KR101261454B1 - Phosphorus-free electroless nickel plating solution and nickle-alloy plating solution and electroless plating method using the same - Google Patents
Phosphorus-free electroless nickel plating solution and nickle-alloy plating solution and electroless plating method using the same Download PDFInfo
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Abstract
The present invention relates to an electroless nickel plating solution of an unmanned type, and an electroless plating method using the same, which is environmentally friendly because it does not contain a phosphorus component, and is resistant to corrosion, chemical resistance, hardness, and wear resistance on the surface of various materials such as iron, nonferrous metals, and plastics. There is an effect of forming this excellent plating film.
Description
The present invention relates to a nickel plating solution, and in particular, does not contain a phosphorus component can reduce the cost of wastewater treatment and can be operated at ambient temperature or slightly higher atmosphere electroless nickel plating solution that can suppress the generation of fume gas and this It relates to the electroless plating method used.
Nickel plating solution according to the present invention can form a plating film excellent in corrosion resistance, chemical resistance, hardness, abrasion resistance, etc. on the surface of the material, since it does not contain a phosphorus component can suppress the occurrence of costs for wastewater treatment of phosphorus and conventional Because it can be used at lower temperature than the plating operation of, it suppresses the generation of fume gas and enables eco-friendly plating operation.
Plating means to finish by coating a metal or nonmetal surface with a thin metal film. This plating is performed for the purpose of giving corrosion resistance, beauty as a decoration, mechanical strength, etc. to a product.
Electroless plating is a method in which metal ions in an aqueous metal salt solution are self-catalytically reduced by the force of a reducing agent without receiving electrical energy from the outside, thereby depositing, ie, plating metal on the surface of the workpiece.
Generally, metals used for electroless plating include copper, nickel, cobalt, cadmium, gold, silver, palladium, platinum, and chromium. Among these metals, nickel has extremely high chemical and mechanical properties, and thus electroless plating It is most developed and used on site.
Although chromium plating is widely used as decorative plating, chromic anhydride, which is a raw material, is not only a compound of hexavalent chromium but also addictive, and thus, a plating method capable of replacing it is required.
Copper plating is used for alkaline plating together with toxic substances containing cyan, which has a great effect on air, water and workers. Acidic copper plating solution is mainly used for the purpose of gloss, and because it is used together with strong sulfuric acid, the effect of acidic gas is threatening the health of facilities and workers and causing peripheral devices to corrode.
Tungsten has excellent corrosion resistance and heat resistance, so it is an excellent material as a plating material, but because it has a very high strength, it must exist in powder form. Therefore, when tungsten is used for surface treatment, tungsten itself does not form a plating film on the surface of the material. can not do it. Therefore, in the case of tungsten plating, there is a problem of activating the surface of the base metal with nickel strike or requiring a pretreatment process such as electroless nickel plating in order to improve plating adhesion and wear resistance.
Electrolytic nickel plating has generally been widely used as a coating material for gloss and decoration, and is a metal material that has many possibilities in the future. The plating of mechanical parts takes up a large proportion with hard hexavalent chromium plating, but the use of electricity makes the plating thicker as it is sharp or closer to the plate, and thinner as it is far away. Could not. In addition, when the exhaust system is not good, the working environment is filled with fume gas, the workers who work in such a working environment was exposed to occupational diseases.
Since most of the conventional electroless nickel plating uses sodium hypophosphite as a reducing agent, it is necessary to treat the phosphorus (P) component during wastewater treatment. Phosphorus component is difficult to treat the wastewater by neutralization and high temperature incineration treatment, so the conventional electroless nickel plating has a problem of increased cost for wastewater treatment.
In addition, the conventional electroless nickel plating is carried out at a temperature of 83 ~ 93 ℃ or more, which is much higher than the ambient temperature, the evaporation of the plating solution is actively generated to generate a large amount of fume gas (fume gas), thereby causing There is also a problem of a large loss of plating solution.
In particular, fume gas is an oxide gas that is much smaller in size than the dust generated by the vaporization of metal with oxygen in the air, and is a major factor that impairs the working environment in the plating industry.
