A kind of all-bright nickel additive and preparation method thereof

Abstract

The present invention relates to the technical field of C23C18 / 32, specifically to a full-bright nickel additive and a preparation method thereof. The additive comprises at least a brightener composition, a softener composition, an auxiliary composition, and a wetting agent. By introducing a formulated amount of the brightener composition into the system, the brightness and levelness of the nickel plating layer are effectively controlled. Even workpieces with deep recesses can be fully covered with a full plating layer, pinholes and blackening of the plating layer are avoided, and the additive meets the requirements of automotive parts, furniture, bathroom parts, electronic components, and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of C23C18 / 32, and in particular to a fully bright nickel additive and a preparation method thereof. Background Art

[0002] As a surface treatment technology, chemical plating has good public welfare and simple process equipment. It is suitable for parts with complex shapes or structures. Therefore, its application scope has gradually covered various fields of industrial production.

[0003] Currently, chemical nickel plating solutions are commercially available, but their stability is low, and the performance of the coating deteriorates with repeated use. A Chinese patent application (publication number CN110055522A) discloses an additive for chemical nickel plating solutions that improves the stability of the solution by introducing a high content of sodium glycolate, but this, to some extent, affects the surface gloss and smoothness of the nickel coating. A Chinese patent application (publication number CN100368595C) specifically discloses an additive for chemical nickel plating and its use. However, the additive incorporates thiourea as a stabilizer, resulting in poor corrosion resistance and the formation of pinholes in the resulting nickel coating. The resulting nickel coating also suffers from poor smoothness and decorative properties, failing to meet the requirements of automotive parts, furniture, bathroom components, electronic components, and the like. Summary of the Invention

[0004] In one aspect, the present invention provides a full-bright nickel additive, which at least comprises a brightener composition, a softener composition, an auxiliary agent composition, and a wetting agent.

[0005] As a preferred technical solution, the gloss agent composition comprises, by weight, at least 5-6 parts of hydrochloric acid, 100-150 parts of pyridinium propanesulfonate, 350-450 parts of water, 2.5-3 parts of sodium 2-ethylhexyl sulfate, 10-15 parts of 3-amino-3-methyl-1-butyne, 150-200 parts of sodium propenyl sulfonate, 100-110 parts of butynediol ethoxylate, 20-25 parts of propargyl alcohol, 50-60 parts of sodium propargyl sulfonate, and 0.1-0.3 parts of lithium chloride.

[0006] As a preferred technical solution, the hydrochloric acid is a hydrochloric acid aqueous solution with a mass concentration of 30-40%;

[0007] As a preferred technical solution, the 2-ethylhexyl sodium sulfate is a 2-ethylhexyl sodium sulfate aqueous solution with a mass concentration of 30-50%;

[0008] As a preferred technical solution, the sodium propylene sulfonate (ALS) is an aqueous solution of sodium propylene sulfonate with a mass concentration of 30-40%.

[0009] As a preferred technical solution, the sodium propargyl sulfonate (PS) is a sodium propargyl sulfonate aqueous solution with a mass concentration of 15-30%.

[0010] As a preferred technical solution, the lithium chloride is a 300-350 g / L lithium chloride aqueous solution.

[0011] The system of the present invention introduces a formulated amount of the brightener composition to effectively control the brightness and levelness of the nickel-plated layer. Even for workpieces with deep recesses, the brightener composition can provide a full coating, avoiding pinholes and blackening of the coating, thus meeting the requirements of automotive parts, furniture, bathroom parts, electronic components, and the like.

[0012] As a preferred technical solution, the softener composition comprises, by weight, at least 120-160 parts of saccharin sodium, 40-60 parts of sodium vinyl sulfonate, 0.1-0.3 parts of lithium chloride aqueous solution, and 1000 parts of water.

[0013] Preferably, the concentration of lithium chloride in the lithium chloride aqueous solution is 300-400 g / L.

[0014] Based on the system of the present invention, the introduction of propargyl alcohol in combination with other raw materials in the brightener composition ensures the bright and level properties of the nickel plating layer, but the brittleness of the nickel plating layer is correspondingly increased. During the research process, the inventors found that the introduction of a softener composition, particularly an aqueous solution containing a formulated amount of saccharin sodium, VS, and lithium chloride aqueous solution as a softener, effectively reduces the stress of the plating layer, increases the ductility of the plating layer, and improves the coverage ability of the nickel plating solution in the low current range.

