KR102161752B1 - Method and component and material mixture for making a corrosion protection layer for an insulating layer consisting of hollow aluminum oxide spheres and an outermost glass layer - Google Patents

Method and component and material mixture for making a corrosion protection layer for an insulating layer consisting of hollow aluminum oxide spheres and an outermost glass layer Download PDF

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KR102161752B1
KR102161752B1 KR1020187015446A KR20187015446A KR102161752B1 KR 102161752 B1 KR102161752 B1 KR 102161752B1 KR 1020187015446 A KR1020187015446 A KR 1020187015446A KR 20187015446 A KR20187015446 A KR 20187015446A KR 102161752 B1 KR102161752 B1 KR 102161752B1
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layer
corrosion protection
aluminum
component
group
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KR1020187015446A
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Korean (ko)
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KR20180077254A (en
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마티아스 갈레츠
사비 몬테로
베르너 슈탐
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지멘스 악티엔게젤샤프트
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C28/3455—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 with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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    • C23C10/26—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions more than one element being diffused
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    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
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    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
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    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
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    • Y10T428/12771—Transition metal-base component
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

본 발명은, 특히 열처리에 의해 생성되는 최외측 유리층과 중공 알루미늄 산화물 입자를 접합함으로써 제조되는 세라믹 단열층을 위한 특수 부식 방지층에 관한 것이다.The present invention relates in particular to a special anti-corrosion layer for a ceramic heat insulating layer produced by bonding the outermost glass layer produced by heat treatment and hollow aluminum oxide particles.

Description

중공 알루미늄 산화물 구체들 및 최외부 유리층으로 구성된 단열층을 위한 부식 방지층을 제조하는 방법 및 구성요소와 재료 혼합물Method and component and material mixture for making a corrosion protection layer for an insulating layer consisting of hollow aluminum oxide spheres and an outermost glass layer

본 발명은, 중공 알루미늄 산화물 구체들을 포함하고, 추가로 유리 종류의 최외부 보호층을 포함할 수 있는, 부식에 대한 단열층 보호에 관한 것이다.The present invention relates to the protection of an insulating layer against corrosion, comprising hollow aluminum oxide spheres and which may further comprise an outermost protective layer of glass type.

고온 가스 경로 내에는 금속 온도를 저하시키기 위해, 부분적으로 안정화된 지르코늄 또는 가돌리늄 지르코네이트로 형성된 단열층으로 코팅된 구성요소가 존재한다. CMAS와 같은 불순물과 조합된 세라믹의 현용의 표면 온도는 세라믹에 대한 화학적 공격 및 세라믹의 기공 내로의 액상물(liquid phases)의 침입을 유도한다. 동시에, 압축기 마멸부(abradables)의 마모는 층 상에 단발성(one-off) 니켈 침착물을 남길 수 있다. 이는 또한, 감소된 열팽창의 결과로서 TBC 박리 유도한다. 이러한 여러번의 공격에 대항하여 장기간에 걸쳐 안정적인 시스템은 지금까지 존재하지 않았다.In the hot gas path there are components coated with an insulating layer formed of partially stabilized zirconium or gadolinium zirconate to lower the metal temperature. The current surface temperature of ceramics combined with impurities such as CMAS induces chemical attack on the ceramic and invasion of liquid phases into the pores of the ceramic. At the same time, wear of the compressor abradables can leave one-off nickel deposits on the layer. This also leads to TBC delamination as a result of reduced thermal expansion. Against these multiple attacks, no system has been stable for a long time.

따라서, 본 발명의 목적은 전술된 문제점을 해결하는 것이다.Accordingly, it is an object of the present invention to solve the above-described problem.

상기 목적은 청구항 1에 청구된 바와 같은 방법에 의해 그리고 청구항 2에 청구된 바와 같은 구성요소에 의해 성취된다.This object is achieved by a method as claimed in claim 1 and by a component as claimed in claim 2.

다른 장점을 성취하기 위해 임의의 방식으로 서로 조합될 수 있는 다른 유리한 조치들은 종속 청구항에 열거되어 있다.Other advantageous measures that can be combined with each other in any way to achieve other advantages are enumerated in the dependent claims.

도 1, 도 2, 도 3은 부식 방지층을 갖는 본 발명에 따른 층 시스템을 개략적으로 도시하고 있다.1, 2 and 3 schematically show a layer system according to the invention with a corrosion protection layer.

도면 및 상세한 설명은 단지 본 발명의 실시예를 제시하고 있다.The drawings and detailed description only present embodiments of the present invention.

진보된 부분은 특히 슬립(slip)에 의한, 알루미늄 입자들로 구성된 층의 도포이다.An advanced part is the application of a layer composed of aluminum particles, in particular by slip.

