JP6358656B2 - Laminated material and method for producing the same - Google Patents
Laminated material and method for producing the same Download PDFInfo
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- JP6358656B2 JP6358656B2 JP2014169617A JP2014169617A JP6358656B2 JP 6358656 B2 JP6358656 B2 JP 6358656B2 JP 2014169617 A JP2014169617 A JP 2014169617A JP 2014169617 A JP2014169617 A JP 2014169617A JP 6358656 B2 JP6358656 B2 JP 6358656B2
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- 239000002648 laminated material Substances 0.000 title claims description 106
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000000463 material Substances 0.000 claims description 83
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 72
- 239000006104 solid solution Substances 0.000 claims description 69
- 239000010419 fine particle Substances 0.000 claims description 60
- 239000000443 aerosol Substances 0.000 claims description 56
- 239000000758 substrate Substances 0.000 claims description 39
- 238000002347 injection Methods 0.000 claims description 27
- 239000007924 injection Substances 0.000 claims description 27
- 238000005507 spraying Methods 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 10
- 238000003475 lamination Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 description 104
- 239000000843 powder Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 238000012545 processing Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229910052727 yttrium Inorganic materials 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- 238000005118 spray pyrolysis Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- -1 rare earth titanate Chemical class 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000012720 thermal barrier coating Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 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
- LRTTZMZPZHBOPO-UHFFFAOYSA-N [B].[B].[Hf] Chemical compound [B].[B].[Hf] LRTTZMZPZHBOPO-UHFFFAOYSA-N 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DLHTWZBWWPZUSD-UHFFFAOYSA-N aluminum nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3] DLHTWZBWWPZUSD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 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 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910001293 incoloy Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 238000007737 ion beam deposition Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000012546 transfer 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
- 229910052725 zinc 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)
- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、耐熱耐久性に優れる積層材料及びその製造方法に関する。 The present invention relates to a laminated material having excellent heat resistance and a method for producing the same.
従来、ガスタービンエンジン、ジェットエンジン等において、その燃焼ガスが高温であるために、動翼、静翼、燃焼器等の高温部品の表面には、遮熱コーティング（Ｔｈｅｒｍａｌ Ｂａｒｒｉｅｒ Ｃｏａｔｉｎｇ：ＴＢＣ）といわれる皮膜が施されている。そして、遮熱コーティングの表面において、耐食性、耐酸化性、耐熱性等を備えるものとなっている。この皮膜の形成には、イットリア安定化ジルコニアを含む材料が広く用いられているものの、近年、他の材料の探索が行われている。 Conventionally, in a gas turbine engine, a jet engine, etc., because the combustion gas is at a high temperature, the surface of a high-temperature part such as a moving blade, a stationary blade, a combustor is referred to as a thermal barrier coating (TBC). A film is applied. The surface of the thermal barrier coating is provided with corrosion resistance, oxidation resistance, heat resistance, and the like. For the formation of this film, a material containing yttria-stabilized zirconia is widely used, but in recent years, other materials have been searched for.
イットリウム元素を含むチタン酸イットリウム（Ｙ２Ｔｉ２Ｏ７）は、例えば、熱反射材等として、アルミニウム又はアルミニウム合金の溶湯を扱う場合の容器や、容器の内表面に形成された皮膜の構成材料として用いられている。具体的には、特許文献１において、チタン酸希土類粒子及びＭｇＡｌ２Ｏ４粒子を主成分とする粒子分散型焼結体からなる熱反射材が開示されている。 Yttrium titanate (Y 2 Ti 2 O 7 ) containing an yttrium element is, for example, a container for handling a molten aluminum or aluminum alloy as a heat reflecting material, or a constituent material of a film formed on the inner surface of the container It is used as. Specifically, Patent Document 1 discloses a heat reflecting material composed of a particle-dispersed sintered body mainly composed of rare earth titanate particles and MgAl 2 O 4 particles.
また、特許文献２には、チタン酸イットリウム層とアルミナ層とが、各々、２層以上交互に積層された熱反射材が開示されており、１４００℃で１時間の加熱処理を行った場合に、安定な積層状態が保持されたことが記載されている。 Patent Document 2 discloses a heat reflecting material in which two or more layers of yttrium titanate layers and alumina layers are alternately laminated. When heat treatment is performed at 1400 ° C. for 1 hour, It is described that a stable laminated state was maintained.
本発明は、アルミナ系材料及びチタン酸イットリウムを用いた積層材料であって、耐熱耐久性に優れ、長期に渡って、層構造が安定に維持される積層材料及びその製造方法を提供することを目的とする。 The present invention provides a laminated material using an alumina-based material and yttrium titanate, which is excellent in heat resistance and durability, and whose layer structure is stably maintained over a long period of time, and a method for producing the same. Objective.
本発明者らは、アルミナ系材料からなる層、及び、Ｙ２Ｔｉ２Ｏ７を含む層が接合された積層材料を、ガスタービンエンジン、ジェットエンジン等の燃焼ガスの温度、例えば、１３００℃で、５０時間以上の条件に曝した場合に、層構造が安定に維持される構成を見い出し、本発明を完成するに至った。
本発明は、以下に示される。
１．アルミナ系材料からなる層（Ａ）と、該層（Ａ）に接合された、Ａｌ原子が固溶しているＹ２Ｔｉ２Ｏ７からなる層（Ｂ）とを備える積層材料であって、
上記層（Ｂ）を構成する上記Ａｌ固溶Ｙ２Ｔｉ２Ｏ７におけるＡｌ原子の含有割合は、Ａｌ原子、Ｙ原子及びＴｉ原子の合計量を１００原子％とした場合に、０．５〜１．８原子％であることを特徴とする積層材料。
２．上記Ａｌ固溶Ｙ２Ｔｉ２Ｏ７からなる基部の表面に、上記層（Ａ）が形成されている上記１に記載の積層材料。
３．上記アルミナ系材料からなる基部の表面に、上記層（Ｂ）が形成されている上記１に記載の積層材料。
４．上記２に記載の積層材料の製造方法であって、
アルミナ系材料からなる微粒子を含むエアロゾルを、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７からなる基材の表面に噴射して、上記微粒子を上記基材の表面に堆積させる噴射工程を備え、
上記基材を構成する上記Ａｌ固溶Ｙ２Ｔｉ２Ｏ７におけるＡｌ原子の含有割合は、Ａｌ原子、Ｙ原子及びＴｉ原子の合計量を１００原子％とした場合に、０．５〜１．８原子％であることを特徴とする積層材料の製造方法。
５．上記３に記載の積層材料の製造方法であって、
Ａｌ固溶Ｙ２Ｔｉ２Ｏ７からなる微粒子を含むエアロゾルを、アルミナ系材料からなる基材の表面に噴射して、上記微粒子を上記基材の表面に堆積させる噴射工程を備え、
上記微粒子を構成する上記Ａｌ固溶Ｙ２Ｔｉ２Ｏ７におけるＡｌ原子の含有割合は、Ａｌ原子、Ｙ原子及びＴｉ原子の合計量を１００原子％とした場合に、０．５〜１．８原子％であることを特徴とする積層材料の製造方法。
The inventors of the present invention apply a laminated material in which a layer made of an alumina-based material and a layer containing Y 2 Ti 2 O 7 are bonded at a temperature of a combustion gas such as a gas turbine engine or a jet engine, for example, 1300 ° C. The inventors have found a structure in which the layer structure is stably maintained when exposed to conditions of 50 hours or longer, and have completed the present invention.
The present invention is shown below.
1. A layered material comprising a layer (A) made of an alumina-based material and a layer (B) made of Y 2 Ti 2 O 7 bonded to the layer (A) and in which Al atoms are dissolved,
The content ratio of Al atoms in the Al solid solution Y 2 Ti 2 O 7 constituting the layer (B) is 0.5 to 0.5 when the total amount of Al atoms, Y atoms and Ti atoms is 100 atomic%. A laminated material characterized by being 1.8 atomic%.
2. 2. The laminated material according to 1 above, wherein the layer (A) is formed on the surface of the base portion made of the Al solid solution Y 2 Ti 2 O 7 .
3. 2. The laminated material according to 1 above, wherein the layer (B) is formed on the surface of the base portion made of the alumina-based material.
4). A method for producing the laminated material according to 2 above,
An injection step of spraying an aerosol containing fine particles made of an alumina-based material onto the surface of a base material made of Al solid solution Y 2 Ti 2 O 7 and depositing the fine particles on the surface of the base material;
The content ratio of Al atoms in the Al solid solution Y 2 Ti 2 O 7 constituting the substrate is 0.5 to 1. When the total amount of Al atoms, Y atoms and Ti atoms is 100 atomic%. A method for producing a laminated material, characterized in that the content is 8 atomic%.