Meanwhile, in the conventional electroless plating method, as a method for improving the corrosion resistance of a plated material, a method of improving corrosion by forming an oxide film on the surface by high temperature heat treatment, and depositing it in a nitric acid or sulfuric acid solution for a predetermined time and passivating it on the surface Although there exist a method of forming a film, these have a problem that the film is thin and the passivation film is often broken, and the problem about corrosion in a chlorine system and a fluorine system environment is not solved.
The present invention has been made to solve the above problems, and an object thereof is to provide a phosphorus free electroless nickel plating solution which is easy to treat wastewater.
Another object of the present invention is to provide an unmanned electroless nickel plating solution capable of minimizing the generation of fume gas.
It is still another object of the present invention to provide an unmanned electroless nickel plating solution capable of meeting the demand for corrosion resistance, heat resistance and wear resistance.
It is another object of the present invention to provide an electroless nickel plating solution prepared by adding various other platingable metal compounds to the nickel plating solution.
Another object of the present invention is to provide an electroless plating method using an electroless nickel plating solution of an unmanned type.
Other objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and preferred embodiments in conjunction with the accompanying drawings.
The unmanned electroless nickel plating solution of the present invention for achieving the above object is characterized in that it contains nickel salt, dimethylamine borane and boric acid as the reducing agent, ammonium acetate as the complexing agent, sodium citrate as the stabilizer.
Here, the unmanned electroless nickel plating solution according to the present invention preferably further comprises at least one metal salt selected from the group consisting of tungsten salt, molybdenum salt, titanium salt, zirconium salt, cobalt salt, zinc salt. Do.
Electroless plating method for achieving another object of the present invention is characterized in that it comprises the step of plating on the workpiece using the electroless nickel plating solution of the unmanned type.
The electroless nickel plating solution of the unmanned type according to the present invention
1) Since no sodium phosphorous hypophosphite used as a reducing agent is used in conventional electroless nickel plating solution, the cost of wastewater treatment can be greatly reduced.
2) The plating process can be performed at much lower temperature than the conventional electroless nickel plating solution, so that the generation of fume gas can be minimized, thereby reducing the production cost and improving the working environment.
3) By achieving a high precipitation rate (about 36 microns per hour) compared to the precipitation rate (about 10 to 14 microns per hour) of conventional electroless nickel plating solutions, energy consumption can be reduced and production efficiency can be improved.
4) various kinds of plating films can be easily formed by adding various other metal salt compounds to the prepared electroless nickel plating solution to prepare a nickel-metal alloy plating solution; and
5) It has the effect of forming a plating film having excellent corrosion resistance, chemical resistance, hardness, and abrasion resistance on the surface of various materials such as iron, nonferrous metal, and plastic.
1 shows a plating apparatus suitable for the plating method according to the present invention.
Hereinafter, an unmanned electroless nickel plating solution and an electroless plating method using the same according to the present invention will be described in detail with reference to the accompanying drawings.
In the unattended electroless nickel plating solution of the present invention, 'unmanned' means phosphorus free, and basically includes a nickel salt, a reducing agent, a complexing agent, and a stabilizing agent, and optionally a surfactant. It may also include.
Nickel sulfate (NiSO 4 ) or nickel ammonium sulfate (NH 4 ) 2 Ni (SO 4 ) 2 is used as the nickel salt in the unattended electroless nickel plating solution of the present invention. Here, the nickel sulfate is preferably contained in a concentration of 10 ~ 55g / l, the nickel ammonium sulfate in a concentration of 0.1 ~ 7g / l based on 1 liter of the plating solution.
These nickel salts may be used alone or in combination in the above concentration ranges, but mixing may be performed in order to reduce adhesion to the plating tank when plating is repeatedly performed continuously during the plating process. More preferred.
If the concentration of nickel sulfate is less than 10 g / l, the desired plating is possible, but the metal salt replenishment cycle for replenishing the amount of nickel metal consumed becomes too frequent. If the concentration of the nickel sulfate exceeds 55 g / l, the metal salt replenishment period becomes longer and complexes with the reducing agent. First, it is not preferable because the coordination with the stabilizers is broken, resulting in rough plating or weak plating.
On the other hand, if the concentration of nickel ammonium sulfate is less than 0.1g / ℓ, the compatibility with nickel sulfate is broken, and the tendency to precipitate in the plating tank is increased, and when the concentration of nickel ammonium exceeds 5g / ℓ 1) The pH of the plating solution increases as the plating proceeds. 2) nickel ammonium sulphate is expensive and unfavorable.