본 발명의 과제는 이하의 방식으로 해결되는데: 단열층 상에, 순 알루미늄 입자; 또는 2 내지 20%의 티타늄계 금속, 바람직하게는 지르코늄, 하프늄 또는 티타늄을 함유하고, 5% 이하의 반금속, 특히 붕소, 실리콘 또는 게르마늄이 첨가된 알루미늄/티타늄계 금속 또는 금속 산화물 입자;로 구성된 층이 슬립의 분무에 의해 도포된다. 알루미늄 입자/지르코늄 산화물 입자는 1 내지 125㎛의 범위의 직경을 가질 수 있지만, 대부분의 경우에 더 작은 직경 범위(2 내지 40㎛)의 입자가 바람직하다. 도포된 입자층의 두께는 5 내지 150㎛의 범위일 수 있다. 이 층은 슬립으로서 도포되는 것이 최적이다. 물론 다른 방법도 가능하다. 적합한(기재, 접합층 및 TBC로 이루어진 각각의 코팅 시스템에 매칭된) 열처리에 의해, 알루미늄 입자로부터, 복합 구조체로서 다른 산화물을 포함하고 이 구조에 기인하여 작동 시 양호한 연성(ductility)을 갖는 중공 알루미나 구체가 형성된다. 붕소, 실리콘 및/또는 게르마늄의 첨가는 원소의 확산 활동도(diffusion activity)를 증가시키고, 궁극적으로 추가 보호층의 접착성을 증대시킨다. 티타늄계 산화물은 기계적 친화성(mechanical compatibility) 및 CMAS 공격에 대한 저항성을 증가시킨다.The subject of the present invention is solved in the following manner: on the heat insulating layer, pure aluminum particles; Or 2 to 20% of a titanium-based metal, preferably zirconium, hafnium or titanium, and containing 5% or less of a semimetal, particularly boron, silicon or germanium-containing aluminum/titanium-based metal or metal oxide particles; The layer is applied by spraying of the slip. The aluminum particles/zirconium oxide particles may have a diameter in the range of 1 to 125 μm, but in most cases particles in the smaller diameter range (2 to 40 μm) are preferred. The thickness of the applied particle layer may range from 5 to 150 μm. This layer is optimally applied as a slip. Of course, other methods are possible. Hollow alumina with good ductility in operation due to this structure, containing other oxides from aluminum particles, as a composite structure, by suitable heat treatment (matched to each coating system consisting of substrate, bonding layer and TBC) A sphere is formed. The addition of boron, silicon and/or germanium increases the diffusion activity of the element and ultimately increases the adhesion of the additional protective layer. Titanium-based oxide increases mechanical compatibility and resistance to CMAS attack.

제2 선택적 층은 그 융점이 바람직하게는 하위 층 내 확산 금속의 융점의 범위 내에 있거나 더 낮은 저융점 점성 유리의 조성을 갖는다. 유리는 특히 실질적으로 SiO2를 포함하고, 바람직하게는 융점을 설정하기 위해 관련되는 마그네슘(Mg), 칼슘(Ca) 또는 붕소(B) 및/또는 나트륨(Na)과 같은 부수 원소를 함유한다.The second optional layer has a composition of a low melting point viscous glass whose melting point is preferably within the range of the melting point of the diffusion metal in the lower layer or lower. The glass in particular substantially comprises SiO 2 and preferably contains minor elements such as magnesium (Mg), calcium (Ca) or boron (B) and/or sodium (Na), which are relevant to set the melting point.

유리는 또한 전구체로서 실라잔 폴리머, 실록산 폴리머 또는 실리콘 폴리머로부터 산소 함유 분위기에서 열처리 중에만 형성될 수도 있다. 이 전구체는 수축 및 열화 거동 및 CMAS 공격에 대한 저항성을 설정하기 위해 무기 충전제를 포함할 수 있다. 어느 경우든, 추가의 유리 층에 의해, 시효 경화(age hardening) 중에 시스템의 표면을 따라 연장하는 구성요소의 구멍들을 폐색하는 순 알루미늄 입자 없이, 알루미늄 입자의 산화가 수행될 수 있다.The glass may also be formed only during heat treatment in an oxygen-containing atmosphere from a silazane polymer, a siloxane polymer or a silicone polymer as a precursor. This precursor may contain inorganic fillers to establish shrinkage and deterioration behavior and resistance to CMAS attack. In either case, with an additional glass layer, oxidation of the aluminum particles can be carried out without the pure aluminum particles occluding the pores of the component extending along the surface of the system during age hardening.

게다가, 열처리 중에 단열층의 표면 상의 알루미늄/티타늄계 금속 입자의 (냉각 공기 구멍의 폐색을 유도할 수 있는) "이동(migration)"은 2개의 공정에 의해 방지될 수 있다. 첫째로, 상기 상황은 입자층으로의 SiO2의 도포에 의한 구멍의 폴리머 마스킹(polymer masking)에 의해 방지될 수 있다. SiO2 층은 초기 상태에서만, 알루미나/지르코니아 층의 형성을 보조하고 이러한 입자가 돌아다니는 것을 방지한다. SiO2 층은 이어서 취성에 기인하여 작동 중에 대부분 층간박리될 것이고, 본질적인 보호층이 보호 작용을 담당할 수 있다.In addition, "migration" of the aluminum/titanium-based metal particles on the surface of the heat insulating layer during heat treatment (which can lead to clogging of the cooling air holes) can be prevented by two processes. First, this situation can be prevented by polymer masking of the pores by application of SiO 2 to the particle layer. The SiO 2 layer assists the formation of the alumina/zirconia layer only in the initial state and prevents these particles from moving around. The SiO 2 layer will then be mostly delaminated during operation due to brittleness, and the intrinsic protective layer can serve as a protective action.