5). A method for producing the laminated material according to 3 above,
An injection step of spraying an aerosol containing fine particles of Al solid solution Y 2 Ti 2 O 7 on the surface of a substrate made of an alumina-based material and depositing the fine particles on the surface of the substrate;
The content ratio of Al atoms in the Al solid solution Y 2 Ti 2 O 7 constituting the fine particles is 0.5 to 1.8 when the total amount of Al atoms, Y atoms and Ti atoms is 100 atomic%. A method for producing a laminated material, characterized in that it is atomic%.
本発明の積層材料は、耐熱耐久性に優れ、１０００℃以上の高い温度（上限は、通常、１４００℃）で使用する各種形状の物品の構成材料として好適である。上記の高い温度において長時間に渡る使用中に、層（Ａ）を構成する原子が層（Ｂ）に移動したり、層（Ｂ）を構成する原子が層（Ａ）に移動したりすることが抑制されるので、層（Ａ）及び層（Ｂ）を１層ずつ備えるものに限られず、交互に複数層を備えるものであっても、安定な層構造を維持することができる。従って、本発明の積層材料は、高い温度における使用が長時間に渡る場合、又は、高い温度における使用を複数回重ねる場合に、不具合の発生が抑制され、各種性能において高い信頼性を得ることができる。
本発明の積層材料の製造方法によれば、耐熱耐久性に優れ、長期に渡って、層構造が安定に維持される積層材料を、効率よく且つ経済的に製造することができる。
The laminated material of the present invention has excellent heat resistance and is suitable as a constituent material for articles of various shapes used at a high temperature of 1000 ° C. or higher (the upper limit is usually 1400 ° C.). During use for a long time at the above high temperature, atoms constituting the layer (A) move to the layer (B), or atoms constituting the layer (B) move to the layer (A). Therefore, the present invention is not limited to the layer (A) and the layer (B) provided one by one, and a stable layer structure can be maintained even if a plurality of layers are alternately provided. Therefore, the laminated material of the present invention can suppress the occurrence of problems when used at a high temperature for a long time, or when used at a high temperature a plurality of times, and can obtain high reliability in various performances. it can.
According to the method for producing a laminated material of the present invention, it is possible to efficiently and economically produce a laminated material that is excellent in heat resistance and has a stable layer structure over a long period of time.
本発明に係るアルミナ系材料としては、アルミナ、及び、他の元素がドープされたアルミナ、のいずれか一方又は両方を用いることができる。後者の場合、他の元素としては、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ等の希土類元素のほか、Ｈｆ、Ｚｒ等が挙げられる。本発明の積層材料に含まれるアルミナ系材料は、結晶質及び非晶質のいずれでもよいが、腐食防止の観点から結晶質であることが好ましい。
一方、本発明に係る、Ａｌ原子が固溶しているＹ２Ｔｉ２Ｏ７（以下、「特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７」という）は、層（Ａ）及び層（Ｂ）を備える積層材料における耐熱耐久性が得られることから、Ａｌ原子の含有割合（固溶量）が、Ａｌ原子、Ｙ原子及びＴｉ原子の合計量を１００原子％とした場合に、０．５〜１．８原子％である物質である。Ａｌ原子の含有割合は、好ましくは０．８〜１．２原子％である。
尚、Ａｌ原子の含有割合が、１．８原子％を超えるＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる層（Ｂ′）と層（Ａ）とを備える積層材料の場合、例えば、１３００℃で５０時間以上の熱処理を行うと、上記アルミナ系材料に由来する粒子が層（Ｂ′）の内部に析出するだけでなく、層（Ａ）との界面にボイドが形成されるので、層（Ａ）及び層（Ｂ′）が剥離しやすくなったり、それに伴って、積層材料としての機械的強度、ガスバリア性等が低下したりすることとなる。
一方、Ａｌ原子の含有割合が、０．５原子％より少ないＡｌ固溶Ｙ２Ｔｉ２Ｏ７又はＹ２Ｔｉ２Ｏ７からなる層（Ｂ″）と層（Ａ）とを備える積層材料は、例えば、１３００℃で５０時間以上の熱処理を行うと、層（Ｂ″）に由来するＹ原子又はＴｉ原子は、層（Ａ）の中に固溶することはなく、界面に偏析するのみであるが、層（Ａ）に由来するＡｌ原子が層（Ｂ″）の中に固溶され、層（Ａ）の厚さによっては、層（Ｂ″）を構成するＡｌ固溶Ｙ２Ｔｉ２Ｏ７の粒界部分の膜部が消失することがあるので、層（Ａ）及び層（Ｂ″）の層構造が不安定となり、やはり、積層材料としての機械的強度、ガスバリア性等が低下したりすることとなる。
本発明では、層（Ａ）及び層（Ｂ）が隣接する構造の積層材料において、上記の高い温度で長時間に渡る使用中に、層（Ａ）を構成する原子が層（Ｂ）に移動したり、層（Ｂ）を構成する原子が層（Ａ）に移動したりすることが抑制されるので、層構造が安定に維持され、機械的強度、ガスバリア性等の性能も長期に渡って維持することができる。
As the alumina material according to the present invention, any one or both of alumina and alumina doped with other elements can be used. In the latter case, other elements such as Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, Hf, Zr, etc. are mentioned. The alumina material contained in the laminated material of the present invention may be either crystalline or amorphous, but is preferably crystalline from the viewpoint of preventing corrosion.
On the other hand, Y 2 Ti 2 O 7 (hereinafter referred to as “specific Al solid solution Y 2 Ti 2 O 7 ”) in which Al atoms are solid-solved according to the present invention is composed of layer (A) and layer (B). When the heat resistance durability in the laminated material comprising is obtained, the content ratio (solid solution amount) of Al atoms is 0.5 to 0.5% when the total amount of Al atoms, Y atoms and Ti atoms is 100 atomic%. It is a substance that is 1.8 atomic%. The content ratio of Al atoms is preferably 0.8 to 1.2 atomic%.
In the case of a laminated material including a layer (B ′) and a layer (A) made of Al solid solution Y 2 Ti 2 O 7 with an Al atom content ratio exceeding 1.8 atomic%, for example, at 1300 ° C. When heat treatment for 50 hours or more is performed, particles derived from the alumina-based material are not only precipitated inside the layer (B ′) but also voids are formed at the interface with the layer (A). ) And the layer (B ′) are easily peeled off, and the mechanical strength, gas barrier properties and the like as the laminated material are lowered accordingly.
On the other hand, a laminated material comprising a layer (B ″) and a layer (A) made of Al solid solution Y 2 Ti 2 O 7 or Y 2 Ti 2 O 7 having a content ratio of Al atoms of less than 0.5 atomic% is For example, when heat treatment is performed at 1300 ° C. for 50 hours or longer, Y atoms or Ti atoms derived from the layer (B ″) do not dissolve in the layer (A) but only segregate at the interface. However, Al atoms derived from the layer (A) are dissolved in the layer (B ″), and depending on the thickness of the layer (A), the Al solid solution Y 2 Ti 2 constituting the layer (B ″). Since the film part of the grain boundary portion of O 7 may disappear, the layer structure of the layer (A) and the layer (B ″) becomes unstable, and the mechanical strength and gas barrier properties as a laminated material are also lowered. Will do.
In the present invention, in the laminated material having a structure in which the layer (A) and the layer (B) are adjacent to each other, the atoms constituting the layer (A) migrate to the layer (B) during use for a long time at the above high temperature. Or the atoms constituting the layer (B) are suppressed from moving to the layer (A), so that the layer structure is stably maintained, and the performance such as mechanical strength and gas barrier properties is also maintained over a long period of time. Can be maintained.
１．積層材料
本発明の積層材料は、アルミナ系材料からなる層（Ａ）と、該層（Ａ）に接合された、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる層（Ｂ）とを備える材料であり、必要に応じて、層（Ａ）及び層（Ｂ）の一体化物における層（Ａ）又は層（Ｂ）の開放面（表面）に他の層が接合されていてもよい積層材料である。このように、本発明の積層材料は、多態様の断面構造を有することができ、層（Ｂ）を基部とした態様を示す図１、層（Ａ）を基部とした態様を示す図２、及び、更に他の態様を示す図３に例示されるが、これらに限定されない。即ち、本発明の積層材料は、層（Ａ）及び層（Ｂ）のいずれか一方が基部（基体）であってよいし、他の材料からなる基体の表面に、層（Ａ）及び層（Ｂ）の順に、又は、層（Ｂ）及び層（Ａ）の順に、備えるものであってもよい。更に、図示していないが、本発明の積層材料は、層（Ａ）及び層（Ｂ）を、交互に、いずれも複数備えるものであってもよい。
本発明において、層（Ａ）及び層（Ｂ）の厚さは、特に限定されないが、これらの厚さは、各層を複数備える場合も含め、互いに、独立して、好ましくは０．１〜３．０μｍ、より好ましくは０．２〜１．０μｍである。
1. Laminate Material The laminate material of the present invention comprises a layer (A) made of an alumina-based material and a layer (B) made of a specific Al solid solution Y 2 Ti 2 O 7 bonded to the layer (A). Laminate material that is a material, and other layers may be bonded to the open surface (surface) of layer (A) or layer (B) in the integrated product of layer (A) and layer (B) as necessary It is. Thus, the laminated material of the present invention can have a multi-dimensional cross-sectional structure, FIG. 1 showing an embodiment based on the layer (B), FIG. 2 showing an embodiment based on the layer (A), And although illustrated in FIG. 3 which shows another aspect, it is not limited to these. That is, in the laminated material of the present invention, one of the layer (A) and the layer (B) may be a base (base), and the layer (A) and the layer ( You may provide in the order of B) or the order of a layer (B) and a layer (A). Furthermore, although not shown, the laminated material of the present invention may include a plurality of layers (A) and layers (B) alternately.
