KR20100121399A - Nickel flash plating solution, zinc-electroplated steel sheet and manufacturing method thereof - Google Patents
Nickel flash plating solution, zinc-electroplated steel sheet and manufacturing method thereof Download PDFInfo
- Publication number
- KR20100121399A KR20100121399A KR1020100001522A KR20100001522A KR20100121399A KR 20100121399 A KR20100121399 A KR 20100121399A KR 1020100001522 A KR1020100001522 A KR 1020100001522A KR 20100001522 A KR20100001522 A KR 20100001522A KR 20100121399 A KR20100121399 A KR 20100121399A
- Authority
- KR
- South Korea
- Prior art keywords
- nickel
- plating solution
- plating
- acid
- flash plating
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
Abstract
Nickel flash plating solution for base plating of galvanized steel sheet is introduced. This plating solution contains a complexing agent and a vacancy agent for stabilizing the plating solution. The complexing agent and the vacancy are combined with iron ions to prevent oxidation of the iron ions and the iron is vaccinated with nickel to prevent the concentration and precipitation of the iron ions inevitably introduced into the plating solution. Examples of the complexing agent include gluconic acid, ethylenediaminetetraacetic acid (EDTA), sodium alkanoic acid, citric acid, tartaric acid, zilopionate ester, alkylcresol, zincnaphrate, thiourea, imidazole and the like.
Description
The present invention mainly relates to a pretreatment step performed in order to improve the coating properties of zinc plating before electro zinc plating in the manufacturing process of the galvanized steel sheet. More specifically, the present invention relates to a nickel flash plating solution used as a base plating solution for base iron in the pretreatment process, an electrogalvanized steel sheet having a nickel plating layer coated with such a nickel flash plating solution, and a manufacturing method thereof.
In general, steel sheets are widely used as structural materials for automobiles, home appliances, and building materials due to their excellent mechanical strength, good workability, and abundant resources. However, steel sheets themselves are extremely poor in corrosion resistance, and thus their lifespan is mainly extended through galvanizing. .
Normally, the corrosion resistance of zinc plating is evaluated based on the period of time until the red metal is formed by corrosion of iron as the base metal when the thickness of zinc plating itself is 0.025mm without post-treatment. Zinc plating has been reported to have corrosion resistance of about 2 years in industrial areas, 3 years in urban areas and about 5 years in rural areas, which may be further reduced depending on the environment. The thicker the galvanizing thickness, the better the ability to protect these irons.
Therefore, galvanized steel sheet, which is widely used for building materials, uses hot dip galvanizing and has a plating adhesion amount of 40g / m 2 or more, but when used as a non-painting material, its resistance is not large. Moreover, hot-dip galvanizing is carried out in the state of immersing the steel plate in hot-dip galvanized zinc which is higher than 400 ° C., which has a significant influence on the mechanical properties of the steel sheet. Follow.
On the other hand, the corrosion protection ability to protect iron is generally better the thicker the thickness of the galvanized, but the high corrosion resistance to the steel sheet alone is limited and uneconomical, so chromate after galvanization, etc. The post-treatment process selects a process to increase the corrosion resistance, and in recent years, research on a new plating technology, for example, electro-galvanizing technology, which can obtain high corrosion resistance with less zinc adhesion amount, has been made. As a result, the galvanized steel sheet having a relatively low amount of zinc adhesion compared to hot dip plating can also be used in structural materials for automobiles, home appliances, and building materials. Electro-galvanization is usually from 0.005mm to more than 0.025mm thickness, but economical thickness is about 0.008mm ~ 0.013mm.
However, the degradation of corrosion resistance due to the thin zinc plated film of the galvanized steel sheet can be compensated by the surface treatment such as chromate, but when the thickness of the zinc plated film is thin, the adhesion of the plated film itself is reduced and the hiding power as the plated film is also reduced. Falls out. As a result, defects existing on the original surface of the base steel appear on the plated film, and as a result, surface defects such as stains and ridge marks are visually confirmed, which causes the smoothness and beauty of the plated surface. .
Specifically, the electro-galvanized steel sheet is manufactured through a process of degreasing, washing with water, electrolytic degreasing, pickling, washing with water, followed by an electro-galvanizing process, but the physical surface state of iron material is bad and various kinds of iron surface are used. If there are impurities, the adhesion between the base iron and the galvanized film is not only degraded, but also causes the plating to be unplated, leaving marks or scratches on the surface that are easily visually confirmed after plating. The aesthetics of the surface of the galvanized steel sheet are greatly impaired. The thinner the galvanized film is, the more serious this poor plating occurs.
As one of the prior arts for solving the problem of surface defects, including the problem of visual damage of galvanized steel sheet manufactured by electro-galvanizing, the current technology is called nickel flash plating before electro-galvanization. Nickel thin plating is performed first. This nickel flash plating not only smoothes the surface of the base iron, but also prevents various impurities present on the surface of the base iron from electro-galvanizing and then coming out of the surface of the electro-galvanizing. To get it.
1 to 3 are electron micrographs of the surface of the steel sheet subjected only to electro zinc plating, the surface of the steel sheet subjected to nickel flash plating only, and the surface of the galvanized steel sheet after nickel flash plating. From these photographs it can be seen that the surface of the steel sheet of FIG. 3 with nickel flash plating underplating has much better smoothness than others.
The nickel flash plating described above is based on nickel plating in principle. Nickel plating is used for the purpose of anticorrosion and decoration for steel and copper, and is also used for underplating during chromium plating. In addition, nickel coating has a good color, relatively little discoloration, and good hardness, and has good mechanical properties. Such nickel plating is mainly performed in a watt bath, a wood bath, a spam acid bath, a black nickel bath, and the like, and is manufactured by an electroplating method in a plating bath composed mainly of nickel sulfate and nickel chloride.
However, the nickel plating has to go through a difficult process such as adjusting the acidity (pH) and the cathode current density of the plating bath. Sometimes, the nickel plating layer does not exhibit the perfect hiding characteristics that the underlying plating layer should achieve depending on the composition of the plating solution and the plating conditions. . In fact, in the large-scale mass production equipment for nickel flash plating, insoluble anodes are used for convenience of the process. In this case, as shown in FIG. 4, the plating liquid is gradually acidified as the number of days of use increases, thereby causing various problems.
