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KR20030032323A - method of manufacturing a hot dip aluminized stainless steel - Google Patents

method of manufacturing a hot dip aluminized stainless steel Download PDF

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KR20030032323A
KR20030032323A KR1020010064047A KR20010064047A KR20030032323A KR 20030032323 A KR20030032323 A KR 20030032323A KR 1020010064047 A KR1020010064047 A KR 1020010064047A KR 20010064047 A KR20010064047 A KR 20010064047A KR 20030032323 A KR20030032323 A KR 20030032323A
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nickel
aluminum
plating
tungsten
steel sheet
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KR100558059B1 (en
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김현태
장삼규
정훤우
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주식회사 포스코
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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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
    • C23C2/0224—Two or more thermal pretreatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)

Abstract

본 발명은 스테인레스 강판을 소지 금속으로 하여 용융알루미늄 도금욕에서 알루미늄을 도금하는 방법에서, 상기 강판의 표면에 용융알루미늄 도금욕에서 알루미늄 도금을 실시하기 전에 스테인레스 선도금법으로 니켈-텅스텐 합금 도금층을 형성시키는 것을 요지로 하며, 본 발명에서 상기 니켈-텅스텐 합금 도금층에는 니켈에 텅스텐의 함유량을 중량%로 0.05 % - 20 %로 하도록 하고, 니켈-텅스텐 합금 도금층에는 도금부착량이 10 mg/m2- 2500 mg/m2로 하는 것을 특징으로 한다.The present invention relates to a method of plating aluminum in a molten aluminum plating bath using a stainless steel plate as a metal, wherein a nickel-tungsten alloy plating layer is formed by a stainless lead gold method before performing aluminum plating on a surface of the steel sheet in a molten aluminum plating bath. and that as a base, the nickel in the present invention and that of 20%, the nickel-tungsten alloy plating layer has the content of tungsten in Ni 0.05% in weight%, the tungsten alloy plating layer coating weight is 10 mg / m 2 - 2500 mg It is characterized by setting as / m 2 .

본 발명에 의하면 젖음성 및 고온 내식성이 향상된 알루미늄 용융도금강판을 제공할 수 있다.According to the present invention, it is possible to provide an aluminum hot dip galvanized steel sheet having improved wettability and high temperature corrosion resistance.

Description

젖음성 및 고온 산화성을 향상시킨 스테인레스 알루미늄 용융도금강판의 제조방법{method of manufacturing a hot dip aluminized stainless steel}Method for manufacturing stainless steel hot-dip galvanized steel sheet with improved wettability and high temperature oxidizing property

본 발명은 젖은성 및 고온 산화성을 향상시킨 스테인레스 알루미늄 용융도금강판의 제조방법에 관한 것으로, 특히 자동차 배기관용으로 사용되는 알루미늄 용융도금 스테인레스강판을 용융도금하기전에 니켈-텅스텐 선도금하는 방법으로, 니켈이 주성분이고 부수적으로 텅스텐이 함유된 코팅층을 만들어 스테인레스 도금강판의 품질을 향상 시키는 것이다.The present invention relates to a method for producing a stainless aluminum hot-dip galvanized steel sheet having improved wettability and high temperature oxidation property, and in particular, nickel-tungsten lead metal prior to hot-dip plating of an aluminum hot-dip plated stainless steel sheet used for automobile exhaust pipes. This is the main ingredient and additionally to make the coating layer containing tungsten to improve the quality of stainless steel plated.

일반적으로 자동차 배기관용으로 사용되는 스테인레스강판은 내식성이 우수하고 표면이 미려하여 북미등에 널리 사용되고 있다. 그러나 스테인레스 강판 자체로는 용접부에서 내식성이 취약하여 녹이 발생되기 쉽고, 염기등에 의하여 쉽게 변색이 일어난다.Generally, stainless steel sheet used for automobile exhaust pipe is widely used in North America because of its excellent corrosion resistance and beautiful surface. However, the stainless steel plate itself is vulnerable to corrosion resistance in the weld portion, rust is likely to occur, and discoloration is easily caused by a base.