In the present invention, the thicknesses of the layer (A) and the layer (B) are not particularly limited, but these thicknesses are preferably 0.1 to 3 independently of each other, including the case where a plurality of layers are provided. 0.0 μm, more preferably 0.2 to 1.0 μm.
図１は、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる基部１４と、この基部１４の表面に形成されたアルミナ系材料からなる膜１２とを備える積層材料１０Ａを示す。この場合、本発明の効果を得るための膜１２の好ましい厚さは、０．１〜３．０μｍであり、より好ましくは０．２〜１．０μｍである。
図１の態様の変形例としては、アルミナ系材料からなる膜１２の表面に、更に、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる膜１４が形成された積層材料；アルミナ系材料からなる膜１２の表面に、更に、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる膜１４及びアルミナ系材料からなる膜１２が、順次、形成された積層材料等とすることができる。
FIG. 1 shows a laminated material 10 </ b > A including a base portion 14 made of a specific Al solid solution Y 2 Ti 2 O 7 and a film 12 made of an alumina-based material formed on the surface of the base portion 14. In this case, the preferable thickness of the film 12 for obtaining the effect of the present invention is 0.1 to 3.0 μm, more preferably 0.2 to 1.0 μm.
As a modification of the embodiment of FIG. 1, a laminated material in which a film 14 made of a specific Al solid solution Y 2 Ti 2 O 7 is further formed on the surface of a film 12 made of an alumina material; made of an alumina material A film 14 made of a specific Al solid solution Y 2 Ti 2 O 7 and a film 12 made of an alumina-based material may be sequentially formed on the surface of the film 12.
図２は、アルミナ系材料からなる基部１２と、この基部１２の表面に形成された特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７膜１４とを備える積層材料１０Ｂを示す。この場合、本発明の効果を得るための膜１４の好ましい厚さは、０．１〜３．０μｍであり、より好ましくは０．２〜１．０μｍである。
図２の態様の変形例としては、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる膜１４の表面に、更に、アルミナ系材料からなる膜１２が形成された積層材料；特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる膜１４の表面に、更に、アルミナ系材料からなる膜１２及び特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる膜１４が、順次、形成された積層材料等とすることができる。
FIG. 2 shows a laminated material 10B including a base portion 12 made of an alumina-based material and a specific Al solid solution Y 2 Ti 2 O 7 film 14 formed on the surface of the base portion 12. In this case, the preferable thickness of the film 14 for obtaining the effect of the present invention is 0.1 to 3.0 μm, and more preferably 0.2 to 1.0 μm.
2 is a laminated material in which a film 12 made of an alumina material is further formed on the surface of a film 14 made of a specific Al solid solution Y 2 Ti 2 O 7 ; a specific Al solid solution On the surface of the film 14 made of Y 2 Ti 2 O 7 , a film 12 made of an alumina-based material and a film 14 made of a specific Al solid solution Y 2 Ti 2 O 7 are sequentially formed. can do.
図３は、他の無機材料からなる基部１６と、この基部１６の表面に、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７層１４及びアルミナ系材料からなる膜１２を、順次、備える積層材料１０Ｃを示す。尚、図示していないが、他の無機材料からなる基部１６と、この基部１６の表面に、アルミナ系材料からなる層１２及び特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる膜１４を、順次、備える積層材料とすることもできる。
基部１６を構成する他の無機材料は、金属及び無機化合物（酸化物、窒化物、炭化物、ホウ化物、硫化物、水酸化物、ハロゲン化物、炭酸塩、硫酸塩、リン酸塩、硝酸塩、アンモニウム塩等）のいずれでもよく、これらの中の２種又は３種以上を組み合わせてなるものであってもよい。本発明の積層材料は、層（Ａ）及び層（Ｂ）を連続する構造を有することで、耐熱耐久性に優れるので、従来では適用困難であった耐熱性の低い金属を含む基部１６の構成材料として用いることもできる。
FIG. 3 shows a laminated material 10C comprising a base 16 made of another inorganic material, and a specific Al solid solution Y 2 Ti 2 O 7 layer 14 and a film 12 made of an alumina-based material on the surface of the base 16 in order. Indicates. Although not shown, a base portion 16 made of another inorganic material, and a layer 12 made of an alumina-based material and a film 14 made of a specific Al solid solution Y 2 Ti 2 O 7 are formed on the surface of the base portion 16. It can also be set as the laminated material provided sequentially.
Other inorganic materials constituting the base 16 are metals and inorganic compounds (oxides, nitrides, carbides, borides, sulfides, hydroxides, halides, carbonates, sulfates, phosphates, nitrates, ammoniums). Any of these may be used, or two or more of these may be combined. Since the laminated material of the present invention has a structure in which the layer (A) and the layer (B) are continuous and is excellent in heat resistance, the structure of the base 16 including a metal having low heat resistance, which has been difficult to apply in the past. It can also be used as a material.
上記酸化物としては、シリカ、チタニア、ジルコニア、ハフニア、マグネシア、カルシア、希土類酸化物（Ｌｎ２Ｏ３、Ｌｎ：Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ）、並びに、これらの複合酸化物（ムライト、コーディエライト等）等が挙げられる。
上記窒化物としては、窒化ケイ素、窒化チタン、窒化ジルコニウム、窒化ハフニウム等が挙げられる。
上記炭化物としては、炭化ケイ素、炭化チタン、炭化ジルコニウム、炭化ハフニウム等が挙げられる。
上記ホウ化物としては、ホウ化ケイ素、ホウ化チタン、ホウ化ジルコニウム、ホウ化ハフニウム等が挙げられる。
上記金属としては、モリブデン、タングステン、チタン、アルミニウム合金（例えば、Ａｌと、Ｆｅ、Ｓｉ、Ｃｕ、Ｎｉ、Ｃｒ、Ｔｉ、Ｚｒ、Ｚｎ、Ｍｎ、Ｍｇ及びＧａから選ばれた少なくとも１種とからなるもの）、Ｆｅ基合金（フェライト系、マルテンサイト系、オーステナイト系等）、Ｎｉ基合金（登録商標インコネル、インコロイ等）、Ｃｏ基合金（ＣＦＹ等）等が挙げられる。
Examples of the oxide include silica, titania, zirconia, hafnia, magnesia, calcia, rare earth oxide (Ln 2 O 3 , Ln: Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb , Dy, Ho, Er, Tm, Yb, Lu), and complex oxides thereof (mullite, cordierite, etc.) and the like.
Examples of the nitride include silicon nitride, titanium nitride, zirconium nitride, and hafnium nitride.
Examples of the carbide include silicon carbide, titanium carbide, zirconium carbide, and hafnium carbide.
Examples of the boride include silicon boride, titanium boride, zirconium boride, and hafnium boride.
Examples of the metal include molybdenum, tungsten, titanium, and an aluminum alloy (for example, Al and at least one selected from Fe, Si, Cu, Ni, Cr, Ti, Zr, Zn, Mn, Mg, and Ga). ), Fe-based alloys (ferritic, martensitic, austenitic, etc.), Ni-based alloys (registered trademark Inconel, Incoloy, etc.), Co-based alloys (CFY, etc.) and the like.
２．積層材料の製造方法
本発明の積層材料は、その層構成に基づいて、各種の製造方法の中から選択して、製造することができる。
図１及び図２のように、アルミナ系材料又は特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる基部の表面に、基部と異なる材料の膜（層）を形成する場合には、アルミナ系材料若しくは特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７又はこれらの前駆体を用いて基部用の物体を製造した後、異なる材料又はその前駆体を用いて、熱蒸着、電子ビーム蒸着、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等の物理蒸着法；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等の化学蒸着法；プラズマ溶射等の溶射法；エアロゾルデポジション法；ゾルゲル法；ディップコート法；スプレーコート法等を利用する手段を備える方法により、積層材料を製造することができる。
また、アルミナ系材料からなる焼成体、及び、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる焼成体を製造した後、これらを接合する方法により、積層材料を製造することができる。
尚、図３のように、他の材料からなる基体の表面に、層（Ｂ）及び層（Ａ）を、順次、形成する場合等にも、上記方法を適用することができる。
2. Method for Producing Laminate Material The laminate material of the present invention can be produced by selecting from various production methods based on the layer configuration.
