl) -pyrrolidin-3-amine dihydrochloride;
the pyrazole is one or more of 5-amino-1- (2-hydroxyethyl) pyrazole, 5-amino-1-ethylpyrazole, 2- (4-bromo-1H-pyrazol-1-yl) ethanol, 2- (4-bromo-1H-pyrazol-1-yl) acetamide, 2- (4-bromo-1H-pyrazol-1-yl) propionamide, 4-amino-1-methyl-3-propylpyrazole-5-carboxamide hydrochloride, 5-amino-1-ethylpyrazole-4-carboxylic acid and 5-amino- (2-hydroxyethyl) -4-pyrazolecarboxylic acid;
the oxazole is one or more of 5-nitro-1,2 benzisoxazole, 3-amino-5-nitro-1,2-benzisoxazole, 3-chloro-7-nitro-1,2-benzisoxazole, 3-methyl-5-nitro-1,2-benzisoxazole, 5-fluoro-3- (4-piperidinyl) -1,2-benzisoxazole, 6-nitro-1,2-benzisoxazole, 6-nitro-1,2-benzisoxazole-3-methanol, 6-nitro-1,2-benzisoxazole-3-carboxylic acid;
the thiazole is one or more of 2-methyl-5-nitrothiazole, 3-amino-5-nitrobenzoisothiazole, 2-methyl-5-nitrobenzothiazole, 2-methyl-5-phenyl-thiazole-4-carboxylic acid, 4-methyl-5-nitrothiazole, 2-amino-5-nitrothiazole and 2-methyl-5-thiazolamine;
the imidazoles are one or more of 2- (difluoromethyl) -1-phenyl-4,5-dihydro-1H-imidazole, 2-methyl-5-nitroimidazole, 1- (2,3-dihydroxypropyl) -2-methyl-5-nitroimidazole, 1-propyl-2,3-methylimidazole tetrafluoroborate, 1- (2-iodoethyl) -2-methyl-5-nitro-1H-imidazole, 2-methyl-5-nitrobenzimidazole, 1-benzyl-2-methyl-5-nitro-1H-1,3-benzimidazole and 2-mercapto-5-nitrobenzimidazole;
the pyridine is one or more of 2- (4-bromo-1H-pyrazol-1-yl) -5-fluoropyridine, 2-bromo-6- (1H-pyrazol-1-yl) pyridine, 2- (pyrrolidin-1-yl) pyridine-3-boronic acid, 2- (4-bromopyrazol-1-yl) pyridine, 2- ((4-iodo-1H-pyrazol-1-yl) methyl) pyridine, 2- (4-bromo-3-methyl-5- (trifluoromethyl) pyrazol-1-yl) -6-chloropyridine, 5- (chloromethyl) -2- (1H-pyrazol-1-yl) pyridine, 2- (4-bromo-1H-imidazol-1-yl) pyridine, 1-benzenesulfonyl-3-iodo-1H-pyrrole [2,3-B ] pyridine;
the pyrimidines are one or more of 2- (4-bromo-1H-pyrazol-1-yl) pyrimidine, 2- (1H-pyrazol-1-yl) -5- (trifluoromethyl) pyrimidine, 2- (4-fluoro-1H-pyrazol-1-yl) pyrimidine-5-carboxylic acid, (9 CI) -4- (1H-pyrazol-1-yl) -pyrimidine, 2,4-dichloro-5- (1H-pyrazolyl) pyrimidine, 2- (1H-pyrazol-1-yl) -5- (trifluoromethyl) pyrimidine, 4- (4-bromo-1H-pyrazol-1-yl) -6-chloropyrimidine, 4-chloro-6- (1H-pyrazol-1-yl) pyrimidine;
the azaindoles are one or more of 4-bromo-2-iodo-N-p-toluenesulfonyl-7-azaindole, 4-bromo-1-p-toluenesulfonyl-7-azaindole, 2-difluoromethyl-1-benzenesulfonyl-7-azaindole, 4-bromo-2-iodo-7-azaindole, N-toluenesulfonyl-5-bromo-4,7-diazaindole, 1-benzenesulfonyl-4-chloro-2-iodo-7-azaindole, 2-iodo-1-benzenesulfonyl-7-azaindole, 2-methyl-1- (benzenesulfonyl) -7-azaindole, 2-difluoromethyl-1-benzenesulfonyl-7-azaindole, 4-bromo-pyrrolo [2,3-F ] -7-azaindole;
the pyrazine is one or more of 2- (4-bromo-1H-pyrazol-1-yl) pyrazine, pyrazine-2-boric acid, 2- (4-bromo-1H-pyrazol-1-yl) pyrazine, 3- (4-bromo-1H-pyrazol-1-yl) -6-chloropyrazine e, 3-chloro-6- (4-iodo-1H-pyrazol-1-yl) pyrazine, 5- (1H-pyrazol-1-yl) pyrazine-2-carboxylic acid and 2-bromo-5- (1H-pyrrol-1-yl) pyrazine.
