KR20160149522A - Aluminum thin film of an electrolyte and aluminum thin film using the plating method for plating and its manufacturing aluminum-coated products - Google Patents
Aluminum thin film of an electrolyte and aluminum thin film using the plating method for plating and its manufacturing aluminum-coated products Download PDFInfo
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- KR20160149522A KR20160149522A KR1020150086655A KR20150086655A KR20160149522A KR 20160149522 A KR20160149522 A KR 20160149522A KR 1020150086655 A KR1020150086655 A KR 1020150086655A KR 20150086655 A KR20150086655 A KR 20150086655A KR 20160149522 A KR20160149522 A KR 20160149522A
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- aluminum
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- coating
- electrolyte
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- 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
- C25D3/42—Electroplating: Baths therefor from solutions of light metals
- C25D3/44—Aluminium
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- 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
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
- C25D5/44—Aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
Abstract
Description
The present invention relates to a coating liquid, a coating method, and a thin film coating product for forming an aluminum thin film on the surface of a relatively inexpensive and unavailable substrate so as to have excellent properties suitable for use. More specifically, And a method of coating an aluminum thin film using the same, and an aluminum coated product manufactured by the method.
The 21st century is referred to as the era of design, and it is developing as a trend across industries such as architecture, IT, transportation, and aerospace. Particularly, importance is increasing in IT fields such as mobile cases, notebooks, and cameras that emphasize personality and texture. Representative materials widely used in these fields include metals such as aluminum and magnesium. The metal makes the feel of the cold and warm touch of the four seasons, and has the luster and color of the metal.
On the other hand, there are dozens of types of metals on the earth including nonferrous metals, and hundreds of kinds of alloys are included. However, most metals require a secondary surface treatment because of their poor resistance to corrosion, durability, and abrasion resistance. In addition, aluminum, titanium, and the like are extremely limited in metals that can reproduce various colors and metallic textures by a post-treatment process. Therefore, there is a need for a surface treatment method which can satisfy the disadvantages of metals and can satisfy both color, metallic texture and corrosion resistance on all metallic materials such as iron and copper.
As the thin film treatment methods known so far, wet methods such as electroplating and hot-dip coating and vacuum deposition (CVD, PVD) have been studied. However, since aluminum has a high ionization tendency, electroplating in a water-soluble state is impossible. In the case of the vacuum deposition method using CVD, PVD, etc., it is disadvantageous in that the substrate can not be mass-produced, the manufacturing cost is high, and the film thickness is thin. In addition, the hot-dip coating has a disadvantage in that it can not obtain a uniform coating film, thereby deteriorating the quality of the product. The development of electroplating through a non-aqueous electrolytic solution capable of minimizing facility cost required for plating and improving workability and securing quality and price competitiveness is intensifying.
For example, Korean Patent Laid-Open Publication No. 10-2014-0129342 discloses a method of preparing a plating solution for low-melting-point electric aluminum plating, a plating solution for electric aluminum plating, a method for producing aluminum foil, and a method for lowering the melting point of a plating solution for electric aluminum plating And Korean Patent Laid-Open Publication No. 10-2015-0054840 "Method for producing aluminum film ". The former can be electroplated without being solidified at 25 DEG C, thereby reducing the amount of electric power used, which is advantageous in terms of economy. The latter is excellent in surface smoothness and enables the aluminum film having a mirror surface to be continuously mass-produced.
However, since the former and the latter only improve certain disadvantages that occur during manufacture, there is a problem that can not be applied to various substrates. And, there is uncertainty about the plating conditions such as plating solution composition, plating temperature and current density, and some conditions depend on know-how only, and quality and compatibility are degraded.
Accordingly, it is an object of the present invention to fundamentally solve the conventional problems as described above, and it is an object of the present invention to provide an aluminum thin film coating which can be applied to various substrates, workability that can be accessed by anyone, excellent corrosion resistance, And a method for coating an aluminum thin film using the electrolytic solution and an aluminum thin film coating product produced therefrom.
In order to achieve the above object, one aspect of the present invention is to provide an electrolytic solution for coating an aluminum thin film, comprising: an organic solvent comprising 10 mol of dimethylsulfone and 2.0 to 6.0 mol of anhydrous aluminum chloride, Wherein the compound is added.
The compound according to the present invention is characterized in that it is composed of 0.1 to 2.0 mol of ammonium chloride and 0.1 to 5.0 mol of xylene or toluene or benzene .
