KR20050110625A - 고온용 물질 - Google Patents

고온용 물질 Download PDF

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Publication number
KR20050110625A
KR20050110625A KR1020057014421A KR20057014421A KR20050110625A KR 20050110625 A KR20050110625 A KR 20050110625A KR 1020057014421 A KR1020057014421 A KR 1020057014421A KR 20057014421 A KR20057014421 A KR 20057014421A KR 20050110625 A KR20050110625 A KR 20050110625A
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South Korea
Prior art keywords
range
alloy
carbon
titanium
present
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KR1020057014421A
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English (en)
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매츠 순트버그
케이젤 린트그렌
타머 엘-래이
구스타프 말름큐비스트
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산드빅 인터렉츄얼 프로퍼티 에이비
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Publication of KR20050110625A publication Critical patent/KR20050110625A/ko

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Abstract

본 발명은, 일반적으로 금속, 알루미늄(Al) 및 탄소(C) 및 질소(N) 간의 합금으로 구성되는, 1200℃를 초과하는 온도 및 산화 대기에서 사용하기 위한 물질에 관한 것이다. 본 발명은, 합금이 조성물 MzAlyXw(단, M은 필수적으로 티탄(Ti), 크롬(Cr) 및/또는 니오븀(Nb)으로 구성되며, X는 탄소(C)이거나, M이 티탄(Ti)인 경우에 X는 질소(N) 및/또는 탄소(C)이다)을 갖는다는 점과; z가 1.8 내지 2.2의 범위이고, y가 0.8 내지 1.2의 범위이고, w가 0.8 내지 1.2의 범위라는 점을 특징으로 하고, 상기 온도로 가열한 후에 Al2O3의 보호 산화물층이 형성되는 것을 특징으로 한다.

