JP6735164B2 - Laminated structure - Google Patents
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- JP6735164B2 JP6735164B2 JP2016126798A JP2016126798A JP6735164B2 JP 6735164 B2 JP6735164 B2 JP 6735164B2 JP 2016126798 A JP2016126798 A JP 2016126798A JP 2016126798 A JP2016126798 A JP 2016126798A JP 6735164 B2 JP6735164 B2 JP 6735164B2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 66
- 229910052760 oxygen Inorganic materials 0.000 claims description 66
- 239000001301 oxygen Substances 0.000 claims description 66
- 150000001875 compounds Chemical class 0.000 claims description 54
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 52
- 150000002910 rare earth metals Chemical class 0.000 claims description 45
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 22
- 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 claims description 17
- 229910052863 mullite Inorganic materials 0.000 claims description 17
- 230000035699 permeability Effects 0.000 claims description 15
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- 150000002484 inorganic compounds Chemical class 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 238000007740 vapor deposition Methods 0.000 description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002648 laminated material Substances 0.000 description 5
- 239000011226 reinforced ceramic Substances 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 229910018557 Si O Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000000567 combustion gas Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 silicate compound Chemical class 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910018885 Pt—Au Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XTDAIYZKROTZLD-UHFFFAOYSA-N boranylidynetantalum Chemical compound [Ta]#B XTDAIYZKROTZLD-UHFFFAOYSA-N 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001182 laser chemical vapour deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、高温の酸素を含む雰囲気下における酸素遮蔽性及び構造安定性に優れる積層構造に関し、更に詳しくは、航空機のエンジン等に配設され、高温の酸素、水蒸気等を含む雰囲気下で用いられる高温部品を与える積層構造に関する。 The present invention relates to a laminated structure having excellent oxygen shielding properties and structural stability in an atmosphere containing high-temperature oxygen, and more specifically, it is disposed in an aircraft engine or the like and is used in an atmosphere containing high-temperature oxygen, water vapor, etc. Laminated structure for providing a high temperature component.
例えば、航空産業において、エンジンの燃費を改善したり、二酸化炭素の排出量を削減したりするために、高圧タービン部材等の高温部品の耐熱性を向上させる検討が進められている。このような高温部品は、一般に、セラミックスからなる基部と、その表面に配設された保護膜とを備える構造を有する。 For example, in the aviation industry, studies are underway to improve the heat resistance of high-temperature parts such as high-pressure turbine members in order to improve the fuel efficiency of engines and reduce the emission of carbon dioxide. Such a high-temperature component generally has a structure including a base made of ceramics and a protective film provided on the surface thereof.
特許文献１には、耐熱性、耐熱衝撃性、耐摩耗性及び耐酸化性に優れる窒化珪素質焼結体又はサイアロン質焼結体を利用した耐食性セラミックス、即ち、窒化珪素及び／又はサイアロンからなる焼結体と、該焼結体の表面に形成された周期律表第３ａ族元素の珪酸化合物からなる表面層と、表面層と焼結体との間に設けられ、焼結体を構成する主結晶と表面層を構成する珪酸化合物とからなる厚さ３〜６０μｍの混合層とを具備し、該混合層における窒化珪素及び／又はサイアロン主結晶の粒子の平均長径が４０μｍ以上であることを特徴とする耐食性セラミックスが開示されている。 Patent Document 1 discloses a corrosion resistant ceramic using a silicon nitride sintered body or a sialon sintered body having excellent heat resistance, thermal shock resistance, wear resistance and oxidation resistance, that is, silicon nitride and/or sialon. The sintered body is provided between the surface layer and the surface of the sintered body, a surface layer formed on the surface of the sintered body, the surface layer being made of a silicate compound of a Group 3a element of the periodic table, and constituting the sintered body. A mixed layer having a thickness of 3 to 60 μm, which comprises a main crystal and a silicate compound constituting a surface layer, and the average major axis of particles of the silicon nitride and/or sialon main crystal in the mixed layer is 40 μm or more. Characteristic corrosion resistant ceramics are disclosed.
高温部品の多くは、積層構造を有するものであり、実用環境においては、積層材料の表面と内部とでは酸素の化学ポテンシャル（それと平衡する酸素分圧）が異なることから、高温の酸素を含む雰囲気の中で、断面方向の酸素遮蔽性及び構造安定性が求められていた。 Most of the high temperature parts have a laminated structure, and in a practical environment, the chemical potential of oxygen (oxygen partial pressure equilibrium with it) is different between the surface and the inside of the laminated material. Among them, the oxygen shielding property in the cross-sectional direction and the structural stability have been required.
本発明は、以下に示される。
１．無機化合物を含む基部の１面側に形成される積層構造であって、ムライトを含む第１層と、ＲＥを希土類元素とした場合に、ＲＥ２Ｓｉ２Ｏ７で表される希土類ダイシリケート化合物及びＲＥ２ＳｉＯ５で表される希土類モノシリケート化合物を含む第２層とが接合されてなり、上記第２層は、上記希土類ダイシリケート化合物を含む母相と、該母相の中に分散された、上記希土類モノシリケート化合物を含む分散相とからなることを特徴とする積層構造。
２．上記第２層における上記希土類ダイシリケート化合物及び上記希土類モノシリケート化合物の含有割合が、上記希土類ダイシリケート化合物及び上記希土類モノシリケート化合物の合計量を１００体積％とした場合に、それぞれ、９０体積％以上１００体積％未満及び０体積％を超えて１０体積％以下である上記項１に記載の積層構造。
３．上記希土類元素がＹｂ、Ｌｕ、Ｓｍ、Ｅｕ、Ｔｍ、Ｙ及びＧｄから選ばれた少なくとも一種である上記項１又は２に記載の積層構造。
４．上記希土類ダイシリケート化合物がＹｂ２Ｓｉ２Ｏ７であり、上記希土類モノシリケート化合物が、Ｙｂ２ＳｉＯ５である上記項１乃至３のいずれか一項に記載の積層構造。
５．上記第２層の表面に、更に、酸素遮蔽層を備える上記項１乃至４のいずれか一項に記載の積層構造。
６．上記酸素遮蔽層の酸素透過係数が、上記第２層の酸素透過係数の０．１倍以下である上記項５に記載の積層構造。
The present invention is shown below.
