KR101789725B1 - Alloy-coated steel sheet and method for manufacturing the same - Google Patents

Alloy-coated steel sheet and method for manufacturing the same Download PDF

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Publication number
KR101789725B1
KR101789725B1 KR1020150186261A KR20150186261A KR101789725B1 KR 101789725 B1 KR101789725 B1 KR 101789725B1 KR 1020150186261 A KR1020150186261 A KR 1020150186261A KR 20150186261 A KR20150186261 A KR 20150186261A KR 101789725 B1 KR101789725 B1 KR 101789725B1
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South Korea
Prior art keywords
steel sheet
layer
alloy
coating
alloy layer
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KR1020150186261A
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Korean (ko)
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KR20170076234A (en
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양지훈
정재인
정용화
김태엽
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주식회사 포스코
재단법인 포항산업과학연구원
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Application filed by 주식회사 포스코, 재단법인 포항산업과학연구원 filed Critical 주식회사 포스코
Priority to KR1020150186261A priority Critical patent/KR101789725B1/en
Priority to PCT/KR2016/015248 priority patent/WO2017111561A1/en
Priority to US16/064,705 priority patent/US20190001623A1/en
Priority to CN201680075926.4A priority patent/CN108463574A/en
Priority to EP16879428.7A priority patent/EP3396017A4/en
Priority to JP2018533192A priority patent/JP6744413B2/en
Publication of KR20170076234A publication Critical patent/KR20170076234A/en
Application granted granted Critical
Publication of KR101789725B1 publication Critical patent/KR101789725B1/en
Priority to US16/790,061 priority patent/US20200180272A1/en
Priority to US17/217,219 priority patent/US11731397B2/en

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    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
    • C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied

Abstract

Alloy coated steel sheet and a method of manufacturing the same, A plating layer containing Al located on one side or both sides of the steel sheet; And a coating layer disposed on the plating layer, wherein the coating layer is divided into two or three layers, and the coating layer is one of Al, Si, and Mg, or And an alloy phase containing at least two of these alloy phases, and a process for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to an alloy-coated steel sheet and a method for manufacturing the same,

Alloy coated steel sheet and a method of manufacturing the same.

Iron is the most widely used metal in the industry due to its abundant resources, excellent properties and low price. Despite these advantages, iron has the disadvantage of corrosion in the atmosphere. Iron corrosion is a phenomenon in which iron ions are eluted due to an electrochemical reaction between iron and oxygen or water. When this reaction proceeds, iron oxide (FeOOH) is formed in the eluted portion, which is called rust. Iron is composed of oxides and hydroxides of various stoichiometries. It is one of the characteristics of iron that oxidation occurs continuously over time. Iron is used in various forms. In the case of automobiles, building materials and household appliances, cold-rolled steel sheets, that is, cold-rolled steel sheets, are mainly used.

A typical method for preventing the corrosion of the steel sheet is to coat the surface of the steel sheet with another metal. The types of plating film can be divided into a sacrificial type film and a blocking type film. The sacrificial type coating film has a metal which is more easily oxidized than iron, such as zinc, magnesium, and aluminum, and is covered with a metal which is easily rusted, so that the coated metal is preferentially corroded to protect the steel sheet. The barrier type coating is coated with a metal that is less corrosive than lead or tin steel, and prevents water and oxygen from reaching the iron.

Zinc plating is one of the most widely used methods to prevent corrosion of steel sheets at present. Since the development of galvanized steel sheets, various efforts have been made to improve the corrosion resistance, one of which is covering the zinc alloy. Zn-Al, Zn-Ni, Zn-Fe, and Zn-Al-Mg. Such zinc or zinc alloy gold-plated steel sheets are widely used in automobiles, building materials and household appliances.

Aluminum is also used for corrosion prevention of steel sheet, and aluminum is different from zinc in its application field. The aluminum film is beautiful in color and has excellent corrosion resistance and heat resistance. It is used for coatings for decorative films such as cosmetic cases and accessories as well as protective films for semiconductor conductive films, magnetic materials and steel sheets, home appliances for automobiles and automobile mufflers .

Coatings of aluminum are prepared by vacuum coating, electroplating or hot dip coating. However, in the case of electroplating, the productivity is low due to its low efficiency, so most of them are using the hot dip coating method and the vacuum coating method.

Aluminum-plated steel sheet is excellent in corrosion resistance, but if there is a defect in the coating, there is a disadvantage that corrosion is intensively occurred in that portion, because aluminum is less sacrificial than zinc. Therefore, the thickness of the molten aluminum-plated steel sheet is over 15 microns (탆), which is overcome. Since the Al-coated steel sheet is also processed at a high temperature, the Al-Fe-Si alloy is formed at the interface, and the workability is deteriorated.

