JP2006143553A - ENVIRONMENTAL BARRIER COATING OF SiC-BASED FIBER-REINFORCED CERAMIC MATRIX COMPOSITE AND ITS PRODUCTION METHOD - Google Patents
ENVIRONMENTAL BARRIER COATING OF SiC-BASED FIBER-REINFORCED CERAMIC MATRIX COMPOSITE AND ITS PRODUCTION METHOD Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 36
- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000011226 reinforced ceramic Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 24
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- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 60
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 49
- -1 rare earth silicate Chemical class 0.000 claims abstract description 42
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021426 porous silicon Inorganic materials 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical group [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
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- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 239000011153 ceramic matrix composite Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 5
- 229910052863 mullite Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 230000001902 propagating effect Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
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- 229910052689 Holmium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
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- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- FIIGRZYDBNZZFN-UHFFFAOYSA-N trioxido(trioxidosilyloxy)silane ytterbium(3+) Chemical compound [Si]([O-])([O-])([O-])O[Si]([O-])([O-])[O-].[Yb+3].[Yb+3] FIIGRZYDBNZZFN-UHFFFAOYSA-N 0.000 description 2
- AFHIIJICYLMCSH-VOTSOKGWSA-N 5-amino-2-[(e)-2-(4-benzamido-2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C(C(=C1)S(O)(=O)=O)=CC=C1NC(=O)C1=CC=CC=C1 AFHIIJICYLMCSH-VOTSOKGWSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000011184 SiC–SiC matrix composite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NAEKEHKTSNMBKE-UHFFFAOYSA-N [Si]([O-])([O-])([O-])O[Si]([O-])([O-])[O-].[Lu+3].[Lu+3] Chemical compound [Si]([O-])([O-])([O-])O[Si]([O-])([O-])[O-].[Lu+3].[Lu+3] NAEKEHKTSNMBKE-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
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Abstract
Description
本発明は、ガスタービンの高温構造部材などとして使用するＳｉＣ系繊維強化セラミックス複合材料の表面に施す耐環境コーティングとコーティングを形成するための施工方法に関する。 The present invention relates to an environment-resistant coating applied to the surface of a SiC fiber reinforced ceramic composite material used as a high-temperature structural member of a gas turbine, and a construction method for forming the coating.
航空機、船舶、発電装置などに用いられるガスタービンは、高効率化、高出力化のためガスタービン燃焼ガスの高温化が趨勢となっている。
炭化ケイ素（ＳｉＣ）を主成分とするＳｉＣ系繊維強化セラミックス複合材料（ＣＭＣ：ceramic matrix composite）は、高い耐熱性と損傷許容性を持つことから、高温化したガスタービンの高温部品用材料として期待されている。
しかし、米国において、ＳｉＣ系繊維強化セラミックス複合材料で製作した部品を用いたガスタービンについて長時間実証試験をした結果、高温高圧かつ水蒸気を含むガスタービン燃焼ガスの雰囲気下で、ＳｉＣ系ＣＭＣが水蒸気との化学反応により損耗することが確認された。
したがって、ＣＭＣをガスタービンに適用するためには、耐水蒸気腐食コーティング（ＥＢＣ：environmental barrier coating）の開発が必須である。ＥＢＣは、水蒸気腐食に対する耐性が強いトップコートを備えると共に、ＣＭＣとトップコートを強度に密着させるものでなければならない。
Gas turbines used in aircraft, ships, power generation devices, and the like are becoming increasingly hot for gas turbine combustion gases for higher efficiency and higher output.
SiC-based fiber reinforced ceramic composite (CMC: ceramic matrix composite) based on silicon carbide (SiC) has high heat resistance and damage tolerance. Has been.
However, in the United States, as a result of a long-term verification test on a gas turbine using a part made of SiC fiber reinforced ceramic composite material, SiC CMC was found to be water vapor in an atmosphere of gas turbine combustion gas containing high temperature and pressure and steam. It was confirmed that it was worn out by the chemical reaction.