1. A rare earth disilicate compound represented by RE 2 Si 2 O 7 , which is a laminated structure formed on one surface side of a base containing an inorganic compound and has a first layer containing mullite and RE is a rare earth element. And a second layer containing a rare earth monosilicate compound represented by RE 2 SiO 5 are joined together, and the second layer is dispersed in the mother phase containing the rare earth disilicate compound and the mother phase. A laminated structure comprising a dispersed phase containing the rare earth monosilicate compound.
2. The content ratio of the rare earth disilicate compound and the rare earth monosilicate compound in the second layer is 90% by volume or more, respectively, when the total amount of the rare earth disilicate compound and the rare earth monosilicate compound is 100% by volume. The laminated structure according to above item 1, which is less than 100% by volume and more than 0% by volume and 10% by volume or less.
3. Item 3. The laminated structure according to Item 1 or 2, wherein the rare earth element is at least one selected from Yb, Lu, Sm, Eu, Tm, Y and Gd.
4. 4. The laminated structure according to any one of Items 1 to 3, wherein the rare earth disilicate compound is Yb 2 Si 2 O 7 and the rare earth monosilicate compound is Yb 2 SiO 5 .
5. Item 5. The laminated structure according to any one of Items 1 to 4, further comprising an oxygen shielding layer on the surface of the second layer.
6. Item 6. The laminated structure according to Item 5, wherein the oxygen barrier layer has an oxygen permeability coefficient of 0.1 times or less the oxygen permeability coefficient of the second layer.
本発明の積層構造は、高い温度、例えば、１３００℃〜１６００℃、特に好ましくは１４００℃以上１５００℃程度までの温度の酸素を含む雰囲気下における断面方向の酸素遮蔽性及び構造安定性（耐熱性）を有する。また、酸素及び水蒸気を含む雰囲気下における断面方向の水蒸気遮蔽性及び耐水蒸気揮散性を有する。従って、本発明の積層構造は、航空機のエンジン、ガスタービン等に配設される高温部品の構成要素として好適である。 The laminated structure of the present invention has an oxygen-shielding property and a structural stability (heat resistance) in a cross-sectional direction under an atmosphere containing oxygen at a high temperature, for example, 1300° C. to 1600° C., particularly preferably 1400° C. to 1500° C. ) Has. Further, it has a water vapor shielding property in the cross-sectional direction and a water vapor volatilization resistance under an atmosphere containing oxygen and water vapor. Therefore, the laminated structure of the present invention is suitable as a constituent element of a high temperature component arranged in an aircraft engine, a gas turbine or the like.
本発明の積層構造は、図１に示されるように、無機化合物を含む基部２０の１面側に形成される積層構造１０であって、ムライトを含む第１層１１と、ＲＥを希土類元素とした場合に、ＲＥ２Ｓｉ２Ｏ７で表される希土類ダイシリケート化合物及びＲＥ２ＳｉＯ５で表される希土類モノシリケート化合物を含む第２層１３とが接合されてなる。そして、第２層は、希土類ダイシリケート化合物を含む母相と、該母相の中に分散された、希土類モノシリケート化合物を含む分散相とからなる。
本発明の積層構造１０の第１層１１と、基部２０とが接合された積層材料１は、特に、酸素、水蒸気等を含む高温ガス環境下で使用される航空機エンジンや発電用タービンにおける高圧タービン部の動翼部品、静翼部品又はシュラウド部品、更には、ロケットエンジンのスラスターや燃焼ガスチューブ等の高温部品の形成に好適である。
As shown in FIG. 1, the laminated structure of the present invention is a laminated structure 10 formed on one surface side of a base 20 containing an inorganic compound, wherein a first layer 11 containing mullite and RE is a rare earth element. In this case, the second layer 13 containing the rare earth disilicate compound represented by RE 2 Si 2 O 7 and the rare earth monosilicate compound represented by RE 2 SiO 5 is joined. The second layer is composed of a mother phase containing a rare earth disilicate compound and a dispersed phase containing a rare earth monosilicate compound dispersed in the mother phase.
The laminated material 1 in which the first layer 11 of the laminated structure 10 of the present invention and the base portion 20 are joined together is a high-pressure turbine in an aircraft engine or a turbine for power generation, which is used particularly in a high-temperature gas environment containing oxygen, steam, and the like. It is suitable for forming a moving blade part, a stationary blade part or a shroud part, and a high temperature part such as a rocket engine thruster or a combustion gas tube.
上記第１層は、ムライトを含む層である。ムライトは、好ましくは、Ａｌ４＋２ｘＳｉ２−２ｘＯ１０−ｘ（０．２０≦ｘ≦０．３９）で表される化合物であり、０．２０≦ｘ≦０．３９の範囲における複数の化合物を用いてもよい。本発明においては、積層構造１０を含む物品（高温部品）を、１１００℃以上の高い温度で、且つ、酸素、水蒸気等を含む雰囲気下で用いた場合に、アルミニウムイオンの、酸素分圧の低い側に位置する第１層の基部側への移動の抑制効果に優れることから、好ましくはＡｌ４＋２ｘＳｉ２−２ｘＯ１０−ｘ（０．２０≦ｘ≦０．３４）で表される化合物、より好ましくはＡｌ４＋２ｘＳｉ２−２ｘＯ１０−ｘ（０．２３≦ｘ≦０．３０）で表される化合物である。尚、第１層は、化学組成が限定されたムライトのみを含んでよいし、化学組成の異なるムライトどうし（２種以上）を含んでもよい。後者の場合、複数のムライトは、混合状態であってよいし、特定の化学組成を有するムライトの分布を、層の一端側から他端側に向かって傾斜させてもよい。化学組成の異なるムライトを傾斜配置する場合には、第２層の構成材料との熱膨張係数差がより小さくなり、また、上記基部の表面（図１の下面側）における耐水蒸気揮散性を高められることから、上記基部側から第１層の表面側に向かって、Ａｌ／Ｓｉ比を大きくすることが好ましい。 The first layer is a layer containing mullite. Mullite is preferably a compound represented by Al 4+2x Si 2-2x O 10-x (0.20≦x≦0.39), and a plurality of compounds in the range of 0.20≦x≦0.39. May be used. In the present invention, when the article (high temperature component) including the laminated structure 10 is used at a high temperature of 1100° C. or higher and in an atmosphere containing oxygen, water vapor, etc., the aluminum ion has a low oxygen partial pressure. The compound represented by Al 4+2x Si 2-2x O 10-x (0.20≦x≦0.34) is preferable because it has an excellent effect of suppressing the movement of the first layer located on the side toward the base side, More preferably, it is a compound represented by Al 4+2x Si 2-2x O 10-x (0.23≦x≦0.30). The first layer may contain only mullite having a limited chemical composition, or may contain mullite (two or more kinds) having different chemical compositions. In the latter case, the mullites may be in a mixed state, or the distribution of mullites having a specific chemical composition may be inclined from one end side to the other end side of the layer. When the mullite having a different chemical composition is inclinedly arranged, the difference in the coefficient of thermal expansion from the constituent material of the second layer becomes smaller, and the vapor volatilization resistance on the surface of the base (the lower surface side in FIG. 1) is increased. Therefore, it is preferable to increase the Al/Si ratio from the base side toward the surface side of the first layer.
