WO2019132525A1 - Procédé de traitement de surface d'une tôle d'acier plaquée d'alliage d'aluminium et tôle d'acier plaquée d'alliage d'aluminium ainsi produite - Google Patents

Procédé de traitement de surface d'une tôle d'acier plaquée d'alliage d'aluminium et tôle d'acier plaquée d'alliage d'aluminium ainsi produite Download PDF

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Publication number
WO2019132525A1
WO2019132525A1 PCT/KR2018/016689 KR2018016689W WO2019132525A1 WO 2019132525 A1 WO2019132525 A1 WO 2019132525A1 KR 2018016689 W KR2018016689 W KR 2018016689W WO 2019132525 A1 WO2019132525 A1 WO 2019132525A1
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WO
WIPO (PCT)
Prior art keywords
steel sheet
aluminum alloy
plated steel
micro
electrolytic solution
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PCT/KR2018/016689
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English (en)
Korean (ko)
Inventor
이강민
백제훈
유혜진
김정수
변창세
Original Assignee
주식회사 포스코
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Publication of WO2019132525A1 publication Critical patent/WO2019132525A1/fr

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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used

Definitions

  • the present invention relates to a surface treatment method of an aluminum alloy plated steel sheet and an aluminum alloy plated steel sheet produced thereby.
  • Micro Arc Oxidation (MAO) or plasma electrolytic oxidation (PEO) in various metal wet surface treatments is a method of applying electricity to a metal surface A number of microdisplays generated at the moment of dielectric breakdown in oxygen gas bubbles react with target metals and electrolytes located on the anode to form an oxide film.
  • Galvanized steel sheets are widely used throughout the industry, from automobiles and building materials to household appliances. In recent years, researches are actively conducted to prolong the lifetime of the plating layer without deteriorating the sacrificial properties of zinc.
  • the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method for surface treatment of a high-aluminum alloy-plated steel sheet having locally induced fine discharge on an aluminum alloy plated steel sheet and having improved corrosion resistance.
  • a method for producing an alkaline electrolytic solution comprising: preparing an alkaline electrolyte by adding alkali to distilled water; And a step of immersing the aluminum alloy plated steel sheet in the alkaline electrolytic solution and micro-discharging oxidation treatment to form an oxide layer on the surface of the steel sheet, wherein the plated layer of the aluminum alloy plated steel sheet comprises 55 to 70% by weight of aluminum and 30 to 45 By weight based on the total weight of the aluminum alloy-plated steel sheet.
  • the concentration of alkali in the alkaline electrolyte may be 0.1 to 1.25 mol / L.
  • the alkali may be at least one selected from potassium hydroxide, sodium hydroxide and sodium silicate.
  • the alkali electrolytic solution may further include at least one metal salt selected from manganese salt, vanadium salt and tungsten salt.
  • the temperature of the alkaline electrolyte may be 80 DEG C or less.
  • the current density applied during the micro-discharge oxidation process may be 50 to 500 mA / cm < 2 >.
  • the voltage applied during the micro-discharge oxidation process may be 180 to 350V.
  • the micro-discharge oxidation treatment may be performed for 0.1 to 10 minutes.
  • the plated layer of the aluminum alloy plated steel sheet may further contain not more than 2% by weight of one element selected from Si, Mg and Ni.
  • an aluminum alloy plated steel sheet excellent in corrosion resistance which is surface-treated by the above method and has an oxide layer formed on the surface of the steel sheet.
  • the thickness of the oxide layer may be 1 to 10 mu m.
  • an aluminum oxide layer having excellent corrosion resistance can be formed on the surface of a steel sheet.
  • FIG. 1 is a process flow chart schematically showing a method for surface treatment of an aluminum alloy plated steel sheet according to an embodiment of the present invention.
  • FIG. 2 is a schematic view of the micro-discharge oxidation treatment step of the present invention.
  • SEM scanning electron microscope
  • the present invention relates to a surface treatment method for an aluminum alloy plated steel sheet and an aluminum alloy plated steel sheet produced thereby.
  • a method for producing an alkaline electrolytic solution comprising: preparing an alkaline electrolyte by adding alkali to distilled water; And a step of immersing the aluminum alloy plated steel sheet in the alkaline electrolytic solution and micro-discharging oxidation treatment to form an oxide layer on the surface of the steel sheet, wherein the plated layer of the aluminum alloy plated steel sheet comprises 55 to 70% by weight of aluminum and 30 to 45 By weight based on the total weight of the aluminum alloy-plated steel sheet.
  • the plating layer of the aluminum alloy plated steel sheet subject to surface treatment contains aluminum in an amount of 55% by weight or more and zinc in an amount of 45% by weight or less.