The acidification of the plating liquid composition directly affects the plating properties, but in particular, the iron material is corroded to continuously increase the content of Fe in the composition of the plating solution. When Fe is concentrated in the plating solution, sludge is formed in the plating solution, which in turn causes color change of the plating layer and poor plating. In addition, it shortens the use time of the plating liquid and causes a problem of changing the plating liquid regularly. It not only lowers the quality of the product but also lowers productivity and raises manufacturing costs. In general, when the Fe concentration reaches 500ppm, the problem starts to occur in nickel flash plating, and when it reaches 1000ppm, the degree is very serious. The increase in impurities may increase the internal stress of the nickel plated layer, which may cause minute cracks in the plated layer, which may cause deterioration of corrosion resistance and deterioration of adhesion to the zinc plated layer.
The acidification of the above-mentioned plating solution can be prevented by replenishing an alkaline solution such as caustic soda, but as time goes by, alkali ions are concentrated to bring about another problem, so temporary prescription is possible, but it cannot be used for a long time. It is ideal to use powdered nickel carbonate or its solution to prevent acidification of the solution and to replenish nickel ions. Nickel carbonate, however, is extremely low in solubility and cannot be used in solution, so it is added to the plating solution in powder form. However, nickel carbonate particles that are not dissolved often cause plating failure. Therefore, in order to use the nickel flash plating solution for a long time, it is possible to suppress the concentration of impurities, especially iron, and to develop an effective nickel flash plating solution to replenish the consumed nickel ions and return the acidification of the solution. This is necessary.
Korean Patent Laid-Open Publication No. 1992-0021742 discloses a technique for improving lubricity, corrosion resistance and paintability using two electroplating layers, a zinc electroplating layer formed on the surface of a steel plate and a zinc-cobalt alloy electroplating layer formed thereon. Doing. This application technique is expected to have the advantage of removing surface defects over the effect of nickel flash plating, but it is more difficult to control the change in liquid composition during plating, and also because of the use of cobalt metal, electro-zinc plating There is a problem of greatly increasing the cost of steel sheet production.
In addition, Korean Patent No. 311796 relates to flash plating of a hot-dip galvanized steel sheet, and applies a vacuum deposition method instead of an electroplating layer on the hot-dip galvanized steel sheet, and uses a Fe-stage instead of a Fe-rich plating system as an upper plating system. By applying a metal and controlling the temperature of a material during deposition, a method of manufacturing a galvanized steel sheet having a simple process, excellent phosphate treatment, electrodeposition coating property, and corrosion resistance is disclosed. However, this patent uses iron deposition method rather than nickel flash plating as a method for improving the paintability of hot-dip galvanized steel sheet, and is far from improving the adhesion of galvanized film and the concealment of the surface of the base steel.
In Japanese Patent Laid-Open No. 57-171692, a technique is disclosed in which a Ni diffusion layer is formed on a steel sheet and heated in a non-oxidizing atmosphere to form a Ni diffusion layer in the steel and Zn-Ni alloy plating on the steel sheet. However, after the loss of the plating layer or corrosion products in the corrosion process, Ni-Fe diffusion layer is expected to contribute to the improvement of corrosion resistance, but the improvement of the surface properties expected in adhesion, smoothness and other nickel flash plating is difficult to expect.
In general, the underlying plating process is to provide a leveling effect to the substrate to smooth the surface and improve the gloss. In Korean Patent Laid-Open No. 1999-0070721, a plating technique that omits the underlying plating process, That is, the base metal is pretreated in the order of cutting polishing, polishing polishing, pickling, alkaline sonication and electrolytic degreasing, followed by electroplating and discoloring the metal to be directly coated on the surface of the base metal without plating. And a direct plating method to prevent corrosion. This invention is different from the present invention in that it is a direct plating method without under plating, and is limited to those suitable for metals such as gold, silver, rhodium, palladium, and thus does not correspond to galvanized steel sheet.
U.S. Patent 5908542 proposes a method of improving the adhesion with epoxy resin by nickel flash plating the surface of metal foil, especially copper foil. Improving the adhesion between the metal foil and the resin often uses a method of increasing the roughness of the metal foil surface. However, when the roughness of the metal surface increases, the mobility of the metal component also increases, which may weaken the insulation characteristics of the resin. Therefore, in this case, nickel flash plating is performed for the purpose of preventing the weakening of the insulation properties of the resin layer by suppressing the movement of metal components while improving the adhesion with the resin layer, and for improving the appearance and corrosion resistance of the galvanized steel sheet. Its purpose is distinguished from the concept of steel plate not plating.
The nickel flash plating solution currently used is based on the existing nickel plating solution composition. Water-soluble single or complex nickel salts are used as a source of nickel in the composition of the plating bath used for continuous plating, such as the production of galvanized steel sheet, and as additives, many of them play different roles such as conductivity aids, pH buffers, and polishes. Organic and inorganic compounds are used in combination.
Among the plating solution components, the most important one is nickel chloride, nickel sulfate, nickel carbonate, nickel nitrate, nickel acetate, nickel oxide, and the like. Halogen compounds such as bromine, iodine, and fluorine are used, although not commonly used. Among them, nickel sulfate is the main component of Watts bath, which is the most used, and concentration and plating rate are closely related. Nickel chloride has a great influence on anode dissolution and electrolyte conductivity improvement. Nickel salts are used either alone or in mixtures. For nickel sulfate the concentration is adjusted between approximately 200 g / l and 500 g / l, with a suitable concentration between 250 g / l and 450 g / l, more precisely between 300 g / l and 400 g / l. Adjusted.
Applied as a constituent of the bath after the nickel salt is a conductivity aid to improve the conductivity of the solution. In the nickel flash plating bath, potassium chloride, sodium chloride, ammonium chloride, ammonium sulfate, etc. are used as conductivity aids.
As the pH buffer, boric acid is mainly used. The boric acid functions not only to adjust the pH of the solution but also to increase the color, uniformity, and flexibility of nickel plating.
In addition, chlorides or sulfides such as manganese, aluminum and beryllium are added as various kinds of precipitation aids used for the purpose of making the crystals of the electrodeposits finer or softer.
