KR19980051207A - Aluminum silicon dioxide composite plated steel sheet with excellent gloss and corrosion resistance and manufacturing method - Google Patents

Abstract

The present invention relates to a plated steel sheet using an electron beam vacuum deposition method and a method for manufacturing the same, and an object thereof is to provide a composite plated steel sheet excellent in gloss and corrosion resistance of a plated aluminum and silicon dioxide at the same time and a method for producing the same.

In order to achieve the above object, the present invention is an aluminum-silicon dioxide composite plated steel sheet having excellent gloss and corrosion resistance, in which an aluminum-silicon dioxide deposition plating layer containing 1-10% by weight of silicon dioxide is formed with an adhesion amount of 2 g / m 2 or more per steel sheet plane. In the method for producing a composite plated steel sheet by vacuum deposition using an electron beam, heating the base steel sheet in the range of 100-350 ℃, and then the aluminum-silicon dioxide containing 1-10% by weight of silicon dioxide The technical gist of the present invention relates to a method for producing an aluminum-silicon dioxide composite plated steel sheet having excellent glossiness and corrosion resistance by vacuum deposition at an adhesion amount of not less than 2 g / m 2.

Description

Aluminum-silicon dioxide composite plated steel sheet with excellent gloss and corrosion resistance and manufacturing method

The present invention relates to a plated steel sheet using an electron beam vacuum deposition method and a method for manufacturing the same, and more particularly, a composite plated steel sheet having excellent gloss and corrosion resistance in which aluminum (Al) and silicon dioxide (SiO ₂ ) are plated at the same time. It relates to a manufacturing method.

In general, electroplated steel sheets and hot-dip galvanized steel sheets used in automobile exteriors and home appliances are required to have excellent surface appearance characteristics such as corrosion resistance, paintability, weldability, and glossiness according to demand quality characteristics.

Conventionally, various methods have been developed to improve such characteristics. A representative method for increasing the corrosion resistance and glossiness is a dispersion plating method in which various other metal ions or oxide ions are simultaneously plated in a zinc plating solution in Japan. It is disclosed in Japanese Patent Application Laid-Open Nos. (S) 64-62498 and (Pyeong) 1-129998 and the like.

In the above-mentioned proposal, in the plating of zinc by the electroplating method, a dispersion plating method in which an oxide, such as Al ₂ O ₃ , SiO ₂ , TiO ₂ , is plated in a plating solution and then plated, is used. It is excellent in quality characteristics such as corrosion resistance than plated steel sheet or zinc-nickel alloy plated steel sheet, and has the characteristic that the glossiness of plated steel sheet is increased by the addition of NO ₃ ions. However, there are some problems in producing and producing a plated steel sheet by the proposed dispersion plating method. First, a separate tank system is required for ultrasonically treating a tank, which is a plating solution container, to prevent agglomeration of the dispersant dispersed in the plating solution. In addition, when the dispersant is exposed to the air for a long time at 0 ° C. or less for a long time, a stable dispersant tends to precipitate in a milky gel state, which makes it difficult to manage the dispersant. In addition, the concentration and pH of the plating solution must be precisely controlled for uniform precipitation of the dispersant in the plating layer. In addition, the dispersion plating method is performed in the wet plating, so the working environment is poor, it is easy to cause environmental pollution problems, and a separate facility for wastewater treatment of the plating solution is required.

Meanwhile, a method of simultaneously plating zinc and silicon dioxide by physical vapor deposition in order to manufacture a plated steel sheet excellent in corrosion resistance has been proposed in Japanese Patent Laid-Open No. 54-11441. The above proposal was to improve the corrosion resistance by producing a single layer of zinc-silicon dioxide composite plated steel sheet, in which the amount of silicon dioxide added in the composite plating layer was 0.1 to 80%, but as the amount of silicon dioxide added increased, the corrosion resistance of the plated layer increased. On the contrary, the greater the amount of dioxide added, the poorer the adhesion of the plated layer, and therefore, there is little possibility of commercial melting.

In addition, when the silicon dioxide is plated by physical vapor deposition, the evaporation rate of the silicon dioxide is very slow compared to zinc, which has a disadvantage of poor productivity. That is, since the evaporation rate of silicon dioxide is usually 100 times less than the evaporation rate of zinc, in order to make a composite plating layer containing 50% by weight of silicon dioxide, the product must be produced according to the evaporation rate of silicon dioxide. Production speed is bound to drop very much.

The present method provides an aluminum-silicon dioxide composite plated steel sheet having excellent corrosion resistance and glossiness by using a vacuum deposition method without dispersing agent, environmental pollution, wastewater treatment, etc., which is a conventional problem, and a manufacturing method thereof. There is a purpose.

One aspect of the present invention for achieving the above object is an aluminum-silicon dioxide having excellent gloss and corrosion resistance that the aluminum-silicon dioxide deposition plating layer containing 1-10% by weight of silicon dioxide is formed with an adhesion amount of 2g / ㎡ or more per sheet steel sheet It is about composite plated steel sheet.