Aluminum coatings using vacuum coatings have been applied to thinner thicknesses in most applications, and coatings on corrosion resistant coatings are often on the order of a few microns in thickness. For aluminum coatings, when the thickness is below a few microns, redness occurs at about 72 hours in the salt spray test. Therefore, in order to apply aluminum to a steel sheet with a corrosion-resistant coating, it is necessary to improve the properties. In addition, since zinc has a weaker sacrificial characteristic than zinc, it has a disadvantage that it spreads in a short time if it occurs once.

Therefore, research for solving the above problems is urgent.

An embodiment of the present invention is to provide an alloy coated steel sheet having a sacrificial type alloy coating on a steel sheet and having high corrosion resistance even at a thin thickness and a method for manufacturing the same.

An embodiment of the present invention is a steel plate comprising: a steel plate; A plating layer containing Al located on one side or both sides of the steel sheet; And a coating layer disposed on the plating layer, wherein the coating layer is divided into two or three layers, and the coating layer is one of a phase of Al, Si, and Mg, Wherein the alloy phase comprises an alloy phase containing at least two of the alloy phases.

Wherein the coating layer is divided into three layers, and the three layers include: an Al-Si alloy layer positioned on the plating layer; An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And a Mg layer located on the Al-Mg-Si alloy layer.

Wherein the coating layer is divided into three layers, and the three layers include: an Al-Si alloy layer positioned on the plating layer; An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And an Al-Mg layer located on the Al-Mg-Si alloy layer.

The coating layer is divided into two layers, and the two layers include an Al-Si alloy layer positioned on the plating layer; And an Al-Mg-Si alloy layer located on the Al-Si alloy layer.

A plating layer containing Al located on one side or both sides of the steel sheet; An Al-Fe-Si alloy layer positioned on one side or both sides of the steel sheet; And an Al-Si alloy layer located on the Al-Fe-Si alloy layer.

According to another embodiment of the present invention, there is provided a method of manufacturing a steel plate, comprising the steps of: preparing an aluminum-plated steel sheet including a plating layer containing Al located on one side or both sides of the steel sheet; Coating the aluminum-coated steel sheet with Mg to form a Mg coating layer; And annealing the Mg-coated aluminum-plated steel sheet to diffuse Mg into the plating layer. The present invention also provides a method of manufacturing an alloy-coated steel sheet.

And heat-treating the Mg-coated aluminum-coated steel sheet to diffuse Mg into the plating layer, thereby forming two or three layers on the plating layer containing Al located on one side or both sides of the steel sheet The coating layer may include one phase of Al, Si, and Mg, or an alloy phase containing at least two of them.

Wherein the coating layer is a coating layer divided into three layers formed on a plating layer containing Al located on one side or both sides of the steel sheet and the coating layer divided into three layers formed on the plating layer is formed on the plating layer An Al-Si alloy layer positioned thereon; An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And a Mg layer located on the Al-Mg-Si alloy layer.

Wherein the coating layer is a coating layer divided into three layers formed on a plating layer containing Al located on one side or both sides of the steel sheet and the coating layer divided into three layers formed on the plating layer is formed on the plating layer An Al-Si alloy layer positioned thereon; An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And an Al-Mg alloy layer positioned on the Al-Mg-Si alloy layer.

Wherein the coating layer is a coating layer divided into two layers formed on a plating layer containing Al located on one side or both sides of the steel sheet and the coating layer divided into two layers formed on the plating layer is formed on the plating layer An Al-Si alloy layer positioned thereon; And an Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; . ≪ / RTI >

The coating of Mg on the aluminum-plated steel sheet may be performed by physical vapor deposition (PVD).

Preparing an aluminum-plated steel sheet including a plated layer containing Al on one surface or both surfaces of the steel sheet, wherein the plated layer containing Al on one surface or both surfaces of the steel sheet is positioned on one or both surfaces of the steel sheet An Al-Fe-Si alloy layer; And an Al-Si alloy layer located on the Al-Fe-Si alloy layer.

An embodiment of the present invention provides an alloy coated steel sheet having a sacrificial type alloy alloy film formed on a steel sheet and having high corrosion resistance even at a thin thickness and a method for manufacturing the same.

