CN110760907A - Alkaline cyanide-free electroplating zinc-nickel alloy additive and electroplating solution - Google Patents
Alkaline cyanide-free electroplating zinc-nickel alloy additive and electroplating solution Download PDFInfo
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Abstract
The invention discloses an alkaline cyanide-free zinc-nickel alloy electroplating additive which comprises the following components in parts by mass: 50-80 parts of a complexing agent, wherein the complexing agent comprises hydroxycarboxylic acid, amines and polyamine compounds; 4-7 parts of a brightening agent, wherein the brightening agent comprises a brightening main agent, a nonionic surfactant and a whitening agent; and 12-21 parts of nickel additive. The invention also discloses an alkaline cyanide-free electroplating zinc-nickel alloy electrolyte, which is characterized by comprising 12-15 parts of zinc ions with the concentration of 10-11 g/L, 20-30 parts of alkali liquor with the concentration of 100-130 g/L, 50-80 parts of complexing agent with the concentration of 50-80 ml/L, 12-21 parts of nickel additive with the concentration of 12-21 ml/L, 4-7 parts of brightener with the concentration of 4-7 ml/L and the balance of water. The alkaline cyanide-free electroplating zinc-nickel alloy additive can improve the brightness of a coating on a steel part, so that the coating achieves the effect of being close to the full brightness of nickel plating color, the light emitting speed is high, and the efficiency of the steel part electroplating operation is improved; the plating layer has good binding force, the corrosion resistance of the plating layer is improved, and the current efficiency of the plating layer is increased.
Description
Technical Field
The invention relates to the technical field of electroplating of zinc-nickel alloys, in particular to an alkaline cyanide-free electroplating zinc-nickel alloy additive and electroplating solution.
Background
The electroplated zinc-nickel alloy is an alloy with low nickel content of less than 20 percent, has high corrosion resistance, can be used as an anode type protective coating of steel and iron to perform rust prevention protection on steel and iron parts, has a melting point as high as 750-800 ℃, and is suitable for electroplating automobile engine parts; hydrogen embrittlement and whisker are not generated in the production process, and the cadmium-titanium alloy plating layer on airplane parts can be replaced, so that the production cost of the airplane is reduced. The preparation of the electroplated zinc-nickel alloy is mainly characterized in that the electroplated zinc-nickel alloy plating solution is subjected to atom migration under the electrified condition and accumulated on the steel piece at the anode of the electrolytic cell, so that the protection of the steel piece is realized. The zinc-nickel alloy plating solution mainly comprises an acid system and an alkaline system, and the zinc-nickel alloy plating solution of the acid system has poor coating dispersibility and is not suitable for parts with complex structures; the alkaline system comprises zinc-nickel alloy plating transition liquid of a plurality of systems such as a zincate system, a pyrophosphate system, a cyanide system and the like, wherein the zinc-nickel alloy plating transition liquid of the zincate system is widely applied due to the advantages of wider current range, excellent dispersing capacity, no hydrogen embrittlement of a plating layer, good feasibility of post processing, simple components of the transition liquid, small corrosion to equipment and the like.
However, the coating prepared by electroplating the zinc-nickel alloy plating solution by adopting the traditional zincate system has poor gloss, low light-emitting speed, poor uniformity and stability of the alloy coating, and easy shedding of the coating from the steel piece, so that the corrosion resistance of the steel piece is poor.
Disclosure of Invention
Therefore, it is necessary to provide an alkaline cyanide-free zinc-nickel alloy electroplating additive and an electroplating solution for solving the technical problems of poor coating gloss and poor corrosion resistance.
An alkaline cyanide-free electroplating zinc-nickel alloy additive comprises the following components in parts by mass: 50-80 parts of a complexing agent, wherein the complexing agent comprises hydroxycarboxylic acid, amines and polyamine compounds; 4-7 parts of a brightening agent, wherein the brightening agent comprises a brightening main agent, a nonionic surfactant and a whitening agent; and 12-21 parts of nickel additive.
In one embodiment, the hydroxycarboxylic acid is one or more of tartaric acid, citric acid, glycine, glycolic acid, gluconic acid, α -aminobutyric acid, and thioglycolic acid.
In one embodiment, the amine is one or more of diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenetetramine and derivatives thereof.
In one embodiment, the polyamine compound is one or two of polyethyleneimine, polyallylamine, polybutylamine, N- (2-hydroxyethyl) -N, N ', N' -triethylethylenediamine, N, N, N ', N' -tetrahydroxyethylethylenediamine, and N, N, N ', N' -tetrahydroxyethylpropylenediamine.
In one embodiment, the brightening main agent is one of reactants of diethoxybutylene glycol ether, polyethyleneimine, pyridinium propanesulfonate, N-phenyl-3-carboxypyridinium chloride, trigonelline, coumarin, sodium propargyl sulfonate, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and hexamethylenetetramine and epichlorohydrin respectively.
In one embodiment, the nonionic surfactant is a reactive polyoxyalkylene compound.
In one embodiment, the whitening agent comprises at least one aromatic aldehyde and at least one nicotinic acid derivative.