According to another aspect of the present invention, there is provided a method of coating an aluminum thin film on a surface of a substrate, comprising: a pretreatment step of sequentially performing washing, degreasing, neutralization and drying on the substrate; Preparing a bath in which an electrolytic solution having at least one compound added to an organic solvent comprising 10 mol of dimethylsulfone and 2.0 to 6.0 mol of anhydrous aluminum chloride is prepared; The substrate is connected to the negative electrode, the bathtub and the aluminum plate used for the coating are connected to the positive electrode, respectively, and are immersed in the electrolyte solution; And a coating step of supplying electric power to the negative and positive electrodes while the electrolytic solution is heated to form an aluminum thin film on the surface of the substrate.
The pretreatment process according to the present invention comprises the steps of washing the base material with distilled water, degreasing the remaining fat component remaining on the washed base material with an electrolyte consisting of sodium carbonate and a surfactant, and removing the degreased base material with a nitric acid solution for 30 seconds And immersing the neutralized substrate in acetone for 10 seconds, followed by drying, in that order.
Also, the degreasing step according to the present invention is characterized in that the substrate connected to the anode is immersed in a bath in which the cathode is connected to the bath containing the electrolytic solution, and is then energized for 30 seconds at a current density of 3 to 4 A / dm 2 .
The compound of the preparation process according to the present invention may be prepared by mixing 0.1 to 2.0 moles of ammonium chloride and 0.1 to 5.0 moles of xylene or any one of toluene or benzene .
In addition, the coating process according to the present invention is characterized in that a power source of 8 to 12 A / dm 2 is energized for 60 to 100 minutes while the electrolyte is heated to 100 to 105 캜.
The coating process according to the present invention is characterized in that the cathode is rotated in order to maintain the temperature of the electrolyte uniformly and to prevent concentration polarization.
It should be understood, however, that the terminology or words of the present specification and claims should not be construed in an ordinary sense or in a dictionary, and that the inventors shall not be limited to the concept of a term It should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be properly defined. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, It is to be understood that equivalents and modifications are possible.
As described in the above constitution and operation, the present invention can simplify the components constituting the electrolytic solution and the coating conditions, thereby making it possible to provide a non-specialist. In addition to securing cost competitiveness by reducing the amount of air consumed in coating, As a matter of course, it is possible to improve overall quality by having excellent corrosion resistance and decorative property.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart illustrating a method of manufacturing in accordance with an embodiment of the present invention.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
One aspect of the present invention relates to an electrolytic solution for coating an aluminum thin film. In the electrolyte of the present invention, at least one organic compound is added to an organic solvent comprising 10 mol of dimethylsulfone and 2.0 to 6.0 mol of anhydrous aluminum chloride. Namely, dimethylsulfone was slowly added to anhydrous aluminum chloride in a nitrogen atmosphere at room temperature and mixed. After mixing, slowly warm to 120 to 150 ° C and dissolve by stirring. When the organic solvent is completed in an optimal molar amount, a compound which improves the adhesion of the aluminum thin film to the surface of the substrate may be added. The compound is composed of 0.1 to 2.0 moles of ammonium chloride and 0.1 to 5.0 moles of xylene or toluene or benzene. The effect of such an electrolytic solution will be demonstrated through the experiments described below.
Another aspect of the present invention relates to a method of coating an aluminum thin film on a surface of a substrate. The method includes a pre-treatment step (S10), a preparation step (S20), an installation step (S30) and a coating step (S40) Aluminum thin film coating product.
- preprocessing step (S10) -
In the pretreatment step (S10), the substrate is processed into a predetermined shape before coating the substrate, and the processed oil or organic impurities and the oxide film are removed on the surface by molding. That is, the surface of the substrate is made most suitable for the coating treatment, and the adhesion of the aluminum thin film is improved, thereby providing a basic step for obtaining excellent quality.
First, the selected substrate is washed with distilled water, and the remaining fat component remaining on the washed substrate is degreased with an electrolyte consisting of sodium carbonate and a surfactant. Here, the degreasing step is connected to the positive electrode, and the substrate to which the negative electrode is connected is immersed in a bath containing the electrolytic solution, and then the current is supplied at a current density of 3 to 4 A / dm 2 for 30 seconds. The electrolytic solution is heated to 70 to 80 ° C It is good to do.