1 is a schematic view of an apparatus that may be used in an exemplary method of making an alloy coated steel sheet according to an embodiment of the present invention.
2 is a schematic diagram of a coating layer of an alloy coated steel sheet according to an embodiment of the present invention.
3 is a graph showing glow discharge light spectroscopy (GDLS) analysis results of the alloy coated steel plate specimens according to Examples 2 and 3 of the present invention.
4 is a graph of X-ray diffraction (XRD) analysis results of Example 2 and Example 3 of the present invention.
5 is a scanning electron microscopy (SEM) photograph of the alloy-coated steel sheet specimen of Example 3 of the present invention before and after heat treatment.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Whenever a component is referred to as "including" an element throughout the specification, it is to be understood that the element may include other elements, not the exclusion of any other element, unless the context clearly dictates otherwise. Also, singular forms include plural forms unless the context clearly dictates otherwise.

In addition, since the sizes and thicknesses of the respective components shown in the drawings are arbitrarily shown for convenience of explanation, the present invention is not necessarily limited to those shown in the drawings.

It is to be understood that throughout the specification, if a section such as a layer, film, region, plate, or the like is referred to as being "on top" Including the case where there is a part.

It is to be understood that throughout the specification, when a portion of a layer, film, region, plate, or the like is referred to as being "on top" or "on" But does not mean that it is located on the upper side with respect to the gravitational direction.

Throughout the specification, unless otherwise defined, the term "A layer" includes not only a case where the layer is composed of only A, but also a case including A.

Throughout the specification, unless otherwise defined, the term "A-B alloy layer" includes not only the case where the layer is composed of the A-B alloy but also the case including the A-B alloy.

Recently, in order to solve the problems of the molten aluminum-plated steel sheet mentioned in the background art, magnesium is added to a molten aluminum-plated steel sheet containing silicon (i.e., an Al-Si plated steel sheet) to improve the corrosion resistance as well as the sacrificial corrosion resistance Research is underway.

For example, there is a research to produce an Al-Mg-Si plated steel sheet by hot-dip coating to produce a coating steel sheet having excellent corrosion resistance. However, when it is manufactured by the hot dip coating method, there is a limitation in control of the Mg content, and in the case of the thin plating of 20 g or less, there is a drawback that the corrosion resistance is rapidly deteriorated. In addition, Mg 2 Si alloy phase is known to play a role in improving corrosion resistance, but in this case, there is a problem that the characteristic is improved only in a narrow range of about 6% of Mg. The Al-Mg-Si plated steel sheet is known to have excellent corrosion resistance due to the Mg 2 Si phase being formed in the plating layer. It has been reported that the corrosion resistance of the Al-Mg-Si plated steel sheet is improved when the Mg 2 Si phase is 0.5% or more and 30% or less in area ratio within the plating layer and the long diameter of the Mg 2 Si phase is 10 탆 or less. However, the Al-Mg-Si coated steel sheet produced by the hot dip coating method has a limitation in controlling the Mg content in the manufacturing process, so that an Al-Mg-Si coated steel sheet having a Mg content (about 15% or more) It is not easy.

As another example, there is a study on a method of forming an Al-Mg alloy layer by vapor-depositing Mg in a state where a substrate coated with aluminum is heated in a vacuum at 350 캜 or higher and 500 캜 or lower. However, this method may cause vapor loss due to the deposition of Mg on a substrate heated to a high temperature in a vacuum, and there is a problem that it is difficult to provide data on the characteristics change of the Al-Mg-Si layer depending on the precise alloy phase.

The present invention has been devised to solve the problems of the above-mentioned hot-dip galvanized steel sheet and the problems of the Al-Mg alloy steel sheet, and since the present invention is coated with Mg by a physical vapor deposition method on a hot- There is no limitation in controlling the Mg content of the coating layer and it is possible to manufacture various coating layer structures.

Specifically, there is provided an alloy-coated steel sheet having a high corrosion resistance property at a thin thickness by forming a multi-layered alloy film through heat treatment by depositing magnesium on a molten aluminum-plated steel sheet containing silicon .

Hereinafter, a method for manufacturing an alloy coated steel sheet according to an embodiment of the present invention and a manufactured alloy coated steel sheet will be described.

According to an embodiment of the present invention, there is provided a method of manufacturing a steel plate, comprising: preparing an aluminum-plated steel sheet including a plating layer containing Al located on one side or both sides of the steel sheet; Coating the aluminum-coated steel sheet with Mg to form a Mg coating layer; And annealing the Mg-coated aluminum-plated steel sheet to diffuse Mg into the plating layer. The present invention also provides a method of manufacturing an alloy-coated steel sheet.

The steel sheet may be a cold rolled steel sheet. However, the present invention is not limited thereto.

The aluminum-plated steel sheet may be a hot-dipped aluminum-coated steel sheet, and specifically includes at least 8 wt% and at most 10 wt% of Si, based on 100 wt% of the total amount of the plated layer. Al: not less than 88% by weight, not more than 90% by weight; And the remainder Fe.