In addition to the above components, various surfactants or polishes are used to increase the smoothness, sealability, uniformity, flexibility and mechanical properties of the plating. Water-soluble organic compounds are used as surfactants and brightening agents, for example, sulfonic acid compounds such as benzenedisulfonic acid, benzenetrisulfonic acid, naphthalindisulfonic acid, naphthalintrisulfonic acid, or benzenesulfamide, benzenesulfimide, Sulfur-containing amides such as saccharin and compounds containing an aldehyde (C═O) group, an olefin (C═C) group, an acetylene (C≡C) group as functional groups, such as formaldehyde, coumarin, butynediol Unsaturated compounds such as These organic additives are mostly decomposed during plating and inserted into the plating layer or can be consumed by electrochemical reduction.
In addition to the composition of the liquid in nickel flash plating, the determinants of the plating characteristics include plating conditions such as current density, plating liquid temperature and pH, and plating time.
The current density is an important factor in determining the thickness or nickel plating amount of the nickel plating layer. Depending on the nickel ion concentration in the plating solution and the plating time, plating is performed in a wide range from about 1 A / dm 2 to 10 A / dm 2 , but mainly between 4 A / dm 2 and 8 A / dm 2 .
The temperature of the plating liquid is controlled between 50 ° C and 60 ° C and plating is possible at pH 1-6, but preferably adjusted to pH 2-5 as much as possible.
Plating time is performed between 0.1 and 40 seconds considering the solution concentration and the plating amount. If the plating time is longer, the plating thickness is increased or the plating amount is increased more than necessary, and in some cases, spherical or dendritic crystals may be made on the plating surface to make poor plating. Current industrial plating equipment in mass production performs plating within a few seconds by precisely controlling the distance between electrodes, the moving speed and current density of steel sheet. Pulse plating is also used to convert the current density periodically, high and low, within the permissible range for uniform plating.
The amount of plating is generally measured by measuring the thickness, and the unit is used in micrometers (millions of meters). However, Ni flash plating is shown in Fig. This is not easy coating thickness very thin accurate measurements per unit area of coating weight (mg / m 2). In particular, the plating of the steel plate to be plated in the continuous plating apparatus may be more rational because the thickness thereof is relatively uniform. Nickel flash plating deposits range from 20 mg / m 2 to 500 mg / m 2 , but are generally plated between 100 and 250 mg / m 2 .
The present invention is based on the recognition of the problems of the prior art as described above, it is possible to easily control the strong acidification of the solution inevitably occurs in the plating apparatus using the current insoluble anode and to remove impurities, especially iron concentrated in the plating solution Or to provide a nickel flash plating solution that can be maintained below a certain level.
In addition, the present invention is to provide a nickel flash plating solution that can be expected to improve the plating quality as well as to improve the plating quality as well as to prevent the problem of regularly changing the plating solution.
In another aspect, the present invention is to provide an electro-galvanized steel sheet having excellent plating quality by having a base plating layer formed using the nickel flash plating solution as described above.
In addition, the present invention is to provide a method for producing such an electrogalvanized steel sheet.
Nickel flash plating solution according to the present invention for achieving the above object, Nickel salt; Conductivity aids to increase conductivity of the plating solution; A complexing agent used for stabilizing the plating solution and combined with at least iron ions contained in the plating solution to help vacancies of iron ions; And a surface improving agent for smoothing the underlying plating film.
According to the present invention, the complexing agent is any one selected from gluconic acid, ethylenediaminetetraacetic acid (EDTA), sodium alkanoic acid, citric acid, tartaric acid, ziopionic acid ester, alkylcresol, zincnafurate, thiourea, imidazole or Composites thereof.
In addition, according to the present invention, the complexing agent may be contained in a concentration of 0.5 ~ 10g / L in the plating solution.
In addition, according to the present invention, the vaccinating agent for assisting the vacancy of the iron ions contained in the plating solution further comprises any one selected from ethyleneimine, sodium gluconate, ethylenediaminetetraacetic acid, sodium citrate or a combination thereof. can do.
In addition, according to the present invention, the vacancy may be contained in a concentration of 0.1 ~ 50g / ℓ in the plating solution.
In addition, according to the present invention, further comprises an antioxidant for preventing the generation of iron hydroxide due to the oxidation of the iron ions, the antioxidant is made of any one or a combination thereof selected from benzoic acid, fluorine resin, the oxidation The inhibitor may be contained at a concentration of 0.1-25 g / L in the plating solution.
In addition, according to the present invention, the nickel salt may be added to the plating solution so that the nickel concentration in the plating solution is 10 ~ 200g / ℓ.
According to the present invention, the conductivity aid is any one selected from sodium sulfate, ammonium sulfate, sulfamic acid, boric acid, ammonium fluoride, sodium formate, ammonium formate, ammonium phosphate, potassium sulfate, ammonium chloride, potassium chloride and sodium chloride as a conductive salt. Or combinations thereof.
In addition, according to the present invention, the conductivity aid may be contained in a concentration of 10 ~ 200g / ℓ in the plating solution.
Meanwhile, the nickel flash plating solution according to the present invention is a nickel flash plating solution used for replenishment of the plating solution during the base plating of the galvanized steel sheet, and in particular, a nickel salt dissolved in a nickel source and showing neutrality may be used.
According to the present invention, the nickel salt of the replenishment nickel flash plating solution may be any one selected from nickel carbonate, nickel sulfamate, nickel acetate, nickel formate, nickel fluoride, and nickel fluoride, or a combination thereof.
Electro-galvanized steel sheet according to the present invention is provided with a nickel plated film using the nickel flash plating solution described above.
Electrolytic galvanized steel sheet manufacturing method according to the invention the steel sheet washing process; Immersing the washed steel sheet in the nickel flash plating solution at a pH of 2.0-6.0 at a temperature of 35-70 ° C. as the nickel flash plating solution and forming a nickel plating film on the surface of the steel sheet; And immersing the steel plate on which the nickel plated film is formed in a zinc plating solution to form an electrogalvanized film. The nickel flash plating solution described above in the nickel flash plating process is used for replenishing the nickel flash plating solution.
According to the present invention as described above, it is possible to replenish nickel and adjust the pH without replacing all the nickel flash plating solution, it is possible to prevent the concentration and precipitation of iron flowing into the plating solution.
In addition, according to the present invention, the nickel flash plating solution can be used for a long time, and an electrogalvanized steel sheet excellent in corrosion resistance, adhesion and hiding properties can be obtained.