5. A method for preparing a forward and reverse pulse electrolytic nickel-tungsten alloy solution according to any one of claims 1 to 4, comprising the steps of:
s1, adding a small amount of nickel sulfate into a part of pure water for multiple times under the conditions of heating and stirring;
s2, after the nickel sulfate is completely dissolved, adding a small amount of organic acid for multiple times;
s3, after the organic acid is completely dissolved, adding a small amount of organic acid salt for multiple times;
s4, after the organic acid salt is completely dissolved, testing the pH value of the solution, and controlling the pH value to be in the range of 7.0-8.0;
s5, adding a small amount of tungstate for multiple times, and adding a small amount of nitrogen-containing heterocyclic compounds for multiple times after the tungstate is completely dissolved;
and S6, after the nitrogenous heterocyclic compounds are completely dissolved, uniformly stirring, and adding part of pure water to obtain the forward and reverse pulse electrolytic nickel-tungsten alloy solution.
6. The formulation process according to claim 5, wherein the heating temperature is 40-60 ℃, and in S4, the pH is adjusted by adding an organic acid salt if the pH is lower than 7.0 and by adding an organic acid if the pH is higher than 8.0.
7. A method for electroplating nickel-tungsten alloy by using forward and reverse pulses is characterized by comprising the following steps:
(1) Putting the nickel-tungsten alloy electrolyte (10) into an electrolytic bath (50), and heating to 40-60 ℃;
(2) The nickel plate (20) is connected to the anode of the pulse reverse power supply (100) through the anode conductive connecting rod (21), and the plating piece (30) is connected to the cathode of the pulse reverse power supply (100) through the cathode conductive connecting rod (31);
(3) Electroplating by adopting forward and reverse pulses: impressed with a positive pulse current I 1 Time t of forward pulse 1 Then applying a reverse pulse current I 2 Time t of reverse pulse 2 Completing one cycle of positive and reverse pulse plating;
(4) And (4) repeating the positive and reverse pulse circulation of the step (3) until the set electroplating time is finished.
8. The method for electroplating Ni-W alloy according to claim 7, wherein the current density of the forward pulse current in step (3) is in the range of 0.5-30.0A/dm 2 The current density of the reverse pulse current is 5.0-100.0A/dm 2 。
9. The method for electroplating nickel-tungsten alloy by using forward and reverse pulses as claimed in claim 7, wherein t is 1 And t 2 The ratio of (1) to (10-100).
10. The method for electroplating nickel-tungsten alloy by using forward and reverse pulses as claimed in claim 7, wherein I is 1 And I 2 The ratio range of (1) to (2-5).
11. The method for electroplating nickel-tungsten alloy by using forward and backward pulses as claimed in claim 7, wherein the electroplating time is 1-100min, and the thickness of the nickel-tungsten alloy coating obtained by electroplating is 0.5-100 μm.
12. The method for electroplating nickel-tungsten alloy by using the forward and reverse pulse as claimed in claim 7, wherein the method is used for barrel plating, rack plating and continuous production lines of nickel-tungsten amorphous alloy materials.
13. The method for electroplating the nickel-tungsten alloy by using the forward and reverse pulses as claimed in claim 12, wherein the method is used for surface electrochemical machining of inner walls of through holes, blind holes and small precision products.
14. A nickel tungsten alloy coating electroplated according to the method of any of claims 7 to 13, wherein the nickel tungsten alloy coating comprises Ni 100-m W m M is the percentage of tungsten atoms, and m is more than or equal to 43.43 percent and less than or equal to 53.52 percent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117779011A (en) * | 2024-02-23 | 2024-03-29 | 昆山一鼎工业科技有限公司 | Wafer electroless tungsten plating alloy solution, preparation method and electroless tungsten plating method |
| CN117779130A (en) * | 2024-02-23 | 2024-03-29 | 昆山一鼎工业科技有限公司 | Wafer electroplated tungsten alloy solution, preparation method and electroplating method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117779011A (en) * | 2024-02-23 | 2024-03-29 | 昆山一鼎工业科技有限公司 | Wafer electroless tungsten plating alloy solution, preparation method and electroless tungsten plating method |
| CN117779130A (en) * | 2024-02-23 | 2024-03-29 | 昆山一鼎工业科技有限公司 | Wafer electroplated tungsten alloy solution, preparation method and electroplating method |
| CN117779011B (en) * | 2024-02-23 | 2024-05-14 | 昆山一鼎工业科技有限公司 | Wafer electroless tungsten plating alloy solution, preparation method and electroless tungsten plating method |
| CN117779130B (en) * | 2024-02-23 | 2024-05-31 | 昆山一鼎工业科技有限公司 | Wafer electroplated tungsten alloy solution, preparation method and electroplating method |
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