Description

고온용 물질{MATERIAL FOR HIGH TEMPERATURES}
본 발명은 고온을 위해 설계된 물질에 대한 것이다.
가열 요소 및 다른 고온 적용례의 세부 구조 구성시에 1100℃보다 높은 고온에서 사용되는 산화물-형성성(oxide-forming) 및 내부식성 고온 물질 그룹은, 특히, 탄화실리콘(SiC), 규화몰리브덴(MoSi2), 질화실리콘(Si3N4)과 같은 SiO2-형성 물질, 및 FeCrAl, MeCrAlY 및 규화알루미늄몰리브덴(Mo(Si1-xAlx)2)와 같은 산화-알루미늄-형성 물질을 포함한다. NiCr 합금은 또한, 표면 상에 산화크롬(Cr2O3)의 패시베이팅 층(passivating layer)을 전개시키는 보호층을 형성한다.
상기된 바에 따른 산화알루미늄 형성 물질은 또한, 알루미늄이 크롬 및 규소보다 산소에 대한 친화도가 더 크다는 사실로 인해, 수소 가스 환경과 같은 환원 대기 중에서 SiO2 및 Cr2O3 빌더(builder)보다 더 안정하다. 이들 층은 염기성 물질을 패시베이션함으로써 산화 대기 및 다른 대기 중의 고온에서 이들이 열화되는 것을 막는다. FeCrAl과 같은 금속성 고온 합금은, 1300℃보다 높은 온도에서의 크리프(creep) 내구성 및 변형 내성 부족으로 인해 사용이 제한된다. 더욱이, 합금 내 제한된 양의 알루미늄은 산화 수명을 단축시킨다. 1200-1300℃보다 높은 온도에서의 긴 산화 수명이 요구되는 경우에, NiCr 합금은 유용한 대안을 제공하지 못한다.
본 발명은 1200℃보다 높은 온도의 산화 대기 중에서 수명이 긴 물질을 제공한다.
따라서, 본 발명은, 일반적으로 금속, 알루미늄(Al) 및 탄소(C) 또는 질소(N) 간의 합금으로 구성되는, 1200℃보다 높은 온도 및 산화 대기에서 사용하기 위한 물질에 관한 것으로, 상기 합금이 조성물 MzAlyXw(단, M은 필수적으로 티탄(Ti), 크롬(Cr) 및/또는 니오븀(Nb)으로 구성되며, X는 탄소(C)이거나, M이 티탄(Ti)인 경우에 X는 질소(N) 및/또는 탄소(C)이다)을 갖는다는 점과; z가 1.8 내지 2.2의 범위이고, y가 0.8 내지 1.2의 범위이고, w가 0.8 내지 1.2의 범위라는 점을 특징으로 하고, 상기 온도로 가열한 후에 Al2O3의 보호 산화물층이 형성된다는 것을 특징으로 한다.
스웨덴 특허 출원 제 0102214-4호는, 단일 상 조성물 Mn +1AzXn(단, n은 0.8 내지 3.2의 범위이고, z는 0.8 내지 1.2의 범위이고, M은 티탄(Ti), X는 탄소(C) 또는 질소(N), A는 알루미늄(Al)이 될 수 있다)의 제조방법을 개시한다. 이 방법은 상기 금속, 비-금속 및 마지막으로 언급된 원소들 또는 상기 원소들의 화합물의 분말 믹스를 형성하는 단계, 및 분해가 촉진되지 않도록 불활성 대기 하에서 분말 믹스를 발화시키고 이를 통해 들어오는 성분을 반응시키는 단계를 포함하며, 이 방법은, 반응 온도를, 상기 성분이 반응하도록 하는 온도 또는 이보다 높은 온도이되, 단일 상 조성물이 분해되는 온도보다 낮은 온도에서 머물도록 하는 것을 특징으로 한다.
본 발명은, 3원 상 다이어그램 Ti-Al-C에서, 물질 Ti2AlC 및 Ti2AlC 조성물의 부근에 있는 조성을 갖는 물질이 놀랍도록 우수한 특성을 가지며, 이들 특성은 특허청구범위 제 1항에 개시된 좁은 간격 밖에서는 나타나지 않는다는 놀라운 발견에 기초한다. Ti2AlN에 대해서도 동일하게 적용된다.
또한 금속 Ti가 크롬(Cr) 및/또는 니오븀(Ni)으로 전부 또는 일부 대체되는 경우에도 동일하게 적용된다.
본 발명에 따르면, M이 티탄(Ti)이면, X는 질소(N) 및/또는 탄소(C)가 될 수도 있다.
본 발명에 의해 얻어지는 한 잇점은, 이를 통해, 금속 합금이 1200℃보다 높은 온도에서 허용가능한 작동 횟수를 견딜 수 없고, 몰리브덴 알루미노-실리사이드와 같은 금속간(intermetals)의 기계적 특성이 한계를 구성하여, 예를 들어 열 쇼크에 대한 내성을 제한하는 산화 대기 중의 고온에서 적용이 가능하다는 것이다.
본발명의 바람직한 실시형태에 따르면, 금속(M)은 상기 합금 내에 합금되는 물질로서 원소 또는 물질인 탄탈(Ta) 및 바나듐(V) 중 하나로 일부 대체될 수 있다.
그러나, 이와 관련하여 특히 유리한 합금은, 조성물 TizAlyCw(단, z는 1.8 내지 2.2의 범위이고, y는 0.8 내지 1.2의 범위이고, w는 0.8 내지 1.2의 범위이고, z, y 및 w는 가열시에 이 물질이 Al2O3의 보호 산화물 층을 형성하도록 선택된다)를 갖는 합금이다.
상기 합금의 바람직한 변형에서, z=2.0이고, y는 1.0 내지 1.2의 범위이고, w는 1.0이다.
3원 탄화물 Ti3SiC2는, 본 발명의 물질과 유사한 기계적 특성을 갖지만, 탄화규소티탄이 TiO2 및 SiO2의 빠르게 성장하는 비-패시베이팅 믹스 산화물을 형성한다는 결정적인 단점을 가지며, 이로 인해 사실상 이 물질을 산화 환경에서 장기간동안 1100℃보다 높은 온도에서 물질의 열화 없이 사용하는 것이 불가능하다.
또한, 본 발명의 물질이 물질 표면 상의 산화알루미늄 형성을 막기 위해 충분히 낮은 산소 분압을 갖는 조건에서 사용되는 경우에, 이 물질은 식 TizAlyXw에 따라 손상되지 않고 남아있을 것임이 강조되어야 한다.
삼원상 Ti3AlC2 및 이에 가까운 조성물은 또한, 특정 환경 하에서 상기 표면 상에 산화알루미늄을 형성할 것이며, 따라서 물질 내에서 이차 상으로 사용될 수 있다.
본 발명의 물질은 또한 Al2O3, TiC 및/또는 티탄 알룸나이드(titanium alumnides)를 포함할 수 있다.
탄화티탄 및 티탄 알룸나이드는, 본 발명의 물질의 복합물의 산화 특성에 불리하게 영향을 주지 않고 이 물질 중에 존재할 수 있다.
Al2O3는 또한 상기 물질의 복합물 내에 증폭 상(amplifying phase)으로서 첨가할 수 있다.
이하에 작업 실시예를 기재한다.