[0015] As a preferred technical solution, the auxiliary agent composition comprises at least 600-700 parts by weight of sodium propylene sulfonate and 300-400 parts by weight of water.

[0016] As a preferred technical solution, the wetting agent is sodium lauryl sulfate and / or sodium dihexyl sulfosuccinate; preferably, the wetting agent is sodium dihexyl sulfosuccinate (MA-80).

[0017] As a preferred technical solution, the volume ratio of the brightener composition, softener composition, auxiliary agent composition, and wetting agent is (0.1-0.3): (7-13): (2-6): (1-2).

[0018] Based on the system of the present invention, by introducing and controlling the volume ratio of the brightener composition, softener composition, auxiliary agent composition and wetting agent in the all-bright nickel additive to be (0.1-0.3): (7-13): (2-6): (1-2), especially when the wetting agent is sodium dihexyl sulfosuccinate, the brightener composition, softener composition and auxiliary agent composition in the system are coordinated to reduce the surface tension of the plating solution, prevent the generation of pinholes, and ensure the corrosion resistance and flatness of the coating.

[0019] Another aspect of the present invention provides a method for using an all-bright nickel additive, comprising adding the all-bright nickel additive to a base nickel plating solution to obtain an electroless nickel plating solution, adding a component to be plated to the electroless nickel plating solution, and performing electroplating at 50-60° C., with a controlled voltage of 2-10 V, a cathode current density of 2-11 ASD, and an anode current density of less than 3.2 ASD.

[0020] As a preferred technical solution, the composition of the base nickel plating solution includes: 280-320g / L nickel sulfate, 50-60g / L nickel chloride, and 40-50g / L boric acid. Preferably, the pH value of the base nickel plating solution is 3.6-4.5.

[0021] As a preferred technical solution, the amount of the all-bright nickel additive added to the chemical nickel plating solution is 10-22 ml / L.

[0022] Beneficial effects

[0023] 1. The present invention provides a full-bright nickel additive. By introducing a formulated amount of a brightener composition into the system, the brightness and levelness of the nickel plating layer can be effectively controlled. Even for workpieces with deep recesses, a full plating layer can be provided to avoid pinholes and blackening of the plating layer, meeting the requirements of automotive parts, furniture, bathroom parts, electronic components, etc.

[0024] 2. The present invention introduces a softener composition, especially an aqueous solution containing a formulated amount of saccharin sodium, VS and lithium chloride aqueous solution as a softener, which effectively reduces the stress of the coating, increases the ductility of the coating, and improves the coverage ability of the nickel plating solution in the low current area.

[0025] 3. Based on the system of the present invention, by introducing and controlling the volume ratio of the brightener composition, softener composition, auxiliary agent composition and wetting agent in the all-bright nickel additive to be (0.1-0.3): (7-13): (2-6): (1-2), especially when the wetting agent is sodium dihexyl sulfosuccinate, the brightener composition, softener composition and auxiliary agent composition in the system are combined to reduce the surface tension of the plating solution, prevent the generation of pinholes, and ensure the corrosion resistance and flatness of the coating. DETAILED DESCRIPTION

[0026] Example 1

[0027] In one aspect, embodiment 1 of the present invention provides a full-bright nickel additive, comprising a brightener composition, a softener composition, an auxiliary agent composition, and a wetting agent.

[0028] The gloss agent composition comprises, by weight, 5.5 parts of hydrochloric acid, 120 parts of pyridinium propanesulfonate, 400 parts of water, 2.71 parts of sodium 2-ethylhexyl sulfate, 11.59 parts of 3-amino-3-methyl-1-butyne, 164.5 parts of sodium propenyl sulfonate, 105.27 parts of butynediol ethoxylate, 21.1 parts of propargyl alcohol, 52.09 parts of sodium propargyl sulfonate, and 0.2 parts of lithium chloride.

[0029] The hydrochloric acid is a hydrochloric acid aqueous solution with a mass concentration of 36%;

[0030] The 2-ethylhexyl sodium sulfate is a 2-ethylhexyl sodium sulfate aqueous solution with a mass concentration of 40%;

[0031] The sodium propylene sulfonate (ALS) is an aqueous solution of sodium propylene sulfonate with a mass concentration of 35%.