The reducing agent is for reducing nickel ions, and it is preferable to use dimethylamine borane ((CH 3 ) 2 NHBH 3 ) and boric acid (H 3 BO 3 ) simultaneously.
Dimethylamine borane and boric acid is a boron compound, while a certain amount of boron precipitates together in the metal deposited during plating, thereby increasing the plating speed and increasing adhesion and hardness corrosion resistance. This can be said to include a phosphorus component such as sodium hypophosphite in the conventional electroless nickel plating solution, it is possible to solve various problems caused by the precipitation of phosphorus together in the plating process.
1 to 12 g / l of dimethylamine borane and 7 to 40 g / l of boric acid are used as the reducing agent. When the concentration of the dimethylamine borane is less than 1 g / l, the reducing power as a reducing agent is weak and the plating rate is also slowed. If it exceeds, the reducing power becomes excessive and the tendency to precipitate in the plating tank becomes stronger, and the adhesion strength and hardness, which are considered to be incompatible with the content of nickel metal and boron to be plated, are not preferable.
Boric acid is essentially a reducing agent, but is used because boron of dimethylamine borane is precipitated and consumed together with a metal salt in the process of nickel plating, and thus plays a stable role as well as a function of controlling the boron consumed. If the concentration of boric acid is less than 7g / ℓ the plating rate is slow and the adhesion is weak. On the other hand, when the concentration of boric acid exceeds 40g / ℓ it is not preferable because there is a problem that the plating reaction is excessively accelerated to generate a rough plating surface, the hardness is weakened, the life of the liquid is also shortened.
The complexing agent controls the plating rate and prevents spontaneous decomposition of the plating. In the nickel plating solution according to the present invention, ammonium acetate (CH 3 COONH 4 ) is 5 to 17 g based on 1 liter of nickel plating solution as the complexing agent. It is preferably included at a concentration of / l. If the concentration of the complexing agent is less than 5 g / l and is too weak, the amount of nickel ions that are not complexed increases and plating becomes ineffective. On the other hand, if the concentration of the complexing agent exceeds 17 g / l and becomes too thick, the stability of the plating liquid increases but the plating rate decreases.
In the nickel plating solution according to the present invention, it is preferable to include sodium citrate (C 6 H 7 NaO 7 ) at 2 to 24 g / L as a stabilizer. The stabilizer is to serve to stabilize the nickel plating solution according to the present invention and to adjust the pH. As such, the unmanned nickel plating solution according to the present invention does not need to include a separate pH adjusting agent by including sodium citrate.
In the nickel plating solution according to the present invention, when the concentration of the stabilizer is less than 2 g / l, the plating solution becomes weakly acidic and the stabilization becomes weak, thereby preventing the plating color from being beautiful by more than necessary reactions. On the other hand, if the concentration of the stabilizer exceeds 24g / ℓ too thick, the plating reaction becomes unstable, the color of the color appears to fade, adhesion and hardness is not preferred because it is weak.
In the nickel plating solution according to the present invention, a nonionic or amphoteric surfactant may be used as the surfactant. These surfactants are intended to give a leveling effect to the plated layer as well as to level the surface to be plated. Such a surfactant is preferably included at a concentration of 0.01 ~ 0.15g / L.
In addition to the nickel salt, the reducing agent, the stabilizer and the complexing agent, the unattended type electroless nickel plating solution of the present invention may further include additives such as a brightening agent as necessary.
Meanwhile, various kinds of metal salts may be added to the electroless nickel plating solution according to the present invention. Such metal salts are selected from the group consisting of tungsten salts, molybdenum salts, titanium salts, zirconium salts, cobalt salts, zinc salts, and are preferably contained at 1.5 to 12 g / l based on 1 liter of nickel plating solution.
As one kind of metal salt, tungsten salt may use sodium tungsten or ammonium tungstate.
As a kind of metal salt, molybdenum salt may use sodium molybdate or ammonium molybdate.
As a kind of metal salt, titanium salt may use titanium sulfate or titanium chloride.
As a kind of metal salt, zirconium salt can use zirconium sulfate or zirconium chloride.
As a kind of metal salt, cobalt salt can use cobalt sulfate or cobalt chloride.
As a kind of metal salt, zinc salt may use zinc sulfate, zinc chloride or zinc oxide.