Further, the plated layer of the aluminum-plated steel sheet may include an Al-Fe-Si alloy layer formed at the time of aluminum plating and an Al-Si alloy layer, and the alloy layers may include an Al-Fe-Si alloy layer, Al-Si alloy layer in this order. The Al-Fe-Si alloy layer may be one in which Fe in the steel sheet diffuses into the Al-Si plating layer during the production of the Al-coated steel sheet.

The coating of Mg on the aluminum-plated steel sheet may be performed by physical vapor deposition (PVD). More specifically, it may be performed with electromagnetic floating physical vapor deposition (EML-PVD). However, the present invention is not limited thereto, and if Mg deposition is possible by a physical method such as an electron beam evaporation apparatus, a thermal evaporation apparatus, or a sputtering source, various methods can be used to coat Mg.

The method of manufacturing the alloy-plated steel sheet may further include the step of heat-treating the Mg-coated aluminum-coated steel sheet to diffuse Mg into the plating layer, On the plated layer, a coating layer is formed which is divided into two or three layers, and the coating layer may include one phase of Al, Si, and Mg, or an alloy phase containing two or more of them have.

The heat treatment method in the heat treatment step can be performed by an induction heating apparatus, but the present invention is not limited thereto, and other suitable heat treatment means can be employed. Further, if the heat treatment is performed by a method other than the induction heating method, the heat treatment temperature may be changed according to the heat treatment method.

Specifically, the coating layer is a coating layer divided into three layers formed on a plating layer including Al located on one side or both sides of the steel sheet, and the coating layer formed on the plating layer is divided into three layers, An Al-Si alloy layer disposed on the Al-Si alloy layer; An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And a Mg layer located on the Al-Mg-Si alloy layer.

Alternatively, the coating layer is a coating layer divided into three layers formed on a plating layer containing Al located on one side or both sides of the steel sheet, and the coating layer divided into three layers formed on the plating layer, An Al-Si alloy layer disposed on the Al-Si alloy layer; An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And an Al-Mg alloy layer positioned on the Al-Mg-Si alloy layer.

That is, a layer structure in the form of a Mg layer (or Al-Mg alloy layer) / Al-Mg-Si alloy layer / Al-Si alloy layer / Al-Fe-Si alloy layer is formed in this order from the surface of the steel sheet. Thus, there is an effect that the metal or alloy present in each layer blocks the corrosion-causing substance from reaching the steel sheet (Al-Si). In addition, corrosion prevention by sacrificial antimicrobial properties (Mg, Al-Mg-Si, Al-Mg) can be prevented in a sequential manner. As a result, it is judged that the corrosion resistance is superior to a general aluminum or zinc plating layer which prevents corrosion in a single way such as a physical barrier method or a sacrificial anticorrosion property.

The coating layer is a coating layer divided into two layers formed on a plating layer containing Al located on one side or both sides of the steel sheet. The coating layer formed on the plating layer is divided into two layers, An Al-Si alloy layer disposed on the Al-Si alloy layer; And an Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; . ≪ / RTI >

That is, a layer structure in the form of Al-Mg-Si alloy layer / Al-Si alloy layer / Al-Fe-Si alloy layer is formed in this order from the surface of the steel sheet. Thus, there is an effect that the metal or alloy present in each layer blocks the corrosion-causing substance from reaching the steel sheet (Al-Si). In addition, it can prevent corrosion in a sequential manner due to the prevention of corrosion by sacrificial antimicrobial (Al-Mg-Si). As a result, it is believed that the corrosion resistance is superior to that of a general aluminum or zinc plated layer in a single method such as a physical barrier method or a sacrificial anticorrosion property.

1 is a schematic view of an apparatus that may be used in an exemplary method of making an alloy coated steel sheet according to an embodiment of the present invention. Referring to FIG. 1, an exemplary method for producing an alloy coated steel sheet according to an embodiment of the present invention will be described.

The apparatus shown in Fig. 1 is a continuous coating apparatus comprising a steel plate feeder 11 for feeding a molten aluminum plated steel sheet 17 in the atmosphere, an inverted magnetron sputtering source 12 for pretreating the steel sheet in vacuum, A physical vapor deposition (PVD) device 13 for coating Mg after the pretreatment, an induction heating device 14 for heat-treating the steel sheet discharged into the atmosphere, a steel sheet discharging device for rewinding the heat-treated coated steel sheet And a device (15). The physical vapor deposition apparatus 13 may be an electromagnetic levitation (EML) source. The inverse magnetron sputtering source 12 and the physical vapor deposition apparatus 13 can be installed and operated in the vacuum container 16. [

An exemplary method of producing an alloy-coated steel sheet using the above apparatus is as follows. First, a molten aluminum-coated steel plate 17 is prepared, and alkali degreasing can be performed to remove residual oil such as rust-preventive oil on the surface of the steel plate.