[0032] The sodium propargyl sulfonate (PS) is a sodium propargyl sulfonate aqueous solution with a mass concentration of 20%.

[0033] The lithium chloride is a 340 g / L lithium chloride aqueous solution.

[0034] The softener composition comprises, by weight, 150 parts of saccharin sodium, 50 parts of sodium vinyl sulfonate, 0.2 parts of lithium chloride aqueous solution, and 1000 parts of water.

[0035] The concentration of lithium chloride in the lithium chloride aqueous solution is 340 g / L.

[0036] The auxiliary agent composition comprises, by weight, 654.3 parts of sodium propylene sulfonate and 345.7 parts of water.

[0037] The wetting agent is sodium dihexyl sulfosuccinate (MA-80).

[0038] The volume ratio of the brightener composition, the softener composition, the auxiliary agent composition and the wetting agent is 0.2:10:4:1.5.

[0039] On the other hand, Example 1 of the present invention provides a method for using an all-bright nickel additive, adding the all-bright nickel additive to a base nickel plating solution to obtain a chemical nickel plating solution, adding the component to be plated to the chemical nickel plating solution, and electroplating is carried out at 55°C, with a control voltage of 5V, a cathode current density of 5ASD, and an anode current density of 2.8ASD.

[0040] The element to be plated is a steel plate of 10 cm×10 cm, the electroplating time is 30 min, and the number of electroplating layers is 5.

[0041] The nickel-plating solution comprises 300 g / L nickel sulfate, 55 g / L nickel chloride, and 45 g / L boric acid. The pH value of the nickel-plating solution is 4.2.

[0042] The amount of the all-bright nickel additive added to the chemical nickel plating solution is 15.7 ml / L.

[0043] Example 2

[0044] Example 2 of the present invention provides a full-bright nickel additive, including a brightener composition, a softener composition, an auxiliary agent composition, and a wetting agent.

[0045] The gloss agent composition comprises, by weight, 6 parts of hydrochloric acid, 130 parts of pyridinium propanesulfonate, 450 parts of water, 3 parts of sodium 2-ethylhexyl sulfate, 15 parts of 3-amino-3-methyl-1-butyne, 170 parts of sodium propenyl sulfonate, 120 parts of butynediol ethoxylate, 25 parts of propargyl alcohol, 55 parts of sodium propargyl sulfonate, and 0.3 parts of lithium chloride.

[0046] The hydrochloric acid is a hydrochloric acid aqueous solution with a mass concentration of 36%;

[0047] The 2-ethylhexyl sodium sulfate is a 2-ethylhexyl sodium sulfate aqueous solution with a mass concentration of 40%;

[0048] The sodium propylene sulfonate (ALS) is an aqueous solution of sodium propylene sulfonate with a mass concentration of 35%.

[0049] The sodium propargyl sulfonate (PS) is a sodium propargyl sulfonate aqueous solution with a mass concentration of 20%.

[0050] The lithium chloride is a 340 g / L lithium chloride aqueous solution.

[0051] The softener composition comprises, by weight, 160 parts of saccharin sodium, 60 parts of sodium vinyl sulfonate, 0.3 parts of lithium chloride aqueous solution, and 1000 parts of water.

[0052] The concentration of lithium chloride in the lithium chloride aqueous solution is 340 g / L.

[0053] The auxiliary agent composition comprises 700 parts of sodium propylene sulfonate and 300 parts of water in parts by weight.

[0054] The wetting agent is sodium dihexyl sulfosuccinate (MA-80).

[0055] The volume ratio of the brightener composition, the softener composition, the auxiliary agent composition and the wetting agent is 0.2:10:4:1.5.

[0056] On the other hand, Example 2 of the present invention provides a method for using an all-bright nickel additive, adding the all-bright nickel additive to a base nickel plating solution to obtain a chemical nickel plating solution, adding the component to be plated to the chemical nickel plating solution, and electroplating is carried out at 55°C, with a control voltage of 5V, a cathode current density of 5ASD, and an anode current density of 2.8ASD.

[0057] The element to be plated is a steel plate of 10 cm×10 cm, the electroplating time is 30 min, and the number of electroplating layers is 5.

[0058] The nickel-plating solution comprises 300 g / L nickel sulfate, 55 g / L nickel chloride, and 45 g / L boric acid. The pH value of the nickel-plating solution is 4.2.