As described above, according to the present invention, an electroless nickel-metal alloy plating solution is prepared by adding various metal salts to an unmanned electroless nickel plating solution, so that the plating film can be easily formed according to the application even without a separate bathing process or a ground process. To form.
On the other hand, the present invention provides an electroless plating method comprising the step of plating on the workpiece using the electroless nickel plating solution or nickel-metal alloy plating solution of the unmanned type. Hereinafter, the electroless plating method according to the present invention will be described in detail.
In the electroless plating method according to the present invention, the plating proceeds at a temperature of 27 to 60 ° C, preferably at a temperature of 30 to 53 ° C. In this temperature range, plating speed and adhesion are very excellent.
In the electroless plating method according to the present invention, the plating is performed at a pH between 7 ± 0.5, in a neutral ph atmosphere.
Electroless plating method according to the present invention is 1) degreasing process, 2) rust or smut (soot) removal process, 3) activation treatment process, 4) unattended electroless nickel plating or unattended electroless nickel-tungsten plating process, 5 A) trivalent chromate treatment step, 6) water repellent treatment step, 7) drying and packing step, and the like.
1) Degreasing process
The coating to be plated is coated with various types of fats and oils through various processing steps prior to the plating process. To maintain a smooth plating, such oils and fats must be removed first. In the plating method according to the present invention, the degreasing liquid used to remove the fat or oil is changed depending on the kind of material.
For iron products, degreasing treatment using strong alkaline degreasing agent is preferred. Strong alkaline degreasing agents are generally widely used because of their excellent saponification to oils and fats. However, if the material to be plated is not an iron product but a non-ferrous product such as copper or aluminum or a composite material such as plastic, there is a high possibility that the deformation or discoloration of the material is caused by the application of a strong alkaline degreasing agent. So at this time apply a weak alkaline degreasing agent.
In the form of degreasing, there is a method by ultrasonic cleaning, a method by electrolytic degreasing, or a method by electrolysis degreasing with PR alternate, and the like, and a degreasing method of a mixture of the above methods is also preferable.
2) Rust or Smut Removal Process
Under various oxidation conditions, the coating to be plated may be rusted, and smut may also occur. These rusts and smuts are factors that adversely affect the adhesion of the plating and should be removed thoroughly. In the plating method according to the present invention, rust and smut are treated by ultrasonic and PR alternating electrolytic apparatus.
3) Electrolytic or chemical polishing
In the plating method according to the present invention, the chemicals themselves are used to give gloss to the coated object.
However, in order to meet customer requirements such as product or hardness considering the uniform surface roughness of the product, electrolytic polishing or chemical polishing treatment should be carried out. I decided not to hit.
4) Activation Treatment Process
Even after degreasing, rust, and smut removal have been completed, activation is required according to the inherent properties of each metal. In order to ensure that the coating on the coating having a metallic property such as hydrogen embrittlement or ductility and malleability by hydrogen, the activation treatment should be performed. In general, the hydrochloric acid aqueous solution is activated by dipping for about 30 seconds to 5 minutes. However, this method causes the plating film to crack or crack due to hydrogen embrittlement.
Therefore, in the plating method according to the present invention, the addition of an aqueous hydrochloric acid solution (30% solution) and fluoride was performed by immersion for 30 seconds to 10 minutes at room temperature as an activation treatment solution.
5) Unattended Electroless Nickel or Unattended Electroless Nickel-Metal Alloy Plating Process
The tank for unmanned type electroless nickel or unmanned type electroless nickel-metal plating may be made of PE or PP material.However, if the tank design is made of a non-conductor material, the liquid ages and precipitates due to reducing power in the plating tank. There can be no phenomenon. Therefore, in the present invention, in order to prevent the precipitation phenomenon to be deposited in the tank, by preventing the precipitation phenomenon in the plating tank by sending a weak current as shown in FIG.
1 shows the configuration of a plating apparatus suitable for the plating method according to the present invention. The apparatus shown in FIG. 1 includes a
The reason why the steel sheet subjected to the passivation treatment after electrolytic polishing treatment to the stainless steel 316L material in the
6) trivalent chromate treatment
Chromium Sulfate or Chromium Chloride: 15g / l, Citric Acid: 15 ~ 75g / l, Temperature: Room temperature
This process is a process for the purpose of making the plated metal coating film more dense and improving hardness and corrosion resistance. Unmanned electroless nickel plating or unmanned electroless nickel-tungsten plating is performed and then washed with water to reach this process. Conventionally, chromate treatment with hexavalent chromium has been pessimistic in hexavalent chromium detection with respect to the environment and RoHS regulation by heavy metal hexavalent chromium.