上記第１層の気孔率の上限は、高い温度の酸素を含む雰囲気下における断面方向の酸素遮蔽性及び構造安定性（耐熱性）の観点から、好ましくは１０体積％、より好ましくは５体積％である。 The upper limit of the porosity of the first layer is preferably 10% by volume, more preferably 5% by volume, from the viewpoint of oxygen shielding property in the cross-sectional direction and structural stability (heat resistance) under an atmosphere containing oxygen at a high temperature. Is.
上記第１層は、ムライトのみからなる層であることが好ましいが、本発明の効果を損なわない範囲において、ムライトと他の化合物とからなる層であってもよい。他の化合物としては、アルミナ等が挙げられる。上記第１層が他の化合物を含む場合、その含有割合の上限は、ムライト及び他の化合物の合計を１００体積％とした場合に、好ましくは３０体積％、より好ましくは２０体積％、更に好ましくは１０体積％である。 The first layer is preferably a layer made of mullite alone, but may be a layer made of mullite and another compound as long as the effects of the present invention are not impaired. Examples of other compounds include alumina. When the first layer contains another compound, the upper limit of the content ratio is preferably 30% by volume, more preferably 20% by volume, and further preferably, when the total amount of mullite and the other compound is 100% by volume. Is 10% by volume.
上記第１層の厚さは、特に限定されないが、本発明の効果が確実に得られることから、好ましくは５〜８００μｍ、より好ましくは１０〜６００μｍである。 The thickness of the first layer is not particularly limited, but is preferably 5 to 800 μm, more preferably 10 to 600 μm, because the effect of the present invention can be reliably obtained.
次に、上記第２層は、希土類ダイシリケート化合物を含む母相と、該母相の中に分散された、希土類モノシリケート化合物を含む分散相とを備える層である。
上記希土類ダイシリケート化合物は、ＲＥ２Ｓｉ２Ｏ７で表され、また、上記希土類モノシリケート化合物は、ＲＥ２ＳｉＯ５で表される。希土類ダイシリケート化合物のＲＥ及び希土類モノシリケート化合物のＲＥは、同一であってよいし、異なってもよいが、ＲＥは、いずれも、好ましくはＹｂ、Ｌｕ、Ｓｍ、Ｅｕ、Ｔｍ、Ｙ又はＧｄであり、特に好ましくはＹｂである。
Next, the second layer is a layer including a mother phase containing a rare earth disilicate compound and a dispersed phase containing a rare earth monosilicate compound dispersed in the mother phase.
The rare earth disilicate compound is represented by RE 2 Si 2 O 7 , and the rare earth monosilicate compound is represented by RE 2 SiO 5 . The RE of the rare earth disilicate compound and the RE of the rare earth monosilicate compound may be the same or different, but each RE is preferably Yb, Lu, Sm, Eu, Tm, Y or Gd. Yes, and particularly preferably Yb.
上記母相に含まれる希土類ダイシリケート化合物の種類は、１種のみであってよいし、２種以上であってもよい。本発明の積層構造において、第１層及び第２層は接合されており、これらの界面では、実質的に、第１層に含まれるムライトと、第２層の母相に含まれる希土類ダイシリケートとが接合している。ムライトの熱膨張係数及び希土類ダイシリケートの熱膨張係数の差は微少であるため、本発明の積層構造は、１３００℃〜１６００℃における断面方向の酸素遮蔽性だけでなく、構造安定性にも優れる。 The rare earth disilicate compound contained in the mother phase may be of only one kind, or may be two or more kinds. In the laminated structure of the present invention, the first layer and the second layer are joined, and at the interface between them, the mullite contained in the first layer and the rare earth disilicate contained in the matrix of the second layer are substantially contained. And are joined. Since the difference between the coefficient of thermal expansion of mullite and the coefficient of thermal expansion of rare earth disilicate is minute, the laminated structure of the present invention is excellent not only in oxygen shielding property in the cross-sectional direction at 1300°C to 1600°C, but also in structural stability. ..
上記分散相に含まれる希土類モノシリケート化合物の種類は、１種のみであってよいし、２種以上であってもよい。また、上記第２層は、本発明の効果を損なわない限りにおいて、アルミナ、ムライト等の他の物質とからなる分散相を含んでもよい。 The rare earth monosilicate compound contained in the dispersed phase may be of one type or two or more types. Further, the second layer may contain a dispersed phase composed of other substances such as alumina and mullite as long as the effect of the present invention is not impaired.
上記第２層において、希土類モノシリケート化合物を含む分散相の形状及び大きさは、特に限定されない。例えば、断面画像の画像処理により求められる数平均粒子径は、本発明の効果が確実に得られることから、好ましくは０．１〜５．０μｍ、より好ましくは０．１〜２．０μｍである。 The shape and size of the dispersed phase containing the rare earth monosilicate compound in the second layer are not particularly limited. For example, the number average particle diameter obtained by image processing of the cross-sectional image is preferably 0.1 to 5.0 μm, more preferably 0.1 to 2.0 μm, in order to reliably obtain the effect of the present invention. ..