As shown in FIGS. 1 and 2, when a film (layer) of a material different from the base is formed on the surface of the base made of an alumina-based material or a specific Al solid solution Y 2 Ti 2 O 7 , the alumina-based material or after the production of the object for the base using a specific Al solid solution Y 2 Ti 2 O 7 or their precursors, using different materials or a precursor thereof, thermal evaporation, electron beam evaporation, ion beam deposition, Physical vapor deposition methods such as sputtering and reactive sputtering; chemical vapor deposition methods such as thermal chemical vapor deposition, plasma chemical vapor deposition, and electron cyclotron resonance source plasma chemical vapor deposition; thermal spraying methods such as plasma spraying; aerosol deposition method; sol-gel method; dip coating method A laminated material can be produced by a method comprising means utilizing a spray coating method or the like.
Further, the sintered body made of alumina-based material, and may be after the production of sintered bodies consisting of a specific Al solid solution Y 2 Ti 2 O 7, the method of joining them to produce a laminate material.
In addition, as shown in FIG. 3, the above method can also be applied to the case where the layer (B) and the layer (A) are sequentially formed on the surface of a substrate made of another material.
本発明において、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７は、アルミニウム化合物と、イットリウム化合物と、チタン化合物とを用いて、各金属原子量が所定の割合となるように含む前駆体水溶液とした後、この前駆体水溶液を加熱して、媒体を除くとともに複合化することにより調製されたものとすることができる。好ましい調製方法は、前駆体水溶液を、霧化装置等により微小液滴とし、その後、この微小液滴を、キャリヤーガスの利用等により、例えば、２００℃〜１０００℃に加熱された雰囲気に供給することにより、原料の乾燥及び熱分解を進めて複合酸化物化する方法である。 In the present invention, the specific Al solid solution Y 2 Ti 2 O 7 is a precursor aqueous solution containing an aluminum compound, an yttrium compound, and a titanium compound so that each metal atom has a predetermined ratio. The precursor aqueous solution can be heated to remove the medium and make a composite. In a preferred preparation method, the precursor aqueous solution is made into fine droplets by an atomizer or the like, and then the fine droplets are supplied to an atmosphere heated to, for example, 200 ° C. to 1000 ° C. by using a carrier gas or the like. In this way, the raw material is dried and thermally decomposed to form a composite oxide.
本発明における積層材料の製造方法は、図１で示した積層材料１０Ａ、及び、図２で示した積層材料１０Ｂを、エアロゾルデポジション法を利用して微粒子を噴射する噴射工程を備える製造方法である。
図１の積層材料１０Ａの製造方法は、アルミナ系材料からなる微粒子を含むエアロゾルを、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる基材の表面に噴射して、上記微粒子を上記基材の表面に堆積させる噴射工程を備える。
また、図２の積層材料１０Ｂの製造方法は、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる微粒子を含むエアロゾルを、アルミナ系材料からなる基材の表面に噴射して、上記微粒子を上記基材の表面に堆積させる噴射工程を備える。
The manufacturing method of the laminated material in the present invention is a manufacturing method including an injection step of injecting fine particles of the laminated material 10A shown in FIG. 1 and the laminated material 10B shown in FIG. 2 using an aerosol deposition method. is there.
In the manufacturing method of the laminated material 10A in FIG. 1, an aerosol containing fine particles made of an alumina-based material is sprayed onto the surface of a base material made of a specific Al solid solution Y 2 Ti 2 O 7 , and the fine particles are injected into the base material. An injection step of depositing on the surface of the substrate.
Further, in the method for producing the laminated material 10B of FIG. 2, the aerosol containing fine particles made of a specific Al solid solution Y 2 Ti 2 O 7 is sprayed onto the surface of a base material made of an alumina-based material, and the fine particles are made into the above A spraying step of depositing on the surface of the substrate;
上記噴射工程において用いるエアロゾルは、アルミナ系材料からなる微粒子又は特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる微粒子を、窒素ガス、アルゴンガス、ヘリウムガス、圧縮空気、酸素ガス等のガス中に分散させて発生させたものである。これらの微粒子の形状及び大きさは、特に限定されない。レーザー回折・散乱法等により測定される平均粒子径は、好ましくは３０００ｎｍ以下、より好ましくは５０〜２５００ｎｍである。 The aerosol used in the above-mentioned spraying process includes fine particles made of an alumina-based material or fine particles made of a specific Al solid solution Y 2 Ti 2 O 7 in a gas such as nitrogen gas, argon gas, helium gas, compressed air or oxygen gas. It is generated by dispersing. The shape and size of these fine particles are not particularly limited. The average particle diameter measured by a laser diffraction / scattering method or the like is preferably 3000 nm or less, more preferably 50 to 2500 nm.
上記噴射工程では、ノズルを用いてエアロゾルを基材に向けて噴射し、基材に微粒子を衝突させ、これを連続的に行うことで基材の表面に微粒子を堆積させる。このとき、エアロゾルを構成するガス及び微粒子の割合、並びに、ノズルによるエアロゾルの噴射方法は、特に限定されない。
また、エアロゾルの噴射速度（供給速度）は、特に限定されないが、緻密な堆積膜を形成することができること等から、好ましくは３〜２０リットル／分である。エアロゾルの噴射速度が上記範囲にあっても、基材の硬度等によって、表面が粗化されて、歪みが形成される場合があるが、緻密な堆積膜を効率よく製造することができる。
尚、エアロゾルの噴射角、即ち、基材に対して、ノズルの開口部と、噴射されたエアロゾルの中心とを結ぶ直線により形成される角度は、特に限定されないが、好ましくは４５〜９０度、より好ましくは５０〜９０度である。
In the spraying step, aerosol is sprayed toward the base material using a nozzle, the fine particles collide with the base material, and this is continuously performed to deposit the fine particles on the surface of the base material. At this time, the ratio of the gas and fine particles constituting the aerosol and the method of injecting the aerosol with the nozzle are not particularly limited.
The aerosol injection speed (supply speed) is not particularly limited, but is preferably 3 to 20 liters / minute because a dense deposited film can be formed. Even if the spraying speed of the aerosol is within the above range, the surface may be roughened due to the hardness of the base material, etc., and distortion may be formed, but a dense deposited film can be efficiently produced.
In addition, the spray angle of the aerosol, that is, the angle formed by a straight line connecting the opening of the nozzle and the center of the sprayed aerosol with respect to the substrate is not particularly limited, but is preferably 45 to 90 degrees, More preferably, it is 50 to 90 degrees.
上記噴射工程は、通常、密閉空間において進められるが、その雰囲気は、特に限定されない。エアロゾルを構成するガスと同じ雰囲気であってよいし、大気雰囲気であってもよい。更に、エアロゾルを噴射する際には、密閉空間は、常圧及び減圧のいずれであってもよい。
また、エアロゾルを噴射する際の基材の温度も特に限定されず、例えば、５０℃以下、好ましくは１０℃〜３０℃といった、穏和な温度条件下で噴射工程を行うことができる。
Although the said injection process is normally advanced in sealed space, the atmosphere is not specifically limited. The atmosphere may be the same as the gas constituting the aerosol, or an air atmosphere. Furthermore, when injecting aerosol, the sealed space may be at normal pressure or reduced pressure.
Moreover, the temperature of the base material at the time of injecting the aerosol is not particularly limited, and the injection process can be performed under a mild temperature condition, for example, 50 ° C. or less, preferably 10 ° C. to 30 ° C.
上記噴射工程において、安定であり且つより厚い堆積膜を形成する好ましい方法としては、例えば、予熱した微粒子を含むエアロゾルを用いる方法が挙げられる。この場合、予熱温度は、好ましくは８０℃〜２００℃、より好ましくは１００℃〜１８０℃、更に好ましくは１２０℃〜１７０℃である。 In the spraying step, a preferable method for forming a stable and thicker deposited film is, for example, a method using an aerosol containing preheated fine particles. In this case, the preheating temperature is preferably 80 ° C to 200 ° C, more preferably 100 ° C to 180 ° C, and still more preferably 120 ° C to 170 ° C.
ここで、上記噴射工程に用いられる装置、即ち、基材２７の表面に、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７微粒子又はアルミナ系材料微粒子からなる堆積膜を形成する装置の一例を図５に示す。 Here, an example of an apparatus used in the above-described spraying process, that is, an apparatus for forming a deposited film made of specific Al solid solution Y 2 Ti 2 O 7 fine particles or alumina-based material fine particles on the surface of the base material 27 is shown in FIG. Shown in
図５の装置２０は、微粒子を含むエアロゾルを発生させるエアロゾル発生機２１と、エアロゾル搬送用配管２２を介して供給されたエアロゾルを粉体噴射用ノズル２５から噴射して基材２７の表面に特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７微粒子又はアルミナ系材料微粒子からなる堆積膜を形成する製膜室２３とを備える。製膜室２３には、製膜室２３の内部を減圧にするための真空ポンプ２９が連結されている。 The apparatus 20 shown in FIG. 5 specifies the surface of the base material 27 by injecting an aerosol supplied via an aerosol generator 21 for generating an aerosol containing fine particles and an aerosol carrying pipe 22 from a powder injection nozzle 25. A film forming chamber 23 for forming a deposited film made of Al solid solution Y 2 Ti 2 O 7 fine particles or alumina-based material fine particles. A vacuum pump 29 for reducing the pressure inside the film forming chamber 23 is connected to the film forming chamber 23.