Accordingly, the present invention is a process suitable for the purpose of the invention for the purpose of environment-friendly as well as the invention of the unmanned type electroless nickel plating solution and the unmanned type electroless nickel-tungsten plating solution.
Trivalent chromium, unlike hexavalent chromium, does not fall under RoHS and does not fall under the classification of odors or heavy metals. According to the present invention, the advantages of trivalent chromium can be replaced with hexavalent chromium with the same performance as hexavalent chromium.
7) water repellent treatment
In this process, the coated object is washed with water and trivalent chromate to be washed and washed with water to dry it.When the temperature of the bath is 80 ° C, a lot of water vapor is generated. Since oxidation becomes more active at higher temperatures, the present invention adopts a process of treating with water cutting agent in order to increase the evaporation efficiency at a relatively low temperature by appropriately diluting water cutting agent. Water cutting agents are not limited as long as they are generally used in the art.
8) drying and packing
As a final process in the plating method which concerns on this invention, an air blower system is applied. This is a role to shake off the remaining water after the water repellent treatment process is rolled into a drop of water particles. The process for the invention is then finished with packaging.
Hereinafter will be described in more detail on the basis of the embodiments illustrated plating plating according to the present invention. However, the present invention is not limited to the illustrated embodiments or the examples. In addition, the following examples only illustrate the results for a specific compound, it will be apparent to those skilled in the art that even when these equivalents are used, similarly similar effects are shown.
≪ Example 1 >
Activate the surface of the coating material by depositing it for 30 seconds to 10 minutes at room temperature with an activated treatment solution in which hydrochloric acid solution (30% solution) and fluoride are added. I was.
A nickel plating solution containing 30 g / l of nickel sulfate, 3 g / l of nickel ammonium sulfate, 24 g / l of boric acid, 10 g / l of ammonium acetate, 16 g / l of sodium citrate, and 7 g / l of dimethylamine borane was prepared on a 1 liter basis. Plating was performed under the same plating conditions. The final electroless plated coating was then obtained through trivalent chromate treatment, water repellent treatment, and the like.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 32 microns / hour
As shown in the plating results of Example 1, when boric acid and dimethylamine borane are simultaneously used as the reducing agent, the state of metal precipitation is the most dense (this is due to the plating thickness being bright and the salt spray test depends on the plating thickness. It can be judged to endure for a long time without discoloration.) The speed is fast and stable.
≪ Comparative Example 1 &
Nickel Sulfate 30g / l, Nickel Ammonium Sulfate 3g / l, Citric Acid 24g / l, Ammonium Acetate 10g / l
Plating was carried out in the same manner as in Example 1, except that 16 g / l sodium citrate and 7 g / l dimethylamine borane were mixed to prepare a plating solution.
Plating conditions: temperature 30-53 degrees, pH 4.2 ± 0.5, plating rate 1.2 microns / hour
In Comparative Example 1, citric acid, which is generally applied in an in-type electroless nickel plating solution without boric acid, was added. Since the temperature is the same but the pH is significantly lowered to 4.2 ± 0.5, which is an acidic region, it is considerably seen in the environment-friendly region of the neutral concept. It was low, the plating rate was too slow, and the coating was also rough.
Comparative Example 2
The above procedure was carried out except that 30 g / l nickel sulfate, 3 g / l nickel ammonium sulfate, 24 g / l malic acid, 10 g / l ammonium acetate, 16 g / l sodium citrate, and 7 g / l dimethylamine borane were mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1. In Comparative Example 2, the pH was higher than that of citric acid, and plating was performed using maleic acid (apple acid), which is a complexing agent used in high-quality plating.
Plating conditions: temperature 30-53 degrees, pH 5.8 ± 0.5, plating rate 5.7 micron / hour
From the above results, it can be seen that the pH of the plating solution is increased by about 1.6 ± 0.5 from 5.8 ± 0.5 to 4.2 ± 0.5 of citric acid. In addition, it can be seen that the plating rate is also much improved at a speed of 5.7 microns per hour, but it is insufficient to the desired level of the present invention.