진보된 부분은 반금속 첨가물과 결합된 알루미늄/티타늄계 금속 입자의 조성 및 도포와, 추가의 SiO2 부가층의 도포에 있다. 20% 초과의 비교적 높은 Zr 함량은 또한 층의 접착성 저하도 야기한다. 그 결과, 알루미늄/지르코늄 입자의 산화는, 시효 경화 중에 냉각 공기 구멍을 폐색하며 시스템의 표면을 따라 연장하는 순 알루미늄 입자 없이 수행될 수 있다. 폴리머 마스킹의 사용이 대안으로서 수행될 수도 있다. 붕소는 부가층의 화학적 접합을 강화한다. 농도는 Al; Zr < 20 중량%, B < 6 중량%의 범위이다.The advanced part is in the composition and application of aluminum/titanium based metal particles combined with semi-metallic additives and the application of an additional SiO 2 additional layer. The relatively high Zr content of more than 20% also causes a decrease in the adhesion of the layer. As a result, the oxidation of the aluminum/zirconium particles can be carried out without pure aluminum particles extending along the surface of the system, occluding the cooling air pores during age hardening. The use of polymer masking may alternatively be carried out. Boron strengthens the chemical bonding of the additional layer. Concentration is Al; Zr <20% by weight, B <6% by weight.

도 1은 기판(4)을 포함하는 본 발명에 따른 층 시스템(1)을 도시하고 있다.1 shows a layer system 1 according to the invention comprising a substrate 4.

기판(4)은 특히 금속이고, 특히 니켈계 또는 코발트계 초합금을 포함한다.The substrate 4 is in particular metal, and in particular comprises a nickel-based or cobalt-based superalloy.

기판(4) 상에 선택적 금속 접합층(7)이 존재한다. 특히 상기 층은 특히 NiCoCrAlY에 기재한 코팅층이다.An optional metal bonding layer 7 is present on the substrate 4. In particular this layer is a coating layer based in particular on NiCoCrAlY.

이 접합층(7) 상에, 추가 코팅 시, 또는 의도적인 산화에 의해, 또는 적어도 작동 중에, 여기에 상세히 도시되지 않은 산화물층(TGO)이 형성된다.On this bonding layer 7 an oxide layer (TGO), which is not shown in detail here, is formed upon further coating, or by intentional oxidation, or at least during operation.

이러한 열적으로 성장된 산화물층(TGO) 상에 또는 금속 접합층(7) 상에 세라믹 단열층(10)이 존재한다. 이 세라믹 단열층은 특히 지르코늄 산화물로 형성된 단일층일 수 있거나, 지르코늄 산화물 및 파이로클로르(pyrochlore) 또는 "DVC" 층을 포함하는 2개의 층으로 구성될 수 있다.The ceramic insulating layer 10 is present on the thermally grown oxide layer TGO or on the metal bonding layer 7. This ceramic insulating layer may in particular be a single layer formed of zirconium oxide, or may consist of two layers comprising zirconium oxide and a pyrochlore or "DVC" layer.

본 발명에 따라 세라믹 단열층(10) 상에 알루미늄 산화물, 특히 알루미늄 산화물 중공 구체들(14)로 형성된 외부 세라믹 부식 방지층(13')이 존재하지만(도 1), 선택적으로 최외부층(16, 도 2)으로서 점성 유리가 도포된다.According to the present invention there is an outer ceramic corrosion protection layer 13' formed of aluminum oxide, in particular aluminum oxide hollow spheres 14, on the ceramic insulating layer 10 (Fig. 1), but optionally the outermost layer 16, Fig. As 2) viscous glass is applied.

코팅 시스템을 제조하기 위해, 세라믹 단열층(10)에 특히 1㎛ 내지 50㎛의 입경을 갖는 알루미늄 입자의 층이 특히 슬립, 기상 증착, 스퍼터링 등에 의해 도포된다.In order to manufacture the coating system, a layer of aluminum particles having a particle diameter of 1 μm to 50 μm in particular is applied to the ceramic insulating layer 10 by slip, vapor deposition, sputtering or the like.

이 층은 수 미크론 내지 최대 300㎛, 특히 200㎛ 이하, 특히 매우 바람직하게는 100㎛ 이하의 범위의 층 두께를 가질 수 있다.This layer can have a layer thickness in the range of a few microns up to 300 μm, in particular up to 200 μm, particularly very preferably up to 100 μm.

알루미늄(Al)의 첨가가 바람직한데: 특히 그룹 I에서 붕소(B), 갈륨(Ga) 및/또는 게르마늄(Ge)으로부터 선택된 적어도 하나의 원소(Z) 및/또는 알루미늄(Al)에 추가하여, 그룹 II에서 지르코늄(Zr), 티타늄(Ti), 탄탈(Ta), 니오브(Nb) 및/또는 하프늄(Hf)으로부터 선택된 적어도 하나의 원소가 부식층(13', 13", 13"')을 위해 재료 혼합물로서 도포되고 그리고/또는 산화되거나, 산화되어 있다. 세륨 산화물(CeO), 란탄 산화물(La2O3) 및/또는 이트륨 산화물(Y2O3)이 외부 세라믹 부식 방지층(13', 13", 13"') 내에 존재한다.The addition of aluminum (Al) is preferred: in particular in group I in addition to at least one element (Z) and/or aluminum (Al) selected from boron (B), gallium (Ga) and/or germanium (Ge), At least one element selected from zirconium (Zr), titanium (Ti), tantalum (Ta), niobium (Nb) and/or hafnium (Hf) in group II is used for the corrosion layers 13', 13", 13"' It is applied and/or oxidized or oxidized as a material mixture. Cerium oxide (CeO), lanthanum oxide (La 2 O 3 ) and/or yttrium oxide (Y 2 O 3 ) are present in the external ceramic corrosion protection layers 13', 13", 13"'.