1 is an electron scanning micrograph (magnification x 4000) of the surface of the specimen subjected to electro zinc plating only;
2 is an electron scanning micrograph (magnification x 4000) of a specimen surface subjected to nickel flash plating only;
3 is an electron scanning micrograph (magnification x 4000) of a specimen surface subjected to electro zinc plating on nickel flash plating;
4 is a graph showing that the Fe concentration (vertical axis, ppm) increases with increasing use days (horizontal axis) of a conventional nickel flash plating solution.
5 is an electron scanning micrograph (magnification × 1500) of the surface of a specimen on which only a nickel flash plating film was formed using a plating solution according to an embodiment of the present invention;
6 is a photograph comparing the characteristics after using the nickel flash plating solution according to an embodiment of the present invention and the conventional nickel flash plating solution for 15 days under the same conditions,
Figures 7a to 7d, while otherwise the nickel geumyang using Ni flash plating solution according to an embodiment of the present invention in each of 50mg / m 2, 100mg / m 2, 200mg / m 2, 300mg / m 2 20g / m 2 Surface electron scanning micrographs (magnification x 500) of the specimens on which the electrogalvanized film was formed.
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
Nickel Flash Plating Solution
First, the composition of the nickel flash plating solution will be described.
Iii) nickel salt
Nickel contained in the nickel flash plating solution is supplied in salt form.
Examples of the salt include nickel sulfate [NiSO 4 · 6H 2 O], nickel chloride [NiCl 2 · H 2 O], nickel carbonate [NiCO 3 · 2Ni (OH) 2 · 4H 2 O], nickel nitrate [Ni (NO 3 ) 2 · 6H 2 O], nickel ammonium sulfate [Ni (SO 3 NH 2 ) 2 · 4H 2 O], nickel sulfamate [(H 2 NSO 3 ) 2 Ni.4H 2 O], nickel acetate, nickel formate, fluoride And various organic-inorganic salts such as nickel, nickel borofluoride and nickel acetate, and mixtures thereof. Salts having low water solubility, such as nickel carbonate, are preferably first solubilized using an appropriate complexing agent such as ammonium or amine.
The nickel concentration in the nickel flash plating solution is 10 to 200 g / l, preferably 30 to 100 g / l. If the concentration of nickel metal is higher than 200g / l, the current efficiency is too high and plating of the high current part is carried out, and the activity of the metal is also increased, resulting in the precipitation of metal crystals on the plating surface, resulting in uneven plating surface and cracking. When is less than 10g / ℓ low current efficiency is poor plating on low current site, and pin holes or pit on the plating surface is likely to occur.
Ii) conductivity aids
In nickel flash plating, a conductive salt is added to the plating solution as an aid to improve the electrical conductivity of the nickel flash plating solution.
The conductive salt should be appropriately selected according to the type of nickel metal salt, sulfate, ammonium salt, boric acid salt and the like can be used, and more specific examples are ammonium sulfate, ammonium chloride, boric acid, ammonium phosphate, potassium sulfate, Potassium chloride, sodium chloride, sodium sulfate, sulfamic acid, ammonium fluoride, sodium formate, ammonium formate alone or mixtures thereof.
The conductive salt is contained in a concentration of 10 ~ 200g / L, preferably 50 ~ 100g / L in the plating solution based on the nickel concentration of 100g / L in the plating solution. If the concentration of the conductive salt is higher than 200 g / l, the current efficiency is increased, so that cracks or uneven plated metal particles are uneven due to the high internal stress of the plating layer formed by plating of the high current portion, and the concentration of the conductive salt is lower than 10 g / l. The plating of the low current site is poor, and the corrosion resistance and the adhesion are inferior.
Iii) complexing agent
A complexing agent is added in the plating solution to prevent the nickel flash plating solution containing various components from being deteriorated due to physicochemical reactions between the components and to prevent the stability from deteriorating with prolonged use and storage.
According to the present invention, a material having a strong complexing property with iron ions, which is an impurity in the nickel flash plating solution, is used as the complexing agent. In other words, iron ions are oxidized due to low stability and are easily precipitated with iron hydroxide in the plating solution. Complexing agents are stabilized and vacancies of iron ions in combination with iron ions. Appropriate ingredients should be selected. As such a complexing agent, an amine system, citric acid system, amino acetic acid system, or a mixture thereof may be used. More specifically, examples thereof include gluconic acid, ethylenediaminetetraacetic acid (EDTA), sodium alginate, citric acid, tartaric acid, and geoopionate, Alkylcresol, zincnafurate, thiourea, imidazole and the like can be used.
The complexing agent is added to the nickel flash plating solution at 0.5 to 10 g / l, preferably 3 to 7 g / l. When the concentration of the complexing agent is higher than 10 g / l or lower than 0.5 g / l, defects in the plating surface as well as the balance of the plating liquid are broken, thereby shortening the life of the plating liquid.
Iii) Vacancies
The above complexing agent is characterized as a vacancy agent, that is, a component for causing iron to be electroplated together with nickel, but it is more preferable to use a vacancy agent which shows more effective characteristics for electroprecipitation of iron ions by adding 0.1 to 50 g / l. Do. Ethyleneimine, sodium gluconate, ethylenediaminetetraacetic acid, sodium citrate may be used as such vaccinating agents, and is added to the nickel flash plating solution at 0.1 to 50 g / l. Citric acid and citric acid are the same substance, but the former is acid and the latter is salt. Therefore, citric acid is used to make acidic solutions, and salts are used for solutions that should not change in acidity.
Iii) antioxidants
Antioxidant is added at 0.1 ~ 25g / l to prevent the generation of iron hydroxide due to the oxidation of iron ions, together with the complexing agent described above contributes to stabilizing the iron ions in the plating solution. Such antioxidants may not be strong reducing agents but should be selected as a component that can at least make the electrical properties of the solution into a reducing atmosphere. These antioxidants may be benzoic acid or fluorine resin, and 0.1 ~ 25g / is added in liters.
표면) Surface improving agent (leveling agent) and stress reducing agent
To the nickel flash plating solution, a surface improving agent and a stress reducing agent are added to form an excellent plating film.
The surface improving agent is added to suppress the generation of gas at the anode and to provide a uniform electron supply during the electrodeposition reaction at the cathode to make the plating film smooth and to have a dense crystal structure.