Therefore, in order to apply CMC to a gas turbine, it is essential to develop an environmental barrier coating (EBC). The EBC must be provided with a top coat that is highly resistant to water vapor corrosion, and the CMC and the top coat must be in close contact with each other.
特許文献１には、トップコートにムライト（３Ａｌ2Ｏ3−２ＳｉＯ2）、中間層にＣＭＣとムライトとの熱膨張率差を緩衝するムライト・アルミナ混合層、ＣＭＣ直上に耐酸化層として金属シリコンおよびＣＶＤ−ＳｉＣの層を形成する構成が開示されている。
しかし、この構成では、耐酸化層として導入した金属Ｓｉが酸化して酸化ケイ素になるときに体積膨張するためコーティングが剥離することが問題となる。この対策として、トップコートを緻密化し、金属シリコンの酸化を防止することが要求されるが、緻密なトップコートを得るためにはより高温のプロセスが必要となるため、基材ＣＭＣの損傷を考慮するとトップコートの緻密化には限界がある。
なお、我が国においては、トップコート材料として、ムライトと同等以上の耐水蒸気性を有し、かつＣＭＣとの熱膨張率差が小さいイッテルビウム（Ｙｂ）シリケートやルテチウム（Ｌｕ）シリケートなどの希土類ケイ酸塩が検討されている。
In
However, in this configuration, there is a problem that the coating is peeled off because the volume of the metal Si introduced as the oxidation resistant layer is oxidized to become silicon oxide to expand. As a countermeasure, it is required to densify the top coat and prevent oxidation of the metal silicon. However, since a higher temperature process is required to obtain a dense top coat, the damage to the substrate CMC is considered. Then, there is a limit to densification of the top coat.
In Japan, rare earth silicates such as ytterbium (Yb) silicate and lutetium (Lu) silicate having a water vapor resistance equivalent to or higher than that of mullite and having a small difference in thermal expansion from CMC are used as top coat materials. Is being considered.
一方、酸化物系セラミック材料をＣＭＣ上に溶射法を用いてコーティングしたものでは、ＣＭＣとコーティングの密着強度が高いほど基材であるＣＭＣの強度が低下する現象が見られる。試験によると、ＣＭＣ自体の強度はサンドブラストした場合が約３００ＭＰａ、サンドブラストしない場合で約３１０ＭＰａと殆ど差がないにもかかわらず、室温における強度が約２１５ＭＰａのＣＭＣについて、サンドブラストした上にＥＢＣを施して強い密着性を有するものの室温における強度が約１４０ＭＰａと明らかに低下した一方、サンドブラストしないままＥＢＣを付けた密着性が弱いものでは約２４０ＭＰａと強度が低下しないことが観測された。なお、１２００℃における強度は、いずれの場合でも余り変化しないことが観察されている。 On the other hand, in the case where an oxide ceramic material is coated on the CMC using a thermal spraying method, a phenomenon is observed in which the strength of the CMC as a base material decreases as the adhesion strength between the CMC and the coating increases. According to the test, the strength of CMC itself was about 300 MPa when sandblasted, and about 310 MPa when it was not sandblasted. Although it had strong adhesion, the strength at room temperature was clearly reduced to about 140 MPa, while it was observed that the strength was not reduced to about 240 MPa in the case of weak adhesion with EBC without sandblasting. It has been observed that the strength at 1200 ° C. does not change much in any case.
ＥＢＣとの密着性が良い方がＣＭＣの強度が低下するのは、ＥＭＣのトップコートに内在した亀裂、あるいはトップコートに発生した亀裂が基材であるＣＭＣに伝播し易く、伝播した亀裂がＣＭＣの表面に応力集中を生じさせるためと考えられる。
したがって、ＥＢＣは、トップコートが十分緻密であると共に、トップコート及びＣＭＣと良く密着し、しかもトップコートの亀裂がＣＭＣに伝播することを効果的に抑制する中間層を備えることが望まれる。一般に密着強度の向上と亀裂の伝搬抑制は相反する特性であるから、適当な材料あるいは構成を得ることは簡単でない。
The better the adhesion to the EBC, the lower the strength of the CMC is because cracks inherent in the EMC top coat or cracks generated in the top coat easily propagate to the CMC as the base material. This is considered to cause stress concentration on the surface of the steel.