  • micro-discharge does not occur in the micro-discharge oxidation treatment to be described later.
  • micro discharge may occur but plating workability may be poor, so that it is preferable that it does not exceed 70% by weight.
  • zinc is contained in an amount of 45 wt% or less.
  • the plating layer contains not more than 45% by weight of zinc and not less than 55% by weight of aluminum, it can be produced at a low cost with excellent durability, and the effect of sacrifice of zinc on the base steel sheet can be maximized.
  • the plating layer of the aluminum alloy plated steel sheet may further include one element selected from Si, Mg, and Ni in order to inhibit the aluminum-zinc alloy solution from causing a violent alloy reaction with the base steel sheet.
  • the content thereof is preferably 2% by weight or less. It is possible to add Si, Mg and Ni for the purpose of controlling the size of the plated layer sequins and improving the durability. When the content exceeds 2% by weight, workability is deteriorated and physical properties such as corrosion resistance are rather low.
  • alkali is first added to distilled water to prepare an alkaline electrolytic solution.
  • the kind of alkali to be added at this time is not specifically limited, but one or more selected from potassium hydroxide, sodium hydroxide and sodium silicate can be used, for example.
  • the concentration of alkali in the alkaline electrolyte is preferably controlled to 0.1 to 1.25 mol / L. If it exceeds 1.25mol / L, not only the economical efficiency is lowered, but also AL Yerokhin et al., Surf. Coat. Technol. (1999), https://doi.org/10.1016/S0257-8972(99)00441-7. , Micro-oxidative discharge treatment is not performed due to the high electrical conductivity of the solution in the high-concentration solution immersed at a certain concentration or more.
  • the alkali electrolytic solution may further contain at least one metal salt selected from manganese salt, vanadium salt and tungsten salt, and TiO 2 , ZrO 2 CeO and may further include a metal oxide selected at least one of the two.
  • the coating layer can be colored by using the color of the metal oxide, or the coating layer having excellent abrasion resistance can be formed by utilizing the high abrasion resistance of the metal oxide.
  • the adhesion between the coating layer and the base material can also be improved by adding a metal salt (oxide).
  • a metal salt oxide
  • an appropriate content of the metal oxide or the metal salt may be added differently depending on each purpose and application range.
  • the temperature of the alkaline electrolyte thus prepared is preferably 80 ⁇ ⁇ or less (excluding 0).
  • the micro-discharge oxidation process is accompanied by the reaction heat because the electrochemical reaction takes place by supplying charges based on the aqueous solution. For this reason, evaporation of the aqueous solution during long-time operation may be caused, so that it is preferably carried out at 80 ° C or less in consideration of workability and reproducibility.
  • an aluminum alloy plated steel sheet is immersed in the alkaline electrolytic solution and micro-discharge oxidation treatment is performed to form an oxide layer on the surface of the steel sheet.
  • micro-discharge oxidation method a large number of fine discharges are generated at the moment of dielectric breakdown in the oxygen gas bubbles generated near the surface of the metal by applying electricity in a state where the target metal is positioned as an anode in the electrolyte. And the oxide film is formed by reacting with the target metal and the electrolyte.
  • the principle thereof is well known to those of ordinary skill in the art, and a detailed description thereof will be omitted.
  • an aluminum alloy plated steel sheet may be positioned as an anode, stainless steel may be disposed on a cathode, and micro-discharge oxidation may be performed to form an oxide layer on the surface of the steel sheet.
  • Hydrogen gas is generated by the decomposition reaction of water on the surface of the stainless steel which is the anode in the electrolyte, and oxygen gas is generated on the surface of the aluminum alloy plated steel sheet as the anode and an oxide film is formed.
  • a high temperature micro discharge (plasma) is generated to form a metal oxide.
  • the current density applied in the microdischarge oxidation treatment is 50 to 500 mA / cm 2 (5 to 50 ASD) . If it is less than 50 mA / cm 2 , micro-discharge may not occur. If it exceeds 500 mA / cm 2 , excessive micro-discharge may cause corrosion of the base material.
  • the voltage applied during the micro-discharge oxidation treatment is 180 to 350V. If it is less than 180, V micro discharge may not occur, and if it exceeds 350 V, excessive micro discharge may cause corrosion of the base material.
  • the micro-discharge oxidation treatment is preferably performed for 0.1 to 10 minutes.