The surface improving agent is preferably a nonionic surfactant or a mixture thereof, and specific examples thereof include ethylene glycol, polyethylene glycol, benzoic acid, sodium alkoxide, ziopionic acid ester, alkyl cresol, thiourea, imidazole, saccharin, and the like. . On the other hand, conventionally, anionic surfactants such as 2-methoxy-1-naphthaldehyde, polyethylene glycol monolauryl ether, and polyimine have been mainly used as surface improving agents, but the use of such anionic surfactants may be possible in the present invention. .
The stress reducing agent is added to prevent the plating film from lifting up. All plating films have some stress when the metal particles are electrodeposited due to defects in the plating structure or disparity of the grain arrangement. In particular, in general nickel plating, such a phenomenon is remarkable. Used. Nickel flash plating, however, is not a big problem even if the plating layer is thin without using a stress reducing agent, but a stress reducing agent is added to the plating solution to improve the quality of the coating film.
As such a stress reducing agent, tridecyloxy poly (ethyleneoxy) ethanol (III), N- (3-hydroxybutyl limemen-P-sulfanoic acid, diisodecyl phthalate, or a mixture thereof is used.
The surface improving agent and the stress reducing agent are each added in a concentration of 0.1 to 2.0 g / l, preferably 0.5 to 1.0 g / l, in the plating solution. If the content is higher than 2.0 g / l, the plating liquid becomes turbid or the equilibrium of the plating liquid is fragile due to the excess of organic matter, and the plating surface also has a narrow current range, which causes the plating to become black without plating at both high and low currents, If pits are severely generated and the content is lower than 0.1 g / l, cracks are severely generated and pits are formed due to the stress of the nickel plating layer.
As described above, conductivity aids, complexing agents, and vacancies are appropriately selected according to the type of nickel salt and added to the nickel flash plating solution. The nickel flash plating solution thus prepared has excellent stability and is not sensitive to impurities for a long time. Even use results in uniform plating. Meanwhile, the pH buffer mentioned in the prior art needs to be used for the nickel flash plating solution.
Supplementary Plating Solution
On the other hand, even when using the improved nickel flash plating solution as described above, insoluble anodes, the pH of the plating solution is gradually lowered with the increase of the service life, the problem remains acidic. Therefore, in order to maintain a constant pH by diluting the plating solution in use and to replenish nickel in the plating solution, a separate supplemental nickel flash plating solution is required.
As a supplementary plating solution, the nickel flash plating solution having the composition range described above is used as it is, except for neutral nickel salts such as nickel sulfate, such as nickel carbonate, nickel sulfate, nickel acetate and nickel formate. , Nickel fluoride, nickel borofluoride and the like are used.
The nickel carbonate is extremely low in water solubility can not be used as it is, it is necessary to use a complexing agent to be dissolved in neutral or alkaline water. For example, when ammonia water or sulfamine soda is added to nickel carbonate, it is dissolved in an aqueous alkali solution, and an ammonium or amine complexing agent, or a complexing agent such as gluconic acid or ethylenediaminetetraacetic acid is added thereto to improve the stability of the aqueous solution. The mixing ratio of the complexing agent in the nickel carbonate solution is about 0.5-10 g / l.
By using the above-mentioned neutral nickel flash plating solution as a supplementary solution to replenish the consumed nickel ions and to restore the acidification of the solution due to the use of an insoluble anode it is possible to extend the service life of the plating solution almost indefinitely.
Electro galvanized steel sheet and manufacturing process
According to the present invention, the galvanized steel sheet may be manufactured using the existing galvanizing process as it is. As an example, ferrous iron is first washed through a first chemical degreasing process, followed by a series of pretreatment processes of electrolytic degreasing, pickling and washing, followed by electroplating after nickel flash plating. It looks at the nickel flash plating process and the electro zinc plating process mainly related to the present invention.
니켈) Nickel Flash Plating Process
According to the present invention, nickel flash plating may be performed by a conventional nickel flash plating process. Therefore, the process conditions to be considered in the plating process using the nickel flash plating solution according to the present invention will be briefly described as follows.
According to the present invention, the pH of the nickel flash plating solution needs to be adjusted in the range of 2.0 to 6.0. The pH of the plating solution is preferably controlled in the range of 2.0 to 6.0 because the surface of the plating becomes dark and semi-gloss at a pH of less than 2.0, in particular less than pH 1.5, and the surface color becomes yellow at a pH of more than 6.0, in particular, more than 6.5.
The temperature of the nickel flash plating solution is required to be adjusted to 35 ~ 70 ℃, more preferably 50 ~ 60 ℃ range. If the plating solution temperature is below 50 ℃, especially below 35 ℃, the plating film is dark and the adhesion of the coating film is poor, resulting in peeling phenomenon. Since the nickel flash plating, it is preferable to plate with a nickel flash plating solution at a temperature of 35 to 70 ° C, more preferably 50 to 60 ° C.
On the other hand, it is preferable that the current density during nickel plating is 5 to 200 A / dm 2 . The reason is that in the applied current density is 5A / dm 2 under the plating grains grow significantly poor film adhesiveness, 200A / dm 2 excess up to a phenomenon in which the edge burning operation becomes difficult.
Ii) Electro zinc plating process
According to the present invention, the electro zinc plating may be performed by a conventional electro zinc plating process. By way of example, conventionally used galvanizing bath is a sulfuric acid bath which can be used as it is in the electro zinc plating process according to the present invention.
On the other hand, the electro-galvanized steel sheet according to the present invention is produced through the above process, wherein the nickel plated layer thickness of the steel sheet is preferably 0.01㎛ or more, the zinc plated layer thickness on the nickel plating layer is preferably 2㎛ or more.
Hereinafter, looks at the superiority of the effect of the present invention through the examples according to the present invention and comparative examples.
Comparative Example 1
As Comparative Example 1, a specimen prepared by galvanizing only without nickel flash plating was prepared, and the state of the galvanized coating was examined.
The specimen of Comparative Example 1 was prepared by conventional pretreatment, that is, after washing with primary chemical degreasing, followed by electrolytic degreasing, pickling, and washing followed by electro zinc plating. As a zinc plating bath, a sulfuric acid bath containing 420 g / l of zinc sulfate, 23 g / l of ammonium sulfate, and 12 g / l of sulfuric acid was used. The temperature of the bath was maintained at 55 ° C. and the current density was 7 A / dm 2 .