In addition, another aspect of the present invention is a method for producing a composite plated steel sheet by vacuum deposition using an electron beam, the substrate is heated to 100-350 ℃ range, and then containing 1-10% by weight of di-silicon The present invention relates to a method for producing an aluminum-silicon dioxide composite plated steel sheet having excellent gloss and corrosion resistance for vacuum-depositing aluminum-silicon dioxide at a deposition amount of ² g / m ² or more per one side of the steel sheet.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

When the content of silicon dioxide in the aluminum-silicon dioxide composite plating layer deposited on the surface of the steel sheet according to the present invention is less than 1% by weight, the increase in corrosion resistance and glossiness is not obvious. Since the adhesion of the resin becomes poor, the content of silicon dioxide in the aluminum-silicon dioxide composite plating layer is preferably in the range of 1 to 10% by weight.

In addition, when the plating adhesion amount of the aluminum-silicon dioxide vacuum deposition composite plating insect is less than 2g / m 2, the corrosion resistance is deteriorated and the plating layer properties are poor. Therefore, the plating deposition amount of the aluminum-silicon dioxide vacuum deposition composite plating layer is preferably 2g / m 2 or more. Do.

Hereinafter, a method of manufacturing a composite plated steel sheet excellent in high corrosion resistance and glossiness according to the present invention will be described.

In the present invention, a conventional electron beam vacuum deposition method is used as a method of depositing an aluminum-silicon dioxide composite plating layer containing 1-10 weight of silicon dioxide on the surface of a steel sheet with an adhesion amount of 2 g / m 2 per single steel sheet.

Referring to the representative manufacturing process for forming the aluminum-silicon dioxide composite plating layer by the electron beam vacuum deposition method according to the present invention.

First, the existing cold rolled steel sheet, which is a small substrate, is cut to an appropriate size, and then charged into a vacuum chamber of a vacuum deposition apparatus, and at the same time, charged into a copper crucible by depositing aluminum and silicon dioxide (SiO ₂ ) as grains. do. Then, the vacuum degree of the vacuum chamber is evacuated to 10 ^-4 torr, and then aluminum and discrete silicon are melted with an electron beam. Where aluminum, the metal, melts and begins to evaporate. Silicon dioxide is semi-melted only on the surface and evaporates. The vaporized gas of aluminum and silicon dioxide meets the steel sheet and is deposited on the surface of the steel sheet to produce a steel sheet compositely plated with aluminum and silicon dioxide.

At this time, the substrate temperature of the steel sheet, which is a small substrate, is very important. If the substrate temperature of the steel sheet is too low below 100 ℃, the adhesion between the plated layer and the steel sheet is weak and peeling occurs during processing. If the substrate temperature is above 350 ℃, it forms an alloy with aluminum in the base steel sheet. It also weakens the adhesion. After all, the temperature of a suitable substrate is preferably carried out between 100 ℃ to 350 ℃.

Hereinafter, the present invention will be described in detail through examples.

Example

In the Invention Example (1-6) and Comparative Example (1-6) of Table 1, a vacuum deposition apparatus after degreasing a general cold rolled steel sheet having a thickness of 8 mm and a roughness range of 0.7-1.2 μm cut to a size of 10 × 15 cm Was loaded into a vacuum crucible, and at the same time, aluminum and silicon dioxide (SiO ₂ ), which were deposited, were loaded into the copper crucible. The vacuum degree of the vacuum chamber was evacuated to 10 ^-4 torr, and the aluminum and silicon dioxide were evaporated with the Hanwoo, the electron beam, and a composite plated steel sheet was plated with an adhesion amount of 20 g / m2 per sheet of steel and composited with aluminum and silicon dioxide. At this time, the silicon dioxide content and the substrate temperature in the aluminum-silicon dioxide composite plating layer deposited on the steel plate surface were set as the conditions shown in Table 1 below.

In addition, in Comparative Example (7-8) of Table 1, after degreasing a general cold rolled steel sheet having a thickness of 10 mm and a roughness range of 0.7-1.2 µm, cut into a size of 10 × 15 cm, the product was charged into a vacuum chamber of a vacuum deposition apparatus. At the same time, the deposited materials zinc and silicon dioxide (SiO ₂ ) were loaded into graphite and copper crucible in the form of grains. The vacuum degree of the vacuum chamber was evacuated to 10 ^-4 torr, followed by evaporation of zinc and silicon dioxide with an electron beam, and a composite plated steel sheet coated with zinc and silicon dioxide at a coating amount of 20 g / m2 per sheet steel sheet. .

At this time, the discrete silicon content and the substrate temperature in the plating layer was set as the conditions of the following Table 1. In the case of Comparative Example (1), zinc is plated by the conventional electroplating method. The plating amount of zinc was 20 g / m <2> here.

In addition, in the case of Comparative Example (10-11) of Table 1 is a case where zinc is plated by the conventional dispersion plating method. As a dispersant, Snowtex-0 manufactured by Ilsan Chemical Co., Ltd. (Japan), in which 10-20 μm of dioxide dioxide (SiO ₂ ) is dispersed, was used. Plating solution is Zn ²⁺ at pH = 2 is 70g / ℓ, Cl ^1- was added 40g / ℓ to 230g / ℓ, SiO _2. Furthermore, in Comparative Example (10), 1.5 g / L of NaNO ₃ was added, and in Comparative Example (11), 30 g / L of Ni ²⁺ ions were added. In addition, the plating solution was left in the air for one week in order to examine the flocculation phenomenon of the dispersant, and then the aggregation was observed.