上記第２層において、上記希土類ダイシリケート化合物及び上記希土類モノシリケート化合物の含有割合は、１３００℃〜１６００℃、特に、１４００℃以上１５００℃程度までの温度における酸素遮蔽性及び構造安定性（耐熱性）の観点から、上記希土類ダイシリケート化合物及び上記希土類モノシリケート化合物の合計量を１００体積％とした場合に、それぞれ、好ましくは９０体積％以上１００体積％未満及び０体積％を超えて１０体積％以下、より好ましくは９２．０〜９９．５体積％及び０．５〜８．０体積％、更に好ましくは９６．０〜９９．０体積％及び１．０〜４．０体積％である。尚、上記各化合物の含有割合は、第２層における希土類元素ＲＥ及び珪素元素のモル比（ＲＥ／Ｓｉ）に反映され、ＲＥ／Ｓｉは、好ましくは１．０００を超えて１．０７０以下、より好ましくは１．００５〜１．０６０、更に好ましくは１．０１０〜１．０３０である。 In the second layer, the content ratio of the rare earth disilicate compound and the rare earth monosilicate compound is 1300° C. to 1600° C., and particularly oxygen shielding property and structural stability (heat resistance at a temperature of 1400° C. to 1500° C.). ), when the total amount of the rare earth disilicate compound and the rare earth monosilicate compound is 100% by volume, preferably 90% by volume or more and less than 100% by volume and more than 0% by volume and 10% by volume. Below, it is more preferably 92.0 to 99.5% by volume and 0.5 to 8.0% by volume, and further preferably 96.0 to 99.0% by volume and 1.0 to 4.0% by volume. The content ratio of each compound is reflected in the molar ratio (RE/Si) of the rare earth element RE and the silicon element in the second layer, and RE/Si is preferably more than 1.000 and 1.070 or less, It is more preferably 1.005 to 1.060, still more preferably 1.010 to 1.030.
上記第２層の気孔率の上限は、高い温度の酸素を含む雰囲気下における断面方向の酸素遮蔽性及び構造安定性（耐熱性）の観点から、好ましくは１０体積％、より好ましくは５体積％である。 The upper limit of the porosity of the second layer is preferably 10% by volume, more preferably 5% by volume from the viewpoint of oxygen shielding property in the cross-sectional direction and structural stability (heat resistance) under an atmosphere containing oxygen at a high temperature. Is.
上記第２層の厚さは、特に限定されないが、本発明の効果が確実に得られることから、好ましくは１〜１００μｍ、より好ましくは２〜５０μｍである。 The thickness of the second layer is not particularly limited, but is preferably 1 to 100 μm, and more preferably 2 to 50 μm in order to reliably obtain the effects of the present invention.
本発明の積層構造は、無機化合物を含む基部の１面側に形成されるものである。この基部は、単層型及び複層型のいずれでもよい。
上記基部を構成する無機化合物は、好ましくは、窒化物、炭化物、ホウ化物等であり、これらは、単独で用いてよいし、２種以上の組み合わせで用いてもよい。
窒化物としては、窒化珪素、サイアロン、窒化アルミニウム、窒化チタン、窒化ジルコニウム、窒化タンタル等を用いることができる。
炭化物としては、炭化硅素、炭化チタン、炭化ジルコニウム、炭化タンタル等を用いることができる。
ホウ化物としては、ホウ化チタン、ホウ化ジルコニウム、ホウ化タンタル等を用いることができる。
これらのうち、上記基部を構成する材料は、炭化珪素、窒化珪素又はサイアロンを含むことが好ましい。
The laminated structure of the present invention is formed on one surface side of the base containing the inorganic compound. This base may be either a single layer type or a multilayer type.
The inorganic compound forming the base is preferably a nitride, a carbide, a boride or the like, and these may be used alone or in combination of two or more.
As the nitride, silicon nitride, sialon, aluminum nitride, titanium nitride, zirconium nitride, tantalum nitride, or the like can be used.
As the carbide, silicon carbide, titanium carbide, zirconium carbide, tantalum carbide or the like can be used.
As the boride, titanium boride, zirconium boride, tantalum boride, or the like can be used.
Of these, the material forming the base preferably contains silicon carbide, silicon nitride, or sialon.
上記基部が複数の材料からなる場合、炭素繊維又はセラミックス繊維が、上記の酸化物、窒化物、炭化物、ホウ化物等を含む母相の中に分散された繊維強化セラミックスを用いることができる。セラミックス繊維としては、アルミナ繊維、炭化珪素繊維、炭窒化チタン繊維、炭化ホウ素繊維等が挙げられる。母相に含まれる炭素繊維又はセラミックス繊維の含有割合は、特に限定されないが、機械的強度、破壊靱性等の観点から、繊維強化セラミックスの全体に対して、好ましくは１０〜５０体積％、より好ましくは２０〜４５体積％である。
上記繊維強化セラミックスとしては、炭化珪素を含む母相の中に炭化珪素繊維が分散されてなる炭化珪素繊維強化セラミックスが好ましい。
When the base is made of a plurality of materials, a fiber-reinforced ceramic in which carbon fibers or ceramic fibers are dispersed in a matrix phase containing the above oxide, nitride, carbide, boride or the like can be used. Examples of the ceramic fibers include alumina fibers, silicon carbide fibers, titanium carbonitride fibers, boron carbide fibers and the like. The content ratio of the carbon fiber or the ceramic fiber contained in the matrix phase is not particularly limited, but from the viewpoint of mechanical strength, fracture toughness, etc., preferably 10 to 50% by volume, more preferably, the whole fiber reinforced ceramics. Is 20 to 45% by volume.
As the fiber-reinforced ceramics, silicon carbide fiber-reinforced ceramics in which silicon carbide fibers are dispersed in a mother phase containing silicon carbide is preferable.