In one embodiment, the nickel additive is one or more of nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, and nickel methylsulfonate.
The invention also discloses an alkaline cyanide-free electroplating zinc-nickel alloy plating solution containing the alkaline cyanide-free electroplating zinc-nickel alloy additive, which comprises 12-15 parts of zinc ions with the concentration of 10-11 g/L, 20-30 parts of alkali liquor with the concentration of 100-130 g/L, 50-80 parts of complexing agent with the concentration of 50-80 ml/L, 12-21 parts of nickel additive with the concentration of 12-21 ml/L, 4-7 parts of brightener with the concentration of 4-7 ml/L, and the balance of water.
In one embodiment, the alkali liquor is sodium hydroxide solution or potassium hydroxide solution.
When the alkaline cyanide-free electroplating zinc-nickel alloy additive is added into electroplating solution to carry out electroplating operation on steel parts, the brightness of a coating on the steel parts can be improved, so that the coating achieves the effect of being close to nickel-plating color and luster and is full-bright, the light-emitting speed is high, and the efficiency of the electroplating operation of the steel parts is improved; meanwhile, less brightener is needed during electroplating operation, the complexing agent is added to enable the plating solution to be always in a stable state, the binding force of the plating layer is better, the corrosion resistance of the plating layer is improved, and the current efficiency of the plating layer is increased, so that the electroplating operation effect is improved.
Drawings
FIG. 1 is a flow chart of the electroplating operation including the alkaline cyanide-free electroplating zinc-nickel alloy additive of example 1;
FIG. 2 is a flow chart of the electroplating operation including the alkaline cyanide-free electroplating zinc-nickel alloy additive of example 2;
FIG. 3 is a flow chart of the electroplating operation including the alkaline cyanide-free electroplating zinc-nickel alloy additive of example 3;
FIG. 4 is a flow chart of the electroplating operation including the alkaline cyanide-free electroplating zinc-nickel alloy additive of example 4.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Example 1
The invention provides an alkaline cyanide-free electroplating zinc-nickel alloy additive which comprises, by mass, 50 parts of a complexing agent, wherein the complexing agent comprises hydroxycarboxylic acid, amine and polyamine compounds, specifically, 20g/L of α -aminobutyric acid 12 parts, 120g/L of diethanolamine 16 parts, 160/L of N, N, N ', N' -tetrahydroxyethyl ethylene diamine 15 parts and 160/L of triethylene tetramine derivative 17 parts, 4 parts of a brightening agent, wherein the brightening agent comprises a brightening main agent, a nonionic surfactant and a whitening agent, specifically, the brightening agent comprises 10g/L of diethoxybutylene glycol ether 1 part, 100g/L of triethylene tetramine and epichlorohydrin reactant 1 part, 50g/L of aromatic aldehyde 0.3 part, 20g/L of nicotinic acid derivative 0.9 part, 10g/L of coumarin 0.8 part, 12 parts of nickel supplementing agent, and the brightening agent comprises nickel supplementing agent, 40g/L of triethylene tetramine, 40g/L of ethylene diamine, 360g/L of epichlorohydrin, 40g/L of ethylene diamine, 2g/L of epichlorohydrin reaction products of ethylene diamine, and 360 parts.
When the alkaline cyanide-free electroplating zinc-nickel alloy additive is added into electroplating solution to carry out electroplating operation on steel parts, the brightness of a coating on the steel parts can be improved, so that the coating achieves the effect of being close to nickel-plating color and luster and is full-bright, the light-emitting speed is high, and the efficiency of the electroplating operation of the steel parts is improved; meanwhile, less brightener is needed during electroplating operation, the complexing agent is added to enable the plating solution to be always in a stable state, the binding force of the plating layer is better, the corrosion resistance of the plating layer is improved, and the current efficiency of the plating layer is increased, so that the electroplating operation effect is improved.
The complexing agent is a compound which can form complexing ions with metal ions, can prevent the metal ions in the electroplating solution from reacting and generating precipitates, and is beneficial to the implementation of the surface coating operation of steel parts, wherein α -aminobutyric acid is taken as hydroxycarboxylic acid, has strong complexing ability, is easy to biodegrade, and reduces the influence on the environment, but the dispersing ability of the complexing agent is poor, and limits the fluidity and uniformity of the electroplating solution to a certain extent.
The brightener is a substance for improving the brightness of the metal surface, and particularly, the brightener removes oil stains, oxidized and unoxidized surface impurities remained on the metal surface through a surfactant so as to keep the exterior of an object clean, glossiness and color fastness. The diethoxybutylene glycol ether is also called BEO, and is used as a main agent of a brightening agent to react with an oxide on the surface of a metal to remove an oxide layer on the surface of the metal and achieve the purpose of improving the glossiness of the metal. During the reaction process of triethylene tetramine and epichlorohydrin, various isomeric reaction products are generated, and the reaction products also react with oxides on the metal surface so as to further improve the glossiness of the metal surface.