Thereafter, the steel sheet is fed to the vacuum container 16 while being conveyed through the steel sheet feeder 11. Then, electric power is applied to the reverse magnetron sputtering source 12 installed in the vacuum container 16 to clean the surface of the steel sheet.

After completing the cleaning, Mg can be vacuum-coated on the Al plating layer through the electromagnetic levitation source 13 provided in the vacuum container 16 while continuously conveying the steel sheet.

After the coating is completed, the steel sheet is continuously conveyed and discharged into the atmosphere, and then heat-treated in the atmosphere at a predetermined temperature and time using an induction heating apparatus 14.

After the heat treatment is completed, an alloy coated steel sheet produced by continuously conveying the steel sheet can be obtained.

Hereinafter, the alloy-coated steel sheet produced by the above-described method for producing an alloy-coated steel sheet will be described in detail.

Another embodiment of the present invention is a steel plate comprising: a steel plate; A plating layer containing Al located on one side or both sides of the steel sheet; And a coating layer disposed on the plating layer, wherein the coating layer is divided into two or three layers, and the coating layer is one of Al, Si, and Mg, or And an alloy phase comprising at least two of them.

The steel sheet may be a cold rolled steel sheet. However, the present invention is not limited thereto.

Specifically, the coating layer is divided into three layers, and the three layers include an Al-Si alloy layer positioned on the plating layer; An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And a Mg layer located on the Al-Mg-Si alloy layer.

Or three layers, and the three layers include: an Al-Si alloy layer positioned on the plating layer; An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And an Al-Mg layer located on the Al-Mg-Si alloy layer.

More specifically, when heat treatment is performed at a relatively low temperature, a part of Mg of the Mg coating layer on the surface of the steel sheet may be diffused into the aluminum plating layer, and un-diffused Mg may remain on the surface to leave a Mg layer. Alternatively, the Mg layer on the surface may disappear and an Al-Mg alloy layer may be formed on the surface.

The Al-Mg-Si alloy layer located on the plating layer may include Al 12 Mg 17 phase generated when the Mg content is higher than the Al content.

By including the Mg layer on the surface or the Al-Mg alloy layer including the Al 12 Mg 17 phase as described above, sacrificial corrosion resistance can be imparted in addition to the corrosion resistance of the plating layer by the blocking method, and the corrosion resistance can be improved. Therefore, even in a thin thickness range, high corrosion resistance can be exhibited.

The coating layer is divided into two layers, and the two layers include an Al-Si alloy layer positioned on the plating layer; And an Al-Mg-Si alloy layer located on the Al-Si alloy layer.

Specifically, as a result of the heat treatment at a relatively high temperature, the amount of surface Mg diffused into the coating layer increases, so that the surface Mg coating layer disappears and Mg diffuses deeper into the Al-Si alloy layer. Relatively low. Thus, when the Mg content is high, the Al 12 Mg 17 phase disappears and an Al 3 Mg 2 phase is formed. In addition, Si and Mg may react with a high Mg content to form a Mg 2 Si phase.

By forming the Al-Mg-Si alloy layer including the Mg 2 Si phase and Al 3 Mg 2 phase as described above, the sacrificial corrosion resistance can be increased and the corrosion resistance of the coated steel sheet can be improved. Therefore, even in a thin thickness range, high corrosion resistance can be exhibited.

The plating layer containing Al may include an Al-Fe-Si alloy layer formed by aluminum plating on the steel sheet, and an Al-Si alloy layer. The alloy layers may be formed of an Al-Fe-Si alloy layer, And an Al-Si alloy layer in this order. The Al-Fe-Si alloy layer may be one in which Fe in the steel sheet diffuses into the Al-Si plating layer during the production of the Al-coated steel sheet.

FIG. 2 is a schematic structural view of an alloy coated steel sheet which can be formed according to the above-mentioned heat treatment temperature range regulation.

2, the structure of a specific alloy coated steel sheet according to an embodiment of the present invention will be described in detail as follows.

In Fig. 2, 20 denotes a cold-rolled steel sheet, 21 denotes an Al-Fe-Si alloy layer, 22 denotes an Al-Si alloy layer, and 25 denotes a general structure of a molten aluminum-plated steel sheet. 26 is a coating layer formed in one embodiment of the present invention.

The Mg coating on the surface reacts with the Al-Si alloy layer 22 to form the Al-Mg-Si alloy layer 23 as shown in FIG. 2 (a) . At a heat treatment temperature of 300 ° C, Mg remains on the surface and a three-layer structure in which an Al-Si alloy layer is also present.