As shown in FIG. 1, the specimen surface of Comparative Example 1 may be confirmed that the crystal grains of the electrodeposited zinc protrude on the surface as shown in FIG. 1. The cause of such poor film formation is that the characteristics of the surface of the base iron influence the crystal formation of the electrodeposited zinc so that the characteristic is projected as it is. For this reason, there is a need for a base plating layer such as nickel flash plating which is less affected by the surface characteristics of the base iron.
Comparative Example 2
As Comparative Example 2, a specimen having a nickel plated film according to a conventional nickel flash plating process was prepared, and the surface state thereof was investigated.
The specimen of Comparative Example 2 was subjected to the same pretreatment process in the preparation of the specimen of Comparative Example 1, and then subjected to the pretreatment process and then flash-plated in the conventional nickel flash plating solution. Nickel sulfate was added to the nickel flash plating bath so that the nickel content in the total solution was 50 g / l, and the plating bath was added with 30 g / l ammonium sulfate, 3 g / l ethylene glycol and 30 g / l boric acid. . The temperature of the plating bath was 55 ° C. and the current density was 7 A / dm 2 . Nickel deposition according to the conventional plating conditions is characterized by a relatively thick, approximately 250mg / m 2 or more.
As a result of nickel flash plating as described above, on the specimen surface of Comparative Example 2, as shown in FIG. 2, unlike the electrogalvanized film according to FIG. It can be confirmed that a film is formed. However, as can be seen in Figure 2, such a nickel film has a problem that the micro-cracks appear due to the strong interstitial stress of the grains. Such cracking of grains may cause deterioration of corrosion resistance.
Comparative Example 3
As Comparative Example 3, after the conventional nickel flash plating as in Comparative Example 2, the conventional zinc plating as in Comparative Example 1 was prepared to prepare a specimen having a nickel flash plating film and a galvanized film, and then examined the surface state thereof. . The pretreatment, the composition of the nickel flash plating solution and the zinc plating solution, and the plating conditions were the same as in Comparative Examples 1 and 2, respectively.
As shown in FIG. 3, the zinc coating on the surface of the specimen according to Comparative Example 3 prepared through the above process did not protrude any traces of stains or defects present on the specimen.
However, in Comparative Example 3 it was a nickel flash coating weight is 350mg / m 2, when only a small coating weight of about 50mg / m 2 to form a nickel flash plating film is difficult to ensure good surface properties and corrosion resistance.
In the following examples, the nickel flash plating according to the present invention will be able to confirm the difference between the functions and characteristics of the existing, and how the surface after the final electro-galvanization of the final process is different from the existing and its difference and superiority.
As Example 1, a nickel-plated specimen was prepared through a nickel flash plating process according to the present invention, and the coating state thereof was investigated.
The pretreatment process before nickel flash plating of the specimen of Example 1 was the same as in Comparative Example 1, nickel sulfate plating solution is added nickel sulfate so that the nickel content is 30g / ℓ, ammonium sulfate 50g / ℓ as the conductive salt 2g / l benzoic acid as antioxidant, 5g / l gluconic acid as complexing agent, 2g / l saccharin as surface improving agent (leveling agent), 0.5g / l ethyleneimine as a vaccinating agent to suppress the concentration of impurities in plating solution, stress An aqueous solution containing 0.2 g / l tridecyloxypoly (ethyleneoxy) ethanol as the reducing agent and 30 g / l boric acid as the buffer was used. Bath temperature was 55 degreeC, pH 2.3, and current density was 7 A / dm <2> .
As a result of nickel flash plating as described above, the amount of nickel deposited is relatively small as 50 mg / m 2 , but as shown in FIG. 5, a smooth nickel plated film having no surface defects, stains, etc. present on the surface can be obtained. In addition, unlike the nickel coating according to Comparative Example 2 in which microcracks appear between the grain structures, it was confirmed that the nickel coating on the surface of the specimen according to Example 1 did not exhibit such microcracks. Without this microcracks, even if the film is thin, the corrosion resistance is not lowered, and the nickel consumption is also low, so that the production cost can be lowered.
After using the nickel flash plating solution according to Example 1 and the conventional nickel flash plating solution according to Comparative Example 2, which does not include the additive according to the present invention, such as a complexing agent, a vacancy agent, an antioxidant, and the like for 15 days, respectively, The properties of the plating solutions were compared.
Referring to FIG. 6, the nickel flash plating solution (left bottle) according to Example 1 maintains its original color and no precipitate is seen, whereas the conventional nickel flash plating solution (right bottle) according to Comparative Example 2 is colored. This thinning and many deposits on the bottom can be seen. This implies that the nickel flash plating solution according to Example 1 is capable of performing plating of excellent quality because the concentration of impurities and sediment are not generated than the conventional nickel flash plating solution, and the liquid life is long and economical.
The nickel flash plating solution according to the present invention prevents impurities, in particular Fe, from vacancy with nickel and concentrates in the plating solution, and also prevents the antioxidant from being precipitated with iron hydroxide by inhibiting oxidation of iron ions.
In order to prove the same phenomenon as in Example 2 above, after the ferrous sulfate was added so that the iron component as an impurity in the nickel flash plating solution according to Example 1 was about 5g / l, to prepare a 10L experimental nickel flash plating solution, Nickel flash plating was performed. The anode is an insoluble anode and the cathode is a tin plated steel plate to block the elution of iron in the iron material, plated for about 2 hours at a current density of 7A / dm 2 and analyzed the composition change of the plating solution as shown in Table 1 below. Indicated.
As can be seen in Table 1 above, after the plating was completed, about 1.9 g of nickel and about 1.1 g of iron were reduced in the plating solution of 1 L, and the pH was lowered to pH 1.3 from pH 1.6 of the plating solution. According to these results, the nickel flash plating solution according to Example 1 shows that iron as an impurity is vaccinated with nickel and has a function of suppressing the concentration of iron.
In general, the increase in iron in the nickel flash plating solution is caused by the flow of water from the wash water and the dissolution of iron in an acidic solution. If the iron is not vaccinated with nickel and consumed, it can only be concentrated in the plating solution. . The present invention solves this problem.