Therefore, it is desired that the EBC has an intermediate layer in which the top coat is sufficiently dense and is in close contact with the top coat and the CMC, and further effectively suppresses the propagation of cracks in the top coat to the CMC. In general, improvement in adhesion strength and suppression of crack propagation are contradictory properties, and it is not easy to obtain an appropriate material or configuration.
希土類ケイ酸塩をトップコートとした場合は、中間層として、希土類ケイ酸塩と結晶化ガラス（ＢａＯ・ＭｇＯ・Ａｌ2Ｏ3・ＳｉＯ2：以後、ＢＭＡＳと呼ぶ）の混合体が好ましいことが知られている。
ＢＭＡＳは、中間層をＣＭＣ上に形成・定着させるときにガラスとして溶融し、ＣＭＣ中に浸透した後にさらに高温で熱処理すると一部が結晶化し、耐熱性が向上する性質を持っている。
トップコートにする希土類ケイ酸塩の熱膨張率が約２×１０-6／Ｋ、ＣＭＣの熱膨張率が約３×１０-6／Ｋであるのに対して、ＢＭＡＳの熱膨張率は約４×１０-6／Ｋであるので、希土類ケイ酸塩と適当な割合で混合することにより、トップコートとＣＭＣの間の熱膨張率差を緩和することができる。
When the rare earth silicate is used as a top coat, a mixture of rare earth silicate and crystallized glass (BaO.MgO.Al 2 O 3 .SiO 2 : hereinafter referred to as BMAS) is preferable as the intermediate layer. Are known.
BMAS has the property that it melts as glass when the intermediate layer is formed and fixed on the CMC, and when it is infiltrated into the CMC, if it is heat-treated at a higher temperature, it partially crystallizes and heat resistance is improved.
The thermal expansion coefficient of the rare earth silicate used as the top coat is about 2 × 10 −6 / K and the thermal expansion coefficient of CMC is about 3 × 10 −6 / K, whereas the thermal expansion coefficient of BMAS is about Since it is 4 × 10 −6 / K, the difference in thermal expansion coefficient between the top coat and the CMC can be reduced by mixing with the rare earth silicate at an appropriate ratio.
ＣＭＣと希土類ケイ酸塩の弾性率がそれぞれ約２００ＧＰａであるのに対して、ＢＭＡＳは高温で１３０ＧＰａ程度に軟化するので、トップコートの亀裂がＣＭＣに伝播するのを効果的に抑制する。
したがって、ＭＢＡＳを混合した中間層は、良好な耐熱性を持ち、トップコートとＣＭＣとの熱膨張差を緩衝し、トップコート亀裂がＣＭＣに伝播することを防止するという、中間層に適した性質を備える。
しかし、ＳｉＣ系繊維強化セラミックス複合材料（ＣＭＣ）の表面には、ＳｉＣ繊維部分、ＳｉＣマトリックス部分、さらに気孔部分が存在するので、処理中に溶融する結晶化ガラス（ＢＭＡＳ）との濡れ性が場所によって異なるため、中間層の厚さにムラが生じ、均質なトップコートを形成することが困難である。
While the elastic modulus of CMC and rare earth silicate is about 200 GPa, respectively, BMAS softens to about 130 GPa at high temperature, so that the crack of the top coat is effectively suppressed from propagating to CMC.
Therefore, the intermediate layer mixed with MBAS has good heat resistance, buffers the difference in thermal expansion between the topcoat and CMC, and prevents the topcoat crack from propagating to the CMC. Is provided.
However, the SiC fiber reinforced ceramic composite material (CMC) has a SiC fiber part, a SiC matrix part, and a pore part on the surface, so that the wettability with the crystallized glass (BMAS) that melts during processing is in place. Therefore, it is difficult to form a uniform top coat because the thickness of the intermediate layer is uneven.