이러한 문제점을 해결하기 위하여 스테인레스 강판에 보통 알루미늄 도금을 행하게 된다. 알루미늄이 도금되면 스테인레스 강판은 가혹한 부식분위기에서도 내식성이 양호하며 용접부 등에도 녹이 발생되지 않으며 표면 변색도 없다.In order to solve this problem, stainless steel plate is usually aluminum plated. When aluminum is plated, the stainless steel plate has good corrosion resistance even in severe corrosion atmosphere, and no rust occurs in welded parts, and there is no surface discoloration.

자동차의 배기계의 재료는 1990년 전에는 주로 일반 알루미늄 도금강판이 사용되다가 그 이후로는 SUS 409L이나, SUS 436L 등이 사용된다. 그러나 이들은 앞서 설명한 바와 같이 다른 처리 없이 사용시 결점이 많으므로 용융도금법으로 알루미늄을 표면에 도금한다. 그러나 이들 강판은 표면에 크롬산화물이 생성되어 있어서 알미늄의 젖음성을 불량하게하여 도금밀착성이 나빠진다. 이를 극복하기 위하여 스테인레스 강판위에 산화성이 비교적 적고 부동태 피막화가 적은 니켈도금(일본특허 : 소60-262950)이나, 니켈-보론 (미국특허-4891274) 도금등을 행한 후 용융도금을 한다.As a material of the exhaust system of automobiles, general aluminum plated steel sheet is used before 1990, and after that, SUS 409L or SUS 436L is used. However, since they have many drawbacks when used without other treatments as described above, aluminum is plated on the surface by hot dip plating. However, these steel sheets produce chromium oxide on the surface, which causes poor wettability of aluminum and degrades plating adhesion. In order to overcome this problem, nickel plating (Japanese Patent No. 60-262950) or nickel-boron (US Patent No. 4891274), which has a relatively low oxidative property and low passivation, is applied on a stainless steel sheet, followed by hot dip plating.

그러나 이러한 하지 도금도 내식성과 젖음성이 미약하며, 특히 용융도금이 된 후로 내 고온산화성을 확보할 필요가 있다.However, the base plating is also poor in corrosion resistance and wettability, and it is necessary to secure high temperature oxidation resistance, especially after hot dip plating.

본 발명은 상기의 문제점 및 요망을 해결하기 위하여 안출된 것으로써, 본 발명자들은 알루미늄 도금강판에 니켈-텅스텐의 합금도금을 행함으로서 내식성과 젖음성을 향상시키고 특히 용융도금이후 고온 산화성을 확보할 수 있는 스테인레스 알루미늄용융도금강판을 제공하는 것을 목적으로 한다.The present invention has been made in order to solve the above problems and desires, the present inventors can improve the corrosion resistance and wettability by performing alloy plating of nickel-tungsten on aluminum plated steel sheet, and in particular, it is possible to secure high temperature oxidation resistance after hot dip plating. An object of the present invention is to provide a stainless aluminum hot dip coated steel sheet.

이하 본 발명을 실시예를 참조하여 더욱 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

본 발명은 상기의 과제를 해결하기 위하여, 스테인레스 강판을 소지 금속으로 하여 용융알루미늄 도금욕에서 알루미늄을 도금하는 방법에서, 상기 강판의 표면에 용융알루미늄 도금욕에서 알루미늄 도금을 실시하기 전에 스테인레스 선도금법으로 니켈-텅스텐 합금 도금층을 형성시키는 것을 특징으로 한다.In order to solve the above problems, in the method of plating aluminum in a molten aluminum plating bath using a stainless steel plate as a metal, the surface of the steel sheet is subjected to a stainless lead gold method before performing aluminum plating in a molten aluminum plating bath. It is characterized by forming a nickel-tungsten alloy plating layer.

또한 본 발명에서 상기 니켈-텅스텐 합금 도금층에는 니켈에 텅스텐의 함유량을 중량%로 0.05 % - 20 %로 하도록 하고, 니켈-텅스텐 합금 도금층에는 도금부착량이 10 mg/m2- 2500 mg/m2로 하는 것을 특징으로 한다.In addition, the nickel in the present invention as 2500 mg / m 2 - and that of 20%, the nickel-tungsten alloy plating layer has the content of tungsten in Ni 0.05% in weight percent tungsten alloy plating layer, the coating weight is 10 mg / m 2 Characterized in that.

