KR20190137170A - 코팅된 금속 기판 및 제조 방법 - Google Patents

코팅된 금속 기판 및 제조 방법 Download PDF

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KR20190137170A
KR20190137170A KR1020197035059A KR20197035059A KR20190137170A KR 20190137170 A KR20190137170 A KR 20190137170A KR 1020197035059 A KR1020197035059 A KR 1020197035059A KR 20197035059 A KR20197035059 A KR 20197035059A KR 20190137170 A KR20190137170 A KR 20190137170A
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South Korea
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coating layer
substrate
weight
intermediate coating
metal substrate
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KR1020197035059A
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KR102168599B1 (ko
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야첵 고니아코브스키
티 하 린 레
끌로딘 노게라
자끄 쥐삐유
레미 라자리
장-미셸 마떼뉴
알렉세이 콜초프
레미 카발로티
다니엘 샤레익
뤼시 가우야
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아르셀러미탈
쏘흐본느 유니베흐시테
상뜨르 나쇼날 드 라 러쉐르쉬 샹띠피끄
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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
    • C23C28/345—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 with at least one oxide layer
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

본 발명은, 적어도, 하나의 산화물들 층을 포함하는 코팅된 금속 기판으로서, 상기 산화물들 층은, Fe, Ni, Cr 및 Ti 을 포함하고 Ti 양이 5 중량% 이상이며 8 중량% < Cr +Ti < 40 중량% 를 만족시키고 잔부가 Fe 및 Ni 인 중간 코팅 층에 의해, 직접 덮이고 (topped), 상기 중간 코팅 층은 내식 금속 코팅인 코팅 층에 의해 직접 덮이는, 코팅된 금속 기판에 관한 것이다.

Description

코팅된 금속 기판 및 제조 방법
본 발명은 코팅된 금속 기판 및 그 제조 방법에 관한 것이다. 코팅된 금속 기판은 특히 자동차의 제조에 적합하다.
강판은 일반적으로 금속 코팅으로 커버되며, 금속 코팅의 조성은 강판의 최종 용도에 따라 달라진다. 이 코팅은, 예를 들어 아연, 알루미늄, 마그네슘 또는 이들의 합금일 수 있고, 하나 이상의 층들을 포함할 수 있으며, 예를 들어 진공 증착 방법, 용융 도금 또는 전착과 같은 본 기술분야의 당업자에게 공지된 다른 코팅 기술들을 사용하여 적용될 수 있다.
일반적으로, 금속 코팅은 용융 도금에 의해 디포짓팅되며, 이 공정은 일반적으로 다음 단계를 포함한다:
- 강판 표면의 산화를 제한하기 위해 불활성 또는 환원성 분위기 하에서 강판이 노를 통과할 때 강판을 어닐링하는 단계;
- 강판이 액체 상태의 금속 또는 금속 합금의 욕에서 나올 때 금속 / 금속 합금으로 코팅되도록, 강판이 상기 욕을 통과할 때 용융 도금하는 단계;
- 강판이 액체 욕에서 나온 후, 금속/금속 합금 층의 균일하고 일정한 두께를 보장하기 위해 표면에 가스를 분사함으로써 금속/금속 합금 층을 와이핑하는 단계.
어닐링 단계 동안, 강판이 금속 욕에 들어가기 전에 (본 명세서의 이하에서 "금속 욕" 및 "금속 층" 이라는 용어는 또한 임의의 금속 합금 욕 및 상응하는 금속 합금 층들을 나타내는데 사용된다), 강판은 일반적으로 직접 화염 또는 복사 튜브 어닐링 노에서 가열된다. 그러나, 불활성 분위기의 제어와 같은 수많은 조치에도 불구하고, 강판을 가열하기 위한 이러한 노의 사용은 표면에 금속 산화물의 형성을 초래하여, 강판 표면에서의 액체 금속의 적절한 젖음성을 방해하고 강판 표면에 비코팅 영역의 발생을 유발할 수 있다.
이러한 문제는 특히 강의 조성이 Si, Mn, Al, Cr, B, P 등과 같은 용이하게 산화되는 원소를 상당량 포함할 때 발생한다. 예를 들어, 0.2 중량% Mn, 0.02 중량% Si 및 5 ppm B 를 함유하는 IF (Interstitial-Free) 강은, 강판 표면으로 빠르게 확산하여 연속 필름들의 형태로 Mn, B 및 Si 의 혼합 산화물을 석출시키는 (불량한 젖음을 유발함) B 가 존재하므로, 이미 이러한 젖음성 문제를 겪고 있다.