The nonionic surfactant is used for reducing the surface activity of the metal, so that the tension of the metal surface is reduced, the adhesive force between oil stains or impurities and the metal surface is reduced, and the oil stains or the impurities are removed from the metal surface, so that the brightening main agent can react with an oxide layer on the metal surface. Preferably, the nonionic surfactant is a reactive polyoxyalkylene compound. The active polyoxyalkylene compound is a nonionic surfactant which can resist hot-pressing sterilization and low-temperature freezing environment, has stronger stability, is not easy to decompose in the electroplating environment, and is beneficial to improving the effect of electroplating operation.
The aromatic aldehyde and nicotinic acid derivative are mainly used as whitening agents, and convert invisible ultraviolet radiation absorbed by metal products into bluish fluorescent radiation which is complementary with original reflected light on the metal surface to form white light, so that the aim of improving the whiteness of the metal products is fulfilled. Preferably, the aromatic aldehyde is a reaction product of anisic aldehyde and sodium bisulfite, and the nicotinic acid derivative is trigonelline hydrochloride. It should be noted that, in the actual production, other substances with whitening performance can be selected as whitening agents to be added to the alkaline cyanide-free electroplated zinc-nickel alloy additive according to the production conditions, and the details are not repeated herein.
The nickel additive is used for supplementing nickel ions into the electroplating solution, so that the electroplating solution is ensured to always contain high-concentration nickel ions, and the forward progress of the electroplating reaction is promoted, so that the generation of a plating layer is accelerated. In the embodiment, nickel sulfate is used as a nickel additive for adding, and the nickel sulfate is a common nickel additive and can provide sufficient nickel ions for electroplating solution. It should be noted that, by adding diethanolamine, N' -tetrahydroxyethylethylenediamine, triethylene tetramine and epichlorohydrin into the nickel additive, the dissolution and mixing of the nickel additive, the brightener and the complexing agent can be promoted, so that the nickel ions can be uniformly mixed in the additive and the electroplating solution, and the stable proceeding of the electroplating reaction can be ensured.
The invention also discloses an alkaline cyanide-free electroplating zinc-nickel alloy plating solution containing the alkaline cyanide-free electroplating zinc-nickel alloy additive, wherein the electroplating solution contains 12 parts of zinc ions with the concentration of 5g/L, 30 parts of sodium hydroxide solution with the concentration of 100g/L, 50 parts of complexing agent with the concentration of 50ml/L, 12 parts of nickel additive with the concentration of 12ml/L, 4 parts of brightener with the concentration of 4ml/L and the balance of water.
It should be noted that zinc ions are mainly derived from soluble zinc salts, such as compounds of zinc oxide, zinc sulfate, zinc carbonate, zinc acetate, zinc sulfate, zinc sulfamate, zinc hydroxide, and zinc tartrate, which are dissociated to form free zinc ions when dissolved in water, so that the zinc ions move between the cathode and the anode of the electrolytic cell to form a plating layer on the metal surface. In actual production, the proper soluble zinc salt can be selected according to the production conditions of a producer, and the concentration of zinc ions is only required to be adjusted to be within the concentration range of 5 g/L-20 g/L, which is not described herein again.
The invention also discloses an electroplating method 10 of the alkaline cyanide-free electroplating zinc-nickel alloy plating solution, and the electroplating method 10 comprises the following steps:
s101: adding 250ml of water into a 500ml Hull cell, sequentially adding a predetermined amount of sodium hydroxide and zinc oxide, stirring and dissolving to form a main electrolyte liquid;
specifically, distilled water is added into the Hull cell until the liquid level reaches one half of the volume of the Hull cell, then 60g of sodium hydroxide and 20g of zinc oxide are sequentially added, and stirring is continuously carried out, so that heat generated when alkali liquor splashes into water is rapidly led out, the Hull cell is prevented from rapidly releasing heat, and the safety of operation is guaranteed. After the stirring operation, an electrolyte main liquid containing 120g/L of sodium hydroxide and 8g/L of zinc ions is formed, and the electrolyte main liquid provides an alkaline environment and zinc ions for the electrolysis operation so as to be beneficial to the continuous electrolysis operation. In the specific production, the addition amount of each component can be converted according to the actual size of the hall cell, and the amplification ratio or the reduction ratio of each component is consistent with the ratio of the preset size to the actual size of the hall cell, which is not described herein again.
S102: after the main liquid of the electrolyte is naturally cooled to below 30 ℃, 25ml of complexing agent, 6ml of nickel additive and 2ml of brightener are added into a Hull cell in sequence and stirred continuously to form a uniform mixed solution.
Specifically, α -aminobutyric acid 6ml, diethanolamine 120 g/L8 ml, diethanolamine 160/L N, N, N ', N' -tetrahydroxyethylethylenediamine 7.5ml and triethylenetetramine 160/L8.5 ml are mixed to form complexing agent 25ml, diethoxybutylene glycol ether 0.5ml, triethylene tetramine 100g/L and epichlorohydrin reactant 0.5ml, aromatic aldehyde 50 g/L0.15 ml, nicotinic acid derivative 20 g/L0.45 ml and coumarin 10 g/L0.4 ml are mixed to form brightening agent 2ml, nickel sulfate 360 g/L4 ml, diethanolamine 40 g/L0.5 ml, diethanolamine 50 g/L0.5 ml, N, N, N ', N' -tetrahydroxyethylethylenediamine 50 g/L0.5 ml and triethylenetetramine 30g/L and epichlorohydrin reaction product 1ml are mixed to form nickel supplement 6ml, and the nickel supplement is added into the mixing tank while stirring to form the mixture.