게다가, 선택적으로 실리콘(Si) 및/또는 망간(Mg)이 함께 도포될 수 있고, 그리고/또는 재료 혼합물 내에 존재할 수 있다.In addition, optionally silicon (Si) and/or manganese (Mg) may be applied together and/or may be present in the material mixture.

이하의 조합이 적어도 가능하다:The following combinations are at least possible:

Al + ZrAl + Zr

Al + Zr + SiAl + Zr + Si

Al + Zr + BAl + Zr + B

Al + Zr + Ge/GaAl + Zr + Ge/Ga

Al + Zr + B + SiAl + Zr + B + Si

Al + Hf + SiAl + Hf + Si

Al + Hf + BAl + Hf + B

Al + Hf + Ge/GaAl + Hf + Ge/Ga

Al + Hf + B + SiAl + Hf + B + Si

Al + Ti + SiAl + Ti + Si

Al + Ti + BAl + Ti + B

Al + Ti + Ge/GaAl + Ti + Ge/Ga

Al + Ti + B + SiAl + Ti + B + Si

Al + Ta + SiAl + Ta + Si

Al + Ta + BAl + Ta + B

Al + Ta + Ge/GaAl + Ta + Ge/Ga

Al + Ta + B + SiAl + Ta + B + Si

Al + Nb + SiAl + Nb + Si

Al + Nb + BAl + Nb + B

Al + Nb + Ge/GaAl + Nb + Ge/Ga

Al + Nb + B + SiAl + Nb + B + Si

Al + Mg + BAl + Mg + B

Al + Mg + Ge/GaAl + Mg + Ge/Ga

Al + Mg + Ge/Ga + BAl + Mg + Ge/Ga + B

Al + Si + ZrAl + Si + Zr

Al + Si + BAl + Si + B

Al + Mg + TiAl + Mg + Ti

Al + Mg + TaAl + Mg + Ta

Al + Mg + ZrAl + Mg + Zr

Ge/Ga는 게르마늄 및/또는 갈륨, 즉, Ge, Ga 또는 Ge + Ga를 의미함.Ge/Ga means germanium and/or gallium, that is, Ge, Ga or Ge + Ga.

그룹 I 및 II의 원소들은 각각 그룹 I, II의 2개, 3개, ... 또는 모든 원소의 혼합물로서 존재할 수 있고 사용될 수 있다.Elements of groups I and II may be present and used as mixtures of two, three, ... or all elements of groups I, II, respectively.

이 층은 CMAS(CMAF) 층의 침입을 방지하고 또한 CMAS(CMAF)와 반응하도록 의도된다. 열처리의 결과로서, 알루미늄 산화물; 및 단열층과 알루미늄층 사이의 반응층;이 형성된다. 이 방식으로 도포된 알루미나는 더 낮은 열팽창 계수를 가지며, 압축기 마멸부로부터 발생하는 니켈(Ni)과 결합하여 알루미늄 산화물의 부분이 벗겨진다. 이후, 나머지 층이 액체 침착물의 침입에 대항하여 보호한다.This layer is intended to prevent intrusion of the CMAS (CMAF) layer and also react with CMAS (CMAF). As a result of heat treatment, aluminum oxide; And a reaction layer between the heat insulating layer and the aluminum layer; is formed. The alumina applied in this way has a lower coefficient of thermal expansion, and a portion of the aluminum oxide is peeled off by bonding with nickel (Ni) arising from the wear of the compressor. The remaining layer then protects against ingress of liquid deposits.

진보된 부분은, Ni 침착물뿐만 아니라 CMAS에 대해서도 보호 작용을 제공하는 상이한 입경의 알루미늄 산화물의 도포에도 있다. 니켈(Ni)의 침착물은 작동 시간의 시작 시 단기간 동안만 발생하므로, 이 경우 단기간 작용하는 층 및 CMAS 또는 유사한 공격에 대항하여 장기간 작용하는 층이 존재한다.An advanced part is in the application of aluminum oxides of different particle diameters which provide protection against not only Ni deposits but also CMAS. Since deposits of nickel (Ni) occur only for a short period of time at the onset of the operating time, in this case there is a layer acting for a short period and a layer acting for a long time against CMAS or similar attack.

알루미늄 산화물로 형성된 층 또는 산화층, 그리고/선택적으로 유리는 각각 세라믹 층 시스템(10)보다 적어도 20% 더 얇다.The layer or oxide layer formed of aluminum oxide, and/optionally the glass, is each at least 20% thinner than the ceramic layer system 10.

유리는 특히 실리콘 산화물, 특히 SiO2일 수 있다.The glass may in particular be a silicon oxide, in particular SiO 2 .

알루미늄(Al) 대신에, 알루미늄(Al) 및 지르코늄(Zr)을 사용하는 것도 가능하다(도 3). 열처리의 결과로서, 지르코늄 산화물 혼입물을 갖는 알루미늄 산화물; 그리고 단열층과 알루미늄/지르코늄층 사이의 반응층;이 부식 방지층(13"')을 위해 형성된다.Instead of aluminum (Al), it is also possible to use aluminum (Al) and zirconium (Zr) (Fig. 3). As a result of the heat treatment, aluminum oxide having zirconium oxide inclusions; And a reaction layer between the heat insulating layer and the aluminum / zirconium layer; is formed for the corrosion protection layer (13"').