In order to evaluate the product characteristics of the aluminum-silicon dioxide composite plating prepared as described above, the adhesion, glossiness and corrosion resistance were evaluated. First, in order to evaluate the adhesion of the plating layer, the specimen was bent 180 degrees and then peeled off using an adhesive tape. Glossiness was measured by reflecting light in the visible sugar region, and near-degree and reflection angles were measured at an angle of 60 ° based on the normal direction of the specimen. And the gloss value of the standard sample as a reference 100 was measured for the gloss value of each specimen. Finally, to evaluate the corrosion resistance of each product, a salt spray test was conducted in a salt atmosphere of 5% according to ASTM Bl17-73. The corrosion resistance was compared and evaluated by observing the time until the red blue development time. The results measured as described above are shown in Table 1 below.

Note) Adhesiveness ◎: Excellent ○: Good △: Partial peeling X: Peeling

As shown in Table 1, in the invention example (1-6), in the deposition of aluminum and silicon dioxide at the same time, the substrate temperature is between 100 ℃ to 350 ℃, the amount of silicon dioxide added from 1% by weight to 10% by weight If it is set to%, it is possible to manufacture a plated steel sheet excellent in gloss and corrosion resistance while maintaining good adhesion.

However, in the case of Comparative Example (1), the adhesion was poor when the substrate temperature was maintained at room temperature, and in the case of Comparative Example (2), when the substrate temperature was maintained at 400 ° C, the adhesion was poor by forming an alloy with iron and aluminum of the substrate. It was. In the case of Comparative Example (3-4), if the amount of added silicon dioxide was 0.5 wt% or less, there was no increase in corrosion resistance. On the other hand, if the added amount of silicon dioxide is 15% by weight and 20% by weight, as in Comparative Example (5-6), the adhesion is reduced, and the value as a product is lowered even if the corrosion resistance is increased. Inventive Example (1-6) according to the present invention, the time until the generation of red blue due to the salt spray was increased up to 10 times or more than in the case of plating only zinc with conventional electroplating as in the case of Comparative Example (9).

On the other hand, in the case of the comparative example (7) which plated zinc and silicon dioxide at the same time, when the addition amount of silicon dioxide was 10 weight%, it turned out that corrosion resistance is inferior to the invention example (5) which plated the same addition amount. This is because not only silicon dioxide but also aluminum has better corrosion resistance to salt water than zinc. In addition, when 50 wt% of the silicon dioxide is soaked as in Comparative Example (8), the corrosion resistance is increased, but the adhesion of the plating layer is poor, so that the plating layer peeling phenomenon occurs during processing.

And the glossiness of the product by this invention showed the resin about 5 times higher than the glossiness of the comparative example (1) which is an electrogalvanized steel sheet. On the other hand, as in the case of Comparative Example (10-11) it can be seen that when the zinc and silicon dioxide is plated with the conventional dispersion plating 뱁 corrosion resistance increases according to the precipitation amount of the silicon dioxide as a dispersant. In particular, the addition of Ni ions as in Comparative Example (11) could increase the glossiness. However, as described above, since the dispersion plating method is a method of treating with a plating solution, a wastewater treatment system is required, and as shown in Table 1 above, when the plating solution is left for a long time, a coagulation phenomenon of the dispersant is generated, and a separate solution for the management of plating solution The disadvantage is the need for a system.

As described above, according to the present invention, since aluminum-silicon dioxide is deposited on a steel sheet by an electron beam vacuum deposition method, plating is performed in a vacuum rather than a wet method as in the conventional dispersion plating method, so there is no environmental pollution problem and wastewater treatment. In addition, since the vacuum evaporation method can simultaneously plate the steel sheet by evaporating the metal and the industrial products, there is no agglomeration phenomenon of the dispersant which is a problem in the dispersion plating method. In particular, since aluminum and silicon dioxide are plated at the same time, it is possible to provide an electrogalvanized steel plate plated with zinc alone or a plated steel plate having better corrosion resistance and glossiness than zinc-silicon dioxide. There is an effect that can be applied to automobile exterior and home appliances building materials.

Claims (2)

An aluminum-silicon dioxide composite plated steel sheet having excellent gloss and corrosion resistance, wherein an aluminum-silicon dioxide deposited plating layer containing 1-10% by weight of silicon dioxide is formed at an adhesion amount of 2 g / m 2 or more per sheet steel sheet. In the method for producing a composite plated steel sheet by vacuum deposition using an electron beam, the base steel sheet is heated to a range of 100-350 ° C., and then aluminum-silicon dioxide containing 1-10% by weight of silicon dioxide per sheet steel sheet A method for producing an aluminum-silicon dioxide composite plated steel sheet having excellent gloss and corrosion resistance, characterized by vacuum deposition at an adhesion amount of 2 g / m 2 or more.