図５の製膜室２３では、粉体噴射用ノズル２５からのエアロゾルが、基材２７に対して斜め方向（角度θ）に吹き付けられるように示しているが、θ＝９０度でもよい。エアロゾルを連続的に噴射する場合、基材２７の表面に堆積せずに跳ね返る微粒子と、粉体噴射用ノズル２５からのエアロゾルとが衝突しないので、好ましい態様である。
基材２７の広い領域に堆積膜を形成する場合には、粉体噴射用ノズル２５及び基材２７の少なくとも一方の位置を変化させる手段を備えることができる。
尚、粉体噴射用ノズル２５の先端部の開口面積、粉体噴射用ノズル２５と基材２７との距離（Ｌ）等は、特に限定されない。
In the film forming chamber 23 of FIG. 5, the aerosol from the powder injection nozzle 25 is shown to be sprayed in an oblique direction (angle θ) with respect to the base material 27, but θ may be 90 degrees. In the case of continuously injecting the aerosol, the fine particles that rebound without being deposited on the surface of the base material 27 and the aerosol from the powder injection nozzle 25 do not collide, which is a preferable embodiment.
In the case where a deposited film is formed in a wide area of the base material 27, a means for changing the position of at least one of the powder injection nozzle 25 and the base material 27 can be provided.
The opening area at the tip of the powder injection nozzle 25, the distance (L) between the powder injection nozzle 25 and the base material 27, etc. are not particularly limited.
図５の装置は、製膜室２３の内部を減圧にするための真空ポンプ２９を備えるが、製膜室２３の内部を減圧にすることにより、エアロゾル発生機２１（エアロゾル搬送用配管２２を含む）と、製膜室２３との差圧を生じさせて、基材２７に対するエアロゾルの衝突効率を向上させることができる。
尚、図５の装置の場合、噴射工程に際して、製膜室２３の内部の雰囲気は、特に限定されないが、エアロゾルを構成するガスと同じ種類のガスを主とすることが好ましい。
The apparatus shown in FIG. 5 includes a vacuum pump 29 for reducing the pressure inside the film forming chamber 23. By reducing the pressure inside the film forming chamber 23, the aerosol generator 21 (including the aerosol transport pipe 22) is included. ) And the film forming chamber 23, and the collision efficiency of the aerosol against the base material 27 can be improved.
In the case of the apparatus of FIG. 5, the atmosphere inside the film forming chamber 23 is not particularly limited during the spraying process, but it is preferable that the same type of gas as that constituting the aerosol is mainly used.
本発明において、図１の積層材料１０Ａを製造するための噴射工程では、アルミナ系材料からなる微粒子を含むエアロゾルを、特定のＡｌ固溶Ｙ２Ｔｉ２Ｏ７からなる基材２７の表面に噴射すると、基材２７が加熱されていなくても、アルミナ系材料の種類によっては、その焼結体と同等の機械的強度を有するアルミナ系材料からなる堆積膜の形成が可能な場合がある。 In the present invention, in the injection process for manufacturing the laminated material 10A of FIG. 1, an aerosol containing fine particles made of an alumina-based material is injected onto the surface of a base material 27 made of a specific Al solid solution Y 2 Ti 2 O 7. Then, even if the base material 27 is not heated, depending on the type of the alumina material, it may be possible to form a deposited film made of an alumina material having a mechanical strength equivalent to that of the sintered body.
一方、エアロゾル搬送用配管２２を介して製膜室２３内の粉体噴射用ノズル２５にエアロゾルを供給するエアロゾル発生機２１は、従来、公知の構成を備えることができる。図５におけるエアロゾル発生機２１は、上記例示したガスと、微粒子とを混合して、エアロゾルを発生させる装置であり、微粒子３３を収容する粉体容器３１と、エアロゾル発生機２１の内部において微粒子３３を撒き上げるための粉体撒き上げ用ガス供給部３５と、エアロゾル搬送用ガス供給部３７とを備える。
粉体撒き上げ用ガス供給部３５から、ガスが微粒子３３の集合体内部に導入されると、エアロゾル発生機２１の内部において、微粒子が撒き上げられ、ガスの中に微粒子３３が分散したエアロゾルとなる。エアロゾル発生機２１の内部が密閉空間であるので、粉体撒き上げ用ガス供給部３５からのガス流量に基づいてエアロゾルを粉体噴射用ノズル２５に送ることができるが、エアロゾル搬送用ガス供給部３７からのガスを併用することにより、噴射に十分な流量のエアロゾルを製膜室２３内の粉体噴射用ノズル２５に送ることができる。
On the other hand, the aerosol generator 21 that supplies aerosol to the powder injection nozzle 25 in the film forming chamber 23 via the aerosol transport pipe 22 can conventionally have a known configuration. The aerosol generator 21 in FIG. 5 is a device that generates the aerosol by mixing the gas exemplified above and the fine particles. The aerosol container 21 contains the fine particles 33 and the fine particles 33 inside the aerosol generator 21. A powder supply gas supply unit 35 and an aerosol transport gas supply unit 37 are provided.
When the gas is introduced into the aggregate of the fine particles 33 from the powder supply gas supply unit 35, the fine particles are lifted up inside the aerosol generator 21, and the aerosol in which the fine particles 33 are dispersed in the gas. Become. Since the inside of the aerosol generator 21 is a sealed space, the aerosol can be sent to the powder injection nozzle 25 based on the gas flow rate from the powder raising gas supply unit 35, but the aerosol supply gas supply unit By using the gas from 37 together, an aerosol having a flow rate sufficient for injection can be sent to the powder injection nozzle 25 in the film forming chamber 23.
上記のように、予熱された微粒子３３を含むエアロゾルを用いることができるので、そのために、粉体容器３１内の微粒子３３を加熱するヒーター３９を配設することができる。 As described above, since the aerosol containing the preheated fine particles 33 can be used, a heater 39 for heating the fine particles 33 in the powder container 31 can be provided.
本発明における積層材料の製造方法では、噴射工程の後、基材の表面に堆積膜が形成されてなる微粒子堆積体を焼成する焼成工程を備えることができる。この焼成工程により、層（Ａ）及び層（Ｂ）の接合強度に優れた積層材料を得ることができる。そして、微粒子堆積体を、下記の好ましい条件をもって焼成工程に供することにより、層（Ａ）及び層（Ｂ）の界面が明瞭であり、耐熱耐久性に優れ、長期に渡って、層構造が安定に維持される積層材料を得ることができる。 In the manufacturing method of the laminated material in this invention, the baking process of baking the fine particle deposit body by which a deposit film is formed on the surface of a base material can be provided after an injection process. By this firing step, a laminated material having excellent bonding strength between the layer (A) and the layer (B) can be obtained. Then, by subjecting the fine particle deposit to the firing step under the following preferable conditions, the interface between the layer (A) and the layer (B) is clear, excellent in heat resistance and durability, and the layer structure is stable over a long period of time. It is possible to obtain a laminated material that is maintained in the above.
上記焼成工程における処理条件は、微粒子堆積体の構成材料の種類等により、適宜、選択され、特に限定されない。上記焼成工程における処理温度の上限は、好ましくは、１７００℃であり、より好ましくは１５００℃であり、下限温度は、通常、８００℃である。また、上記温度における処理時間は、好ましくは１〜１００時間、より好ましくは１０〜５０時間である。更に、上記焼成工程における雰囲気は、大気雰囲気等とすることができる。特に、図１の積層材料１０Ａを製造する場合、噴射工程により得られた微粒子堆積体を焼成工程に供することにより、粒成長したアルミナ系材料からなる層（Ａ）を備える積層材料１０Ａとすることができる。 The treatment conditions in the firing step are appropriately selected depending on the type of constituent material of the fine particle deposit and the like and are not particularly limited. The upper limit of the treatment temperature in the firing step is preferably 1700 ° C, more preferably 1500 ° C, and the lower limit temperature is usually 800 ° C. The treatment time at the above temperature is preferably 1 to 100 hours, more preferably 10 to 50 hours. Furthermore, the atmosphere in the firing step can be an air atmosphere or the like. In particular, when the laminated material 10A shown in FIG. 1 is produced, the laminated material 10A including the layer (A) made of the grain-grown alumina-based material is obtained by subjecting the fine particle deposit obtained in the injection process to the firing process. Can do.