≪ Comparative Example 3 &
Except that 30 g / l nickel sulfate, 3 g / l nickel ammonium sulfate, 24 g / l succinic acid, 10 g / l ammonium acetate, 16 g / l sodium citrate, and 7 g / l dimethylamine borane were mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1. In Comparative Example 3, succinic acid having a slightly higher pH than malic acid was used as a complexing agent, and succinic acid is a substance having excellent complexing performance with nickel ammonium sulfate and relatively weak pH.
Plating conditions: temperature 30-53 degrees, pH 6.2 ± 0.5, plating rate 4.7 micron / hour
As can be seen from Comparative Example 3, the pH of the plating solution was 6.2 ± 0.5, which was relatively close to the neutral region. However, the coating film was rough and some metal debris was generated. As a result of the investigation, the succinic acid is not stabilized, but the reducing agent contains boron, but it is determined that boron, which is specific to the reducing agent, is consumed, and thus it does not satisfy the consumed boron.
In Examples 2 to 5 below, the effect of the amount of boric acid on the plating was investigated in the relationship between boric acid and dimethylamine borane.
<Example 2>
Except that 30 g / l nickel sulfate, 3 g / l nickel ammonium sulfate, 24 g / l boric acid, 10 g / l ammonium acetate, 16 g / l sodium citrate, and 7 g / l dimethylamine borane were mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 32 microns / hour
<Example 3>
The above-mentioned procedure was carried out except that 30 g / l nickel sulfate, 3 g / l nickel ammonium sulfate, 4 g / l boric acid, 10 g / l ammonium acetate, 16 g / l sodium citrate, and 7 g / l dimethylamine borane were mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 3.7 microns / hour
<Example 4>
Except that 30 g / l nickel sulfate, 3 g / l nickel ammonium sulfate, 8 g / l boric acid, 10 g / l ammonium acetate, 16 g / l sodium citrate, and 7 g / l dimethylamine borane were mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 7.2 microns / hour
<Example 5>
The above-mentioned procedure was carried out except that 30 g / l nickel sulfate, 3 g / l nickel ammonium sulfate, 12 g / l boric acid, 10 g / l ammonium acetate, 16 g / l sodium citrate, and 7 g / l dimethylamine borane were mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 12.7 microns / hour
As can be seen from the results of Examples 2 to 5 above, when the amount of boric acid is 24 g / l, the plating rate is fast and shows good plating characteristics, and when the amount is large, the adhesion to the plating is weakened or the metal powder falls off. It was checked during the experiment. In addition, when the amount of boric acid is small, the plating rate is also lowered and the adhesion is weakened, so the content of boric acid is preferably 4 to 32 g / L.
In the following Example 6, and Comparative Examples 4 to 6 as to confirm the effect of ammonium acetate as a complexing agent, the effect of using the above-mentioned ammonium acetate and other complexing agents in place of it was compared.
<Example 6>
Except that 30 g / l nickel sulfate, 3 g / l nickel ammonium sulfate, 24 g / l boric acid, 10 g / l ammonium acetate, 16 g / l sodium citrate, and 7 g / l dimethylamine borane were mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 32 microns / hour
≪ Comparative Example 4 &
The above-mentioned procedure was carried out except that 30 g / l nickel sulfate, 3 g / l nickel ammonium sulfate, 24 g / l boric acid, 10 g / l russel salt, 16 g / l sodium citrate, and 7 g / l dimethylamine borane were mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 5.7 micron / hour
≪ Comparative Example 5 &
Except that 30 g / l of nickel sulfate, 3 g / l of nickel ammonium sulfate, 24 g / l of boric acid, 10 g / l of ammonium chloride, 16 g / l of sodium citrate, and 7 g / l of dimethylamine borane are mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 4.2 microns / hour
≪ Comparative Example 6 >
Except that 30 g / l of nickel sulfate, 3 g / l of nickel ammonium sulfate, 24 g / l of boric acid, 10 g / l of ammonium sulfate, 16 g / l of sodium citrate, and 7 g / l of dimethylamine borane are mixed to prepare a plating solution. Plating was performed in the same manner as in Example 1.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 7.2 microns / hour
As a result of the above Example 6, and Comparative Examples 4 to 6, the most preferred complexing agent is ammonium acetate, it was confirmed that the plating rate is excellent when used in combination with boric acid in the present invention.