또한 본 발명에서 상기 니켈-텅스텐 합금 도금층에는 니켈에 텅스텐의 함유량을 중량%로 1 - 5%로하고, 도금부착량은 200 mg/m2로 - 1500 mg/m2로 하는 것이 가장 바람직하다.In addition, the nickel in the present invention, and to 5%, the coating weight to 200 mg / m 2 - - the content of tungsten in the nickel-tungsten alloy plating layer is 1% by weight is most preferably to 1500 mg / m 2.

본 발명은 상기와 같은 방법을 통하여 자동차 배기계용 알루미늄 용융도금 스테인레스 강판의 제조에 있어서 용융도금전에 니켈-텅스텐 선 도금에 의하여 용융도금 젖음성을 양호하게하며, 고온 산화성을 양호하게하는 방법을 제공할 수 있는 것이다.The present invention in the manufacture of aluminum hot-dip galvanized stainless steel sheet for automobile exhaust system through the method as described above can provide a method for improving the hot-dip wettability by nickel-tungsten wire plating before hot-dip plating, and high temperature oxidative properties. It is.

즉, 본 발명은 자동차 배기관용 알루미늄 용융도금된 스테인레스 강판을 제조함에 있어서 스테인레스 표면에 존재하는 크롬산화물 때문에 알루미늄 용융도금시 젖음성이 나쁘고, 고온산화성이 양호하지 못한 결점을 개선한 것이다.That is, the present invention improves the drawbacks of poor wettability and poor high temperature oxidation resistance due to the chromium oxide present on the stainless surface in manufacturing aluminum hot-dip plated stainless steel sheet for automobile exhaust pipe.

스테인레스 409L은 크롬의 함유량이 9-12%정도 함유되고 나머지는 철로 되어있으며 타 원소는 불순물 정도로 되어있는 강판이나, 436L강판은 15-17%크롬과 1%내외의 몰리브덴으로 구성되고 나머지가 철이며 또한 타 원소는 불순물 정도로 함유된 원판 소지를 사용한다.409L stainless steel contains 9-12% of chromium and the rest is made of iron and other elements are impurity, while 436L steel is composed of 15-17% chromium and about 1% molybdenum. In addition, the other element uses the base material which contained the impurity grade.

니켈-텅스텐의 도금 방법에 무관하게 도금층의 텅스텐 량이 0.05%이하이면 고온 산화성을 향상시키지 못하며, 20% 이상이 되면 젖음성이 개선되지 못한다. 바람직하기로는 1 ~5%의 텅스텐이 포함된 것이다. 또한 도금량이 10mg/m2이하이면 젖음성과 고온 내식성이 향상되지 못하며, 2500mg/m2이상에서는 더 이상의 젖음성을 향상 시키지 못하며, 생산성이 감소되어 비용이 증가된다. 우수하게는 200 ~ 1500 mg/m2이다.Regardless of the nickel-tungsten plating method, when the amount of tungsten in the plating layer is 0.05% or less, high temperature oxidative property cannot be improved, and when 20% or more, wettability is not improved. Preferably 1 to 5% of tungsten is included. In addition, when the plating amount is 10mg / m 2 or less, the wettability and high temperature corrosion resistance does not improve, 2500mg / m 2 or more does not improve the additional wettability, productivity is reduced and the cost is increased. Excellently between 200 and 1500 mg / m 2 .

이상 선 도금된 스테인레스 강판은 용융도금법으로 알루미늄도금을 행한다. 소지 강판을 850oC에서 분위기가 20% H2+80%N2인 소둔로에서 7-10분간 유지된 후 660oC로 냉각된 후 660oC의 알루미늄도금욕에서 약 15-30um의 두께로 용융도금된다.The stainless steel plate pre-plated is subjected to aluminum plating by hot dip plating. The steel sheet was held at 850 o C for 7-10 minutes in an annealing furnace with 20% H 2 + 80% N 2 atmosphere, then cooled to 660 o C and then about 15-30um thick in an 660 o C aluminum plating bath. It is hot dip plated.