더 일반적으로, 액체 금속에 의한 불량한 젖음 위험은 또한 모든 고강도 강에서 존재하는데, 그 이유는 2상 강, TRIP (변태 유기 소성) 강, TWIP (쌍정 유기 소성), 전기강 등과 같이 고강도 강이 철보다 더 쉽게 산화되는 원소들 중 적어도 하나를 함유하기 때문이다.
2상 강의 경우, Mn 의 양은 일반적으로 3 중량% 미만이고, Cr, Si 또는 Al 의 첨가량은 일반적으로 1 중량% 미만이다. TRIP 강의 경우, Mn 의 양은 일반적으로, 최대 2 중량% 의 Si 또는 Al 과 연관된 2 중량% 미만이다. TWIP 강의 경우, Mn 의 양은 Al 또는 Si (최대 3 중량%) 와 조합된, 최대 25 중량% 일 수 있다.
금속 코팅은 전착에 의해 또한 적용될 수 있다. 일반적으로, 전착 공정 전에, 강판은 표면에 존재하는 금속 산화물을 제거하기 위해 산세 단계를 거쳐야 한다. 실제로, 전기분해 공정이 효과적이기 위해서는, 매체는 반드시 도체이어야 하지만, 코팅될 강판 표면에 금속 산화물이 존재한다면 그렇지는 않다. 더욱이, 금속 산화물의 존재는 코팅 디포지션에 영향을 미칠 수 있으므로, 코팅의 접착성 및 품질 (미세구조, 밀도 등) 의 문제를 야기할 수 있다.
금속 코팅은 또한 진공 증착에 의해 적용될 수 있다. 특히 증기 상을 형성하는데 사용된 수단에 따라 진공 증착의 상이한 유형들이 구별된다. 증기 상이 화학 반응 또는 분자의 분해로부터 유래한다면, 공정은 CVD, 또는 화학 기상 증착으로 불린다. 반면, 이 증기가 열 증발 또는 이온 스퍼터링과 같은 순전히 물리적 현상에 의해 생성된다면, 공정은 물리 기상 증착 또는 PVD 이다. PVD 증착 공정은 스퍼터링, 이온 주입 및 진공 증발을 포함한다.
하지만, 일반적으로, 사용된 진공 증착 기법에 관계없이, 금속 코팅의 적절한 부착을 보장하여 코팅 박리 문제를 방지하기 위해 코팅될 강판 표면이 금속 산화물을 갖지 않도록 표면 준비가 요구된다.
사용된 코팅 방법에 관계없이, 코팅 전 강 스트립의 표면 상태가 최종 코팅 품질에서 중요한 인자이다. 코팅될 강판의 표면에서의 금속 산화물의 존재는 적용될 코팅의 적절한 부착을 막고, 최종 제품 상에 코팅이 없는 구역 또는 코팅의 박리에 관한 문제를 초래할 수 있다. 이 금속 산화물은 강판 표면 상의 연속 필름 형태로 또는 불연속 점들의 형태로 존재할 수 있다. 금속 산화물은 또한 공정의 다른 단계들 중에 형성될 수 있고, 그 조성은 해당 판을 이루는 강의 등급에 따라 달라진다. 이러한 유형의 산화물은 예를 들어 철 산화물 FeOx, Fe304, Fe2O3, 및 철 수산화물, 알루미늄 산화물 Al2O3 및 알루미늄 수산화물, 규소 산화물 (SiOx), 및 혼합 산화물 MnSixOy, AlSixOy 또는 MnBxOy 를 포함한다.
이 금속 산화물의 제거는 부가적인 공정 단계, 즉 산세척의 실행을 필요로 한다. 본 설명의 이하에서, 산세척은, 예를 들어, 금속 산화물을 제거하는 공정이지만 하부 (underlying) 금속층을 노출시키지 않으면서 단지 금속 산화물의 표면층을 제거하려는 브라이트닝법과 비교하여, 하부 금속층이 표면에 나타나도록 하부 금속층의 산화에 의해 형성된 금속 산화물을 제거하는 임의의 방법을 의미한다.