  • the micro-discharge oxidation treatment time that is, the thickness of the oxide layer is set differently depending on the product use and operating conditions. Products that require wear resistance such as bearings and gears that require a thick oxide film of tens to hundreds of micrometers are known to process for about 10 minutes. Alkali black masking, which is used in UV processes where energization and tinting properties are required, In the case of the product, it is treated within about 1 minute to form less than 10 microns in thickness. However, in the present invention, even when treated for 10 to 30 seconds, the difference in terms of surface shape and corrosion resistance can be ensured.
  • an aluminum alloy plated steel sheet having an oxide film formed on its surface by the above-described surface treatment method.
  • the thickness of the oxide layer may vary depending on the micro-discharge oxidation treatment, but even in the case of 1 to 10 ⁇ , the difference in surface shape and corrosion resistance can be ensured.
  • the aluminum alloy plated steel sheet was cut into a thin plate of 50 mm width, 75 mm length and 0.8 mm thickness, washed with distilled water and dried.
  • the sample of aluminum-plated steel sheet was placed in the alkaline electrolytic solution and the stainless steel was installed on the cathode.
  • DC power was applied through a power supply of 1.5 kW to the micro electrolytic oxidation treatment at a current density of 50 ASD at 10 and 20 For 30 seconds to form an oxide film on the surface of the aluminum-plated steel sheet.
  • the temperature of the electrolytic solution was kept at 20 to 30.
  • micro electrolytic oxidation treatment was carried out in the same manner as in Example 1, except that 0.25M NaOH was used instead of 0.125M NaOH.
  • a microstructure photograph of the surface-treated aluminum alloy plated steel sheet as described above was photographed by a scanning electron microscope and is shown in Fig.
  • Example 1 it can be observed that many micro pores are formed randomly on the surface due to the micro-discharge, and the size of the micro pores gradually grows with time.
  • the specific surface area of the high-aluminum alloy-plated steel sheet was measured according to the NaOH concentration and time of the electrolyte solution, and the results are shown in Table 1. In the conditions of Example 1, in the case of Comparative Examples 1 and 2 The specific surface area was increased more than two times, which is consistent with the contents taught in Fig.
  • the composition of the plating layer of the aluminum alloy plated steel sheet was controlled as shown in Table 3, micro discharge oxidation treatment was performed under the same conditions as in Example 1, Table 3 shows the results.
  • the evaluation criteria are as follows.
  • the constant temperature and humidity test was conducted according to KS M ISO 6270-1.
  • the cut surfaces before and after the test of the specimen were photographed using an optical microscope, and the area of occurrence of rust was measured and evaluated.
  • Example 2 satisfying the aluminum and zinc contents of the plating layer in the present invention shows excellent plating workability and corrosion resistance.
  • Comparative Example 3 in which the aluminum content was too large and the zinc content was relatively low, the plating workability was poor, whereas in Comparative Examples 4 to 6 in which the aluminum content was too small and the zinc content was relatively large, micro- It is possible to confirm that the plating workability and the corrosion resistance are poor even if the plating process is not performed or the plating process is not performed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention concerne un procédé pour le traitement de surface d'une tôle d'acier plaquée d'alliage d'aluminium, comprenant les étapes consistant : à ajouter un alcali à de l'eau distillée en vue de préparer un électrolyte alcalin; et à immerger une tôle d'acier plaquée d'alliage d'aluminium dans l'électrolyte alcalin et à former une couche d'oxyde sur la surface de la tôle d'acier par traitement d'oxydation par micro-arc, une couche plaquée de la tôle d'acier plaquée d'alliage d'aluminium contenant de 55 à 70 % en poids d'aluminium et de 30 à 45 % en poids de zinc. Selon la présente invention, en appliquant une technique d'oxydation par micro-arc à une tôle d'acier plaquée d'alliage d'aluminium, une couche d'oxyde d'aluminium possédant une excellente résistance à la corrosion peut être formée sur la surface de la tôle d'acier. De plus, il est possible de commander l'épaisseur et la densité de la couche d'oxyde par le biais de la commande de la densité de courant, du temps d'application et des électrolytes, de sorte que la tôle d'acier puisse être appliquée non seulement à des champs de construction tels que des toits et des murs, mais également à des zones où une résistance à la corrosion est requise, telles que des tuyaux pour des fermes et des logements de bétail.
PCT/KR2018/016689 2017-12-26 2018-12-26 Procédé de traitement de surface d'une tôle d'acier plaquée d'alliage d'aluminium et tôle d'acier plaquée d'alliage d'aluminium ainsi produite WO2019132525A1 (fr)