S103: and continuously adding water into the Hull cell until the liquid level in the Hull cell reaches 80% of the volume of the Hull cell to form electrolyte.
S104: placing an iron sheet with the thickness of 20cmx6cm on an anode of a hall bath, and introducing 2A current into the hall bath at the temperature of 26 ℃ to continuously electroplate the iron sheet for 20min until a uniform coating is formed on the surface of the iron sheet, thereby completing the electroplating operation on the surface of the iron sheet.
The base material to which the above-mentioned electrolyte is applied may be a metal base material such as steel, copper alloy, and aluminum alloy, that is, a metal base material such as steel, copper alloy, and aluminum alloy may be used instead of an iron sheet to perform an electroplating operation, so as to realize a plating film on the surface of each metal base material, improve the strength and corrosion resistance of the surface of the metal base material, improve the surface characteristics thereof, and extend the service life thereof and the application range thereof. During the actual electroplating operation, the temperature of the electroplating solution can be adjusted to 23-28 ℃ according to the production conditions, and the current density of the electroplating operation is 0.5A/dm2To 8A/dm2And the area ratio of the cathode and the anode of the Hull cell is between 1.5:1 and 3:1, preferably, the area ratio of the cathode and the anode of the Hull cell is 2:1, so as to be beneficial to effectively carrying out electroplating operation.
Example 2
The invention provides an alkaline cyanide-free electroplating zinc-nickel alloy additive, which comprises the following components in parts by mass: 60 parts of a complexing agent, wherein the complexing agent comprises hydroxycarboxylic acid, amines and polyamine compounds, and concretely comprises 14 parts of tartaric acid of 30g/L, 18 parts of triethanolamine of 150g/L, 17 parts of polybutene amine of 220g/L and 21 parts of ethylenediamine of 170 g/L; 5 parts of brightening agent, wherein the brightening agent comprises a brightening main agent, a nonionic surfactant and a whitening agent, and specifically, the brightening agent comprises 20g/L of pyridinium propanesulfonate 1.5 parts, 110g/L of a reactant of diethylenetriamine and epichlorohydrin 1.2 parts, 65g/L of aromatic aldehyde 0.3 parts, 30g/L of nicotinic acid derivative 1.2 parts and 15g/L of triethanolamine 0.8 parts; 15 parts of nickel additive, wherein the nickel additive comprises 9 parts of 380g/L nickel carbonate, 2 parts of 45g/L diethanolamine, 2 parts of 60g/L N, N, N ', N' -tetrahydroxyethyl ethylene diamine and 3 parts of 35g/L reaction product of triethylene tetramine and epoxy chloropropane.
When the alkaline cyanide-free electroplating zinc-nickel alloy additive is added into electroplating solution to carry out electroplating operation on steel parts, the brightness of a coating on the steel parts can be improved, so that the coating achieves the effect of being close to nickel-plating color and luster and is full-bright, the light-emitting speed is high, and the efficiency of the electroplating operation of the steel parts is improved; meanwhile, less brightener is needed during electroplating operation, the complexing agent is added to enable the plating solution to be always in a stable state, the binding force of the plating layer is better, the corrosion resistance of the plating layer is improved, and the current efficiency of the plating layer is increased, so that the electroplating operation effect is improved.
The invention also discloses an alkaline cyanide-free electroplating zinc-nickel alloy plating solution containing the alkaline cyanide-free electroplating zinc-nickel alloy additive, wherein the electroplating solution contains 13 parts of zinc ions with the concentration of 12g/L, 28 parts of sodium hydroxide solution with the concentration of 110g/L, 60 parts of complexing agent with the concentration of 60ml/L, 15 parts of nickel additive with the concentration of 15ml/L, 5 parts of brightener with the concentration of 5ml/L and the balance of water.
The invention also discloses an electroplating method 20 of the alkaline cyanide-free electroplating zinc-nickel alloy plating solution, and the electroplating method 20 comprises the following steps:
s201: adding 250ml of water into a 500ml Hull cell, sequentially adding a predetermined amount of sodium hydroxide and zinc oxide, stirring and dissolving to form a main electrolyte liquid;
specifically, distilled water is added into the Hull cell until the liquid level reaches one half of the volume of the Hull cell, then 60g of sodium hydroxide and 20g of zinc oxide are sequentially added, and stirring is continuously carried out, so that heat generated when alkali liquor splashes into water is rapidly led out, the Hull cell is prevented from rapidly releasing heat, and the safety of operation is guaranteed. After the stirring operation, an electrolyte main liquid containing 120g/L of sodium hydroxide and 8g/L of zinc ions is formed, and the electrolyte main liquid provides an alkaline environment and zinc ions for the electrolysis operation so as to be beneficial to the continuous electrolysis operation.