금속 산화물의 이러한 제거는, 예를 들어, 에칭으로도 불리는, 마그네트론 분쇄에 의한 진공 산세척에 의해 달성될 수 있다. 스트립을 염산 또는 황산과 같은 강산의 하나 이상의 연속적인 욕에 통과시킴으로써 스트립을 산세척하는 것이 또한 가능하다. 마지막으로, 기계적 작용에 의해, 예를 들어 금속 산화물이 제거되는 숏 블라스팅 공정을 사용함으로써, 금속 산화물 층들의 전부 또는 일부를 제거할 수 있다. 그러나, 이러한 방법은 항상 산업적 규모로 구현하고 제어하기 어렵다.
하나의 알려진 표면 처리는 금속 기판 상에 존재하는 산화물 층의 제거를 피할 수 있게 한다. 실제로, 특허출원 WO2015/150850 은 복수의 층들을 포함하는 기판을 개시하는데, 이 층들 중 적어도 하나는 금속 산화물을 포함하고, 적어도 8 중량% 의 니켈과 적어도 10 중량% 의 크롬을 함유하고 잔부가 철, 부가적인 원소 및 제조 공정으로부터 기인한 불순물인 금속 코팅층에 의해 직접 덮이고 (topped), 이 금속 코팅층 자체가 내식 코팅층에 의해 직접 덮인다. 예를 들어, 금속 코팅 층은 16-18 중량% Cr 및 10-14 중량% Ni 을 포함하며 잔부가 Fe 인 316 스테인리스 강이다. 이 금속 코팅 층은 기판 상의 후속 코팅의 접착성을 향상시키고, 표면 상에 존재하는 산화물을 제거하는 단계를 필요로 하지 않는다.
그러나, 금속 기판 상에 니켈, 크롬 및 철을 함유하는 금속 코팅 층을 추가하는 것을 포함하는 이러한 표면 처리는 유일한 공지된 표면 처리이고, 따라서 기판 표면에 존재하는 산화물을 제거하는 단계를 필요로 하지 않는 시장에서 이용 가능한 하나이다.
따라서, 본 발명의 목적은, 특히 기판에 후속 코팅의 부착을 향상시킬 수 있으며 표면에 존재하는 산화물을 제거하는 단계를 필요로 하지 않는 다른 표면 처리 방법을 제공하는 것이다.
이러한 목적은 청구항 1 에 따른 코팅된 금속 기판을 제공함으로써 달성된다. 기판은 청구항 2 내지 청구항 19 의 특징을 또한 포함할 수 있다.
이러한 목적은 청구항 20 에 따른 코팅된 금속 기판의 제조 방법을 제공함으로써 또한 달성된다. 방법은 청구항 21 내지 청구항 24 의 특징을 또한 포함할 수 있다.
마지막으로, 청구항 25 에 따른 코팅된 금속 기판의 용도를 제공함으로써 목적이 달성된다.
본 발명의 다른 특징 및 이점은 본 발명에 대한 이하의 상세한 설명으로부터 명백해질 것이다.
본 발명을 설명하기 위해, 다양한 실시형태들 및 비제한적인 예들의 시험들이 특히 다음의 도면을 참조하여 설명될 것이다.
도 1 은 본 발명의 제 1 실시형태의 기판의 개략도이다.
도 2 는 본 발명의 제 2 실시형태의 기판의 개략도이다.
도 3 은 본 발명의 제 3 실시형태의 기판의 개략도이다.
모든 도면에서, 나타낸 층들의 두께는 전적으로 예시를 위한 것이고, 다른 층들을 일정한 비율로 나타낸 것으로 간주될 수 없다.
이하의 용어들이 정의된다:
- 모든 백분율 "%" 는 중량으로 규정된다.
"강" 또는 "강판" 이라는 표현은 모든 공지된 강 등급을 포함하고, 예를 들어, HSS (High Strength Steel, 일반적으로 450 내지 900 MPa) 또는 AHSS (Advanced High Strength Steels, 일반적으로 900 MPa 초과), 다량의 산화가능한 원소들을 함유하는 강의 이하의 등급들 중 하나일 수 있다:
- 최대 0.1 중량% Ti 을 함유할 수 있는, 침입형 원소가 없는 강 (IF - Interstitial Free);
- 최대 1 중량% Si, Cr 및/또는 Al 과 함께 최대 3 중량% Mn 을 함유할 수 있는, DP 500 강 내지 DP 1200 강과 같은 2상 강;
- 예를 들어 약 1.6중량% Mn 및 1.5중량% Si 를 함유하는, TRIP 780 과 같은 TRIP (TRansformation Induced Plasticity) 강;
- 인을 함유하는 TRIP 또는 2상 강;
- TWIP (TWinning-Induced Plasticity) 강 - 고함량의 Mn (일반적으로 17 ~ 25 중량%) 을 갖는 강;
- 예를 들어, 최대 10 중량% Al 을 함유할 수 있는 Fe-Al 강과 같은 저밀도 강;
- 고함량의 크롬 (일반적으로 13 ~ 35 중량%) 과 다른 합금 원소 (Si, Mn, Al 등) 를 가지는 스테인리스 강.