지르코늄(Zr)은 단열층으로의 보호층의 접착성을 향상시킨다. 게다가, 지르코늄(Zr)은 CMAS의 점도를 감소시키고, CMAS의 침윤을 방지하거나 느리게 하며, 그럼으로써 층 시스템의 수명을 증가시킨다.Zirconium (Zr) improves the adhesion of the protective layer to the heat insulating layer. In addition, zirconium (Zr) reduces the viscosity of CMAS, prevents or slows the infiltration of CMAS, thereby increasing the life of the layer system.

더욱이, 붕소(B), 갈륨(Ga) 및/또는 게르마늄(Ge) 및 선택적으로 실리콘(Si)으로 이루어진 그룹으로부터의 적어도 하나의 원소가 부가적으로 존재한다.Moreover, at least one element from the group consisting of boron (B), gallium (Ga) and/or germanium (Ge) and optionally silicon (Si) is additionally present.

알루미늄 산화물/지르코늄 산화물의 층의 상부에, 또는 금속 알루미늄/지르코늄의 상부에, 또는 알루미늄 및 원소(Z)의 상부에도 전술한 바와 같이 유리층이 도포될 수 있거나, 도포되어 있을 수 있다.A glass layer may or may be applied on top of the layer of aluminum oxide/zirconium oxide, or on top of metal aluminum/zirconium, or on top of aluminum and element (Z) as described above.

알루미늄 산화물, 또는 알루미늄 산화물/지르코늄 산화물, 또는 알루미늄 산화물 및 원소(Z)의 산화물을 형성하기 위한 열처리는 구성요소의 첫 번째 사용에 의해 수행될 수 있거나; 첫 번째 사용 전에 또는 고온 사용을 위해 기계 내에 설치된 후에 선행된 열처리에 의해 수행될 수 있다.The heat treatment to form aluminum oxide, or aluminum oxide/zirconium oxide, or aluminum oxide and oxide of element (Z), may be carried out by first use of the component; It can be carried out by prior heat treatment before the first use or after being installed in the machine for high temperature use.

Claims (39)