이하 본 발명의 실시예를 살펴본다.Hereinafter, an embodiment of the present invention will be described.

(실시예)(Example)

409L 스테인레스 강판을 소지 금속으로 하여 하기 표 1에 나타난 도금액 조성을 가진 용액으로 전류밀도 60A/dm2, 온도 45oC, 유속 1.5m/sec에서 선 도금을 행하고 용융도금을 20um두께로 행한 후 아래와 같은 시험 법으로 젖음성 시험과 고온 내식성 시험을 행하였다.A solution having the plating solution composition shown in Table 1 below using a 409L stainless steel sheet as a base metal, pre-plating at a current density of 60 A / dm 2 , a temperature of 45 o C, and a flow rate of 1.5 m / sec, followed by hot dip plating at a thickness of 20 μm. Wetting test and high temperature corrosion resistance test were done by the test method.

1) 젖음성 시험1) wetting test

시편의 젖음성은 용융도금시 스테인레스 강판에 알루미늄이 표면을 적시는 표면의 넓이에 대한 것으로 본 실시예에서의 판정은 선 도금된 면의 알루미늄 용탕에 용융도금한 후 표면에 도금된 면적으로 96% 이상은 양호, 그 이하는 불량으로나타내었다.The wettability of the specimen is the area of the surface where aluminum wets the surface of the stainless steel sheet during hot dip plating. The judgment in this embodiment is more than 96% of the surface plated on the surface after hot plating on the aluminum molten metal of the preplated surface. Is good and the following is shown as bad.

2) 고온 산화시험2) High temperature oxidation test

고온로 900oC로에서 20시간 유지후 께내어 상온에서 5시간 유지하며, 이러한 경우를 10회 반복하여 무게 감량으로 나타내어 표면 cm2당 20mg 이하이면 양호, 이상이면 불량으로 판정 하였다. 사용된 도금액은 염화니켈과 염산 및 텅스텐산나트륨으로 제조하였다.After maintaining for 20 hours in a high temperature furnace at 900 ° C. and kept for 5 hours at room temperature, this case was repeated 10 times to represent a weight loss to determine that less than 20mg per cm 2 surface, good, if abnormal. The plating solution used was made of nickel chloride, hydrochloric acid and sodium tungstate.

품질 현황Quality Status 품질quality 도금층Plating layer 품질quality 텅스텐함량 (%)Tungsten Content (%) 도금층의부착량(mg/m2)Coating amount of coating layer (mg / m 2 ) 젖음성Wettability 고온 내식성High temperature corrosion resistance 비교예Comparative example 1One 0.040.04 10001000 불량Bad 불량Bad 발명예Inventive Example 22 0.050.05 10001000 양호Good 양호Good 발명예Inventive Example 33 0.10.1 10001000 양호Good 양호Good 발명예Inventive Example 44 1.01.0 10001000 양호Good 양호Good 발명예Inventive Example 55 1010 10001000 양호Good 양호Good 발명예Inventive Example 66 2020 10001000 양호Good 양호Good 비교예Comparative example 77 2121 10001000 불량Bad 불량Bad 발명예Inventive Example 88 33 9.09.0 양호Good 양호Good 발명예Inventive Example 99 33 10.010.0 양호Good 양호Good 발명예Inventive Example 1010 33 100100 양호Good 양호Good 발명예Inventive Example 1111 33 500500 양호Good 양호Good 발명예Inventive Example 1212 33 15001500 양호Good 양호Good 발명예Inventive Example 1313 33 25002500 양호Good 양호Good 비교예Comparative example 1414 33 25102510 불량Bad 불량Bad

상기 표 1에 나타낸 바와 같이 본발명에 부합되는 발명예는 젖음성 및 고온 내식성이 양호함을 나타낸다. 따라서 상술한 바와 같이 본 발명은 알루미늄 용융도금을 행하는 텅스텐강판의 품질에 본 발명이 우수한 효과를 나타낸다.As shown in Table 1, the invention example consistent with the present invention shows good wettability and high temperature corrosion resistance. Therefore, as described above, the present invention exhibits an excellent effect of the present invention on the quality of tungsten steel sheet subjected to hot dip aluminum plating.