이러한 목적을 위해, 본 발명은, 적어도, 하나의 산화물들 층을 포함하는 코팅된 금속 기판으로서, 상기 산화물들 층은, Fe, Ni, Cr 및 Ti 을 포함하고 Ti 양이 5 중량% 이상이며 8 중량% < Cr +Ti < 40 중량% 를 만족시키고 잔부가 Fe 및 Ni 인 중간 코팅 층에 의해, 직접 덮이고, 상기 중간 코팅 층은 내식 금속 코팅인 코팅 층에 의해 직접 덮이는, 코팅된 금속 기판을 제공한다.
어떠한 이론에도 구속됨이 없이, 본 발명에 따른 Fe, Ni, Cr 및 Ti 을 포함하는 중간 코팅 층이 후속 코팅의 접착을 향상시키고, 금속 기판 상에 존재하는 자연 산화물들 층의 제거를 필요로 하지 않는 것으로 보인다. 실제로, 중간 층에 존재하는 크롬 또는 티타늄 산화물이 금속 기판 상에 존재하는 자연 산화물과 내식 금속 코팅 사이의 계면에서 강한 링크를 초래하는 것으로 여겨진다.
Ti 양이 5 중량% 미만인 때에 Fe, Ni, Cr 및 Ti 을 포함하는 중간 코팅 층이 산화물 층 상에 잘 부착되지 않을 위험이 존재한다고 여겨진다. 또한, Cr 및 Ti 양이 8 중량% 미만인 때, 산화물 층이 강판 표면에 충분히 커버되지 않아서 내식 금속 코팅의 부착이 나빠질 위험이 존재한다. 마지막으로, Cr + Ti 양이 40 중량% 를 초과할 때. 중간 층에서 산화된 티탄과 Cr-Ti 금속 층 사이에 약한 연결이 나타나서 금속 기판 표면에 내식 금속 코팅의 불량한 부착을 초래하므로 접착이 감소할 위험이 존재한다.
도 1 은 본 발명에 따른 제 1 실시형태를 도시한다. 이 실시형태에서, 금속 기판은 그의 표면들 중 적어도 하나에 산화물들 층 (2) 을 포함하는 강판 (1) 이다. 이 산화물 층 (2) 은 강 표면 (1) 에서 연속적이거나 불연속적일 수 있고, 철 산화물, 크롬 산화물, 망간 산화물, 알루미늄 산화물, 규소 산화물, 붕소 산화물, 또는 강 합금 원소를 함유하는 하나 이상의 혼합 산화물 (혼합 Mn-Si 또는 Al-Si 산화물 등) 을 포함하는 그룹으로부터의 금속 산화물을 포함할 수 있다. 이 제 1 금속 산화물 층 (2) 의 두께는 예를 들어 일반적으로는 3 ~ 대략 60 ㎚, 바람직하게는 3 ~ 대략 20 ㎚ 로 다양할 수 있다.
따라서, 산화물 층 (2) 은 제거되지 않고, Fe, Ni, Cr 및 Ti 을 포함하고 Ti 양은 5 중량% 이상이고 8 중량% < Cr + Ti < 40 중량% 를 만족시키며 잔부가 Fe 및 Ni 인 중간 코팅 층 (3) 으로 커버된다. 예컨대, 이 코팅 (3) 은 27 중량% 의 Ni, 10 중량% 의 Cr, 10 중량% 의 Ti, 잔부인 Fe 를 포함할 수 있다. Fe-Ni-Cr-Ti 금속 코팅 층 (3) 은 내식 금속 코팅 층 (4) 으로 커버된다.
본 발명에 따르면, 중간 코팅 층은 15 내지 42 중량%, 더 바람직하게는 22 내지 40 중량%, 유리하게는 25 내지 30 중량% 의 Ni 을 포함한다.
바람직하게는, 중간 코팅 층은 10 내지 60%, 더 바람직하게는 30 내지 60% 의 철을 포함한다.