On the other hand, the hydrogen ion concentration of the plating solution increases when using an insoluble anode as shown in Table 1 above. The acidification of the plating liquid can be adjusted back to the pH of the lower plating liquid through replenishment of the neutral nickel flash plating liquid as shown in Example 4 below, and can also replenish the consumed nickel.
A nickel flash plating solution having the same composition as in Example 1 was prepared except that nickel carbonate was used instead of nickel sulfate as the nickel salt.
Nickel carbonate is extremely low in water solubility and cannot be used as it is, so some complexing agents are used to dissolve in neutral or alkaline water. Specifically, the nickel carbonate solution was prepared by dissolving nickel carbonate with 25% ammonia water so that the nickel content was 30 g / l, and then stabilizing by adding 5 g / l gluconic acid and 2 g / l ethylenediaminetetraacetic acid to the whole solution. After that, the same additive as in Example 1 was added to the nickel carbonate solution to prepare a replenishment nickel flash plating solution.
The supplementary plating solution prepared as above had a pH of 6.7, and supplemented with 1 liter of the supplementary plating solution in 10 liter of the plating solution used in Example 2 for 15 days to investigate its composition. The findings are shown in Table 2 below.
The results of Table 2 above, using the replenishment plating solution according to the present invention, it is possible to replenish the nickel ions consumed in the nickel flash plating solution during the nickel plating and to re-acidify the plating solution acidified due to the use of an insoluble anode It can be restored to a state, which means that the service life of the nickel flash plating solution can be extended almost indefinitely.
As Example 5, after the nickel plating using the nickel flash plating solution of Example 1, a conventional electro-zinc plating as in Comparative Example 1 was carried out to prepare a specimen having a nickel coating and a zinc coating, but the amount of nickel plating on the surface of the specimen. The surface properties and the corrosion resistance of the galvanized specimens were evaluated at 50 mg / m 2 , 100 mg / m 2 , 200 mg / m 2 and 300 mg / m 2 . In addition, the surface properties and the corrosion resistance were evaluated together with the specimens according to Comparative Examples 1 and 3 described above. The results are shown in Table 3 below. The galvanized film of the specimens used for the evaluation was 20 g / m 2 .
In Table 3 above, corrosion resistance is measured by using a 5% saline sprayer to measure the time of occurrence of red blue red (at least 5% of the total surface area until the occurrence of red blue). The progress was made by observing the damage situation. In Table 3, (circle) shows the degree to which a damage | damage agent or microcracks generate | occur | produces, (triangle | delta) shows the case where generation | occurrence | production of a large crack or peeling of a plating piece is confirmed, and x shows the case where plating peeling extensively occurs. The paintability was developed by evaluating the coating film adhesion by cross-cut and tape test after chemical treatment and electrodeposition coating of the plating specimen under normal conditions. The evaluation is performed when no peeling occurs at all, when the peeling part is within 5% of the whole, when the peeling part is within 50% of the whole, and when the peeling occurs at an area exceeding 50%. It was made into the system shown by x.
Comparing the physical properties of the galvanized specimens shown in Table 3 above, the corrosion resistance tended to increase as the amount of nickel deposition increased, but the difference was not very large. The paintability was also generally similar, but the difference between the nickel flash plating and the non-nickel plating was significantly different in corrosion resistance and plating adhesion. Comparing Comparative Example 3 and Examples 5a to 5d, although the electro-galvanized film formed according to the present invention has a relatively small nickel deposition amount of about 50 to 300 mg / m 2 , the physical properties thereof are 350 mg / m 2 . Compared with the existing galvanized film, there was no inferiority.
Meanwhile, for reference, surface photographs of specimens corresponding to Examples 5a to 5d of Table 3, respectively, are shown in FIGS. 7A to 7D.
Although specific embodiments of the present invention have been shown and described, the present invention may be variously modified and changed without departing from the spirit of the invention as set forth in the claims below, and this is in the technical field of the present invention. It should be understood that it is self-evident to those of ordinary knowledge.
Claims (14)
Nickel salts;
Conductivity aids to increase conductivity of the plating solution;
A complexing agent used for stabilizing the plating solution and combined with at least iron ions contained in the plating solution to help vacancies of iron ions; And
Nickel flash plating solution comprising a; surface improving agent for smoothing the underlying plating film.
Nickel, characterized in that any one or a combination thereof selected from gluconic acid, ethylenediaminetetraacetic acid (EDTA), sodium alkanoic acid, citric acid, tartaric acid, ziopionate ester, alkylcresol, zincnaphrate, thiourea, imidazole Flash plating solution.
Nickel flash plating solution, characterized in that contained in the plating solution at a concentration of 0.5 ~ 10g / ℓ.
Nickel further comprises any one selected from ethyleneimine, sodium gluconate, ethylenediaminetetraacetic acid, sodium citrate as a vaccinating agent for assisting the vacancy of iron ions contained in the plating solution. Flash plating solution.
Nickel flash plating solution, characterized in that contained in a concentration of 0.1 ~ 50g / L in the plating solution.
It further comprises an antioxidant for preventing the generation of iron hydroxide due to the oxidation of the iron ion, the antioxidant is composed of any one or a combination thereof selected from benzoic acid, fluorine resin, the antioxidant is 0.1 in the plating solution Nickel flash plating solution, characterized in that contained in a concentration of ~ 25g / ℓ.
Nickel flash plating solution, characterized in that it is added to the plating solution so that the nickel concentration in the plating solution is 10 ~ 200g / ℓ.
The conductive salt is any one selected from sodium sulfate, ammonium sulfate, sulfamic acid, boric acid, ammonium fluoride, sodium formate, ammonium formate, ammonium phosphate, potassium sulfate, ammonium chloride, potassium chloride, sodium chloride, or a combination thereof. Flash plating solution.
Nickel flash plating solution, characterized in that contained in a plating solution at a concentration of 10 ~ 200g / ℓ.
Nickel salts dissolved and neutral;
Conductivity aids to increase conductivity of the plating solution;
A complexing agent used to stabilize the plating solution and combined with at least iron ions in the plating solution to help vacancies of iron ions; And
Nickel flash plating solution comprising a; surface improving agent for smoothing the underlying plating film.
Nickel carbonate, nickel sulfamate, nickel acetate, nickel formate, nickel fluoride, nickel fluoride, any one or a combination thereof, nickel flash plating solution.