なお、特許文献２には、炭化珪素を含有する第１層と、一般式ＲＥ2Ｓｉ2Ｏ7（式中のＲＥは、Ｙ，Ｙｂ，Ｅｒ，Ｄｙのいずかの希土類元素）で表される希土類珪酸化合物（シリケート）を含有する第２層とを酸化珪素の層で接合した積層セラミックスが開示されている。接合層は、酸化珪素層とムライト層やアルミナ層の多層構造を有するものであっても良い。高温強度に優れる炭化珪素を、高温での耐酸化性、耐食性が優れる酸化物系セラミックスで被覆することで、優れた構造用材料、特に高温ガスタービン用部材等を製造するための材料として利用することができる。希土類珪酸化合物は耐酸化性に優れ炭化珪素に近い熱膨張率を持つのでコーティングに適しているが、炭化珪素との接着性が悪いので両者を接合する中間層を導入して炭化珪素との接着性を改善しようとしたものである。
また、特許文献３には、ＳｉＣ繊維の焼結結合体の表面に希土類酸化物を主成分とする被覆層を形成したセラミックス複合材料が開示されている。この技術はＳｉＣ／ＳｉＣ複合材料にも適用できるとされている。希土類酸化物を主成分とする層は、一般式ＲＥ2Ｓｉ2Ｏ7またはＲＥ2ＳｉＯ5（式中のＲＥは、Ｙ，Ｙｂ，Ｅｒ，Ｈｏ，Ｄｙのいずれかの希土類元素）で表される希土類酸化物からなるトップコートである第１層と、少なくとも１種の希土類酸化物を含む２種以上の金属の酸化物の共晶で形成される第２層から構成される。なお、この第２層は一般式ＲＥ3Ａｌ5Ｏ12またはＲＥＡｌＯ3（式中のＲＥは、Ｙ，Ｙｂ，Ｅｒ，Ｈｏ，Ｄｙ，Ｇｄ，Ｓｍ，Ｎｄ，Ｌｕのいずれかの希土類元素）で表される希土類酸化物で置き換えることもできる。本文献開示の被覆を付することにより、母材の焼結ＳｉＣ繊維結合体の強度特性を損なうことなく、高温化での酸化及び腐食に十分に耐え、長時間使用可能な高温構造部材を得ることができる。 Patent Document 3 discloses a ceramic composite material in which a coating layer mainly composed of a rare earth oxide is formed on the surface of a sintered combination of SiC fibers. This technique is also applicable to SiC / SiC composite materials. The layer containing a rare earth oxide as a main component is represented by the general formula RE 2 Si 2 O 7 or RE 2 SiO 5 (where RE is a rare earth element selected from Y, Yb, Er, Ho, and Dy). The first layer is a top coat made of a rare earth oxide, and the second layer is formed of a eutectic of two or more metal oxides including at least one rare earth oxide. The second layer has a general formula RE 3 Al 5 O 12 or REAlO 3 (where RE is a rare earth element of Y, Yb, Er, Ho, Dy, Gd, Sm, Nd, or Lu). It can also be replaced by the rare earth oxides represented. By applying the coating disclosed in this document, a high-temperature structural member that can sufficiently withstand oxidation and corrosion at high temperatures and can be used for a long time without impairing the strength characteristics of the sintered SiC fiber bonded body of the base material is obtained. be able to.
これら文献に記載された、トップコートとＳｉＣ基材の間に介装されるこれらの接合層は、互いに接合しにくいトップコートと基材を接合する機能に加えて、両者の熱膨張挙動の差を緩和する機能を備え、セラミックス複合材料を長寿命化する効果を有する。しかし、柔軟性が小さいのでトップコートで発生する亀裂が伝播するのを防ぐ機能は持たない。
本発明が解決しようとする課題は、炭化ケイ素繊維強化セラミックス複合材料（ＣＭＣ）表面に結晶化ガラス（ＢＭＡＳ）を介して耐水蒸気腐食コーティング（ＥＢＣ）を施すときに、ＣＭＣ表面の濡れ性不均一性を改善して、厚さが均一なコーティングを可能にすることである。 The problem to be solved by the present invention is that when wet corrosion resistance coating (EBC) is applied to the surface of silicon carbide fiber reinforced ceramic composite material (CMC) via crystallized glass (BMAS), the wettability of the CMC surface is not uniform. To improve the properties and to enable a coating with a uniform thickness.