유리하게는, 중간 코팅은 5 내지 30 중량%, 바람직하게는 5 내지 20 중량% 의 Ti 을 포함한다.
바람직하게는, 중간 코팅은 5 내지 30 중량%, 더 바람직하게는 5 내지 20 중량% 의 Cr 을 포함한다.
바람직한 실시형태에서, 중간 코팅 층은 1 내지 100 nm, 바람직하게는 1 내지 50 nm, 더 바람직하게는 1 내지 20 nm 의 두께를 갖는다.
다른 바람직한 실시형태에서, 금속 기판은 내식 층으로 직접 코팅되고, 내식 층은 산화물들 층에 의해 직접 덮인다.
바람직하게는, 내식 코팅 층(들)은 아연, 알루미늄, 구리, 규소, 철, 마그네슘, 티타늄, 니켈, 크롬, 망간 및 이들의 합금들을 포함하는 그룹에서 선택된 금속을 포함한다.
더 바람직하게는, 내식 코팅은 15% 미만 Si, 5.0% 미만 Fe, 선택적으로 0.1 내지 8.0% Mg 및 선택적으로 0.1 내지 30.0% Zn, 잔부인 Al 을 포함하는 알루미늄계 코팅이다.
다른 바람직한 실시형태에서, 내식 코팅은 0.01 내지 8.0% Al, 선택적으로 0.2 내지 8.0% Mg, 잔부 Zn 을 포함하는 아연계 코팅이다.
금속 기판은 알루미늄 기판, 강 기판, 스테인리스 강 기판, 구리 기판, 철 기판, 구리 합금 기판, 티타늄 기판, 코발트 기판 또는 니켈 기판 중에서 선택될 수 있다. 바람직하게는, 금속 기판은 강판이다.
도 2 는 본 발명의 제 2 실시형태를 도시한다. 이 실시형태에서, 기판은 강판 (21) 이다. 이 강판 (21) 은 예컨대 9 내지 12 중량% 의 Si 를 포함하는 알루미늄계 코팅과 같은 내식 코팅 층 (25) 으로 코팅된다. 알루미늄계 코팅 (25) 은 예컨대 10 내지 30 ㎛ 의 두께를 가질 수 있다. 이 알루미늄계 코팅 층 (25) 은 금속 산화물들 층 (22) 에 의해 덮인다. 이 층 (22) 은 해당 알루미늄계 코팅 (25) 의 표면에 걸쳐 연속적이거나 불연속적일 수 있고, 알루미늄 산화물 및/또는 Al-Si 산화물과 같은 혼합된 알루미늄 산화물을 포함할 수 있다. 이 금속 산화물 층 (22) 의 두께는 일반적으로 3 ~ 대략 60 ㎚, 바람직하게 3 ~ 대략 20 ㎚ 로 다양할 수 있다.
따라서, 이 산화물 층 (22) 은 제거되지 않고, Fe, Ni, Cr 및 Ti 을 포함하고 Ti 양은 5 중량% 이상이고 8 중량% < Cr + Ti < 40 중량% 를 만족시키며 잔부가 Fe 및 Ni 인 중간 코팅 층 (23) 에 의해 커버된다. 예컨대, 이 코팅 (23) 은 29 중량% 의 Ni, 12 중량% 의 Cr, 22 중량% 의 Ti, 잔부인 Fe 를 포함한다.
이 제 2 실시형태에서 이 금속 코팅 층 (23) 은 예컨대 아연계 코팅인 내식 금속 코팅 층 (24) 에 의해 덮인다. 이 경우, 바람직하게는, 아연계 코팅은 0.01 내지 0.2% 의 Al, 1.0 내지 5% 의 Mg, 잔부인 Zn 을 포함하는 Zn-Mg 합금 내식 코팅이다.
도 3 은 본 발명의 제 3 실시형태를 도시한다. 이 제 3 실시형태에서, 기판은 그의 표면들 중 적어도 하나에 제 1 산화물들 층 (32) 을 포함하는 강판 (31) 이다.
산화물들 층 (32) 은 제거되지 않고, Fe, Ni, Cr 및 Ti 을 포함하고 Ti 양은 5 중량% 이상이고 8 중량% < Cr + Ti < 40 중량% 를 만족시키며 잔부가 Fe 및 Ni 그리고 제조 공정으로 인한 불순물인 중간 코팅 층 (33) 에 의해 커버된다.