上記基部が複層型である場合、炭素繊維又はセラミックス繊維が、上記の酸化物、窒化物、炭化物、ホウ化物等を含む母相の中に分散された繊維強化セラミックスからなる層と、サイアロンを含む層とからなるものとし、サイアロン層が第１層側に配されていることが好ましい。このときのサイアロンは、特に限定されず、α’−サイアロン、β’−サイアロン、（α’＋β’）複合サイアロン等とすることができる。これらのうち、β’−サイアロンが好ましい。このβ’−サイアロンは、β−Ｓｉ３Ｎ４のＳｉ原子の位置にＡｌ原子が、Ｎ原子の位置にＯ原子が置換型に固溶した固溶体であり、一般式Ｓｉ６−ＺＡｌＺＯＺＮ８−Ｚ（０＜ｚ≦４．２）で表される化合物である。本発明においては、この一般式において０＜ｚ≦３．５の化合物が好ましい。 When the base is a multi-layered type, carbon fiber or ceramic fiber, a layer made of fiber reinforced ceramics dispersed in the mother phase containing the above oxide, nitride, carbide, boride, and Sialon. It is preferable that the sialon layer is disposed on the first layer side. The sialon at this time is not particularly limited, and may be α′-sialon, β′-sialon, (α′+β′) composite sialon, or the like. Of these, β'-sialon is preferred. This β'-sialon is a solid solution in which an Al atom is a substitutional solid solution at the Si atom position of β-Si 3 N 4 and an O atom is a substitutional solid solution at the N atom position, and has a general formula of Si 6-Z Al ZO. It is a compound represented by Z N 8-Z (0<z≦4.2). In the present invention, compounds of 0<z≦3.5 in this general formula are preferable.
上記基部の形状は、特に限定されず、板状、筒状、棒状、各種複雑三次元形状等の定形又はこれらを変形させた不定形とすることができる。また、第１層と面する部分における基部の形状は、平面、曲面及び凹凸面のいずれでもよい。 The shape of the base is not particularly limited, and may be a fixed shape such as a plate shape, a cylindrical shape, a rod shape, various complicated three-dimensional shapes, or an irregular shape obtained by modifying these. In addition, the shape of the base portion in the portion facing the first layer may be a flat surface, a curved surface, or an uneven surface.
本発明の積層構造は、酸素遮蔽性に優れ、例えば、１４００℃の場合、１面側から他面側への酸素透過係数（単位粒界長さ１ｍあたりの酸素透過係数）は、好ましくは２×１０−１７ｍｏｌ／（ｍ・ｓ）以下、より好ましくは１×１０−１７ｍｏｌ／（ｍ・ｓ）以下である。 The laminated structure of the present invention has excellent oxygen shielding properties, and for example, at 1400° C., the oxygen permeability coefficient from one side to the other side (oxygen permeability coefficient per unit grain boundary length of 1 m) is preferably 2 It is not more than ×10 -17 mol/(m·s), and more preferably not more than 1×10 -17 mol/(m·s).
本発明の積層構造は、第２層の表面に、更に、酸素遮蔽層を備えることができる。この酸素遮蔽層の酸素透過係数は、第２層の酸素透過係数に対して、好ましくは０．１倍以下、より好ましくは０．０５倍以下である。
上記酸素遮蔽層は、単層型及び複層型のいずれでもよいが、アルミナ、ムライト等を含むことが好ましい。
The laminated structure of the present invention may further include an oxygen shielding layer on the surface of the second layer. The oxygen permeability coefficient of the oxygen shielding layer is preferably 0.1 times or less, more preferably 0.05 times or less, that of the oxygen permeability coefficient of the second layer.
The oxygen-shielding layer may be either a single-layer type or a multi-layer type, but preferably contains alumina, mullite or the like.
本発明の積層構造が、酸素遮蔽層を備える場合、この酸素遮蔽層の厚さは、好ましくは５〜５００μｍ、より好ましくは１０〜３００μｍである。 When the laminated structure of the present invention includes an oxygen shielding layer, the thickness of the oxygen shielding layer is preferably 5 to 500 μm, more preferably 10 to 300 μm.
本発明の積層構造は、基部材料の表面に、第１層及び第２層を、順次、形成することにより製造することができる。
上記第１層は、ムライト粉末の加熱処理又はエアロゾルデポジション、電子ビーム蒸着、レーザー化学蒸着、アルミナ粉末及び酸化珪素粉末の混合粉末の加熱処理等により形成することができる。
上記第２層は、希土類酸化物粉末及び酸化珪素粉末の混合粉末の加熱処理、電子ビーム蒸着、熱蒸着、イオンビーム蒸着、スパッタリング、反応性スパッタリング、熱化学蒸着、プラズマ化学蒸着、電子サイクロトロン共鳴源プラズマ化学蒸着、プラズマ溶射等により形成することができる。例えば、希土類酸化物粉末及び酸化珪素粉末の混合粉末を加熱処理する場合、これら原料粉末の元素比を調整することにより、希土類ダイシリケート化合物を含む母相の中に希土類モノシリケート化合物を含む分散相を有する膜を形成することができる。具体的には、希土類酸化物を構成する希土類元素ＲＥと、酸化珪素を構成する珪素元素とのモル比（ＲＥ／Ｓｉ）を、好ましくは０．９９以上、より好ましくは１．００以上とする。但し、上限は、通常、１．０７である。
また、電子ビーム蒸着の場合、希土類酸化物及び酸化珪素を蒸着原料として使用し、それぞれを、独立した電子ビームにより蒸発させることで、希土類ダイシリケート化合物及び希土類モノシリケート化合物を含む膜を形成することができる。
The laminated structure of the present invention can be manufactured by sequentially forming the first layer and the second layer on the surface of the base material.
The first layer can be formed by heat treatment of mullite powder, aerosol deposition, electron beam vapor deposition, laser chemical vapor deposition, heat treatment of mixed powder of alumina powder and silicon oxide powder, or the like.
The second layer is formed by heating a mixed powder of rare earth oxide powder and silicon oxide powder, electron beam vapor deposition, thermal vapor deposition, ion beam vapor deposition, sputtering, reactive sputtering, thermochemical vapor deposition, plasma chemical vapor deposition, electron cyclotron resonance source. It can be formed by plasma chemical vapor deposition, plasma spraying or the like. For example, when heat treating a mixed powder of a rare earth oxide powder and a silicon oxide powder, by adjusting the element ratio of these raw material powders, a dispersed phase containing a rare earth monosilicate compound in a mother phase containing a rare earth disilicate compound. Can be formed. Specifically, the molar ratio (RE/Si) of the rare earth element RE forming the rare earth oxide and the silicon element forming the silicon oxide is preferably 0.99 or more, more preferably 1.00 or more. .. However, the upper limit is usually 1.07.