부가의 외부 세라믹 부식 방지층(13', 13", 13"')을 갖는 세라믹층 시스템(1', 1", 1"')을 제조하기 위한 방법이며,
기판(4) 상에 적어도 하나의 세라믹 단열층(10)이 도포되고,
상기 세라믹 단열층(10) 상에 알루미늄(Al)의 입자가 도포되며,
상기 알루미늄의 입자는 열처리의 결과로서 알루미늄 산화물을 형성하고,
상기 알루미늄 산화물은 외부 세라믹 부식 방지층(13', 13", 13"')을 형성하고,
상기 외부 세라믹 부식 방지층은 상기 세라믹 단열층(10)보다 적어도 50% 더 얇게 형성되며,
알루미늄(Al)에 추가하여:
그룹: 붕소(B), 게르마늄(Ge), 갈륨(Ga)으로부터의 적어도 하나의 원소가 외부 세라믹 부식 방지층(13', 13", 13"')을 위해 도포되는, 방법.A method for manufacturing ceramic layer systems 1', 1", 1"' with additional external ceramic corrosion protection layers 13', 13", 13"',
At least one ceramic insulating layer 10 is applied on the substrate 4,
Particles of aluminum (Al) are coated on the ceramic insulating layer 10,
The particles of aluminum form aluminum oxide as a result of heat treatment,
The aluminum oxide forms external ceramic corrosion protection layers 13', 13", 13"',
The external ceramic corrosion prevention layer is formed to be at least 50% thinner than the ceramic insulating layer 10,
In addition to aluminum (Al):
Group: At least one element from boron (B), germanium (Ge), gallium (Ga) is applied for the outer ceramic corrosion protection layers (13', 13", 13"'). 제1항에 따라 제조되는 구성요소이며,
적어도:
기판(4),
상기 기판(4) 상의, 단열을 위한 세라믹 단열층(10), 그리고
상기 세라믹 단열층(10) 상에 제공되며, 상기 세라믹 단열층(10)보다 적어도 50% 더 얇은 외부 세라믹 부식 방지층(13', 13", 13"')을 포함하며,
상기 외부 세라믹 부식 방지층(13', 13", 13"')을 위해, 적어도 하나의 알루미늄 산화물 및
붕소(B), 게르마늄(Ge) 및/또는 갈륨(Ga)으로 이루어진 그룹으로부터의 적어도 하나의 원소 또는 혼합물을 포함하는 구성요소.It is a component manufactured according to claim 1,
At least:
Substrate 4,
On the substrate 4, a ceramic insulation layer 10 for insulation, and
It is provided on the ceramic insulating layer 10, and includes an external ceramic corrosion protection layer (13', 13", 13"') that is at least 50% thinner than the ceramic insulating layer 10,
For the external ceramic corrosion protection layer (13', 13", 13"'), at least one aluminum oxide and
A component comprising at least one element or mixture from the group consisting of boron (B), germanium (Ge) and/or gallium (Ga). 제1항에 있어서,
알루미늄(Al); 그리고 외부 세라믹 부식 방지층(13', 13", 13"')을 위한 적어도 하나의 추가 원소;는 슬립, 기상 증착 또는 스퍼터링에 의해 도포되는, 방법.The method of claim 1,
Aluminum (Al); And at least one additional element for the outer ceramic corrosion protection layer (13', 13", 13"'); is applied by slip, vapor deposition or sputtering. 제1항 또는 제3항에 있어서,
알루미늄(Al)과 붕소(B), 게르마늄(Ge) 및 갈륨(Ga)으로 이루어진 그룹으로부터의 적어도 하나의 원소와 지르코늄(Zr)의 혼합물이 상기 외부 세라믹 부식 방지층(13', 13", 13"')을 위해 도포되는, 방법.The method of claim 1 or 3,
A mixture of zirconium (Zr) and at least one element from the group consisting of aluminum (Al) and boron (B), germanium (Ge) and gallium (Ga) is the outer ceramic corrosion protection layer 13', 13", 13" Applied for'), how. 제1항 또는 제3항에 있어서,
상기 외부 세라믹 부식 방지층(13', 13", 13"')을 위한 금속 입자가 1㎛ 내지 50㎛의 입경을 갖는, 방법.The method of claim 1 or 3,
The method, wherein the metal particles for the external ceramic corrosion protection layer (13', 13", 13"') have a particle diameter of 1 µm to 50 µm. 제1항 또는 제3항에 있어서,
상기 외부 세라믹 부식 방지층(13', 13", 13"')에 저융점 점성 유리(16)가 도포되는, 방법.The method of claim 1 or 3,
The method, wherein the low melting point viscous glass (16) is applied to the outer ceramic corrosion protection layers (13', 13", 13"'). 제6항에 있어서,
상기 저융점 점성 유리는 실리콘 산화물을 포함하는, 방법.The method of claim 6,
Wherein the low melting point viscous glass comprises silicon oxide. 제6항에 있어서,
상기 저융점 점성 유리는 마그네슘(Mg), 칼슘(Ca), 붕소(B) 및/또는 나트륨(Na)과 같은 부수 원소를 포함하는, 방법.The method of claim 6,
The method, wherein the low melting point viscous glass comprises minor elements such as magnesium (Mg), calcium (Ca), boron (B) and/or sodium (Na). 제6항에 있어서,
저융점 점성 유리를 위한 실리콘 함유 전구체가 도포되는, 방법.The method of claim 6,
A method, wherein a silicon containing precursor for a low melting point viscous glass is applied. 제1항 또는 제3항에 있어서,
알루미늄 산화물을 포함하는 외부 세라믹 부식 방지층(13") 위에 최외부 유리층(16)이 존재하는, 방법.The method of claim 1 or 3,
The method, wherein an outermost glass layer 16 is present over an outer ceramic anticorrosion layer 13" comprising aluminum oxide. 제1항 또는 제3항에 있어서,
상기 외부 세라믹 부식 방지층(13', 13", 13"')은 세라믹 단열층(10)보다 적어도 30% 더 얇게 형성되는, 방법.The method of claim 1 or 3,
The method, wherein the outer ceramic anticorrosion layer (13', 13", 13"') is formed to be at least 30% thinner than the ceramic insulating layer (10). 제1항에 있어서,
상기 외부 세라믹 부식 방지층(13"')은 알루미늄 산화물, 붕소(B), 게르마늄(Ge) 및/또는 갈륨(Ga)으로 이루어진 그룹으로부터의 적어도 하나의 원소의 산화물 및 지르코늄 산화물을 포함하는, 방법.The method of claim 1,
The method, wherein the outer ceramic anticorrosion layer (13"') comprises an oxide of at least one element from the group consisting of aluminum oxide, boron (B), germanium (Ge) and/or gallium (Ga) and zirconium oxide. 제2항에 있어서,