３．積層材料の利用
本発明の積層材料は、耐熱耐久性が求められる、例えば、プラント関係（製造プラント、エネルギー供給プラント等）、輸送機器関係（車両、船舶、航空機、宇宙機器等）、その他の施設、設備、機器等における内燃機関、ボイラー、蒸気タービン、ガスタービン等における耐熱部材（炉壁材等）等に利用することができる。また、本発明の積層材料を、自動車用エンジンのピストンヘッド、シリンダーの内壁等に利用することにより、「燃焼温度の高温化」と「システムの軽量化」（熱容量が大きく、重量の大きな断熱材を使用した冷却システム等の除去による軽量化）による一層の燃費向上が可能になる。
また、本発明の積層材料を用いて、各種の耐熱部品とした場合、使用時においてその表面の温度上昇を低減することもできる。
3. Use of laminated material The laminated material of the present invention is required to have heat resistance and durability, for example, plant-related (manufacturing plant, energy supply plant, etc.), transportation equipment-related (vehicle, ship, aircraft, space equipment, etc.), and other facilities. It can be used for heat-resistant members (furnace wall materials, etc.) in internal combustion engines, boilers, steam turbines, gas turbines and the like in facilities and equipment. In addition, by using the laminated material of the present invention for the piston head of an automobile engine, the inner wall of a cylinder, etc., "higher combustion temperature" and "lighter system" It is possible to further improve fuel efficiency by reducing the weight by removing the cooling system etc. using the.
Moreover, when it is set as various heat-resistant components using the laminated material of this invention, the temperature rise of the surface at the time of use can also be reduced.
以下に、実施例を挙げ、本発明を更に詳細に説明するが、本発明の主旨を超えない限り、本発明は、かかる実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.
１．Ｙ２Ｔｉ２Ｏ７の中へのＡｌ原子の固溶限の確認実験
関東化学社製硝酸アルミニウム９水和物（純度９８．０％以上）と、関東化学社製硝酸イットリウム６水和物（高純度試薬、純度９９．９９％）と、東邦チタニウム社製四塩化チタン水溶液（高純度試薬、Ｔｉ：１６．０〜１７．０％）と、純水とを用いて、噴霧熱分解法により前駆体（Ａｌ固溶Ｙ２Ｔｉ２Ｏ７用前駆体）を得た後、焼結を行って、Ａｌ原子の固溶量の異なるＡｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体を得た。そして、各Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体について、Ｘ線回折測定を行い、内部標準法により格子定数を求め、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体に含まれるＡｌ原子の量、及び、格子定数の関係をグラフ化し、Ｙ２Ｔｉ２Ｏ７の中にＡｌ２Ｏ３を析出させないＡｌ原子の含有量を決定した。
1. Experiment for confirming solid solubility limit of Al atom in Y 2 Ti 2 O 7 Aluminum nitrate nonahydrate (purity: 98.0% or more) manufactured by Kanto Chemical Co., Ltd. and yttrium nitrate hexahydrate manufactured by Kanto Chemical Co., Ltd. Using a high-purity reagent, purity 99.99%), titanium tetrachloride aqueous solution manufactured by Toho Titanium Co., Ltd. (high-purity reagent, Ti: 16.0 to 17.0%), and pure water, by spray pyrolysis method After obtaining the precursor (precursor for Al solid solution Y 2 Ti 2 O 7 ), sintering was performed to obtain Al solid solution Y 2 Ti 2 O 7 sintered bodies having different solid solution amounts of Al atoms. . For each of Al solid solution Y 2 Ti 2 O 7 sinter, subjected to X-ray diffraction measurement, determine the lattice constants by the internal standard method, Al atoms contained in the Al solid solution Y 2 Ti 2 O 7 sinter And the relationship between the lattice constants were graphed, and the content of Al atoms that did not precipitate Al 2 O 3 in Y 2 Ti 2 O 7 was determined.
噴霧熱分解によりＡｌ固溶Ｙ２Ｔｉ２Ｏ７用前駆体を合成する際の硝酸アルミニウム９水和物の使用量は、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７におけるＡｌ原子の含有割合が、Ａｌ原子、Ｙ原子及びＴｉ原子の合計量を１００原子％とした場合に、それぞれ、０原子％、０．２原子％、０．３原子％、０．５原子％、０．７原子％、１．０原子％、２．０原子％、３．０原子％、５．０原子％、８．０原子％及び１５．０原子％となるように調整した。尚、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７用前駆体を焼結した後のＡｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体に含まれるＡｌ原子の量は、硝酸アルミニウム９水和物の使用量に基づくものとは異なるため、各焼結体について、ＩＣＰ発光分析（エスアイアイ・ナノテクノロジー社製ＩＣＰ発光分光分析装置「ＳＰＳ−３１００」）により、正確なＡｌ量を求めた。Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体を得るための詳細な方法を以下に示す。 The amount of aluminum nitrate nonahydrate used in synthesizing the precursor for Al solid solution Y 2 Ti 2 O 7 by spray pyrolysis is such that the content ratio of Al atoms in Al solid solution Y 2 Ti 2 O 7 is Al. When the total amount of atoms, Y atoms, and Ti atoms is 100 atomic%, 0 atomic%, 0.2 atomic%, 0.3 atomic%, 0.5 atomic%, 0.7 atomic%, It adjusted so that it might become 0.0 atomic%, 2.0 atomic%, 3.0 atomic%, 5.0 atomic%, 8.0 atomic%, and 15.0 atomic%. The amount of Al atoms contained in the Al solid solution Y 2 Ti 2 O 7 sintered body after sintering the Al solid solution Y 2 Ti 2 O 7 precursor is the amount of aluminum nitrate nonahydrate used. Therefore, for each sintered body, an accurate Al amount was obtained by ICP emission analysis (ICP emission spectroscopic analyzer “SPS-3100” manufactured by SII Nanotechnology Inc.). A detailed method for obtaining an Al solid solution Y 2 Ti 2 O 7 sintered body is shown below.
まず、硝酸イットリウム６水和物と、四塩化チタン水溶液と、純水とを用いて、Ｙ２Ｔｉ２Ｏ７とした場合の濃度が０．０５ｍｏｌ／Ｌである水溶液を調製し、次いで、硝酸アルミニウム９水和物を添加して、前駆体水溶液を得た。その後、この前駆体水溶液を冷却し、チューブポンプで霧化部へ循環し、超音波（周波数１．６〜１．７５ＭＨｚ）により液滴を発生させた。次いで、液滴を、マントルヒーターと、炉心管を含む電気炉と、粉末回収フィルターと、捕集器とを、順次、備える噴霧熱分解装置の前段部と後段部との圧力差（−４ｋＰａ）及びキャリアガス（空気：７．５Ｌ／分）により炉心管内を通過させ、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７前駆体の熱分解及び乾燥を行って、捕集器でＡｌ固溶Ｙ２Ｔｉ２Ｏ７粉末を回収した。尚、液滴を導入する際の各部の温度は、最前段のマントルヒーターでは１２０℃とし、電気炉を構成する第１炉では２００℃、第２炉では５００℃、第３炉では８００℃とし、粉末回収フィルターでは１３０℃とした。
次に、得られたＡｌ固溶Ｙ２Ｔｉ２Ｏ７粉末を、大気雰囲気下、８００℃で１時間仮焼した後、４８μｍメッシュのふるいを通した。次いで、一軸加圧の予備成形（２０ＭＰａ）を行った後、ＣＩＰ成形（２５０ＭＰａ）に供し、板体を得た。
その後、この板体を、大気雰囲気下、１５００℃で５時間加熱して焼結体とし、更に、大気雰囲気下、１３００℃で５０時間アニールして、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体を得た。
First, using yttrium nitrate hexahydrate, titanium tetrachloride aqueous solution, and pure water, an aqueous solution having a concentration of 0.05 mol / L in the case of Y 2 Ti 2 O 7 was prepared. Aluminum nonahydrate was added to obtain an aqueous precursor solution. Then, this precursor aqueous solution was cooled, and it circulated to the atomization part with the tube pump, and the droplet was generated with the ultrasonic wave (frequency 1.6-1.75MHz). Next, the pressure difference (−4 kPa) between the front part and the rear part of the spray pyrolysis apparatus, which sequentially includes droplets, a mantle heater, an electric furnace including a furnace core tube, a powder recovery filter, and a collector. And a carrier gas (air: 7.5 L / min) to pass through the core tube, pyrolyze and dry the Al solid solution Y 2 Ti 2 O 7 precursor, and collect Al solution Y 2 Ti 2 with a collector. O 7 powder was collected. In addition, the temperature of each part at the time of introducing the droplets is 120 ° C. in the first mantle heater, 200 ° C. in the first furnace constituting the electric furnace, 500 ° C. in the second furnace, and 800 ° C. in the third furnace. In the powder recovery filter, the temperature was 130 ° C.
Next, the obtained Al solid solution Y 2 Ti 2 O 7 powder was calcined at 800 ° C. for 1 hour in an air atmosphere, and then passed through a 48 μm mesh sieve. Subsequently, after performing uniaxial pressurization preforming (20 MPa), it was subjected to CIP molding (250 MPa) to obtain a plate.