이 실시형태에서, Fe-Ni-Cr-Ti 금속 코팅 층 (33) 은 제 1 내식 금속 코팅 층 (34) 에 의해 커버된다. 이 제 1 내식 금속 코팅 층 (34) 은 예컨대 순수 아연, 또는 Zn-Al, Zn-Al-Mg, Zn-Mg 또는 Zn-Ni 와 같은 아연 합금을 포함할 수 있다. 그것은 알루미늄, 구리, 마그네슘, 티타늄, 니켈, 크롬, 순수 망간 (제조 공정으로 인한 잠재적 불순물 함유) 또는 예컨대 Al-Si 또는 Mg-Al 과 같은 그의 합금을 또한 포함할 수 있다.
이 제 3 실시형태에서, 제 1 내식 금속 코팅 층 (34) 은 제 2 금속 산화물 층 (36) 에 의해 덮인다. 이 층 (36) 은 내식 금속성 코팅 (34) 의 표면에서 연속적이거나 불연속적일 수 있고 산화물을 포함할 수 있으며, 그 조성은 내식 금속 코팅 (34) 의 구성 재료에 의존한다. 예를 들어, 이 산화물은 아연 산화물, 알루미늄 산화물 또는 혼합된 Al-Si, Zn-Mg 또는 Zn-Al 산화물일 수 있다. 이 금속 산화물 층 (36) 의 두께는 일반적으로 예를 들어 3 ~ 대략 60 ㎚, 바람직하게 3 ~ 대략 20 ㎚ 로 달라질 수 있다.
이 제 2 산화물 층 (36) 은 제거되지 않고 Fe-Cr-Ni-Ti 을 포함하는 중간 코팅 층에 의해 커버된다. 이 금속 코팅 층 (37) 의 두께는 예를 들어 2 ㎚ 이상일 수 있다.
이 제 3 실시형태에서, 이 금속 코팅 층 (37) 은 제 2 내식 금속 코팅 층 (38) 에 의해 덮인다. 예를 들어, 강 층 (31), 제 1 철 산화물 층 (32), Fe-Cr-Ni-Ti 을 포함하는 제 1 중간 코팅 (33), Al-Si 합금으로 이루어진 제 1 내식 금속 코팅 (34), 혼합 Al-Si 산화물로 이루어진 제 1 산화물 층 (36), Fe-Cr-Ni-Ti 을 포함하는 제 2 중간 코팅 (37) 및 Zn-Al-Mg 합금으로 이루어진 제 2 내식 금속 코팅 (38) 을 고려할 수 있다.
본 발명은 또한,
A. 적어도 하나의 산화물들 층을 포함하는 금속 기판을 제공하는 단계,
B. 진공 증착 또는 전착 공정에 의해 중간 코팅 층을 디포짓팅하는 단계,
C. 내식 금속 코팅인 코팅 층을 디포짓팅하는 단계
를 포함하는, 본 발명에 따른 코팅된 금속 기판의 제조 방법에 관한 것이다.
바람직하게는, 단계 B) 에서, 중간 코팅 층의 디포짓팅은 마그네트론 캐소드 분쇄 공정 또는 제트 증기 증착 공정에 의해 수행된다.
바람직하게는, 단계 C) 에서, 코팅 층의 디포짓팅은 용융 도금에 의해, 전착 공정에 의해 또는 진공 증착에 의해 수행된다. 코팅이 진공 증착에 의해 디포짓팅되는 때, 이는 마그네트론 캐소드 분쇄 공정 또는 제트 증기 증착 공정에 의해 수행될 수 있다.
바람직하게는, 상기 방법은 중간 코팅의 디포짓팅 전에 금속 기판 상에서 산화물들 층을 제거하기 위한 산세척을 포함하지 않는다.
마지막으로, 본 발명은 자동차 부품의 제조를 위한 코팅된 금속 기판의 용도에 관한 것이다.
본 발명은 이하에서, 제한적인 것이 아니라 단지 예시 목적으로 수행된 테스트에 기초하여 설명될 것이다.
예 1 : 부착
T-벤드 테스트를 수행하였다. 이 테스트의 목적은 코팅된 판을 180°의 각도로 굽힘으로써 코팅의 부착력을 결정하는 것이다. 적용된 굽힘 반경은 사용된 기판 두께의 2 배와 같다 ("2T" 벤드에 해당함). 코팅의 부착력은 접착 테이프의 적용에 의해 검증된다. 코팅이 테스트된 판에 유지되며 테이프가 제거된 후 접착 테이프 상에 나타나지 않는다면, 테스트 결과는 긍정적으로 판단된다.