상기 열처리는 고온에서 상기 구성요소의 첫 번째 사용에 의해 성취되는, 구성요소.The method of claim 2,
The component, wherein the heat treatment is achieved by first use of the component at high temperature. 제2항에 있어서,
상기 열처리는 상기 구성요소의 첫 번째 사용 전에 그리고/또는 기계 내로의 구성요소의 설치 전에 수행되는, 구성요소.The method of claim 2,
The component, wherein the heat treatment is performed prior to first use of the component and/or prior to installation of the component into a machine. 제1항 또는 제3항에 있어서,
상기 외부 세라믹 부식 방지층(13', 13", 13"')은 5㎛ 내지 300㎛의 두께를 갖는, 방법.The method of claim 1 or 3,
The external ceramic corrosion protection layer (13', 13", 13"') has a thickness of 5㎛ to 300㎛, the method. 제1항 또는 제3항에 있어서,
알루미늄(Al)과; 붕소(B), 게르마늄(Ge) 및 갈륨(Ga)으로 이루어진 그룹으로부터의 적어도 하나의 원소와; 마그네슘(Mg), 지르코늄(Zr), 티타늄(Ti), 탄탈(Ta), 니오브(Nb) 및/또는 하프늄(Hf)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소;가 상기 외부 세라믹 부식 방지층(13', 13", 13"')을 위해 도포되는, 방법.The method of claim 1 or 3,
Aluminum (Al); At least one element from the group consisting of boron (B), germanium (Ge) and gallium (Ga); At least one element selected from the group consisting of magnesium (Mg), zirconium (Zr), titanium (Ti), tantalum (Ta), niobium (Nb) and/or hafnium (Hf); the external ceramic corrosion protection layer 13' Applied for, 13", 13"'). 제1항 또는 제3항에 있어서,
알루미늄(Al) 및 붕소(B), 게르마늄(Ge) 및 갈륨(Ga)으로 이루어진 그룹으로부터의 적어도 하나의 원소 외에도; 실리콘(Si)이 상기 외부 세라믹 부식 방지층(13', 13", 13"')을 위해 도포되는, 방법.The method of claim 1 or 3,
In addition to at least one element from the group consisting of aluminum (Al) and boron (B), germanium (Ge) and gallium (Ga); A method, wherein silicon (Si) is applied for the outer ceramic anticorrosion layer (13', 13", 13"'). 제1항 또는 제3항에 있어서,
세륨 산화물(CeO), 란탄 산화물(La2O3) 및/또는 이트륨 산화물(Y2O3)이 상기 외부 세라믹 부식 방지층(13', 13", 13"') 내에 존재하는, 방법.The method of claim 1 or 3,
The method, wherein cerium oxide (CeO), lanthanum oxide (La 2 O 3 ) and/or yttrium oxide (Y 2 O 3 ) are present in the external ceramic corrosion protection layer (13', 13", 13"'). 제1항 또는 제3항에 따른 방법을 위한 재료 혼합물이며,
적어도:
알루미늄
및
붕소(B), 게르마늄(Ge) 및/또는 갈륨(Ga)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소를 포함하는, 재료 혼합물.A material mixture for the method according to claim 1 or 3,
At least:
aluminum
And
A material mixture comprising at least one element selected from the group consisting of boron (B), germanium (Ge) and/or gallium (Ga). 제19항에 있어서,
실리콘(Si) 및/또는 마그네슘(Mg)을 추가로 포함하는 재료 혼합물.The method of claim 19,
A material mixture further comprising silicon (Si) and/or magnesium (Mg). 제2항에 있어서,
알루미늄(Al)과 붕소(B), 게르마늄(Ge) 및 갈륨(Ga)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소와 지르코늄(Zr)의 혼합물이 상기 외부 세라믹 부식 방지층(13', 13", 13"')을 위해 도포되어 있는, 구성요소.The method of claim 2,
A mixture of zirconium (Zr) and at least one element selected from the group consisting of aluminum (Al) and boron (B), germanium (Ge), and gallium (Ga) is the outer ceramic corrosion protection layer 13', 13", 13"') applied for, the component. 제2항 또는 제21항에 있어서,
상기 외부 세라믹 부식 방지층(13', 13", 13"')을 위한 금속 입자가 1㎛ 내지 50㎛의 입경을 갖는, 구성요소.The method of claim 2 or 21,
A component, wherein the metal particles for the external ceramic corrosion protection layers (13', 13", 13"') have a particle diameter of 1 µm to 50 µm. 제2항 또는 제21항에 있어서,
상기 외부 세라믹 부식 방지층(13', 13", 13"')에 저융점 점성 유리(16)가 도포되어 있는, 구성요소.The method of claim 2 or 21,
A component, wherein a low melting point viscous glass (16) is applied to the outer ceramic corrosion protection layers (13', 13", 13"'). 제23항에 있어서,
상기 저융점 점성 유리는 실리콘 산화물을 포함하는, 구성요소.The method of claim 23,
The component of the low melting point viscous glass comprising silicon oxide. 제23항에 있어서,
상기 저융점 점성 유리는 마그네슘(Mg), 칼슘(Ca), 붕소(B) 및/또는 나트륨(Na)과 같은 부수 원소를 포함하는, 구성요소.The method of claim 23,
The low-melting viscous glass contains minor elements such as magnesium (Mg), calcium (Ca), boron (B) and/or sodium (Na). 제23항에 있어서,
저융점 점성 유리를 위한 실리콘 함유 전구체가 도포되어 있는, 구성요소.The method of claim 23,
A component having a silicon-containing precursor for a low melting point viscous glass applied thereto. 제2항 또는 제21항에 있어서,
알루미늄 산화물을 포함하는 외부 세라믹 부식 방지층(13") 위에 최외부 유리층(16)이 존재하는, 구성요소.The method of claim 2 or 21,
A component, in which an outermost glass layer 16 is present over an outer ceramic anticorrosion layer 13" comprising aluminum oxide. 제2항 또는 제21항에 있어서,
상기 외부 세라믹 부식 방지층(13', 13", 13"')은 세라믹 단열층(10)보다 적어도 30% 더 얇은, 구성요소.The method of claim 2 or 21,
The external ceramic corrosion protection layer (13', 13", 13"') is at least 30% thinner than the ceramic insulating layer (10). 제2항 또는 제21항에 있어서,