Thereafter, the plate is heated at 1500 ° C. for 5 hours in an air atmosphere to obtain a sintered body, and further annealed at 1300 ° C. for 50 hours in an air atmosphere to sinter Al solid solution Y 2 Ti 2 O 7. Got the body.
（格子定数の決定）
上記で得られた各Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体の粉砕物、及び、後述する比較例１で合成したＡｌ未固溶のＹ２Ｔｉ２Ｏ７焼結体の粉砕物に対して、Ｘ線回折を行い、内部標準法により格子定数を求めた。
具体的には、まず、Ｘ線回折の測定において、内部標準物質として標準シリコン粉末（６４０ｃ、ＮＩＳＴ）を用いて回折ピークの補正を行い、格子面間隔を、下記式（１）により求めた。
そして、これらの面指数と格子面間隔とから、下記式（２）を用いて、格子定数ａを算出し、その平均値を格子定数とした。
Milling of each Al solid solution Y 2 Ti 2 O 7 sinter obtained above, and, in the pulverized Y 2 Ti 2 O 7 sinter the synthesized Al undissolved in Comparative Example 1 to be described later On the other hand, X-ray diffraction was performed, and a lattice constant was determined by an internal standard method.
Specifically, first, in the X-ray diffraction measurement, the diffraction peak was corrected using standard silicon powder (640c, NIST) as an internal standard substance, and the lattice spacing was obtained by the following formula (1).
Then, the lattice constant a was calculated from the surface index and the lattice spacing using the following formula (2), and the average value was taken as the lattice constant.
図４は、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体に含まれるＡｌ原子の量（ＩＣＰ発光分析による定量値）と、格子定数との関係を示すグラフであり、描かれた曲線について、次のように推定した。即ち、Ａｌ原子の量が増加するにつれて、「Ｉ」の領域では、Ａｌの固溶が進行し、１％を超えた「ＩＩ」の領域においてＡｌ２Ｏ３の核が生成し、約３．２％に至るまでにＡｌ原子が核界面に引き寄せられ、Ａｌ原子の偏析が発生する。そして、「ＩＩＩ」の領域では、Ａｌ原子の偏析量が飽和して、Ｙ２Ｔｉ２Ｏ７の中にＡｌ原子が再固溶され、８％以上では、Ａｌ２Ｏ３の核が成長している。「ＩＶ」の領域における曲線（直線）を縦軸に向かって延長すると、図４の曲線との交点は２つあるが、交点を示す横軸の値の範囲（０．５％〜１．８％）を、Ｙ２Ｔｉ２Ｏ７の中にＡｌ２Ｏ３を析出させないＡｌ原子の含有量であると判断した。 FIG. 4 is a graph showing the relationship between the amount of Al atoms (quantitative value by ICP emission analysis) contained in the Al solid solution Y 2 Ti 2 O 7 sintered body and the lattice constant. The estimation was as follows. That is, as the amount of Al atoms increases, the solid solution of Al progresses in the “I” region, and Al 2 O 3 nuclei are generated in the “II” region exceeding 1%. Al atoms are attracted to the nuclear interface up to 2%, and segregation of Al atoms occurs. In the region “III”, the segregation amount of Al atoms is saturated and Al atoms are re-dissolved in Y 2 Ti 2 O 7 , and at 8% or more, Al 2 O 3 nuclei grow. ing. When the curve (straight line) in the region of “IV” is extended toward the vertical axis, there are two intersections with the curve in FIG. 4, but the range of values on the horizontal axis indicating the intersection (0.5% to 1.8%). %) Was determined to be the content of Al atoms that did not precipitate Al 2 O 3 in Y 2 Ti 2 O 7 .
２．積層材料の製造及び評価
下記の実施例１並びに比較例２及び３では、上記で得られたＡｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体と、大明化学工業社製α−アルミナ微粒子「ＴＭ−ＤＡＲ」（純度９９．９９％、Ｄ５０＝１４０ｎｍ、ランダム形状のα−アルミナ結晶微粒子）とを用いて、図１の構造を有する積層材料を製造した。実施例２では、上記の噴霧熱分解法により得られたＡｌ固溶Ｙ２Ｔｉ２Ｏ７粉末と、大明化学工業社製α−アルミナ微粒子「ＴＭ−ＤＡＲ」（純度９９．９９％、Ｄ５０＝１４０ｎｍ）とを用いて、図２の構造を有する積層材料を製造した。また、比較例１及び４では、噴霧熱分解法により得たＡｌ未固溶のＹ２Ｔｉ２Ｏ７粉末と、大明化学工業社製α−アルミナ微粒子「ＴＭ−ＤＡＲ」（純度９９．９９％、Ｄ５０＝１４０ｎｍ）とを用いて、Ａｌを含まないＹ２Ｔｉ２Ｏ７基板の表面にアルミナ膜を有する積層材料、及び、アルミナ基板の表面にＡｌを含まないＹ２Ｔｉ２Ｏ７膜を有する積層材料を、それぞれ、得た。尚、実施例１では、耐久性を評価するために、積層材料に対して、１３００℃で１００時間の熱処理を行っているが、この熱処理物も本発明の積層材料に含まれる。
2. Production and Evaluation of Laminate Material In Example 1 and Comparative Examples 2 and 3 below, the Al solid solution Y 2 Ti 2 O 7 sintered body obtained above and α-alumina fine particles “TM- A laminated material having the structure of FIG. 1 was manufactured using “DAR” (purity 99.99%, D 50 = 140 nm, randomly shaped α-alumina crystal fine particles). In Example 2, Al solid solution Y 2 Ti 2 O 7 powder obtained by the above-mentioned spray pyrolysis method, α-alumina fine particles “TM-DAR” (purity 99.99%, D 50) manufactured by Daimei Chemical Industry Co., Ltd. = 140 nm) was used to manufacture a laminated material having the structure of FIG. In Comparative Examples 1 and 4, Al insoluble Y 2 Ti 2 O 7 powder obtained by spray pyrolysis and α-alumina fine particles “TM-DAR” (purity 99.99%, manufactured by Daimei Chemical Industry Co., Ltd.) , D 50 = 140 nm), and a laminate material having an alumina film on the surface of the Y 2 Ti 2 O 7 substrate not containing Al, and a Y 2 Ti 2 O 7 film not containing Al on the surface of the alumina substrate. Laminate materials having respectively were obtained. In Example 1, in order to evaluate the durability, the laminated material was heat-treated at 1300 ° C. for 100 hours. This heat-treated product is also included in the laminated material of the present invention.
実施例１
Ａｌの固溶量が１原子％であるＹ２Ｔｉ２Ｏ７焼結体の表面を研磨して、鏡面基板（φ２３．５ｍｍ、厚さ０．２５ｍｍ）とした。この鏡面基板を基材２７（図５）として用い、図５の噴射工程用装置２０内にセットし、下記の条件により、上記α−アルミナ微粒子を衝突させて、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体基板の表面に、厚さ０．３μｍのα−アルミナ微粒子堆積膜を形成して、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体基板１４の表面にアルミナ膜１２を有する積層材料（Ｍ１）１０Ａを得た（図１参照）。
＜製造条件＞
（１）エアロゾル発生機
α−アルミナ微粒子の温度：１５０℃
α−アルミナ微粒子の使用量：５０ｇ
微粒子撒き上げ用ヘリウムガスの流量：３Ｌ／分
エアロゾル搬送用ヘリウムガスの流量：６．５Ｌ／分
（２）製膜室
微粒子噴射用ノズルの開口サイズ：５ｍｍ×０．３ｍｍ
ノズルと、基板との距離（Ｌ）：７．０ｍｍ
基板に対するエアロゾルの吹き付け角度θ：６０度
基板の温度：２５℃
基板の移動速度：５０ｍｍ／分
Example 1
The surface of the Y 2 Ti 2 O 7 sintered body in which the solid solution amount of Al was 1 atomic% was polished to obtain a mirror substrate (φ23.5 mm, thickness 0.25 mm). Using this mirror substrate as the base material 27 (FIG. 5), it is set in the injection process apparatus 20 of FIG. 5, and the α-alumina fine particles collide with each other under the following conditions to obtain an Al solid solution Y 2 Ti 2 O. 7 Laminated material having an α-alumina fine particle deposition film having a thickness of 0.3 μm formed on the surface of a sintered body substrate and an alumina film 12 formed on the surface of an Al solid solution Y 2 Ti 2 O 7 sintered body substrate 14 (M1) 10A was obtained (see FIG. 1).