上記課題を解決するため本発明のＳｉＣ系繊維強化セラミックス複合材料耐環境コーティングは、ＳｉＣ系繊維強化セラミックス（ＣＭＣ）基材表面層に形成されたＢａＯ・ＭｇＯ・Ａｌ2Ｏ3・ＳｉＯ2からなる結晶化ガラス（ＢＭＡＳ）と希土類ケイ酸塩の混合体が含浸した層と、混合体が含浸した基材表面層の上に形成されたＢＭＡＳと希土類ケイ酸塩の混合体が含浸した多孔質の炭化ケイ素層との２層からなる中間層が形成され、さらに多孔質炭化ケイ素層上にトップコートとして希土類ケイ酸塩層が形成されていることを特徴とする。
希土類ケイ酸塩は、一般式ＲＥ2Ｓｉ2Ｏ7（式中のＲＥは希土類元素）で表される希土類酸化物のジシリケートであることが好ましく、特にイッテルビウムシリケート（Ｙｂ2Ｏ3−２ＳｉＯ2）またはルテチウムシリケート（Ｌｕ2Ｏ3−２ＳｉＯ2）であることが好ましい。
In order to solve the above-described problems, the SiC fiber reinforced ceramic composite environmental resistant coating of the present invention comprises BaO.MgO.Al 2 O 3 .SiO 2 formed on the surface layer of a SiC fiber reinforced ceramic (CMC) substrate. A layer impregnated with a mixture of crystallized glass (BMAS) and a rare earth silicate, and a porous material impregnated with a mixture of BMAS and a rare earth silicate formed on a substrate surface layer impregnated with the mixture; An intermediate layer composed of two layers with a silicon carbide layer is formed, and a rare earth silicate layer is formed as a top coat on the porous silicon carbide layer.
The rare earth silicate is preferably a disilicate of a rare earth oxide represented by the general formula RE 2 Si 2 O 7 (where RE is a rare earth element), and particularly ytterbium silicate (Yb 2 O 3 -2SiO 2 ). or is preferably lutetium silicate (Lu 2 O 3 -2SiO 2) .
本発明のＳｉＣ系繊維強化セラミックス複合材料耐環境コーティングは、ＳｉＣ系繊維強化セラミックスの表面に形成された多孔質の炭化ケイ素層にＢＭＡＳが含浸するようにしたため、ＣＭＣ表面の濡れ性不均一が改善され、厚さが均一な中間層およびトップコートが容易に形成される。
また、高温水蒸気による腐食に強い耐性を有する希土類ケイ酸塩で形成されたトップコートで被覆してＣＭＣの損傷を防止し高い耐熱性能と強度を維持すると共に、トップコートとＣＭＣの中間層に高温で軟化し室温でも弾性率が低いＢＭＡＳを充填したためトップコートに発生する亀裂がＣＭＣに伝播するのを防いで複合材料として基材の強度と同じ水準の強度を保持させることができる。
The SiC fiber reinforced ceramic composite environment-resistant coating of the present invention improves the non-uniform wettability of the CMC surface because the porous silicon carbide layer formed on the surface of the SiC fiber reinforced ceramic is impregnated with BMAS. Thus, an intermediate layer and a top coat having a uniform thickness can be easily formed.
In addition, it is coated with a top coat made of rare earth silicate that has strong resistance to corrosion by high temperature steam to prevent damage to the CMC and maintain high heat resistance and strength, while the intermediate layer between the top coat and the CMC has a high temperature. Since it is filled with BMAS which is softened and has a low elastic modulus even at room temperature, the crack generated in the top coat is prevented from propagating to the CMC, and the composite material can maintain the same strength as the strength of the base material.