Subsequently, the degreased base material is immersed in a nitric acid solution for 30 seconds to neutralize, and the neutralized substrate is immersed in acetone for 10 seconds and then dried. The neutralization step neutralizes the alkali remaining on the surface of the substrate to convert the surface to an activated state. In order to prevent corrosion due to excessive acidity, the nitric acid solution is suitably mixed with 85 to 90 wt% of distilled water so as to contain 10 to 15 wt% of nitric acid. The reason for drying after immersing in acetone in the drying step is to prevent moisture from being mixed on the surface of the substrate.
- Preparation step (S20) -
In the preparation step (S20), an electrolytic solution inducing a reaction by electrolysis is formed when the surface is coated with a base material. The electrolytic solution is prepared by adding 0.1 to 2.0 mol of ammonium chloride and 0.1 to 5.0 mol of xylene to an organic solvent composed of 10 mol of dimethylsulfone and 2.0 to 6.0 mol of aluminum chloride, Or a compound composed of any one of toluene (Toluene) and benzene (Benzene) is added. The process of forming the electrolytic solution is the same as that described above, so that a separate explanation will be omitted.
- Installation process (S30) -
The installation process (S30) is a process of connecting the power source. That is, the substrate to be coated is connected to the negative electrode, and the aluminum plate, which is the raw material of the bathtub and the coating, is connected to the positive electrode and immersed in the electrolyte solution. Here, the aluminum plate has a relatively wide purity of 99% and a thinner thickness. A power supply and a feedback thermometer are also installed to measure the temperature according to the solidification point of the electrolyte.
- coating process (S40) -
In the coating step (S40), an aluminum thin film is formed on the surface of the substrate to complete the product. That is, power is supplied to the negative electrode in a state where the electrolytic solution contained in the bath is warmed to form an aluminum thin film having a predetermined thickness on the surface of the substrate . Here, the temperature of the electrolytic solution is in a liquid state at room temperature by an eutectic reaction between anhydrous aluminum chloride, dimethylsulfone and ammonium chloride. However, in order to smoothly move the electrolyte, It is preferable to conduct current with a constant current of 8 to 12 A / dm 2 for a minute. It is also desirable to rotate the cathode to prevent concentration polarization while maintaining the temperature of the electrolyte uniformly.
The coated aluminum coated product has an aluminum thin film of 10 탆 or more densely formed on the surface of the substrate and has excellent corrosion resistance and electrical and thermal conductivity. On the other hand, finished aluminum coated products may be further roughened to meet the desired properties.
<< Experimental Method >>
In this experiment, Al-Si-Zn based alloys produced by casting using a mold were used as base materials. This material is lightweight but has excellent mechanical properties and is most widely used in IT fields such as smartphone cases, notebooks, and netbooks. However, there is a drawback that the corrosion resistance and electrical and thermal conductivity are poor. In order to overcome these drawbacks and improve the quality, we will try to coat the aluminum film on the surface and investigate the effect of the film. The specifications of the substrate are as follows.
Street
(G)
(w)
(T)
radius
(R)
Jong Gil
(L)
Length
(A)
width
(C)
Unit: mm
<Electrolyte Raw Material>
(99%, Sigma-Aldrich), anhydrous aluminum chloride (99%, Sigma-Aldrich), ammonium chloride (99%, Sigma-Aldrich) and xylene (99% Was used.
<Procedure>
The coating of the aluminum thin film is preferably carried out by a pretreatment step for rusting and maintenance of the base material and for improving adhesion with the thin film, a preparation step for preparing an electrolyte solution for inducing precipitation of metal ions when the base material is coated on the surface, An aluminum foil was formed on the surface of the substrate, and a coating process for completing the product was performed in sequence.
<Experimental Conditions>
In order to calculate the optimum molar amount at the time of coating the aluminum thin film, the electrolytic solutions classified into the plural examples and the comparative examples were respectively used. The coating temperature was 100 ° C and the coating time was 60 minutes. Here, only one shoulder (B) was treated in order to observe the change of the characteristics of the substrate according to the coating.
<Characteristic evaluation>
The microstructure and cross section of the aluminum thin film were observed by coating and the effect of salt spraying on the corrosion resistance was investigated. The surface was observed by FE-SEM (Hitachi / Horiba, Horiba, S-4800 / EX-250) and sprayed with sodium hydroxide solution at 35 ℃ and 5% I left it.