In the case of electron beam vapor deposition, rare earth oxide and silicon oxide are used as vapor deposition raw materials, and each is vaporized by an independent electron beam to form a film containing a rare earth disilicate compound and a rare earth monosilicate compound. You can
本発明の積層構造は、１３００℃〜１６００℃、特に、１４００℃以上１５００℃程度までの高い温度であって、酸素、水蒸気等を含む雰囲気下において、第１層側の第２層における粒界溝の形成が抑制され、接合状態が良好に保持される。従って、本発明の積層構造は、上記の温度において酸素遮蔽性だけでなく、構造安定性（耐酸化性、耐水蒸気性、耐剥離性、防食性等）が求められる用途に好適である。
例えば、航空機エンジン等に配設されるタービン部品等の高温部品は、水蒸気を含む高温ガス環境下（例えば、燃焼ガス中の水蒸気分圧が１０１．３ｋＰａ）において、高温（例えば、部品表面温度が７００℃〜１４００℃）と、低温（例えば、部品表面温度が５０℃以下）とを繰り返す熱サイクルに曝される。本発明の積層構造を利用して高温部品を形成した場合には、特に、第１層及び第２層の剥離又は積層構造の薄肉化がないだけでなく、全体の層構造が安定である。
The laminated structure of the present invention has a high temperature of 1300° C. to 1600° C., particularly 1400° C. to 1500° C., and in an atmosphere containing oxygen, water vapor, etc., the grain boundary in the second layer on the first layer side. The formation of the groove is suppressed, and the bonded state is maintained well. Therefore, the laminated structure of the present invention is suitable for applications requiring not only oxygen shielding property but also structural stability (oxidation resistance, water vapor resistance, peeling resistance, corrosion resistance, etc.) at the above temperature.
For example, a high temperature component such as a turbine component disposed in an aircraft engine or the like has a high temperature (for example, a component surface temperature of a component surface temperature under a high temperature gas environment containing water vapor (for example, a partial pressure of steam in combustion gas is 101.3 kPa)). It is exposed to a thermal cycle in which 700° C. to 1400° C.) and a low temperature (for example, the surface temperature of the component is 50° C. or less) are repeated. When a high temperature component is formed by using the laminated structure of the present invention, not only peeling of the first layer and the second layer or thinning of the laminated structure, but also the entire layer structure is stable.
本発明の効果である実用上の酸素遮蔽性は、第２層のみの単層型基板、あるいは、基部を備えない、第１層及び第２層からなる積層構造物、を用いて確認することができる。前者の場合、単層型基板の両面側の酸素分圧に差をつけた状態で、その断面方向に酸素透過試験を行うことにより確認することができる。また、後者の場合、ムライト薄肉板の上に、噴霧熱分解等により希土類ダイシリケート化合物及び希土類モノシリケート化合物を含む膜を形成し、得られた積層構造物の断面方向に第２層側からの酸素透過試験を行うことにより確認することができる。 The practical oxygen-shielding property, which is the effect of the present invention, should be confirmed by using a single-layer type substrate having only the second layer or a laminated structure composed of the first layer and the second layer without a base portion. You can In the former case, it can be confirmed by conducting an oxygen permeation test in the cross-sectional direction in a state where the oxygen partial pressures on both sides of the single-layer substrate are made different. In the latter case, a film containing a rare earth disilicate compound and a rare earth monosilicate compound is formed on the mullite thin plate by spray pyrolysis or the like, and the film is formed from the second layer side in the cross-sectional direction of the obtained laminated structure. It can be confirmed by performing an oxygen permeation test.
以下、実施例を挙げて、本発明を更に具体的に説明する。但し、本発明は、下記の実施例に制約されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
実施例１
日本イットリウム社製硝酸イッテルビウム及び日産化学社製シリカゾルを、Ｙｂ及びＳｉのモル比がＹｂ／Ｓｉ＝１．００となるように用い、イオン交換水を媒体とした混合液を得た。次いで、この混合液を噴霧熱分解法に供し、Ｙｂ２Ｓｉ２Ｏ７基粉末（ｐ１）を得た。その後、このＹｂ２Ｓｉ２Ｏ７基粉末（ｐ１）を大気雰囲気中、１４００℃で２時間仮焼した。そして、仮焼物を粉砕し、圧力２０ＭＰａでプレス成形、及び、圧力２５０ＭＰａでＣＩＰ成形を、順次、行った。次いで、得られた円板状成形体を、大気雰囲気中、１５００℃で５時間焼成した。その後、切削加工及び鏡面仕上げを行い、直径２３．５ｍｍ、厚さ２５０μｍの焼結体試験片（Ａ）を得た。この焼結体試験片（Ａ）の走査型電子顕微鏡による断面拡大画像を図２に示す。この図２において矢印で示した部分はＹｂ２ＳｉＯ５であり、画像処理によるＹｂ２ＳｉＯ５の割合は、４体積％であった。また、ＩＣＰ分析により、焼結体試験片（Ａ）におけるＹｂ及びＳｉのモル比はＹｂ／Ｓｉ＝１．０３であった。
Example 1
Ytterbium nitrate manufactured by Yttrium Japan Co., Ltd. and silica sol manufactured by Nissan Chemical Co., Ltd. were used so that the molar ratio of Yb and Si was Yb/Si=1.00 to obtain a mixed solution using ion-exchanged water as a medium. Next, this mixed solution was subjected to a spray pyrolysis method to obtain a Yb 2 Si 2 O 7 base powder (p1). Then, the Yb 2 Si 2 O 7 -based powder (p1) was calcined at 1400° C. for 2 hours in the air atmosphere. Then, the calcined product was crushed and press-molded at a pressure of 20 MPa and CIP-molded at a pressure of 250 MPa in order. Then, the obtained disk-shaped compact was fired at 1500° C. for 5 hours in the air atmosphere. Then, cutting and mirror finishing were performed to obtain a sintered body test piece (A) having a diameter of 23.5 mm and a thickness of 250 μm. FIG. 2 shows an enlarged cross-sectional image of this sintered body test piece (A) by a scanning electron microscope. The portion shown by the arrow in FIG. 2 is Yb 2 SiO 5 , and the proportion of Yb 2 SiO 5 obtained by image processing was 4% by volume. Further, by ICP analysis, the molar ratio of Yb and Si in the sintered test piece (A) was Yb/Si=1.03.