S202: after the main liquid of the electrolyte is naturally cooled to below 30 ℃, 30ml of complexing agent, 7.5ml of nickel additive and 2.5ml of brightener are added into a Hull cell in sequence and stirred continuously to form a uniform mixed solution.
Specifically, 30ml of tartaric acid 7ml, 150g/L of triethanolamine 9ml, 220g/L of polybutylamine 8.5ml and 170g/L of ethylenediamine 10.5ml are mixed to prepare a complexing agent 30 ml; mixing 0.75ml of pyridinium propanesulfonate of 20g/L, 0.6ml of a reactant of diethylenetriamine of 110g/L and epichlorohydrin, 0.15ml of aromatic aldehyde of 65g/L, 0.6ml of nicotinic acid derivative of 30g/L and 0.4ml of triethanolamine of 15g/L to prepare 2.5ml of brightening agent; 380g/L of nickel carbonate 4.5ml, 45g/L of diethanolamine 1ml, 60g/L of N, N, N ', N' -tetrahydroxyethyl ethylene diamine 1ml, 35g/L of triethylene tetramine and epichlorohydrin reaction product 1.5ml are mixed to form 7.5ml of nickel additive, and the three are sequentially added into a hall tank while stirring is continued, so that a uniform mixed solution is formed in the hall tank.
S203: and continuously adding water into the Hull cell until the liquid level in the Hull cell reaches 80% of the volume of the Hull cell to form electrolyte.
S204: placing an iron sheet with the thickness of 20cmx6cm on an anode of a hall bath, and introducing 2A current into the hall bath at the temperature of 26 ℃ to continuously electroplate the iron sheet for 20min until a uniform coating is formed on the surface of the iron sheet, thereby completing the electroplating operation on the surface of the iron sheet.
Example 3
The invention provides an alkaline cyanide-free electroplating zinc-nickel alloy additive, which comprises the following components in parts by mass: 70 parts of complexing agent, wherein the complexing agent comprises hydroxycarboxylic acid, amine and polyamine compound, and concretely comprises 16 parts of citric acid of 40g/L, 20 parts of tetraethylenepentamine of 220g/L, 20 parts of polyacrylamide of 260g/L and 24 parts of hexamethylenetetramine of 260 g/L; 6 parts of brightening agent, wherein the brightening agent comprises a brightening main agent, a nonionic surfactant and a brightening agent, and specifically, the brightening agent comprises 2 parts of 30g/L N-phenyl-3-carboxypyridine chloride, 1.5 parts of a reactant of 120g/L propargyl sodium sulfonate and epoxy chloropropane, 0.5 part of 80g/L aromatic aldehyde, 1.2 parts of 40g/L nicotinic acid derivative and 0.8 part of 25g/L triethylene tetramine. 18 parts of nickel additive, wherein the nickel additive comprises 10 parts of 400g/L nickel chloride, 3 parts of 50g/L diethanolamine, 2.5 parts of 70g/L N, N, N ', N' -tetrahydroxyethyl ethylene diamine and 3.5 parts of 40g/L reaction product of triethylene tetramine and epoxy chloropropane.
When the alkaline cyanide-free electroplating zinc-nickel alloy additive is added into electroplating solution to carry out electroplating operation on steel parts, the brightness of a coating on the steel parts can be improved, so that the coating achieves the effect of being close to nickel-plating color and luster and is full-bright, the light-emitting speed is high, and the efficiency of the electroplating operation of the steel parts is improved; meanwhile, less brightener is needed during electroplating operation, the complexing agent is added to enable the plating solution to be always in a stable state, the binding force of the plating layer is better, the corrosion resistance of the plating layer is improved, and the current efficiency of the plating layer is increased, so that the electroplating operation effect is improved.
The invention also discloses an alkaline cyanide-free electroplating zinc-nickel alloy plating solution containing the alkaline cyanide-free electroplating zinc-nickel alloy additive, wherein the electroplating solution contains 14 parts of zinc ions with the concentration of 18g/L, 24 parts of potassium hydroxide solution with the concentration of 120g/L, 70 parts of complexing agent with the concentration of 70ml/L, 18 parts of nickel additive with the concentration of 18ml/L, 6 parts of brightener with the concentration of 6ml/L and the balance of water.
The invention also discloses an electroplating method 30 of the alkaline cyanide-free electroplating zinc-nickel alloy plating solution, and the electroplating method 30 comprises the following steps:
s301: adding 250ml of water into a 500ml Hull cell, sequentially adding a predetermined amount of potassium hydroxide and zinc oxide, stirring and dissolving to form a main electrolyte liquid;
specifically, distilled water is added into the Hull cell until the liquid level reaches one half of the volume of the Hull cell, then 60g of potassium hydroxide and 20g of zinc oxide are sequentially added, and stirring is continuously carried out, so that heat generated when alkali liquor splashes into water is rapidly led out, the Hull cell is prevented from rapidly releasing heat, and the safety of operation is guaranteed. After the stirring operation, an electrolyte main liquid containing 120g/L potassium hydroxide and 8g/L zinc ions is formed, and the electrolyte main liquid provides an alkaline environment and zinc ions for the electrolysis operation so as to be beneficial to the continuous electrolysis operation.