FIG. 2 (b) is a schematic view of a coating layer structure in which Mg is coated on a hot-dip coated steel sheet and then heat-treated at 375.degree. Mg coated on the molten aluminum-plated steel sheet is diffused into the Al-Si alloy layer 22 by heat treatment at 375 ° C. The Mg of the Mg coating layer present on the surface is completely diffused into the Al-Si alloy layer, so that the Mg layer disappears and only the Al-Mg-Si alloy layer 23 and the Al-Si layer 22 remain. However, Mg does not diffuse to the interface with the Al-Si-Fe alloy layer, and an Al-Si alloy layer remains.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Example: Preparation of alloy coated steel sheet

Example 1

A hot-dip coated steel sheet on which an Al plating layer containing 9% by weight of Si, 88% by weight of Al and Fe as the balance was formed on the cold-rolled steel sheet with a side-coated amount of 15 g / m 2 was prepared. The thickness of the Al plated layer was about 6 μm.

Alkali degreasing was performed to remove residual oil such as rust-preventive oil on the surface of the steel sheet.

Thereafter, the steel sheet was cleaned with a reverse magnetron sputtering source installed in a vacuum vessel while supplying the steel sheet through the steel sheet feeder to the vacuum vessel.

After completing the cleaning, Mg was vacuum-coated on the Al plating layer through an electromagnetic levitation source provided in the vacuum container while moving the steel sheet continuously.

After the coating was completed, the steel sheet was continuously moved to discharge into the atmosphere, and then heat-treated at 375 DEG C using an induction heating apparatus in the air. After the heat treatment was completed, the steel sheet was continuously transferred to obtain an alloy coated steel sheet.

Example 2

An alloy coated steel sheet was prepared in the same manner as in Example 1, except that Mg was vacuum-coated to a thickness of 1 탆 and heat treatment was performed at 300 캜.

Example 3

Alloy coated steel sheet was prepared in the same manner as in Example 1 except that Mg was vacuum-coated to a thickness of 1 탆 and heat treatment was performed at 375 캜.

Example 4

Alloy coated steel sheet was prepared in the same manner as in Example 1 except that Mg was vacuum-coated to a thickness of 1.5 탆 and heat treatment was performed at 375 캜.

Comparative Example 1

A hot-dip coated steel sheet on which an Al plating layer containing 9% by weight of Si, 88% by weight of Al and Fe as the balance was formed on the steel sheet with a single-side coated amount of 15 g / m 2 was prepared.

Comparative Example 2

An electrogalvanized steel sheet having a single-sided coating amount of 40 g / m 2 was prepared.

Comparative Example 3

A hot-dip galvanized steel sheet having a single-side coated amount of 137.5 g / m 2 was prepared.

Information on the specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 3 is summarized in Table 1 below.

division Plated material Amount of plating
(Single side, g / m 2 ) Coating material Coating thickness
(um) Heat treatment temperature
(° C) Example 1 Al-Si 15 Mg 0.5 375 Example 2 Al-Si 15 Mg 1.0 300 Example 3 Al-Si 15 Mg 1.0 375 Example 4 Al-Si 15 Mg 1.5 375 Comparative Example 1 Al-Si 15 - - - Comparative Example 2 Zn 40 - - - Comparative Example 3 Zn 137.5 - - -

Experimental Example

Experimental Example 1: Glow discharge spectrometer analysis

The components of the coating layer formed on the steel sheet were analyzed using the glow discharge spectrometer (GDS 850A, manufacturer: NECO) for the alloy coated steel sheets prepared in Examples 2 and 3.

The results are shown in Fig. 3, 31 represents Mg, 32 represents Al, 33 represents Si, and 34 represents Fe.

3 (a) is an analysis result of the alloy-coated steel sheet of Example 2 in which the heat treatment was performed at 300 ° C. As a result, it can be seen that Mg exists on the surface of the coating layer, but a part of Mg diffuses into the Al-Si alloy layer.

FIG. 3 (b) is an analysis result of the alloy-coated steel sheet of Example 3 in which the heat treatment was performed at 375 ° C. As a result, it can be seen that all Mg coated on the molten aluminum-coated steel sheet is diffused into the Al-Si alloy layer. However, Mg does not diffuse to the interface with the Al-Si-Fe alloy layer, and the Al-Si alloy layer remains.

Experimental Example 2: XRD analysis results

XRD analysis was performed on the alloy coated steel sheets prepared in Examples 2 and 3 using an X-ray diffraction apparatus (D / MAX-2500V-PC, manufactured by Rigaku).