≪ Example 7 >
Nickel sulfate 30g / l, nickel ammonium sulfate 3g / l, boric acid 24g / l, ammonium acetate 10g / l, sodium citrate 2 ~ 24g / l, dimethylamine borane 7g / l was mixed to prepare a plating solution.
Plating conditions: temperature 30-53 degrees, pH 7 ± 0.5, plating rate 32 microns / hour
In this embodiment, the experiment was conducted while changing the content of sodium citrate as the largest stabilizer that can maintain the hardness and corrosion resistance of the metal while having adhesion. Next, the plating thickness and speed of Table 1 were measured for 30 minutes, and the measurement equipment used a German dry X-ray transmission plating thickness automatic measuring device.
As can be seen in Table 1, the content of sodium citrate was found to be almost the same performance between 4 ~ 16g / ℓ. In addition, the formation of the complexation in the plating state was carried out to see the complexation in the general tank without any treatment in the tank, in the actual plating operation, if the passivation treatment and weak DC electricity flows almost no complexation phenomenon.
In Table 1 above, state 2 is the best, but it is shown to be an influence zone of fine pH. As a result, it was confirmed that sodium citrate acts as a pH regulator. Therefore, in the present invention, it is not necessary to use ammonia water, caustic soda solution, sulfuric acid, hydrochloric acid, etc., which are used as pH regulators in general nickel plating solutions. It is effective in providing a type nickel-metal alloy plating solution.
In Examples 8 to 10, various metal salts were added to measure physical properties of the electroless nickel-metal alloy plating solution.
≪ Example 8 >
The electroless plating was carried out in the same manner as in Example 1, except that 8 to 12 g / l of sodium tungsten oxide was added to the nickel plating solution as Example 1 to prepare an electroless nickel-metal alloy plating solution. It was.
Plating conditions: temperature 30-53 degrees, pH 7, plating rate about 12-15 microns / hour
The addition of the sodium tungsten oxide enables a nickel tungsten alloy plating solution excellent in heat resistance, hardness and corrosion resistance.
≪ Example 9 >
The electroless plating was carried out in the same manner as in Example 1, except that 2 to 12 g / L of sodium molybdate was added as the metal salt to the nickel plating solution of Example 1 to prepare an electroless nickel-metal alloy plating solution. It was.
Plating conditions: temperature 30-53 degrees, pH 7, plating rate about 8-12 microns / hour
The addition of sodium molybdate allows electrolytic treatment of the plated surface as a result of heat resistance, hardness and post-treatment, thereby enabling color development peculiar to molybdenum.
≪ Example 10 >
Except for the addition of 2 to 24 g / L zinc sulfate and 2 to 35 g / L of zinc chloride as a metal salt to the nickel plating solution of Example 1, except that an electroless nickel-metal alloy plating solution is prepared. Electroless plating was performed as a process.
Plating conditions: temperature 30-53 degrees, pH 7, plating rate about 4-10 microns / hour
Nickel zinc alloy prepared by the addition of zinc sulfate and zinc chloride is excellent in corrosion resistance as well as chromate treatment, and the salt water test results, withstand more than about 78 hours to produce red rust.
As in the results of Examples 8 to 10, it was confirmed that the unmanned electroless nickel plating solution of the present invention can be alloyed with various metals.
<Experimental Example>
Example 1 (unattended electroless nickel plating solution), Example 8 (unattended electroless nickel-metal alloy plating solution), Comparative Example 1 (phosphorus type electroless nickel plating solution), and ordinary electric nickel polish ( Adhesion, corrosion resistance, hardness, heat resistance of the coating plated with the control) was measured as follows, and the results are shown in Table 2 below.
1) Adhesion: X-ray permeation thickness automatic measuring device was used. At this time, the nickel plating thickness was measured sufficiently, but the accurate measurement of nickel-tungsten alloy was difficult.
2) Corrosion resistance: The salt spray test was continuously performed to visually observe the time of turning into red rust.
3) Hardness: The hardness was measured after heat treatment at 400 ° C. for 1 hour.
4) Heat resistance: It measures whether it maintains a stable state without affecting the structure, adhesion, hardness, corrosion resistance, plating color, roughness of metal film even if it is heated up to a certain temperature.The heat resistance test in plating sets a constant temperature in the dryer oven. Measure change or alteration.