S302: after the main liquid of the electrolyte is naturally cooled to below 30 ℃, 35ml of complexing agent, 9ml of nickel additive and 3ml of brightener are added into the Hull cell in sequence and stirred continuously to form a uniform mixed solution.
Specifically, 8ml of citric acid of 40g/L, 10ml of tetraethylenepentamine of 220g/L, 10ml of polyacrylamide of 260g/L and 12ml of hexamethylenetetramine of 260g/L are respectively mixed to form 35ml of complexing agent; mixing 1ml of N-phenyl-3-carboxypyridine chloride of 30g/L, 0.75ml of reactant of propargyl sodium sulfonate and epichlorohydrin of 120g/L, 0.25ml of aromatic aldehyde of 80g/L, 0.6ml of nicotinic acid derivative of 40g/L and 0.4ml of triethylene tetramine of 25g/L to prepare a brightening agent of 3 ml; 5ml of nickel chloride of 400g/L, 1.5ml of diethanolamine of 50g/L, 1.25ml of N, N, N ', N' -tetrahydroxyethylethylenediamine of 70g/L and 1.75ml of a reaction product of triethylene tetramine and epichlorohydrin of 40g/L are mixed to form 9ml of nickel additive, and the nickel additive, the nickel additive and the epoxy chloropropane additive are sequentially added into a hall tank while stirring is continuously carried out, so that a uniform mixed solution is formed in the hall tank.
S303: and continuously adding water into the Hull cell until the liquid level in the Hull cell reaches 80% of the volume of the Hull cell to form electrolyte.
S304: placing an iron sheet with the thickness of 20cmx6cm on an anode of a hall bath, and introducing 2A current into the hall bath at the temperature of 26 ℃ to continuously electroplate the iron sheet for 20min until a uniform coating is formed on the surface of the iron sheet, thereby completing the electroplating operation on the surface of the iron sheet.
Example 4
The invention provides an alkaline cyanide-free electroplating zinc-nickel alloy additive, which comprises the following components in parts by mass: 80 parts of complexing agent, wherein the complexing agent comprises hydroxycarboxylic acid, amine and polyamine compound, and concretely comprises 19 parts of 50g/L glycine, 22 parts of 240g/L diethylenetriamine, 22 parts of 300g/L polyethyleneimine and 17 parts of 200g/L diethanolamine; 7 parts of brightening agent, wherein the brightening agent comprises a brightening main agent, a nonionic surfactant and a whitening agent, and specifically, the brightening agent comprises 2.5 parts of 40g/L tetraethylenepentamine, 2 parts of 130g/L hexamethylene tetramine and epichlorohydrin reactant, 1 part of 100g/L aromatic aldehyde, 1.2 parts of 50g/L nicotinic acid derivative and 0.3 part of 30g/L triethylene tetramine; 21 parts of nickel additive, wherein the nickel additive comprises 12 parts of nickel sulfamate with the concentration of 420g/L, 4 parts of diethanolamine with the concentration of 60g/L, 2 parts of N, N, N ', N' -tetrahydroxyethyl ethylene diamine with the concentration of 80g/L and 3 parts of reaction product of 50g/L triethylene tetramine and epichlorohydrin.
When the alkaline cyanide-free electroplating zinc-nickel alloy additive is added into electroplating solution to carry out electroplating operation on steel parts, the brightness of a coating on the steel parts can be improved, so that the coating achieves the effect of being close to nickel-plating color and luster and is full-bright, the light-emitting speed is high, and the efficiency of the electroplating operation of the steel parts is improved; meanwhile, less brightener is needed during electroplating operation, the complexing agent is added to enable the plating solution to be always in a stable state, the binding force of the plating layer is better, the corrosion resistance of the plating layer is improved, and the current efficiency of the plating layer is increased, so that the electroplating operation effect is improved.
It should be noted that the hydroxycarboxylic acid of the present invention may be one or more of tartaric acid, citric acid, glycine, glycolic acid, gluconic acid, α -aminobutyric acid and thioglycolic acid, and in the actual production, an appropriate hydroxycarboxylic acid may be selected according to production conditions, and details are not repeated herein.
The invention also discloses an alkaline cyanide-free electroplating zinc-nickel alloy plating solution containing the alkaline cyanide-free electroplating zinc-nickel alloy additive, wherein the electroplating solution contains 15 parts of zinc ions with the concentration of 20g/L, 20 parts of potassium hydroxide solution with the concentration of 130g/L, 80 parts of complexing agent with the concentration of 80ml/L, 21 parts of nickel additive with the concentration of 21ml/L, 7 parts of brightener with the concentration of 7ml/L and the balance of water.