상술한 바와 같이, 본 발명에 의하면, 알루미늄 용융도금을 행하는 텅스텐강판의 품질이 향상된 효과를 가진다, 특히 젖음성 및 고온 내산화성 혹은 고온 내식성에 우수한 효과를 가진다.As described above, according to the present invention, the quality of the tungsten steel sheet to be subjected to aluminum hot dip plating has an improved effect, in particular, it has an excellent effect on wettability and high temperature oxidation resistance or high temperature corrosion resistance.

Claims (4)

스테인레스 강판을 소지 금속으로 하여 용융알루미늄 도금욕에서 알루미늄을 도금하는 방법에서,In a method of plating aluminum in a molten aluminum plating bath using a stainless steel plate as a base metal, 상기 강판의 표면에 용융알루미늄 도금욕에서 알루미늄 도금을 실시하기 전에 스테인레스 선도금법으로 니켈-텅스텐 합금 도금층을 형성시키는 것을 특징으로 하는 젖음성 및 고온 산화성을 향상시킨 스테인레스 알루미늄 용융도금강판의 제조방법.The method of manufacturing a stainless aluminum hot-dip plated steel sheet having improved wettability and high temperature oxidizing property, wherein a nickel-tungsten alloy plating layer is formed on the surface of the steel sheet by performing a stainless lead plating method before aluminum plating in a molten aluminum plating bath. 제1항에 있어서,The method of claim 1, 상기 니켈-텅스텐 합금 도금층에는 니켈에 텅스텐의 함유량을 중량%로 0.05 % - 20 %로 하는 것을 특징으로 하는 방법.The nickel-tungsten alloy plating layer is characterized in that the content of tungsten in the weight of 0.05% to 20% by weight. 제1항 또는 제2항에 있어서,The method according to claim 1 or 2, 상기 니켈-텅스텐 합금 도금층에는 도금부착량이 10 mg/m2- 2500 mg/m2로 하는 것을 특징으로 하는 방법.The nickel-methods characterized in that a 2500 mg / m 2 - tungsten alloy plating layer has a coating weight 10 mg / m 2. 제3항에 있어서,The method of claim 3, 상기 니켈-텅스텐 합금 도금층에는 니켈에 텅스텐의 함유량을 중량%로 1 -5%로하고, 도금부착량은 200 mg/m2로 - 1500 mg/m2로 하는 것을 특징으로 하는 방법.The nickel-tungsten alloy plating layer has the content of tungsten in the nickel to 1% -5% by weight, and the coating weight is a 200 mg / m 2 - characterized in that to a 1500 mg / m 2.
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WO2008078914A1 (en) * 2006-12-27 2008-07-03 Posco Method for producing hot-dip aluminized stainless steel sheet using atmospheric pressure plasma
US8083122B2 (en) 2003-06-05 2011-12-27 Lg Electronics Inc. Drum for washer and dryer

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JPS6428349A (en) * 1987-07-24 1989-01-30 Nippon Steel Corp Manufacture of aluminum-plated steel sheet and steel foil using stainless steel as base material
JP2769350B2 (en) * 1989-03-28 1998-06-25 新日本製鐵株式会社 Manufacturing method of hot-dip coated steel sheet
KR100286661B1 (en) * 1996-12-23 2001-04-16 이구택 Pretreatment method of aluminized stainless steel sheet
KR100376522B1 (en) * 1996-12-24 2003-06-09 주식회사 포스코 Manufacturing method of hot-dip aluminum coated stainless steel plate with excellent plating adhesion and corrosion resistance

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US8083122B2 (en) 2003-06-05 2011-12-27 Lg Electronics Inc. Drum for washer and dryer
US8365437B2 (en) 2003-06-05 2013-02-05 Lg Electronics Inc. Drum for washer and dryer
WO2008078914A1 (en) * 2006-12-27 2008-07-03 Posco Method for producing hot-dip aluminized stainless steel sheet using atmospheric pressure plasma
KR101372624B1 (en) * 2006-12-27 2014-03-10 주식회사 포스코 Method for producing hot-dip aluminized stainless steel sheet using atmospheric pressure plasma

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