The results of the analysis are shown in FIG.

It can be confirmed that Mg 2 phase, Al phase and Al 12 Mg 17 phase are mixed in Example 2 in which heat treatment is performed at 300 ° C. At the diffusion heat treatment temperature of 300 ° C, Mg remains in the uppermost layer of the coating layer and a part diffuses into the Al-Si alloy layer. Therefore, the Al 12 Mg 17 phase formed when the Mg content is higher than the Al content is observed Respectively.

In Example 3, which was heat-treated at 375 ° C, no Mg phase was observed and it was confirmed that Al phase, Al 3 Mg 2 phase and Mg 2 Si phase were mixed. The absence of Mg phase is considered to be due to diffusion of Al-Si alloy layer, and Mg 2 Si phase appears to react with Si and Mg existing in Al-Si alloy layer. When annealed at 375 ℃, Mg diffuses deeper into the Al-Si alloy layer, lowering the Mg content compared to the Al content, and thus the Al 12 Mg 17 phase formed when the Mg content is higher is observed and the Al 3 Mg 2 phase appears .

Experimental Example  3: Scanning Electron Microscope, SEM ) Photo observation

5 is a scanning electron micrograph of a hot-dip coated steel sheet coated with 1um of Mg before and after heat treatment.

5A is a scanning electron microscope (SEM) image of a steel sheet coated with Mg on a hot-dip galvanized steel sheet and not subjected to heat treatment, and is composed of a cold-rolled steel sheet 51, an Al-Fe-Si alloy layer 52, The layer 53 and the Mg coating layer 54 can be distinguished.

5B is a scanning electron micrograph of Example 3 in which heat treatment was performed at 375 ° C. The interface between the Mg coating layer 54 and the Al-Si alloy layer 53 is not clearly distinguished, and Mg is Al-Si It is confirmed that the Al-Mg-Si alloy layer 55 is formed by diffusing into the alloy layer.

Experimental Example  4: Evaluation of corrosion resistance

The surface corrosion resistance of steel plate specimens of Examples 1 to 4 and Comparative Examples 1 to 3 was evaluated based on the initial erosion time using a salt spray test (ASTM B-117). The results are shown in Table 2 below.

division Plated material Amount of plating
(Single side, g / m 2 ) Coating material Coating thickness
(탆) Heat treatment temperature
(° C) Red rush hour
(time) Example 1 Al-Si 15 Mg 0.5 375 1536 Example 2 Al-Si 15 Mg 1.0 300 432 Example 3 Al-Si 15 Mg 1.0 375 1464 Example 4 Al-Si 15 Mg 1.5 375 1536 Comparative Example 1 Al-Si 15 - - - 48 Comparative Example 2 Zn 40 - - - 24 Comparative Example 3 Zn 137.5 - - - 96

The heat-treated Al-Mg-Si coated steel sheet did not show any significant difference depending on the thickness of the Mg coating layer. It can be confirmed that the redness occurred after about 1464 ~ 1536 hours from the start of the salt spray test. This shows a corrosion resistance that is 30 times or more improved as compared with the molten aluminum-plated steel sheet of Comparative Example 1 in which Mg is not coated. The specimens annealed at 375 ℃ showed better corrosion resistance than those specimens annealed at 300 ℃.

Al-Mg-Si alloy layer and Al-Si alloy layer coexist in the coating layer structure. It is confirmed that the most excellent corrosion resistance is obtained when the coating layer is composed of Al phase, Al 3 Mg 2 phase and Mg 2 Si phase in proper ratio .

Experimental Example 5: Analysis of Mg content in the coating layer

By analyzing the coating layer with glow discharge spectroscopy, the Mg content can be numerically confirmed in the interface direction between the coating layer and the steel sheet on the surface of the coating layer. The results of the glow discharge spectroscopy of the coating layer shown in FIG. 3 show that the coating layer having a three-layer structure except for the Al-Fe-Si layer contains most of Mg in the pure Mg layer and the Al-Mg layer. Except for the Al-Fe-Si layer, 90 wt% Mg is distributed on the surface of the coating layer, which accounts for about 20% of the total thickness.