[0059] The amount of the all-bright nickel additive added to the chemical nickel plating solution is 15.7 ml / L.

[0060] Example 3

[0061] Example 3 of the present invention provides a full-bright nickel additive, including a brightener composition, a softener composition, an auxiliary agent composition, and a wetting agent.

[0062] The gloss agent composition comprises, by weight, 5 parts of hydrochloric acid, 100 parts of pyridinium propanesulfonate, 350 parts of water, 2.5 parts of sodium 2-ethylhexyl sulfate, 10 parts of 3-amino-3-methyl-1-butyne, 150 parts of sodium propenyl sulfonate, 100 parts of butynediol ethoxylate, 20 parts of propargyl alcohol, 50 parts of sodium propargyl sulfonate, and 0.1 part of lithium chloride.

[0063] The hydrochloric acid is a hydrochloric acid aqueous solution with a mass concentration of 36%;

[0064] The 2-ethylhexyl sodium sulfate is a 2-ethylhexyl sodium sulfate aqueous solution with a mass concentration of 40%;

[0065] The sodium propylene sulfonate (ALS) is an aqueous solution of sodium propylene sulfonate with a mass concentration of 35%.

[0066] The sodium propargyl sulfonate (PS) is a sodium propargyl sulfonate aqueous solution with a mass concentration of 20%.

[0067] The lithium chloride is a 340 g / L lithium chloride aqueous solution.

[0068] The softener composition comprises, by weight, 120 parts of saccharin sodium, 40 parts of sodium vinyl sulfonate, 0.1 parts of lithium chloride aqueous solution, and 1000 parts of water.

[0069] The concentration of lithium chloride in the lithium chloride aqueous solution is 340 g / L.

[0070] The auxiliary agent composition comprises, by weight, 600 parts of sodium propylene sulfonate and 400 parts of water.

[0071] The wetting agent is sodium dihexyl sulfosuccinate (MA-80).

[0072] The volume ratio of the brightener composition, the softener composition, the auxiliary agent composition and the wetting agent is 0.2:10:4:1.5.

[0073] On the other hand, Example 3 of the present invention provides a method for using an all-bright nickel additive, adding the all-bright nickel additive to a base nickel plating solution to obtain a chemical nickel plating solution, adding the component to be plated to the chemical nickel plating solution, and electroplating is carried out at 55°C, with a control voltage of 5V, a cathode current density of 5ASD, and an anode current density of 2.8ASD.

[0074] The element to be plated is a steel plate of 10 cm×10 cm, the electroplating time is 30 min, and the number of electroplating layers is 5.

[0075] The nickel-plating solution comprises 300 g / L nickel sulfate, 55 g / L nickel chloride, and 45 g / L boric acid. The pH value of the nickel-plating solution is 4.2.

[0076] The amount of the all-bright nickel additive added to the chemical nickel plating solution is 15.7 ml / L.

[0077] Comparative Example 1

[0078] Comparative Example 1 of the present invention provides a full-bright nickel additive, including a brightener composition, an auxiliary agent composition, and a wetting agent.

[0079] The gloss agent composition comprises, by weight, 5 parts of hydrochloric acid, 100 parts of pyridinium propanesulfonate, 350 parts of water, 2.5 parts of sodium 2-ethylhexyl sulfate, 10 parts of 3-amino-3-methyl-1-butyne, 150 parts of sodium propenyl sulfonate, 100 parts of butynediol ethoxylate, 20 parts of propargyl alcohol, 50 parts of sodium propargyl sulfonate, and 0.1 part of lithium chloride.

[0080] The hydrochloric acid is a hydrochloric acid aqueous solution with a mass concentration of 36%;

[0081] The 2-ethylhexyl sodium sulfate is a 2-ethylhexyl sodium sulfate aqueous solution with a mass concentration of 40%;

[0082] The sodium propylene sulfonate (ALS) is an aqueous solution of sodium propylene sulfonate with a mass concentration of 35%.

[0083] The sodium propargyl sulfonate (PS) is a sodium propargyl sulfonate aqueous solution with a mass concentration of 20%.

[0084] The lithium chloride is a 340 g / L lithium chloride aqueous solution.

[0085] The concentration of lithium chloride in the lithium chloride aqueous solution is 340 g / L.