1. 4000g Ti, 1240 Al 및 501g C(조성물 Ti2Al1 .1C에 대응)를 4시간동안 볼밀에서 분말 형태로 혼합하였다.
2. 분말 믹스를 수소 가스를 포함하는 산화알루미늄의 튜브-형 로에 넣었다.
3. 분말을 하기 사이클에 따라 열-처리하였다:
·400℃의 온도까지 3℃/분.
·분말을 400℃의 온도에서 4시간동안 유지.
·800℃의 온도까지 2℃/분.
·분말을 800℃의 온도에서 4시간동안 유지.
·1400℃의 온도까지 2℃/분.
·분말을 1400℃의 온도에서 4시간동안 유지.
4. 자연 냉각.
5. 반응된 분말을 분쇄 및 325 메쉬로 그라인딩.
6. 분말의 XRD 분석을 통해, 주 상이 Ti2AlC이고 Ti3AlC2 및 Al3Ti이 약간 존재하는 것으로 나타났다.
7. (단계 1에서의 조건에 따른) Ti, Al, C의 혼합물 및 20 중량%의 반응성 분말(단계 5)을 포장하여 물-냉각된 철강 용기에 넣었다. 용기는 탈기하고 순수한 아르곤 가스로 충전하였다.
8. 분말을 전기 가열로 발화시켰다. 이 방법은 SHS(Self propagating High temperature Synthesis)으로 공지되어 있다.
9. 반응된 물질은 자연 냉각시켰다.
10. 반응 물질을 325 메쉬로 그라인딩.
11. 분말의 XRD 분석을 통해, 주상은 Ti2AlC이고 Ti3AlC2, TiC 및 Al3Ti가 약간(10% 미만) 존재하는 것으로 나타났다.
12. 분말을 냉각, 냉간 압착, 1500℃에서 1시간동안 질소 가스와 함께 소결.
13. 소결된 물질의 광학 현미경 사용 및 SEM(Sweep Electron Microscope) 분석을 통해, 시료가 다공도 2% 미만으로 고밀도인 것으로 나타났다. Ti3AlC2의 일부 그레인은 그레인 경계에서 5% 미만의 TiAl3가 관찰되었다. 그레인 크기는 약 30㎛였고, 일부 그레인은 약 200㎛였다.
14. 시료를 이의 산화 특성을 연구하기 위한 장치에 넣었다. 시료를 1100℃의 온도에서 8시간동안, 1200℃에서 8시간동안 및 1300℃에서 8시간동안 유지시켰다. 산화 과정은 거의 포물선모양인 것으로 밝혀졌다. 산화 표면은 희게 표백되었으며, 이는 얇은 산화물 층을 나타낸다.
15. SEM 분석을 통해, 산화물 층이 5 미크론의 두께를 가지며 고밀도의 부착 Al2O3로 구성된 것으로 나타났다.
16. 소결된 로드의 일부를 1000 그릿으로 폴리싱하였다.
17. 이 시료를 이의 주기적 행동을 연구하기 위한 장치에 넣었다. 시료를 1200℃에서 4시간동안 유지시킨 후 자연냉각하였다. 사이클을 10회 반복하였다.
18. 산화 표면은 희게 표백되었고, 이는 얇은 산화물 층을 나타낸다.
19. SEM 분석을 통해, 산화물 층이 3㎛의 두께를 가지며 고밀도의 부착 Al2O3로 구성된 것으로 나타났다.
20. 소결된 로드를 1000 그릿으로 폴리싱하였다.
21. 시료를 공기-포함 박스 로에 1200℃에서 980시간동안 넣었다.
22. 산화 표면은 희게 표백되었고, 이는 얇은 산화물 층을 나타낸다.
23. 시료는 중량이 10mg 증가하였고, Al2O3의 백색 표면층을 가졌다.
본 발명의 물질의 다른 바람직한 적용례는, 이 물질이 방사선 방사 표면으로서 작용하는 가스-가열되거나 휘발성 연료 가열된 적외선 열 방사체와 관련있다. 이러한 종류의 IR 방사체는 특히, 종이 및 유사 물질을 건조, 수분 프로파일링(profiling) 및 표면 코팅하기 위하여 종이 산업에서 사용된다. 이러한 방사선 방사 표면은 편리하게는 플레이트 형태이다. 플레이트는, 예를 들어 벌집 구조 형태의 홀 패턴을 갖는, 스로우-패싱 홀(through-passing holes)을 포함하는 플레이트로서 구성될 수 있다. 대안적으로, 표면은 예를 들어 다수의 평행한 박벽 플레이트(thin-walled plates)로 구성될 수 있다. 본 발명의 물질은, 1400℃의 온도까지의 느린 산화 속도, 우수한 열 전도도, 다른 세라믹에 비해 단순화된 작업성(workability)(제조 비용을 낮춤), 열 쇼크에 대한 탁월한 내성의 우수한 특성의 독특한 조합으로 인해, 강한 열-방사 플레이트가 되도록 기여하며, 날카로운 모서리 및 다양한 물질 두께를 갖는 디자인 상에 제한을 두지 않는다.
본 발명의 물질은 전기 전도성이고 실온에서 약 0.5Ωmm2/m 및 1200℃에서 약 2.5Ωmm2/m의 저항률을 갖는다. 이 물질의 우수한 기계적 특성 및 이의 여전한 고온 특성과 조합하여, 이 물질은 산화 및 환원 대기 모두에서 및 진공 조건 하에서 전기 저항 요소로서 유리하게 사용될 수 있다. 본 발명의 물질에 의해 주어지는 잇점이 도움이 되는 다른 적용례에는, 예를 들어 가스 점화기, 불꽃 탐지기, 히터 플러그 및 이러한 용도들이 포함된다. 로에서의 이 물질의 용도가 상기된 실시예에 제한되지 않는다. 이러한 용도에 추가로, 이 물질은 트레이, 기판 홀더, 내부 피팅(fitting), 지지체 롤러(support rollers) 등의 장치의 일부 또는 전부를 포함할 수 있다.
본 발명의 물질은 또한 편리하게는, 표면 코팅을 위해 분말 형태로 HVOF와 같은 열 스프레이 법, 플라즈마 스프레잉 등을 통해 사용될 수도 있다. 소위 PVD(물리적 증착) 및 CVD(화학적 증착)를 이용한 기상 증착 공정을 사용한 표면 코팅은 또한 고온 내부식성인 층을 제조할 수 있다. 적합한 전기 저항을 위해 설계된 회로 패턴 형태인 경우, 이러한 표면 코팅은 또한 실리콘 웨이퍼 또는 플레이트를 열처리하기 위한 평평한 가열 요소로서 작용할 수 있다.
상기된 사용 영역에 추가로, 에틸렌 생산 튜브, 열 교환기, 버너 노즐, 가스 터빈 구성성분 등와 관련하여, 본 발명의 물질을 사용할 수도 있다.
본 발명이 상이한 적용례를 참조하여 앞서 기재되었다고 하더라도, 이 물질의 특성이 이익이 되는 다른 적용례에 본 발명의 물질을 사용할 수 있다는 것은 당업자에게 명백할 것이다.
따라서, 본 발명은 상기된 이의 예시적인 실시형태로 제한되지 않으며, 이하 특허청구범위의 범위 내에서 변형 및 변화가 가능할 것으로 이해될 것이다.