Except for the Al-Fe-Si layer, except for the Al-Fe-Si layer, the coating layer having a two-layer structure has an average of 40% by weight of Mg in the coating layer occupying about 40% of the total thickness.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

11: steel plate feeder 12: reverse magnetron sputtering source
13: physical vapor deposition apparatus 14: induction heating apparatus
15: steel plate discharging device 16: vacuum container
17: molten aluminum-plated steel sheet 20: cold-rolled steel sheet
21: Al-Si-Fe alloy layer 22: Al-Si alloy layer
23: Al-Mg-Si alloy layer 24: Mg coating layer
25: molten aluminum-plated steel sheet 26: coating layer
31: Magnesium (Mg) 32: Aluminum (Al)
33: silicon (Si) 34: iron (Fe)
51: Cold rolled steel plate 52: Al-Fe-Si alloy layer
53: Al-Si alloy layer 54: Mg coating layer
55: Al-Mg-Si alloy layer

Claims (12)

Steel plate;
A plating layer containing Al located on one side or both sides of the steel sheet; And
And a coating layer disposed on the plating layer,
Wherein the coating layer comprises:
An Al-Si alloy layer positioned on the plating layer;
An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And
And a Mg layer positioned on the Al-Mg-Si alloy layer.
Alloy coated steel sheet. Steel plate;
A plating layer containing Al located on one side or both sides of the steel sheet; And
And a coating layer disposed on the plating layer,
Wherein the coating layer comprises:
An Al-Si alloy layer positioned on the plating layer;
An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And
And an Al-Mg alloy layer positioned on the Al-Mg-Si alloy layer.
Alloy coated steel sheet. delete delete 3. The method according to claim 1 or 2,
A plating layer containing Al located on one side or both sides of the steel sheet; silver
And an Al-Fe-Si alloy layer positioned on one side or both sides of the steel sheet.
Alloy coated steel sheet. Preparing an aluminum-plated steel sheet including a plating layer containing Al located on one side or both sides of the steel sheet;
Coating the aluminum-coated steel sheet with Mg to form a Mg coating layer; And
Heat-treating the aluminum-coated steel sheet coated with Mg to diffuse Mg into the plating layer,
Heat-treating the aluminum-coated steel sheet coated with Mg to diffuse Mg into the plating layer,
On the plating layer containing Al located on one side or both sides of the steel sheet,
A coating layer divided into three layers is formed,
The coating layer, which is formed on the plating layer and divided into three layers,
An Al-Si alloy layer positioned on the plating layer;
An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And
And a Mg layer located on the Al-Mg-Si alloy layer.
A method for producing an alloy coated steel sheet. delete Preparing an aluminum-plated steel sheet including a plating layer containing Al located on one side or both sides of the steel sheet;
Coating the aluminum-coated steel sheet with Mg to form a Mg coating layer; And
Heat-treating the aluminum-coated steel sheet coated with Mg to diffuse Mg into the plating layer,
Heat-treating the aluminum-coated steel sheet coated with Mg to diffuse Mg into the plating layer,
On the plating layer containing Al located on one side or both sides of the steel sheet,
A coating layer divided into three layers is formed,
The coating layer, which is formed on the plating layer and divided into three layers,
An Al-Si alloy layer positioned on the plating layer;
An Al-Mg-Si alloy layer positioned on the Al-Si alloy layer; And
And an Al-Mg alloy layer positioned on the Al-Mg-Si alloy layer.
A method for producing an alloy coated steel sheet. delete delete The method as claimed in claim 6 or 8,
Coating the aluminum-coated steel sheet with Mg,
Lt; RTI ID = 0.0 > (PVD). ≪
A method for producing an alloy coated steel sheet. The method as claimed in claim 6 or 8,
Preparing an aluminum-plated steel sheet including a plated layer containing Al on one surface or both surfaces of the steel sheet,
The plating layer containing Al on one surface or both surfaces of the steel sheet,
And an Al-Fe-Si alloy layer positioned on one side or both sides of the steel sheet.
A method for producing an alloy coated steel sheet.
KR1020150186261A 2015-12-24 2015-12-24 Alloy-coated steel sheet and method for manufacturing the same KR101789725B1 (en)

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PCT/KR2016/015248 WO2017111561A1 (en) 2015-12-24 2016-12-23 Alloy-coated steel sheet and manufacturing method therefor
US16/064,705 US20190001623A1 (en) 2015-12-24 2016-12-23 Alloy-coated steel sheet and manufacturing method therefor
CN201680075926.4A CN108463574A (en) 2015-12-24 2016-12-23 Alloy-coated steel plate and its manufacturing method
EP16879428.7A EP3396017A4 (en) 2015-12-24 2016-12-23 Alloy-coated steel sheet and manufacturing method therefor
JP2018533192A JP6744413B2 (en) 2015-12-24 2016-12-23 Alloy coated steel sheet and method for producing the same
US16/790,061 US20200180272A1 (en) 2015-12-24 2020-02-13 Alloy-coated steel sheet and manufacturing method therefor
US17/217,219 US11731397B2 (en) 2015-12-24 2021-03-30 Alloy-coated steel sheet and manufacturing method therefor

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