さらに、本発明のＳｉＣ系繊維強化セラミックス複合材料耐環境コーティングの製造方法は、ＳｉＣ系繊維強化セラミックス（ＣＭＣ）基材上にＣＶＤ法によりＳｉＣの多孔質膜を形成し、ＢａＯ・ＭｇＯ・Ａｌ2Ｏ3・ＳｉＯ2からなる結晶化ガラス（ＢＭＡＳ）と希土類ケイ酸塩の混合液を多孔質膜表面に塗布して高温処理することにより、ＢＭＡＳと希土類ケイ酸塩をＳｉＣ多孔質膜と基材表面層に含浸させるとともに、多孔質膜表面に残存した希土類ケイ酸塩の層を形成することを特徴とする。
多孔質膜表面に、さらに、希土類ケイ酸塩の割合を増加したＢＭＡＳとの混合体を塗布して加熱処理することにより、多孔質膜表面上の希土類ケイ酸塩層を形成してもよい。
なお、基材表面層まで含浸させる混合液におけるＢＭＡＳ粉末と希土類ケイ酸塩粉末の割合を重量比でほぼ１対１とし、多孔質膜表面に処理する混合液における割合を重量比でほぼ１対３とすることが好ましい。
Furthermore, the manufacturing method of the SiC fiber-reinforced ceramic composite material environment-resistant coating according to the present invention comprises forming a SiC porous film on a SiC-based fiber reinforced ceramic (CMC) substrate by a CVD method, and BaO · MgO · Al 2. A mixed liquid of crystallized glass (BMAS) and rare earth silicate composed of O 3 · SiO 2 is applied to the surface of the porous film and subjected to high temperature treatment, whereby BMAS and the rare earth silicate are converted into a SiC porous film and a substrate. The surface layer is impregnated and a rare earth silicate layer remaining on the surface of the porous membrane is formed.
A rare earth silicate layer on the surface of the porous film may be formed by further applying a mixture with BMAS having an increased proportion of the rare earth silicate to the surface of the porous film and performing a heat treatment.
In addition, the ratio of the BMAS powder and the rare earth silicate powder in the mixed liquid impregnated to the surface layer of the base material is approximately 1: 1, and the ratio of the mixed liquid to be treated on the porous membrane surface is approximately 1: 1. 3 is preferable.
以下、図面を用いて、本発明の炭化ケイ素（ＳｉＣ）系繊維強化セラミックス複合材料耐環境コーティングの最良の形態について詳細に説明する。本発明は、ＳｉＣ繊維で強化したＳｉＣマトリックスで構成される繊維強化セラミックスに耐環境コーティングを施して、高温水蒸気に対する耐性が大きく、高温強度が大きく、寿命が長い複合材料を得ることに関するものである。
図１は本発明の１実施例に係る耐環境コーティングの施工方法を説明する工程図、図２はコーティング強度を比較して示すグラフである。
Hereinafter, the best mode of an environmental resistant coating of a silicon carbide (SiC) -based fiber reinforced ceramic composite material of the present invention will be described in detail with reference to the drawings. The present invention relates to obtaining a composite material having a high resistance to high temperature steam, a high temperature strength and a long life by applying an environment resistant coating to a fiber reinforced ceramic composed of a SiC matrix reinforced with SiC fibers. .
FIG. 1 is a process diagram for explaining a method for applying an environment-resistant coating according to one embodiment of the present invention, and FIG. 2 is a graph showing a comparison of coating strength.
本実施例では、ＳｉＣ系繊維強化セラミックスに対して、図１に示した工程により耐環境コーティングを施して複合材料を製造する。
すなわち、（ａ）炭化ケイ素（ＳｉＣ）系繊維強化セラミックス（ＣＭＣ）の基材１の上にＣＶＤ法によりＳｉＣ被膜を積層する。このとき、ＣＶＤ−ＳｉＣ被膜２が多孔質になるように温度やプロセスガス濃度などの積層条件を調整して堆積させる。ＣＭＣはＳｉＣマトリックスにＳｉＣ繊維を混合して強化したもので、内部に多数の空孔３が存在する。
In the present embodiment, a composite material is manufactured by applying an environment-resistant coating to the SiC fiber reinforced ceramic by the process shown in FIG.