The invention also discloses an electroplating method 40 of the alkaline cyanide-free electroplating zinc-nickel alloy plating solution, wherein the electroplating method 40 comprises the following steps:
s401: adding 250ml of water into a 500ml Hull cell, sequentially adding a predetermined amount of potassium hydroxide and zinc oxide, stirring and dissolving to form a main electrolyte liquid;
specifically, distilled water is added into the Hull cell until the liquid level reaches one half of the volume of the Hull cell, then 60g of potassium hydroxide and 20g of zinc oxide are sequentially added, and stirring is continuously carried out, so that heat generated when alkali liquor splashes into water is rapidly led out, the Hull cell is prevented from rapidly releasing heat, and the safety of operation is guaranteed. After the stirring operation, an electrolyte main liquid containing 120g/L potassium hydroxide and 8g/L zinc ions is formed, and the electrolyte main liquid provides an alkaline environment and zinc ions for the electrolysis operation so as to be beneficial to the continuous electrolysis operation.
S402: after the main liquid of the electrolyte is naturally cooled to below 30 ℃, 40ml of complexing agent, 10.5ml of nickel additive and 3.5ml of brightener are added into a Hull cell in sequence and stirred continuously to form a uniform mixed solution.
Specifically, 9.5ml of glycine of 50g/L, 11ml of diethylenetriamine of 240g/L, 11ml of polyethyleneimine of 300g/L and 8.5ml of diethanolamine of 200g/L are respectively mixed and prepared to form 40ml of complexing agent; mixing 1.25ml of 40g/L tetraethylenepentamine, 1ml of 130g/L reactant of hexamethylenetetramine and epichlorohydrin, 0.5ml of 100g/L aromatic aldehyde, 0.6ml of 50g/L nicotinic acid derivative and 0.15ml of 30g/L triethylene tetramine to prepare 3.5ml brightener; 6ml of nickel sulfamate of 420g/L, 2ml of diethanolamine of 60g/L, 1ml of N, N, N ', N' -tetrahydroxyethylethylenediamine of 80g/L and 1.5ml of a reaction product of triethylene tetramine and epichlorohydrin of 50g/L are mixed to form 10.5ml of nickel additive, and the nickel additive, the nickel sulfamate and the ethylene diamine are sequentially added into a hall tank while stirring is continuously carried out, so that a uniform mixed solution is formed in the hall tank.
S403: and continuously adding water into the Hull cell until the liquid level in the Hull cell reaches 80% of the volume of the Hull cell to form electrolyte.
S404: placing an iron sheet with the thickness of 20cmx6cm on an anode of a hall bath, and introducing 2A current into the hall bath at the temperature of 26 ℃ to continuously electroplate the iron sheet for 20min until a uniform coating is formed on the surface of the iron sheet, thereby completing the electroplating operation on the surface of the iron sheet.
The invention inspects the plating layers formed on the iron sheets in the electroplating operations of the embodiments 1 to 4, and the plating layers on the iron sheets in the electroplating operations of the embodiments have uniform and bright appearance and no visible defects, so that the alkaline zinc-nickel alloy additive can effectively improve the glossiness of the plating layers, thereby improving the quality of the plating layers.
The present invention examined the plating formed on the iron sheet in the electroplating operation of examples 1 to 4 using a Fischer X-ray system XDL230, and the following comparative tables were obtained:
the thickness of the coating and the nickel content in the table are respectively 4A/dm2、2A/dm2、0.5A/dm2The point measurements under three different current density conditions are shown in the table above, and the plating operation resulted in a plating layer of 4A/dm after the addition of the alkaline cyanide-free zinc-nickel alloy plating additive2And 0.5A/dm2The ratio of the point measurement values under the two conditions is stable, so that the alkaline zinc-nickel alloy additive has good dispersing capacity and high current efficiency, and can form a coating with stable nickel content in a wide current range.
The invention also tests the depth capability of the alkaline zinc-nickel alloy additives of examples 1 to 4, respectively. Specifically, a copper pipe with the inner diameter of 10mm and the length of 100mm is used as a test piece, in the plating process of the plating layer, the pipe hole of the copper pipe is vertically faced to the anode plate of the Hull cell, and the pipe opening of the copper pipe is 100mm away from the anode and is 2A/dm2Taking the copper tube out of the cathode after the cathode current density electroplating is carried out for 15 min. After the copper pipe is cleaned and dried, the copper pipe is cut along the axial direction of the copper pipe, and the plating depth of the pipe hole of the copper pipe is measured, so that the following comparison table is obtained:
as can be seen from the above table, when the distance between the plating layer and the pipe orifice of the copper pipe is 90mm, the plating layer can still be seen to be dipped at the pipe orifice, that is, the alkaline zinc-nickel alloy additive has better deep plating capability, thereby further improving the plating effect of the plating solution.
The corrosion resistance of the zinc-nickel alloy plating layers produced by the electroplating operations of examples 1 to 4 and the conventional alkali-zinc plating layers were respectively tested by the present invention, and the following comparative tables were obtained:
the above table shows that the gamma zinc-nickel alloy coating has higher polarization resistance and better corrosion resistance compared with the zinc coating, that is, the corrosion resistance of the coating formed by the alkaline zinc-nickel alloy additive is obviously improved, thereby improving the quality of the coating.