[0086] The auxiliary agent composition comprises, by weight, 600 parts of sodium propylene sulfonate and 400 parts of water.

[0087] The wetting agent is sodium dihexyl sulfosuccinate (MA-80).

[0088] The volume ratio of the gloss agent composition, the auxiliary agent composition and the wetting agent is 0.2:4:1.5.

[0089] On the other hand, Comparative Example 1 of the present invention provides a method for using an all-bright nickel additive, adding the all-bright nickel additive to a base nickel plating solution to obtain a chemical nickel plating solution, adding the component to be plated into the chemical nickel plating solution, and electroplating is carried out at 55°C, with a control voltage of 5V, a cathode current density of 5ASD, and an anode current density of 2.8ASD.

[0090] The element to be plated is a steel plate of 10 cm×10 cm, the electroplating time is 30 min, and the number of electroplating layers is 5.

[0091] The nickel-plating solution comprises 300 g / L nickel sulfate, 55 g / L nickel chloride, and 45 g / L boric acid. The pH value of the nickel-plating solution is 4.2.

[0092] The amount of the all-bright nickel additive added to the chemical nickel plating solution is 5.7 ml / L.

[0093] Comparative Example 2

[0094] Comparative Example 2 of the present invention provides a fully bright nickel additive and a preparation method thereof, and its specific implementation manner is the same as that of Example 1, except that the wetting agent is sodium lauryl sulfate.

[0095] Comparative Example 3

[0096] Comparative Example 3 of the present invention provides a fully bright nickel additive and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that the brightener composition is replaced by ceric sulfate.

[0097] Performance testing methods

[0098] 1. The plated parts provided in the examples and comparative examples were placed in a 0.5 M NaCl solution to test the corrosion rates of the plated parts. The results are shown in Table 1.

[0099] 2. Evaluate the appearance of the plated parts. If the plated parts have a mirror gloss, good flatness and no blackening on the surface, the appearance evaluation of the plated parts is recorded as "qualified". If the plated parts do not have a mirror gloss or poor flatness or the surface is blackened, the gloss of the plated parts is recorded as "unqualified".

[0100] Table 1

[0101]

Claims

1. A bright nickel additive, characterized in that: The invention comprises at least a glossing agent composition, a softening agent composition, an auxiliary agent composition, and a wetting agent; the glossing agent composition comprises, by weight, at least 5-6 parts of hydrochloric acid, 100-150 parts of pyridinium propanesulfonate, 350-450 parts of water, 2.5-3 parts of sodium 2-ethylhexyl sulfate, 10-15 parts of 3-amino-3-methyl-1-butyne, 150-200 parts of sodium propenylsulfonate, 100-110 parts of butynediol ethoxylate, 20-25 parts of propargyl alcohol, 50-60 parts of sodium propargylsulfonate, and 0.1-0.3 parts of lithium chloride. The wetting agent is sodium dihexyl sulfosuccinate; the softener composition, calculated by weight, comprises at least 120-160 parts of sodium saccharin, 40-60 parts of sodium vinyl sulfonate, 0.1-0.3 parts of lithium chloride aqueous solution, and 1000 parts of water; the volume ratio of the glossing agent composition, the softening agent composition, the auxiliary agent composition, and the wetting agent is (0.1-0.3): (7-13): (2-6): (1-2); the auxiliary agent composition, calculated by weight, comprises at least 600-700 parts of sodium propylene sulfonate and 300-400 parts of water.

2. A method for using the all-bright nickel additive according to claim 1, characterized in that: A full-bright nickel additive is added to a base nickel plating solution to obtain a chemical nickel plating solution. The component to be plated is added to the chemical nickel plating solution. Electroplating is carried out at 50-60°C, with a controlled voltage of 2-10V, a cathode current density of 2-11ASD, and an anode current density of less than 3.2ASD.

3. The method for using the all-bright nickel additive according to claim 2, wherein: The components of the base nickel plating solution include: 280-320 g / L of nickel sulfate, 50-60 g / L of nickel chloride, and 40-50 g / L of boric acid.

4. The method for using the all-bright nickel additive according to claim 2, wherein: The pH value of the base nickel plating solution is 3.6-4.

5.

5. The method for using the all-bright nickel additive according to claim 2, wherein: The amount of the all-bright nickel additive added to the chemical nickel plating solution is 10-22 ml / L.

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