That is, (a) a SiC film is laminated on a
（ｂ）次に、多孔質ＣＶＤ−ＳｉＣ被膜を形成させたＣＭＣ基材１をＢａＯ・ＭｇＯ・Ａｌ2Ｏ3・ＳｉＯ2からなる結晶化ガラス（ＢＭＡＳ）の粉末と希土類ケイ酸塩の粉末を混ぜた溶液に漬けてＳｉＣ被膜表面に塗布し、高温度で処理する。
なお、希土類ケイ酸塩は、一般式ＲＥ2Ｓｉ2Ｏ7（式中のＲＥは希土類元素）で表される希土類酸化物のジシリケートであることが好ましく、特にイッテルビウムジシリケート（Ｙｂ2Ｏ3−２ＳｉＯ2：Ｙｂ２Ｓと略称する）またはルテチウムジシリケート（Ｌｕ2Ｏ3−２ＳｉＯ2）であることが好ましい。
また、希土類ケイ酸塩粉末はＢＭＡＳ粉末に対して重量比でほぼ１対１に混合することが好ましい。
(B) Next, the
The rare earth silicate is preferably a disilicate of a rare earth oxide represented by the general formula RE 2 Si 2 O 7 (where RE is a rare earth element), and particularly ytterbium disilicate (Yb 2 O 3 − 2SiO 2 : abbreviated as Yb2S) or lutetium disilicate (Lu 2 O 3 -2SiO 2 ).
The rare earth silicate powder is preferably mixed with the BMAS powder in a weight ratio of approximately 1: 1.
（ｃ）すると、ＳｉＣ被膜表面に塗布た混合体は溶融して多孔質ＣＶＤ−ＳｉＣ被膜層２を透過し、ＣＭＣ基材１の内側まで浸透してＣＭＣ内の比較的浅いところに存在する空孔３を充填し、かつＣＭＣ表層部にＢＭＡＳ成分の多いＢＭＡＳ−希土類ケイ酸塩系中間層４が形成される。また多孔質ＣＶＤ−ＳｉＣ被膜２中の隙間にもＢＭＡＳが充填される。さらに、被膜表面上に希土類ケイ酸塩が残存し、トップコート５を形成する。
（ｄ）さらに、被膜表面を、希土類ケイ酸塩の濃度が高い、たとえばＢＭＡＳ粉末１対Ｙｂ２Ｓ粉末３の割合で混ぜた溶液に漬けて、焼成することにより、希土類ケイ酸塩のトップコート層５をより厚く確実に形成させるようにしてもよい。
(C) Then, the mixture applied to the surface of the SiC coating melts and permeates through the porous CVD-
(D) Furthermore, the surface of the coating is immersed in a solution in which the concentration of the rare earth silicate is high, for example, in a ratio of
上の施工方法にしたがってＳｉＣ系繊維強化セラミックス（ＣＭＣ）表面に耐環境コーティングを施すことによって得られた複合材料は、ＣＭＣ基材１の上に基材表面層にＢＭＡＳとＹｂ２Ｓの混合体が含浸した層４と、基材表面上にＢＭＡＳとＹｂ２Ｓの混合体が含浸した多孔質のＣＶＤ−ＳｉＣ層２が形成され、さらにＣＶＤ−ＳｉＣ層２上にＹｂ２Ｓトップコート層５が形成されたものである。基材表面層にＢＭＡＳとＹｂ２Ｓが含浸した層４と多孔質ＣＶＤ−ＳｉＣ層２で中間層を構成する。
図２に示すように、ＣＭＣ単体では２００ＭＰａ程度の座屈強度を有するが、ＣＭＣ表面にＣＶＤ−ＳｉＣ層を形成しただけでは１４０ＭＰａ程度に強度が低下する。しかし、さらにＢＭＡＳと希土類ケイ酸塩を含浸させ希土類ケイ酸塩のコーティング層を形成することによって、基材強度が約２５０ＭＰａと大きく回復する結果を得ている。
The composite material obtained by applying an environmental coating to the surface of SiC fiber reinforced ceramics (CMC) according to the above construction method is impregnated with a mixture of BMAS and Yb2S on the surface layer of the base material on the
As shown in FIG. 2, the CMC alone has a buckling strength of about 200 MPa, but the strength is reduced to about 140 MPa only by forming a CVD-SiC layer on the CMC surface. However, by further impregnating BMAS and rare earth silicate to form a rare earth silicate coating layer, the strength of the base material is greatly recovered to about 250 MPa.