상기 외부 세라믹 부식 방지층(13"')은 알루미늄 산화물, 붕소(B), 게르마늄(Ge) 및 갈륨(Ga)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소의 산화물 및 지르코늄 산화물을 포함하는, 구성요소.The method of claim 2 or 21,
The external ceramic corrosion protection layer (13"') comprises an oxide of at least one element selected from the group consisting of aluminum oxide, boron (B), germanium (Ge), and gallium (Ga) and zirconium oxide. 제2항 또는 제21항에 있어서,
상기 외부 세라믹 부식 방지층(13', 13", 13"')은 5㎛ 내지 300㎛의 두께
를 갖는, 구성요소.The method of claim 2 or 21,
The external ceramic corrosion protection layers 13', 13", 13"' have a thickness of 5㎛ to 300㎛
Having, component. 제2항 또는 제21항에 있어서,
알루미늄(Al)과; 붕소(B), 게르마늄(Ge) 및 갈륨(Ga)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소와; 마그네슘(Mg), 지르코늄(Zr), 티타늄(Ti), 탄탈(Ta), 니오브(Nb) 및/또는 하프늄(Hf)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소;가 외부 세라믹 부식 방지층(13', 13", 13"')을 위해 도포되어 있는, 구성요소.The method of claim 2 or 21,
Aluminum (Al); At least one element selected from the group consisting of boron (B), germanium (Ge) and gallium (Ga); At least one element selected from the group consisting of magnesium (Mg), zirconium (Zr), titanium (Ti), tantalum (Ta), niobium (Nb) and/or hafnium (Hf); an external ceramic corrosion protection layer 13', Component applied for 13", 13"'). 제2항 또는 제21항에 있어서,
알루미늄(Al)과 붕소(B), 게르마늄(Ge) 및 갈륨(Ga)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소 외에도; 실리콘(Si)이 외부 세라믹 부식 방지층을 위해 도포되어 있는, 구성요소.The method of claim 2 or 21,
In addition to at least one element selected from the group consisting of aluminum (Al) and boron (B), germanium (Ge) and gallium (Ga); A component in which silicon (Si) is applied for an outer ceramic corrosion protection layer. 제2항 또는 제21항에 있어서,
세륨 산화물(CeO), 란탄 산화물(La2O3) 및/또는 이트륨 산화물(Y2O3)이 외부 세라믹 부식 방지층(13', 13", 13"') 내에 존재하는, 구성요소.The method of claim 2 or 21,
A component, wherein cerium oxide (CeO), lanthanum oxide (La 2 O 3 ) and/or yttrium oxide (Y 2 O 3 ) are present in the outer ceramic anti-corrosion layer (13', 13", 13"'). 제2항 또는 제21항에 따른 구성요소를 위한 재료 혼합물이며,
적어도:
알루미늄
및
붕소(B), 게르마늄(Ge) 및/또는 갈륨(Ga)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소를 포함하는, 재료 혼합물.A material mixture for a component according to claim 2 or 21,
At least:
aluminum
And
A material mixture comprising at least one element selected from the group consisting of boron (B), germanium (Ge) and/or gallium (Ga). 제34항에 있어서,
실리콘(Si) 및/또는 마그네슘(Mg)을 추가로 포함하는 재료 혼합물.The method of claim 34,
A material mixture further comprising silicon (Si) and/or magnesium (Mg). 제1항에 있어서,
알루미늄(Al) 및 붕소(B), 게르마늄(Ge) 및 갈륨(Ga)으로 이루어진 그룹으로부터의 적어도 하나의 원소 외에도; 지르코늄(Zr), 티타늄(Ti), 탄탈(Ta), 니오브(Nb) 및 하프늄(Hf)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소가 상기 외부 세라믹 부식 방지층(13', 13", 13"')을 위해 도포되는, 방법.The method of claim 1,
In addition to at least one element from the group consisting of aluminum (Al) and boron (B), germanium (Ge) and gallium (Ga); At least one element selected from the group consisting of zirconium (Zr), titanium (Ti), tantalum (Ta), niobium (Nb), and hafnium (Hf) is the external ceramic corrosion protection layer (13', 13", 13"') Applied for, how. 제2항에 있어서,
알루미늄(Al)과 붕소(B), 게르마늄(Ge) 및 갈륨(Ga)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소 외에도; 지르코늄(Zr), 티타늄(Ti), 탄탈(Ta), 니오브(Nb) 및 하프늄(Hf)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소가 외부 세라믹 부식 방지층(13', 13", 13"')을 위해 도포되어 있는, 구성요소.The method of claim 2,
In addition to at least one element selected from the group consisting of aluminum (Al) and boron (B), germanium (Ge) and gallium (Ga); At least one element selected from the group consisting of zirconium (Zr), titanium (Ti), tantalum (Ta), niobium (Nb), and hafnium (Hf) forms the external ceramic corrosion protection layers 13', 13", 13"' Applied to the component. 제19항에 있어서,
지르코늄(Zr), 티타늄(Ti), 탄탈(Ta), 니오브(Nb) 및 하프늄(Hf)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소를 추가로 포함하는 재료 혼합물.The method of claim 19,
A material mixture further comprising at least one element selected from the group consisting of zirconium (Zr), titanium (Ti), tantalum (Ta), niobium (Nb), and hafnium (Hf). 제34항에 있어서,
지르코늄(Zr), 티타늄(Ti), 탄탈(Ta), 니오브(Nb) 및 하프늄(Hf)으로 이루어진 그룹으로부터 선택된 적어도 하나의 원소를 추가로 포함하는 재료 혼합물.
The method of claim 34,
A material mixture further comprising at least one element selected from the group consisting of zirconium (Zr), titanium (Ti), tantalum (Ta), niobium (Nb), and hafnium (Hf).
KR1020187015446A 2015-11-05 2016-10-11 Method and component and material mixture for making a corrosion protection layer for an insulating layer consisting of hollow aluminum oxide spheres and an outermost glass layer KR102161752B1 (en)

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