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KR10-2017-0179049 2017-12-26
KR1020170179049A KR102153162B1 (ko) 2017-12-26 2017-12-26 알루미늄합금 도금강판의 표면처리방법 및 이에 따라 제조된 알루미늄합금 도금강판

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112458453A (zh) * 2020-11-24 2021-03-09 安徽盈锐优材科技有限公司 一种高结合强度陶瓷绝缘涂层及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102341118B1 (ko) * 2021-04-29 2021-12-17 조용민 비내식성이 향상된 알루미늄 합금 및 이의 제조 방법

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KR20100116546A (ko) * 2009-04-22 2010-11-01 한양대학교 산학협력단 금속의 표면처리 방법
KR20110117395A (ko) * 2010-04-21 2011-10-27 한양대학교 산학협력단 고강도 및 검은색 착색 효과를 갖는 알루미늄재의 표면 처리 방법
JP2012036491A (ja) * 2010-08-12 2012-02-23 Jfe Steel Corp 溶融Ａｌ−Ｚｎ系めっき鋼板
KR20150112413A (ko) * 2014-03-28 2015-10-07 케이씨케미칼 주식회사 금속의 플라즈마 전해 산화방법
KR101709602B1 (ko) * 2015-12-10 2017-02-23 영남대학교 산학협력단 마이크로 아크 전해 산화 처리를 통한 알루미늄 합금 내산화 코팅층 제조방법

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KR100573027B1 (ko) * 2003-07-30 2006-04-25 김나래 알루미늄 합금으로 제조된 물품의 마이크로아크 산화 공정

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Publication number Priority date Publication date Assignee Title
KR20100116546A (ko) * 2009-04-22 2010-11-01 한양대학교 산학협력단 금속의 표면처리 방법
KR20110117395A (ko) * 2010-04-21 2011-10-27 한양대학교 산학협력단 고강도 및 검은색 착색 효과를 갖는 알루미늄재의 표면 처리 방법
JP2012036491A (ja) * 2010-08-12 2012-02-23 Jfe Steel Corp 溶融Ａｌ−Ｚｎ系めっき鋼板
KR20150112413A (ko) * 2014-03-28 2015-10-07 케이씨케미칼 주식회사 금속의 플라즈마 전해 산화방법
KR101709602B1 (ko) * 2015-12-10 2017-02-23 영남대학교 산학협력단 마이크로 아크 전해 산화 처리를 통한 알루미늄 합금 내산화 코팅층 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112458453A (zh) * 2020-11-24 2021-03-09 安徽盈锐优材科技有限公司 一种高结合强度陶瓷绝缘涂层及其制备方法
CN112458453B (zh) * 2020-11-24 2023-09-15 安徽盈锐优材科技有限公司 一种高结合强度陶瓷绝缘涂层及其制备方法

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