As a result of observation, in Examples 1 to 4 in which anhydrous aluminum chloride was excessively formed, an aluminum thin film was formed, but it was confirmed that the particle size was large and coarse. However, it can be seen that in Example 5 and Example 6 in which a small amount of aluminum chloride is present, they have comparatively small particle size and low surface roughness. On the other hand, in Comparative Examples 1 and 2, it was found that the formation of the thin film was not uniform and the aluminum thin film was not formed in part.
As a result, the aluminum thin film was uniformly and densely formed on the surface of the substrate, but the thin film was not uniformly formed in the comparative example.
As a result, it was found that the surface of the sample of Comparative Example in which the formation of the aluminum thin film of high purity was not formed was strongly corroded by the salt water. It was found that when the aluminum thin film of high purity was densely formed, the corrosion resistance of the substrate was enhanced.
<Experimental Results>
The electrolytic solution for coating the aluminum thin film was composed of 10 mol of dimethyl sulfone, 3 mol of aluminum chloride, 0.3 mol of ammonium chloride and 5.0 mol of xylene and the electrolytic solution was heated at 100 DEG C for 8 to 12 A / dm 2 was most ideal.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined by the appended claims. It is therefore intended that such variations and modifications fall within the scope of the appended claims.
S10: Pretreatment Step S20: Preparation Step
S30: Installation process S40: Coating process
Claims (9)
Characterized in that at least one compound is added to an organic solvent comprising 10 mol of dimethylsulfone and 2.0 to 6.0 mol of anhydrous aluminum chloride (Aluminum chloride, anhydrous).
Wherein the compound is composed of 0.1 to 2.0 moles of ammonium chloride and 0.1 to 5.0 moles of xylene or toluene or benzene.
A pretreatment step of washing, degreasing, neutralizing and drying the substrate sequentially;
Preparing a bath in which an electrolytic solution having at least one compound added to an organic solvent comprising 10 mol of dimethylsulfone and 2.0 to 6.0 mol of anhydrous aluminum chloride is prepared;
The substrate is connected to the negative electrode, the bathtub and the aluminum plate used for the coating are connected to the positive electrode, respectively, and are immersed in the electrolyte solution;
And a coating step of supplying electric power to the negative and positive electrodes while heating the electrolytic solution to form an aluminum thin film on the surface of the substrate.
The pretreatment includes washing the substrate with distilled water, degreasing the remaining component of the washed substrate with an electrolyte solution composed of sodium carbonate and a surfactant, neutralizing the degreased substrate with a nitric acid solution for 30 seconds, , And the step of immersing the neutralized substrate in acetone for 10 seconds and then drying is carried out in this order.
Wherein the degreasing step is carried out at a current density of 3 to 4 A / dm < 2 > for 30 seconds after the substrate connected to the cathode is immersed in a bath containing the electrolytic solution.
Wherein the compound of the preparing step is composed of 0.1 to 2.0 moles of ammonium chloride and 0.1 to 5.0 moles of xylene or toluene or benzene. Coating method.
Wherein the coating process is performed by supplying a power of 8 to 12 A / dm 2 for 60 to 100 minutes while the electrolyte is heated to 100 to 105 캜.
Wherein the coating step comprises rotating the cathode to maintain the temperature of the electrolyte uniformly and to prevent concentration polarization.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140129342A (en) | 2012-02-29 | 2014-11-06 | 히타치 긴조쿠 가부시키가이샤 | Method for preparing low-melting-point plating solution for electrical aluminum plating, plating solution for electrical aluminum plating, method for producing aluminum foil, and method for lowering melting point of plating solution for electrical aluminum plating |
| KR20150054840A (en) | 2012-09-18 | 2015-05-20 | 스미토모덴키고교가부시키가이샤 | Method for producing aluminum film |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140129342A (en) | 2012-02-29 | 2014-11-06 | 히타치 긴조쿠 가부시키가이샤 | Method for preparing low-melting-point plating solution for electrical aluminum plating, plating solution for electrical aluminum plating, method for producing aluminum foil, and method for lowering melting point of plating solution for electrical aluminum plating |
| KR20150054840A (en) | 2012-09-18 | 2015-05-20 | 스미토모덴키고교가부시키가이샤 | Method for producing aluminum film |
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