Nickel, characterized in that any one or a combination thereof selected from gluconic acid, ethylenediaminetetraacetic acid (EDTA), sodium alkanoic acid, citric acid, tartaric acid, ziopionate ester, alkylcresol, zincnaphrate, thiourea, imidazole Flash plating solution.
A nickel plated film formed on the surface of the steel sheet using the nickel flash plating solution according to any one of claims 1 to 9; And
The galvanized steel sheet formed on the nickel plated film and comprises a zinc plated film containing at least iron.
Immersing the washed steel sheet as a nickel flash plating solution according to any one of claims 1 to 9 in a nickel flash plating solution having a pH of 2.0 to 6.0 and a temperature of 35 to 70 ° C. to form a nickel plated film on the surface of the steel sheet; And
And immersing the steel plate on which the nickel plated film is formed in a zinc plating solution to form an electrogalvanized film.
The method of manufacturing an electro-zinc plated steel sheet comprising using the nickel flash plating solution according to any one of claims 10 to 12 as a solution for replenishing the nickel flash plating solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100001522A KR20100121399A (en) | 2010-01-08 | 2010-01-08 | Nickel flash plating solution, zinc-electroplated steel sheet and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100001522A KR20100121399A (en) | 2010-01-08 | 2010-01-08 | Nickel flash plating solution, zinc-electroplated steel sheet and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20100121399A true KR20100121399A (en) | 2010-11-17 |
Family
ID=43406747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020100001522A KR20100121399A (en) | 2010-01-08 | 2010-01-08 | Nickel flash plating solution, zinc-electroplated steel sheet and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20100121399A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017026683A1 (en) * | 2015-08-11 | 2017-02-16 | 주식회사 포스코 | Zinc flash plating solution for galvanized steel sheet having excellent surface appearance, method for manufacturing galvanized steel sheet using same, and galvanized steel sheet |
| CN107460506A (en) * | 2017-09-29 | 2017-12-12 | 佛山市春暖花开科技有限公司 | A kind of electroplate liquid of nickel |
| KR20200036340A (en) * | 2018-09-28 | 2020-04-07 | 주식회사 포스코 | High strength Electroplated Steel Sheet Having Excellent Hydrogen Crack Resistance |
| KR102587490B1 (en) * | 2022-12-05 | 2023-10-11 | 동국제강 주식회사 | Plating method of slab for clad steel plate with excellent corrosion resistance and slab for clad steel plate with excellent corrosion resistance manufactured therewith |
-
2010
- 2010-01-08 KR KR1020100001522A patent/KR20100121399A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017026683A1 (en) * | 2015-08-11 | 2017-02-16 | 주식회사 포스코 | Zinc flash plating solution for galvanized steel sheet having excellent surface appearance, method for manufacturing galvanized steel sheet using same, and galvanized steel sheet |
| CN107460506A (en) * | 2017-09-29 | 2017-12-12 | 佛山市春暖花开科技有限公司 | A kind of electroplate liquid of nickel |
| KR20200036340A (en) * | 2018-09-28 | 2020-04-07 | 주식회사 포스코 | High strength Electroplated Steel Sheet Having Excellent Hydrogen Crack Resistance |
| KR102587490B1 (en) * | 2022-12-05 | 2023-10-11 | 동국제강 주식회사 | Plating method of slab for clad steel plate with excellent corrosion resistance and slab for clad steel plate with excellent corrosion resistance manufactured therewith |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100976787B1 (en) | Zinc plated steel having iron flash plating film thereon and composition of bath of iron flash plating and method for manufacturing the zinc plated steel | |
| EP2980279B1 (en) | Zinc-nickel alloy plating solution and plating method | |
| KR101502804B1 (en) | Pd and Pd-Ni electrolyte baths | |
| KR101046301B1 (en) | Nickel flash plating solution, electric zinc steel sheet and manufacturing method thereof | |
| CN102171386B (en) | Zinc alloy electroplating baths and processes | |
| CN109137007A (en) | Environmentally friendly nickel electroplating composition and method | |
| EP3428323B1 (en) | Nickel electroplating compositions with cationic polymers and methods of electroplating nickel | |
| KR20100121399A (en) | Nickel flash plating solution, zinc-electroplated steel sheet and manufacturing method thereof | |
| US20090159453A1 (en) | Method for silver plating | |
| US20040074775A1 (en) | Pulse reverse electrolysis of acidic copper electroplating solutions | |
| KR101288085B1 (en) | Zinc plated steel having iron flash plating film thereon and bath of iron flash plating and method for manufacturing the zinc plated steel | |
| KR20190009357A (en) | Zinc-nickel-iron ternary alloy and an alkaline electrolyte for such an alloy plating | |
| EP3642396B1 (en) | Nickel electroplating bath for depositing a decorative nickel coating on a substrate | |
| EP2096193A1 (en) | Process for the preparation of corrosion resistant zinc and zinc-nickel plated linear or complex shaped parts | |
| CA2247440A1 (en) | Tin plating method and bath having wide optimum current density range | |
| CN114164466B (en) | Alkaline electrogalvanized ferroalloy additive and electroplating solution | |
| KR101173879B1 (en) | Multi-functional super-saturated slurry plating solution for nickel flash plating | |
| JPS5841357B2 (en) | Acidic zinc plating solutions and plating methods using ethoxylated/propoxylated polyhydric alcohols | |
| KR102524409B1 (en) | Composition for alkaline zinc-nickel alloy plating solution | |
| KR102578696B1 (en) | Method of manufacturing zn-ni alloy plating solution and method of plating using the same | |
| WO2010101212A1 (en) | Copper-zinc alloy electroplating bath and method of plating using same | |
| KR20130070235A (en) | Fe-based eletrolyte for galvanized steel sheets in sulfuric bath | |
| KR102173164B1 (en) | Mixed brighteners for zincate plating solution and Zincate plating solution containing the same | |
| KR102336506B1 (en) | A Cyanide Copper Plating Solution And A Method for Cyanide Copper Plating Using The Same | |
| EP3428322B1 (en) | Nickel electroplating compositions with copolymers of arginine and bisepoxides and methods of electroplating nickel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| G15R | Request for early opening | ||
| A302 | Request for accelerated examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application |