また、希土類酸化物のうちでも特にシリケートであることが好ましい。たとえばイッテルビウムアルミネート（ＹｂＡｌＯ3：ＹＡと略称する）をコーティングしたものでは化学反応により強度が低下するので、図２に示した通り、強度が５０ＭＰａ程度にしかならず、Ｙｂ２Ｓを用いたもののような基材強度回復効果が見られなかった。なお、図中ＹＡに異なるサフィックス（１）（２）が付いているのは、ＢＭＡＳとの配合比が異なることを意味する。 Of the rare earth oxides, silicate is particularly preferable. For example, in the case of coating with ytterbium aluminate (abbreviated as YbAlO 3 : YA), the strength decreases due to a chemical reaction. Therefore, as shown in FIG. 2, the strength is only about 50 MPa, and a substrate such as that using Yb2S is used. Strength recovery effect was not seen. In the figure, YA with different suffixes (1) and (2) means that the blending ratio with BMAS is different.
本実施例により得られるＳｉＣ系繊維強化セラミックス複合材料は、ＣＶＤ−ＳｉＣ層が導入されたことにより、高温処理中に中間層とトップコート成分の濡れ性不均一が改善され、厚さが均一なコーティングが形成されている。
トップコートは耐水蒸気性に優れる希土類ケイ酸塩で形成され、基材との間には室温で柔軟性を持ちかつ高温で軟化する結晶化ガラスを充填した中間層を有するのでトップコート亀裂が基材まで伝播することを抑制するので、高温水蒸気雰囲気中でもＳｉＣ系繊維強化セラミックスの高い耐熱性と損傷許容性を発揮する。この特性を生かしてガスタービン高温部品用材料としても利用することができる。特にイッテルビウムジシリケートでトップコートを形成すると、極めて耐環境性の高い複合材料を得ることができる。
In the SiC fiber reinforced ceramic composite material obtained in this example, the introduction of the CVD-SiC layer improves the wettability non-uniformity of the intermediate layer and the top coat component during the high temperature treatment, and the thickness is uniform. A coating is formed.
The topcoat is made of rare earth silicate with excellent water vapor resistance, and has an intermediate layer filled with crystallized glass that is flexible at room temperature and softens at high temperature between the topcoat and the topcoat cracks. Since the propagation to the material is suppressed, the high heat resistance and damage tolerance of the SiC fiber reinforced ceramics is exhibited even in a high-temperature steam atmosphere. Taking advantage of this property, it can also be used as a material for gas turbine high-temperature components. In particular, when the top coat is formed of ytterbium disilicate, a composite material having extremely high environmental resistance can be obtained.
１ ＣＭＣ基材
２ ＣＶＤ−ＳｉＣ層
３ 空孔
４ ＢＭＡＳ−Ｙｂ２Ｓ層
５ トップコート
1
Claims (5)
Furthermore, a rare earth silicate layer on the surface of the porous film is formed by applying a heat treatment by applying a mixture of BMAS and rare earth silicate with an increased proportion of the rare earth silicate to the surface of the porous film. The method for producing a thermal barrier coating according to claim 4, wherein a top coat is used.
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