후술하는 테스트들에서 이 테스트의 수행에 사용된 접착 테이프는 상업용 접착제 TESA4104 이다.
샘플들에 사용된 강의 조성은 0.15% C, 1.9% Mn, 0.2% Si, 0.2% Cr, 및 0.013% Ti 이다. 백분율은 중량 퍼센트이고, 잔부는 철 및 제조로부터 기인한 잠재적 불순물이다.
시험 1 내지 11 은 비교예이다.
시험 1 내지 9 는 WO2015/150850 에 따라 준비된다.
시험 10 의 경우, Fe, Ni, Cr 및 Ti 을 포함하는 중간 코팅의 조성은 다음과 같다: 3 중량% 의 Cr, 15 중량% 의 Ni, 3 중량% 의 Ti, 잔부인 Fe.
시험 11 의 경우, Fe, Ni, Cr 및 Ti 을 포함하는 중간 코팅의 조성은 3 중량% 의 Cr, 40 중량% 의 Ni, 47 중량% 의 Ti, 잔부인 Fe 이다.
시험 12 의 경우, Fe, Ni, Cr 및 Ti 을 포함하는 중간 코팅의 조성은 다음과 같다: 3 중량% 의 Cr, 15 중량% 의 Ni, 6 중량% 의 Ti, 잔부인 Fe.
시험 13 의 경우, Fe, Ni, Cr 및 Ti 을 포함하는 중간 코팅의 조성은 다음과 같다: 3 중량% 의 Cr, 40 중량% 의 Ni, 10 중량% 의 Ti, 잔부인 Fe.
시험 10 내지 13 은 후술하는 단계들을 거쳤다:
- 10-3 mbar 미만의 압력 P 을 갖는 진공 챔버에의 스트립의 삽입.
- 10 nm 의 Fe-Ni-Cr-Ti 코팅 층의 진공 증발 증착.
- 5 ㎛ 의 아연 층의 진공 증발 증착.
각 시험의 특징은 아래 표에 제공된다:
Figure pct00001
그 후, 이 시편들 전부가 전술한 T-벤드를 거쳤다. 결과는 아래 표에 제공된다.
Figure pct00002
본 발명에 따른 시험 12 내지 13 은 시험 1, 5 및 9 와 같이 아연의 양호한 접착을 나타내었다.

Claims (25)

  1. 적어도, 하나의 산화물들 층을 포함하는 코팅된 금속 기판으로서,
    상기 산화물들 층은, Fe, Ni, Cr 및 Ti 을 포함하고 Ti 양이 5 중량% 이상이며 8 중량% < Cr +Ti < 40 중량% 를 만족시키고 잔부가 Fe 및 Ni 인 중간 코팅 층에 의해, 직접 덮이고 (topped), 상기 중간 코팅 층은 내식 금속 코팅인 코팅 층에 의해 직접 덮이는, 코팅된 금속 기판.
  2. 제 1 항에 있어서,
    상기 중간 코팅 층은 15 내지 42 중량% 의 Ni 을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  3. 제 2 항에 있어서,
    상기 중간 코팅 층은 22 내지 40 중량% 의 Ni 을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  4. 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,
    상기 중간 코팅 층은 25 내지 30 중량% 의 Ni 을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  5. 제 1 항 내지 제 4 항 중 어느 한 항에 있어서,
    상기 중간 코팅 층은 10 내지 60% 의 철을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  6. 제 1 항 내지 제 5 항 중 어느 한 항에 있어서,
    상기 중간 코팅 층은 30 내지 60% 의 철을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  7. 제 1 항 내지 제 6 항 중 어느 한 항에 있어서,
    상기 중간 코팅 층은 5 내지 30 중량% 의 Ti 을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  8. 제 7 항에 있어서,
    상기 중간 코팅 층은 5 내지 20 중량% 의 Ti 을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  9. 제 1 항 내지 제 8 항 중 어느 한 항에 있어서,
    상기 중간 코팅 층은 5 내지 30 중량% 의 Cr 을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  10. 제 9 항에 있어서,
    상기 중간 코팅 층은 5 내지 20 중량% 의 Cr 을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  11. 제 1 항 내지 제 10 항 중 어느 한 항에 있어서,
    상기 중간 코팅 층은 1 내지 100 nm 의 두께를 갖는 것을 특징으로 하는, 코팅된 금속 기판.