The neutral salt spray test was conducted on the zinc-nickel alloy plating layers produced by the plating operations of examples 1 to 4. Specifically, a square groove is adopted for plating, the thickness of a plating layer reaches 8.5 microns, after trivalent chromium blue-white passivation is carried out, the area, not covered by the plating layer, of the back surface of the test piece is coated, and a 5% neutral salt spray test is carried out. Through tests, the time for the zinc-nickel alloy coating to generate red rust is 1500 hours, while the time for the common zinc coating to generate red rust under the same conditions is about 120 hours, namely, the time for the zinc-nickel alloy coating to generate red rust is about 10 times longer than that of the common zinc coating, and the zinc-nickel alloy coating is more suitable for the requirement on the corrosion resistance of the coating.
The invention also tests the binding capacity of the zinc-nickel alloy coating, and concretely, 25 squares of 1mmx1mm are drawn on the test piece coating, and the small squares have no peeling and falling phenomena, thereby showing that the binding force of the zinc-nickel alloy coating and the iron sheet is good. And then, performing a bending test on the test piece, specifically, repeatedly bending the test piece until the test piece is broken, wherein the zinc-nickel alloy coating on the surface does not peel or fall off, thereby showing that the bonding force between the zinc-nickel alloy coating and the iron sheet is good. In addition, a thermal shock test is carried out on the test piece, specifically, the test piece is placed in a muffle furnace at 300 ℃ to be heated for 30min, then the test piece is taken out and put into water at room temperature, and the alloy coating on the surface of the test piece does not drop or bubble, so that the good binding force of the zinc-nickel alloy coating and the iron sheet is shown. Therefore, the alloy plating layer formed by the zinc-nickel alloy electroplating solution containing the zinc-nickel alloy additive has good bonding force with the steel substrate, and the quality of the plating layer is effectively improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The alkaline cyanide-free electroplating zinc-nickel alloy additive is characterized by comprising the following components in parts by mass: 50-80 parts of a complexing agent, wherein the complexing agent comprises hydroxycarboxylic acid, amines and polyamine compounds; 4-7 parts of a brightening agent, wherein the brightening agent comprises a brightening main agent, a nonionic surfactant and a whitening agent; and 12-21 parts of nickel additive.
2. The additive for alkaline cyanide-free electroplated zinc-nickel alloy as claimed in claim 1, wherein the hydroxycarboxylic acid is one or more of tartaric acid, citric acid, glycine, glycolic acid, gluconic acid, α -aminobutyric acid and thioglycolic acid.
3. The additive for alkaline cyanide-free electroplated zinc-nickel alloy as claimed in claim 1, wherein the amine is one or more of diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenetetramine and their derivatives.
4. The additive for alkaline cyanide-free electroplated zinc-nickel alloy as claimed in claim 1, wherein the polyamine compound is one or two of polyethyleneimine, polypropyleneamine, polybutyleneamine, N- (2-hydroxyethyl) -N, N ' -triethylethylenediamine, N ' -tetrahydroxyethylethylenediamine, and N, N ' -tetrahydroxyethylpropylenediamine.
5. The additive for alkaline cyanide-free electroplated zinc-nickel alloy as claimed in claim 1, wherein the brightening main agent is one of reactants of diethoxybutylene glycol ether, polyethyleneimine, pyridinium propanesulfonate, N-phenyl-3-carboxypyridinium chloride, trigonelline, coumarin, sodium propargylsulfonate, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and hexamethylenetetramine and epichlorohydrin.
6. The additive for alkaline cyanide-free electroplated zinc-nickel alloy as claimed in claim 1, characterized in that the nonionic surfactant is an active polyoxyalkylene compound.
7. The additive for alkaline cyanide-free electroplated zinc-nickel alloy as claimed in claim 1, wherein the brightener contains at least one aromatic aldehyde and at least one nicotinic acid derivative.
8. The additive for alkaline cyanide-free electroplated zinc-nickel alloy as claimed in claim 1, wherein the nickel additive is one or more of nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate and nickel methylsulfonate.
9. An alkaline cyanide-free zinc-nickel alloy electroplating bath comprising the alkaline cyanide-free zinc-nickel alloy electroplating additive according to any one of claims 1 to 8, wherein the bath comprises 12 to 15 parts of zinc ions with a concentration of 10 to 11g/L, 20 to 30 parts of alkaline solution with a concentration of 100 to 130g/L, 50 to 80 parts of complexing agent with a concentration of 50 to 80ml/L, 12 to 21 parts of nickel additive with a concentration of 12 to 21ml/L, and 4 to 7 parts of brightener with a concentration of 4 to 7ml/L, with the balance being water.
10. The alkaline cyanide-free electrogalvanizing zinc-nickel alloy electroplating bath according to claim 9, characterized in that the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution.
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| CN116288561A (en) * | 2023-02-01 | 2023-06-23 | 江苏苏大特种化学试剂有限公司 | Cyanide-free gold plating solution and method for electroplating gold by using same |
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