Hammer Impact Test: Lifted.
(About 800)
Hammer impact test: no lifting
(Approximately 880)
Hammer impact test: no lifting
(About 1100)
Hammer Impact Test: Lifted.
(About 320)
As a result, it can be seen that the unmanned electroless nickel plating solution and the electroless nickel-tungsten plating solution are excellent in adhesion, hardness and heat resistance.
In the corrosion resistance test, the phosphorus type electroless nickel plating liquid and the unmanned type electroless nickel plating liquid are almost the same, but the unmanned type electroless nickel-tungsten plating liquid shows that the corrosion resistance to saline is poor. However, hardness and heat resistance are characterized by the characteristics of tungsten metal. In addition, when the dry heat treatment after the plating it can be seen that the hardness and heat resistance is further increased.
Claims (12)
An electroless nickel plating solution of an unmanned type, characterized in that the nickel plating solution contained 20 to 35g / l nickel sulfate and 0.1 ~ 5g / l nickel ammonium sulfate based on 1 liter of nickel plating solution.
Unattended electroless nickel plating solution, characterized in that it is contained in 3 ~ 10g / l dimethylamine borane and 20 ~ 30g / l boric acid based on 1 liter of nickel plating solution.
An electroless nickel plating solution of an unmanned type, characterized in that it is contained in 5 to 15 g / l ammonium acetate based on 1 liter of the nickel plating solution.
An unattended electroless nickel plating solution, characterized in that it is contained in the sodium plating citric acid 10 ~ 20g / l based on 1 liter of nickel plating solution.
An electroless nickel plating solution of an unmanned type, further comprising a nonionic or amphoteric surfactant in an amount of 0.01 to 0.15 g / l based on 1 liter of nickel plating solution.
Unattended electroless nickel plating solution, characterized in that it is contained in 1.5 ~ 12g based on 1 liter of nickel plating solution.
Before plating the workpiece, further comprising activating the workpiece using a mixed solution of an aqueous hydrochloric acid solution and a fluoride solution.
Electroless plating method characterized in that carried out for 30 seconds to 10 minutes at room temperature.
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| BR112015001113B1 (en) * | 2012-07-17 | 2021-05-18 | Coventya, Inc | method of forming a black autocatalytic nickel coating of a substrate |
| KR101386019B1 (en) * | 2012-08-16 | 2014-04-21 | 강진규 | Electroless plating method using nikel-phosphorus-tungsten-zirconium alloy electroless plating solution |
| KR102036334B1 (en) * | 2017-09-20 | 2019-10-25 | 한국기계연구원 | Electroless plating solution and electroless plating method |
| KR102036329B1 (en) * | 2017-09-20 | 2019-10-25 | 한국기계연구원 | Electroless plating solution, electroless plating method and plating layer formed thereby |
| CN113789504A (en) * | 2021-08-20 | 2021-12-14 | 清远敏惠汽车零部件有限公司 | Chemical plating method |
| CN114481103B (en) * | 2021-12-08 | 2023-10-20 | 胜宏科技（惠州）股份有限公司 | Chemical nickel solution and preparation method thereof |
| CN114182240A (en) * | 2021-12-13 | 2022-03-15 | 四川川油天然气科技股份有限公司 | Hydrogen blocking process for inner wall of hydrogen storage well of hydrogen storage container |
| CN114657544B (en) * | 2022-03-24 | 2023-10-27 | 彭州航大新材料有限公司 | Cobalt aluminizing process and cobalt aluminizing layer for inner cavity surface of nickel-based superalloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10208980A (en) | 1997-01-21 | 1998-08-07 | Nippon Chem Ind Co Ltd | Transfer sheet for internal electrode of laminated electronic parts |
| JP2008063644A (en) | 2006-09-11 | 2008-03-21 | Okuno Chem Ind Co Ltd | Electroless nickel alloy plating liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10208980A (en) | 1997-01-21 | 1998-08-07 | Nippon Chem Ind Co Ltd | Transfer sheet for internal electrode of laminated electronic parts |
| JP2008063644A (en) | 2006-09-11 | 2008-03-21 | Okuno Chem Ind Co Ltd | Electroless nickel alloy plating liquid |
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