  12. 제 11 항에 있어서,
    상기 중간 코팅 층은 1 내지 50 nm 의 두께를 갖는 것을 특징으로 하는, 코팅된 금속 기판.
  13. 제 12 항에 있어서,
    상기 중간 코팅 층은 1 내지 20 nm 의 두께를 갖는 것을 특징으로 하는, 코팅된 금속 기판.
  14. 제 1 항 내지 제 13 항 중 어느 한 항에 있어서,
    상기 금속 기판은 내식 층으로 직접 코팅되고, 상기 내식 층은 상기 산화물들 층에 의해 직접 덮이는 것을 특징으로 하는, 코팅된 금속 기판.
  15. 제 1 항 내지 제 14 항 중 어느 한 항에 있어서,
    내식 코팅 층(들)은 아연, 알루미늄, 구리, 규소, 철, 마그네슘, 티타늄, 니켈, 크롬, 망간 및 이들의 합금들을 포함하는 그룹에서 선택된 금속을 포함하는 것을 특징으로 하는, 코팅된 금속 기판.
  16. 제 15 항에 있어서,
    내식 코팅은 15% 미만 Si, 5.0% 미만 Fe, 선택적으로 0.1 내지 8.0% Mg 및 선택적으로 0.1 내지 30.0% Zn, 잔부 Al 을 포함하는 알루미늄계 코팅인 것을 특징으로 하는, 코팅된 금속 기판.
  17. 제 16 항에 있어서,
    내식 코팅은 0.01 내지 8.0% Al, 선택적으로 0.2 내지 8.0% Mg, 잔부 Zn 을 포함하는 아연계 코팅인 것을 특징으로 하는, 코팅된 금속 기판.
  18. 제 1 항 내지 제 17 항 중 어느 한 항에 있어서,
    상기 금속 기판은 알루미늄 기판, 강 기판, 스테인리스 강 기판, 구리 기판, 철 기판, 구리 합금 기판, 티타늄 기판, 코발트 기판 또는 니켈 기판 중에서 선택되는 것을 특징으로 하는, 코팅된 금속 기판.
  19. 제 18 항에 있어서,
    상기 금속 기판은 강판인 것을 특징으로 하는, 코팅된 금속 기판.
  20. 제 1 항 내지 제 18 항 중 어느 한 항에 따른 코팅된 금속 기판의 제조 방법으로서,
    A. 적어도 하나의 산화물들 층을 포함하는 금속 기판을 제공하는 단계,
    B. 진공 증착 또는 전착 공정에 의해 제 1 항 내지 제 13 항 중 어느 한 항에 따른 중간 코팅 층을 디포짓팅하는 단계,
    C. 제 1 항 내지 제 17 항 중 어느 한 항에 따른 내식 금속 코팅인 코팅 층을 디포짓팅하는 단계
    를 포함하는, 코팅된 금속 기판의 제조 방법.
  21. 코팅된 금속 기판의 제조 방법으로서,
    단계 B) 에서, 상기 중간 코팅 층의 디포짓팅은 마그네트론 캐소드 분쇄 공정 또는 제트 증기 증착 공정에 의해 수행되는, 코팅된 금속 기판의 제조 방법.
  22. 제 20 항 또는 제 21 항에 있어서,
    단계 C) 에서, 상기 코팅 층의 디포짓팅은 용융 도금에 의해, 전착 공정에 의해 또는 진공 증착에 의해 수행되는 것을 특징으로 하는, 코팅된 금속 기판의 제조 방법.
  23. 제 20 항 내지 제 22 항 중 어느 한 항에 있어서,
    단계 C) 에서, 상기 코팅 층의 디포짓팅은 마그네트론 캐소드 분쇄 공정 또는 제트 증기 증착 공정에 의해 수행되는 것을 특징으로 하는, 코팅된 금속 기판의 제조 방법.
  24. 제 20 항 내지 제 23 항 중 어느 한 항에 있어서,
    상기 방법은 중간 코팅의 디포짓팅 전에 상기 금속 기판 상에서 상기 산화물들 층을 제거하기 위한 산세척을 포함하지 않는 것을 특징으로 하는, 코팅된 금속 기판의 제조 방법.
  25. 자동차 부품의 제조를 위한, 제 1 항 내지 제 19 항 중 어느 한 항에 따른 코팅된 금속 기판 또는 제 20 항 내지 제 24 항 중 어느 한 항에 따른 방법으로부터 획득할 수 있는 코팅된 금속 기판의 용도.
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