次に、この焼結体試験片（Ａ）に対し、図３に示す熱処理装置を用いて、酸素透過試験を行い、酸素遮蔽性を評価した。
具体的には、２本のアルミナ保護管の間に、Ｐｔ製シールリングを介して焼結体試験片（Ａ）を配置し、上側のアルミナ保護管に対して錘で一定荷重を加え、焼結体試験片（Ａ）とＰｔ−Ａｕ製シールリングとの間に面圧を負荷した。その後、図３の上側に「Ｘ」と表記したところ、及び、下側に「Ｙ」と表記したところから、焼結体試験片（Ａ）の両面に、ドライアイスが投入されたエタノール浴中を通過させて−７２℃に冷却した高純度Ａｒガスを、毎分１００ｍｌの流速で供給した。
次いで、焼結体試験片（Ａ）の上側チャンバー及び下側チャンバーの酸素分圧を、それぞれ、酸素センサ（ジルコニアセンサ）により計測しながら、電気炉を駆動して１４００℃まで昇温させてＰｔ−Ａｕ製シールリングによるシールを完成させた。そして、「Ｘ」から、上側チャンバーのみにＡｒ−Ｈ２系ガスを供給し続けて、焼結体試験片（Ａ）の上側で、ＰＯ２（ｌｏ）＝１０−９Ｐａ、１０−７Ｐａ及び１０−５Ｐａ、下側で、ＰＯ２（ｈｉ）＝１Ｐａの各酸素分圧差として、単位粒界長さ１ｍあたりの酸素透過係数を測定した。その結果を図４に示す。
また、図３の「Ｘ」から、上側チャンバーにＡｒ−Ｈ２系ガスを供給して焼結体試験片（Ａ）の上側の酸素分圧ＰＯ２（ｌｏ）を１０−９Ｐａで一定とし、「Ｙ」から、下側チャンバーに酸素を供給して、ＰＯ２（ｈｉ）＝１０５Ｐａとした場合、酸素透過係数は２．５×１０−１６ｍｏｌ／ｓであった。この値は、図４のＰＯ２（ｌｏ）＝１０−９Ｐａのときの酸素透過係数１．７×１０−１６ｍｏｌ／ｓよりも高かったが、酸素分圧が１０５倍であっても、透過率の上昇率が４７％に留まった。
Next, the sintered body test piece (A) was subjected to an oxygen permeation test using the heat treatment apparatus shown in FIG. 3 to evaluate the oxygen shielding property.
Specifically, a sintered body test piece (A) is placed between two alumina protection tubes via a Pt seal ring, and a constant weight is applied to the upper alumina protection tube with a weight to burn the sintered body. A surface pressure was applied between the bonded test piece (A) and the Pt-Au seal ring. Then, from the place where "X" is written on the upper side of Fig. 3 and the place where "Y" is written on the lower side, both sides of the sintered body test piece (A) are in an ethanol bath in which dry ice is put. The high-purity Ar gas that had been passed through and cooled to -72° C. was supplied at a flow rate of 100 ml/min.
Next, while measuring the oxygen partial pressures of the upper chamber and the lower chamber of the sintered compact test piece (A) with an oxygen sensor (zirconia sensor), respectively, the electric furnace was driven to raise the temperature to 1400° C. and Pt. -Completed the seal with Au seal ring. Then, from “X”, the Ar—H 2 system gas was continuously supplied only to the upper chamber, and P O2 (lo)=10 −9 Pa, 10 −7 Pa on the upper side of the sintered body test piece (A). And 10 −5 Pa, the oxygen permeability coefficient per unit grain boundary length of 1 m was measured as the oxygen partial pressure difference of P O2 (hi)=1 Pa on the lower side. The result is shown in FIG.
Further, from “X” in FIG. 3, an Ar—H 2 system gas was supplied to the upper chamber to keep the oxygen partial pressure P O2 (lo) on the upper side of the sintered body test piece (A) constant at 10 −9 Pa. , “Y”, oxygen was supplied to the lower chamber to set P O2 (hi)=10 5 Pa, the oxygen permeability coefficient was 2.5×10 −16 mol/s. This value was higher than the oxygen permeability coefficient of 1.7×10 −16 mol/s when P O2 (lo)=10 −9 Pa in FIG. 4, but even if the oxygen partial pressure is 10 5 times. The increase rate of the transmittance was 47%.
比較例１
日本イットリウム社製硝酸イッテルビウム及び日産化学社製シリカゾルを、Ｙｂ及びＳｉのモル比がＹｂ／Ｓｉ＝０．９８となるように用いた以外は、実施例１と同様の操作を行い、Ｙｂ２Ｓｉ２Ｏ７基粉末（ｐ２）を得た。そして、このＹｂ２Ｓｉ２Ｏ７基粉末（ｐ２）を用いて、実施例１と同様の操作を行い、直径２３．５ｍｍ、厚さ２５０μｍの焼結体試験片（Ｂ）を得た。ＩＣＰ分析により、焼結体試験片（Ｂ）におけるＹｂ及びＳｉのモル比はＹｂ／Ｓｉ＝１．００であった。
図５は、焼結体試験片（Ｂ）の走査型電子顕微鏡による断面拡大画像である。この図５において矢印で示した部分はＳｉ−Ｏを含む非晶質相であり、粒界に存在すること、及び、実施例１の図２で観察されたＹｂ２ＳｉＯ５が確認されず、焼結体試験片（Ｂ）はＹｂ２ＳｉＯ５を含まず、実質的にＹｂ２Ｓｉ２Ｏ７からなることが分かった。
Comparative Example 1
Yb 2 Si was performed in the same manner as in Example 1 except that ytterbium nitrate manufactured by Yttrium Japan and silica sol manufactured by Nissan Chemical Co., Ltd. were used so that the molar ratio of Yb and Si was Yb/Si=0.98. 2 O 7 base powder (p2) was obtained. Then, using this Yb 2 Si 2 O 7 based powder (p2), the same operation as in Example 1 was performed to obtain a sintered body test piece (B) having a diameter of 23.5 mm and a thickness of 250 μm. According to ICP analysis, the molar ratio of Yb and Si in the sintered compact test piece (B) was Yb/Si=1.00.