Claims (4)

  1. 일반적으로 금속, 알루미늄(Al) 및 탄소(C) 또는 질소(N) 간의 합금으로 구성되는, 1200℃보다 높은 온도 및 산화 대기에서 사용하기 위한 물질로서, 상기 합금이 조성물 MzAlyXw(단, M은 필수적으로 티탄(Ti), 크롬(Cr) 및/또는 니오븀(Nb)으로 구성되며, X는 탄소(C)이거나, M이 티탄(Ti)인 경우에 X는 질소(N) 및/또는 탄소(C)이다)을 갖는다는 점과; z가 1.8 내지 2.2의 범위이고, y가 0.8 내지 1.2의 범위이고, w가 0.8 내지 1.2의 범위라는 점을 특징으로 하고, 상기 온도로 가열한 후에 Al2O3의 보호 산화물층이 형성된다는 것을 특징으로 하는 물질.
  2. 제 1항에 있어서,
    상기 금속(M)이 상기 합금 내에 합금되는 물질로서 탄탈(Ta) 및 바나듐(V) 중 하나의 물질로 일부 구성되는 것을 특징으로 하는 물질.
  3. 제 1항 또는 제 2항에 있어서,
    상기 합금이 조성물 TizAlyXw(단, z는 1.8 내지 2.2의 범위이고, y는 0.8 내지 1.2의 범위이고, w는 0.8 내지 1.2의 범위이고, z,y 및 w는 가열시에 상기 물질이 Al2O3의 보호 산화물 층을 형성하도록 선택된다)을 갖는 것을 특징으로 하는 물질.
  4. 제 3항에 있어서,
    z=2.0이고, y는 1.0 내지 1.2의 범위이고, w=1.0인 것을 특징으로 하는 물질.
KR1020057014421A 2003-02-07 2004-01-27 고온용 물질 KR20050110625A (ko)

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