FIG. 5 is an enlarged cross-sectional image of a sintered body test piece (B) by a scanning electron microscope. The portion indicated by the arrow in FIG. 5 is an amorphous phase containing Si—O, and it is not confirmed that it exists in the grain boundary and Yb 2 SiO 5 observed in FIG. It was found that the sintered test piece (B) did not contain Yb 2 SiO 5 and consisted essentially of Yb 2 Si 2 O 7 .
次に、実施例１と同様にして、焼結体試験片（Ｂ）の上側で、ＰＯ２（ｌｏ）＝５×１０−７Ｐａ、２×１０−５Ｐａ及び１０−３Ｐａ、下側で、ＰＯ２（ｈｉ）＝１Ｐａの各酸素分圧差として、酸素透過係数を測定した。その結果を図４に示す。 Next, in the same manner as in Example 1, P O2 (lo)=5×10 −7 Pa, 2×10 −5 Pa and 10 −3 Pa on the upper side of the sintered body test piece (B), lower side. Then, the oxygen permeability coefficient was measured as each oxygen partial pressure difference of P O2 (hi)=1 Pa. The result is shown in FIG.
図４より、実施例１の焼結体試験片（Ａ）の酸素透過係数は、比較例１の焼結体試験片（Ｂ）の酸素透過係数より小さく、酸素遮蔽性に優れることが分かる。 From FIG. 4, it is understood that the oxygen permeability coefficient of the sintered body test piece (A) of Example 1 is smaller than that of the sintered body test piece (B) of Comparative Example 1 and is excellent in oxygen shielding property.
尚、図３の「Ｘ」から、上側チャンバーにＡｒ−Ｈ２系ガスを供給して焼結体試験片（Ｂ）の上側の酸素分圧ＰＯ２（ｌｏ）を１０−９Ｐａで一定とし、「Ｙ」から、下側チャンバーに酸素を供給して、ＰＯ２（ｈｉ）＝１０５Ｐａとした場合、酸素透過が確認されなかった。これは、粒界に偏析するＳｉ−Ｏを含む非晶質相に沿って焼結体試験片（Ｂ）の上側方向に透過してきた酸素が、焼結体試験片（Ｂ）の上側に存在するＨ２と反応して水蒸気を生成し、それが、焼結体試験片（Ｂ）の表面粒界に存在するＳｉ−Ｏを含む非晶質相と反応して、ガス種のＳｉ（ＯＨ）４を生成したためと考えられる。
この反応が継続的に進行すると、焼結体試験片（Ｂ）を構成するＹｂ２Ｓｉ２Ｏ７の粒界部分からＳｉ−Ｏを含む非晶質相が消失し、構造を維持することができず崩壊に至る。
From "X" in FIG. 3, an Ar-H2 system gas was supplied to the upper chamber to keep the oxygen partial pressure P O2 (lo) on the upper side of the sintered body test piece (B) constant at 10 -9 Pa, When oxygen was supplied to the lower chamber from “Y” to set P O2 (hi)=10 5 Pa, oxygen permeation was not confirmed. This is because oxygen that has permeated toward the upper side of the sintered body test piece (B) along the amorphous phase containing Si—O segregated at the grain boundaries exists on the upper side of the sintered body test piece (B). Reacts with H2 to generate water vapor, which reacts with the amorphous phase containing Si—O existing at the surface grain boundaries of the sintered body test piece (B) to produce Si(OH) gas species. It is considered that 4 is generated.
When this reaction proceeds continuously, the amorphous phase containing Si—O disappears from the grain boundary portion of Yb 2 Si 2 O 7 forming the sintered body test piece (B), and the structure can be maintained. It cannot be done and it collapses.
本発明の積層構造を備える積層材料は、１３００℃〜１６００℃の高い温度であって、１面側と他面側との間で酸素ポテンシャル差のある、酸素、水蒸気等を含む雰囲気下に曝されても、酸素遮蔽性に優れるため、このような条件下、耐熱性（耐酸化性、耐水蒸気性、耐剥離性、防食性等）、形状安定性等が求められる用途に好適である。特に、酸素、水蒸気等を含む高温ガス環境下で使用される航空機エンジンや発電用タービンにおける高圧タービン部の動翼部品、静翼部品又はシュラウド部品、更には、ロケットエンジンのスラスターや燃焼ガスチューブ等の高温部品の形成に好適である。 The laminated material having the laminated structure of the present invention is exposed to an atmosphere containing oxygen, water vapor, etc., which has a high temperature of 1300° C. to 1600° C. and has an oxygen potential difference between the one surface side and the other surface side. However, since it has an excellent oxygen shielding property, it is suitable for applications requiring heat resistance (oxidation resistance, water vapor resistance, peeling resistance, corrosion resistance, etc.) and shape stability under such conditions. In particular, a moving blade part, a stationary blade part or a shroud part of a high pressure turbine part of an aircraft engine or a power generation turbine used in a high temperature gas environment containing oxygen, water vapor, etc., further, a thruster of a rocket engine, a combustion gas tube, etc. It is suitable for forming high temperature parts.
１：積層材料、１０：積層構造、１１：第１層、１３：第２層、２０：基部 1: laminated material, 10: laminated structure, 11: first layer, 13: second layer, 20: base
Claims (6)
前記第２層は、前記希土類ダイシリケート化合物を含む母相と、該母相の中に分散された、前記希土類モノシリケート化合物を含む分散相とからなることを特徴とする積層構造。 A rare earth disilicate compound represented by RE 2 Si 2 O 7 , which is a laminated structure formed on one surface side of a base containing an inorganic compound and has a first layer containing mullite and RE is a rare earth element. And a second layer containing a rare earth monosilicate compound represented by RE 2 SiO 5 are joined,
The second layer is composed of a mother phase containing the rare earth disilicate compound and a dispersed phase containing the rare earth monosilicate compound dispersed in the mother phase.
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