<Production conditions>
(1) Aerosol generator Temperature of α-alumina fine particles: 150 ° C
Use amount of α-alumina fine particles: 50 g
Flow rate of helium gas for lifting fine particles: 3 L / min Flow rate of helium gas for transporting aerosol: 6.5 L / min (2) Film forming chamber Opening size of nozzle for spraying fine particles: 5 mm × 0.3 mm
Distance between nozzle and substrate (L): 7.0 mm
Aerosol spray angle to substrate: 60 degrees Substrate temperature: 25 ° C
Substrate moving speed: 50 mm / min
得られた積層材料（Ｍ１）の表面及び断面を、日立ハイテクノロジーズ社製電界放出型走査電子顕微鏡「ＳＵ８０００」を用いて観察した（図６及び図７参照）。尚、加速電圧は、表面観察時３ｋＶ、断面観察時０．８ｋＶとした。また、断面観察時の試料は、日立ハイテクノロジーズ社製イオンミリング装置「ＩＭ４０００」を用いた断面ミリング法により行った。 The surface and cross section of the obtained laminated material (M1) were observed using a field emission scanning electron microscope “SU8000” manufactured by Hitachi High-Technologies Corporation (see FIGS. 6 and 7). The acceleration voltage was 3 kV during surface observation and 0.8 kV during cross-sectional observation. Moreover, the sample at the time of cross-sectional observation was performed by a cross-sectional milling method using an ion milling device “IM4000” manufactured by Hitachi High-Technologies Corporation.
次に、積層材料（Ｍ１）を、モトヤマ社製電気炉の中に載置して、大気雰囲気中、１３００℃で１００時間熱処理を行い、上記と同様にして、積層材料（Ｍ１）の表面及び断面を観察した（図８及び図９参照）。図９から、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体基板の内部にアルミナ粒子が見られず、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体基板の表面にアルミナ膜が安定に残存していることが分かる。
また、熱処理後の積層材料（Ｍ１）の界面を、日本電子社製電界放出型透過電子顕微鏡「ＪＥＭ−２１００Ｆ」及び日本電子社製ＥＤＳ分析装置「ＪＥＤ２３００Ｔ」を用いて、加速電圧２００ｋＶ及びプローブ径１ｎｍの条件で測定した。尚、観察用の試料は、収束イオンビーム装置（ＦＩＢ）を備える走査型電子顕微鏡（エスアイアイ・ナノテクノロジー社製「ＳＭＩ−３０５０ＳＥ」）を使用し、ＦＩＢ−マイクロサンプリング法にて作製した。図１０に積層界面を示す画像を、図１１にＥＤＳ分析結果（プロファイル）を、それぞれ、示す。図１１から、熱処理後の積層材料（Ｍ１）では、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７焼結体基板のアルミナ膜側界面近傍で、Ａｌ原子が濃化していることが分かる。
Next, the laminated material (M1) is placed in an electric furnace manufactured by Motoyama and heat treated at 1300 ° C. for 100 hours in an air atmosphere. A cross section was observed (see FIGS. 8 and 9). From Figure 9, Al solid solution Y 2 Ti 2 O 7 without alumina particles was observed in the interior of the sintered body substrate, an alumina film is left stable on the Al solid solution Y 2 Ti 2 O 7 the surface of the sintered body of the substrate I understand that
In addition, the interface of the laminated material (M1) after the heat treatment was subjected to acceleration voltage 200 kV and probe diameter using a field emission transmission electron microscope “JEM-2100F” manufactured by JEOL Ltd. and an EDS analyzer “JED2300T” manufactured by JEOL Ltd. Measurement was performed under the condition of 1 nm. In addition, the sample for observation was produced by the FIB-microsampling method using the scanning electron microscope ("SMI-3050SE" by the SII nanotechnology company) provided with a focused ion beam apparatus (FIB). FIG. 10 shows an image showing a laminated interface, and FIG. 11 shows an EDS analysis result (profile). From FIG. 11, it can be seen that in the laminated material (M1) after the heat treatment, Al atoms are concentrated in the vicinity of the interface on the alumina film side of the Al solid solution Y 2 Ti 2 O 7 sintered body substrate.
比較例１
東邦チタニウム社製四塩化チタン水溶液（高純度試薬、Ｔｉ：１６．０〜１７．０％）と、関東化学社製硝酸イットリウム六水和物（高純度試薬、純度９９．９９％）と、純水とを用いて、Ｙ２Ｔｉ２Ｏ７とした場合の濃度が０．０５ｍｏｌ／Ｌである前駆体水溶液を調製した。
その後、このＹ２Ｔｉ２Ｏ７前駆体水溶液を冷却し、チューブポンプで霧化部へ循環し、超音波（周波数１．６〜１．７５ＭＨｚ）により液滴を発生させた。次いで、液滴を、マントルヒーターと、炉心管を含む電気炉と、粉末回収フィルターと、捕集器とを、順次、備える噴霧熱分解装置の前段部と後段部との圧力差（−４ｋＰａ）及びキャリアガス（空気：７．５Ｌ／分）により炉心管内を通過させ、Ｙ２Ｔｉ２Ｏ７前駆体の熱分解及び乾燥を行って、捕集器でＡｌ未固溶のＹ２Ｔｉ２Ｏ７粉末を回収した。このとき、液滴を導入する際の各部の温度は、最前段のマントルヒーターでは１２０℃とし、電気炉を構成する第１炉では２００℃、第２炉では５００℃、第３炉では８００℃とし、粉末回収フィルターでは１３０℃とした。
次に、得られたＡｌ未固溶のＹ２Ｔｉ２Ｏ７粉末を、大気雰囲気下、８００℃で１時間仮焼した後、４８μｍメッシュのふるいを通した。次いで、一軸加圧の予備成形（２０ＭＰａ）を行った後、ＣＩＰ成形（２５０ＭＰａ）に供し、板体を得た。そして、この板体を、大気雰囲気下、１７００℃で５時間加熱し、焼結体を得て、表面を研磨して、鏡面を有するＹ２Ｔｉ２Ｏ７基板（φ２３．５ｍｍ、厚さ０．２５ｍｍ）を作製した。
その後、このＹ２Ｔｉ２Ｏ７基板を基材２７（図５）として用い、α−アルミナ微粒子を用いて、実施例１と同様の操作を行い、Ｙ２Ｔｉ２Ｏ７基板の表面に、厚さ０．３μｍのアルミナ膜を有する積層材料（Ｍ２）を得た。
Comparative Example 1
Titanium tetrachloride aqueous solution (high purity reagent, Ti: 16.0 to 17.0%) manufactured by Toho Titanium Co., Ltd., yttrium nitrate hexahydrate (high purity reagent, purity 99.99%) manufactured by Kanto Chemical Co., Inc. with water, the concentration in the case of a Y 2 Ti 2 O 7 was prepared precursor solution is 0.05 mol / L.
Then, the Y 2 Ti 2 O 7 aqueous precursor solution was cooled, circulated to the atomization unit in the tube pump was generated droplets by ultrasound (frequency 1.6~1.75MHz). Next, the pressure difference (−4 kPa) between the front part and the rear part of the spray pyrolysis apparatus, which sequentially includes droplets, a mantle heater, an electric furnace including a furnace core tube, a powder recovery filter, and a collector. And a carrier gas (air: 7.5 L / min) to pass through the core tube, pyrolyze and dry the Y 2 Ti 2 O 7 precursor, and Al 2 insoluble Y 2 Ti 2 O in the collector Seven powders were collected. At this time, the temperature of each part at the time of introducing the droplets is 120 ° C. in the first mantle heater, 200 ° C. in the first furnace constituting the electric furnace, 500 ° C. in the second furnace, and 800 ° C. in the third furnace. And 130 ° C. for the powder recovery filter.
Next, the obtained Al insoluble Y 2 Ti 2 O 7 powder was calcined at 800 ° C. for 1 hour in an air atmosphere, and then passed through a 48 μm mesh sieve. Subsequently, after performing uniaxial pressurization preforming (20 MPa), it was subjected to CIP molding (250 MPa) to obtain a plate. Then, this plate was heated at 1700 ° C. for 5 hours in an air atmosphere to obtain a sintered body, the surface was polished, and a Y 2 Ti 2 O 7 substrate having a mirror surface (φ23.5 mm, thickness 0) .25 mm).
Then, using this Y 2 Ti 2 O 7 substrate as the base material 27 (FIG. 5), using α-alumina fine particles, the same operation as in Example 1 was performed, and the surface of the Y 2 Ti 2 O 7 substrate was A laminated material (M2) having an alumina film having a thickness of 0.3 μm was obtained.
得られた積層材料（Ｍ２）を、モトヤマ社製電気炉の中に載置して、大気雰囲気中、１３００℃で１００時間熱処理を行い、実施例１と同様にして、積層材料の表面及び断面を観察した（図１２及び図１３参照）。図１２及び図１３から、Ｙ２Ｔｉ２Ｏ７基板の粒界部分でアルミナ膜が消失していることが分かる。 The obtained laminated material (M2) was placed in an electric furnace manufactured by Motoyama, and was heat-treated at 1300 ° C. for 100 hours in the atmosphere, and the surface and cross section of the laminated material were obtained in the same manner as in Example 1. Was observed (see FIGS. 12 and 13). From FIG. 12 and FIG. 13, it can be seen that the alumina film disappears at the grain boundary portion of the Y 2 Ti 2 O 7 substrate.
次に、アルミナ膜が残存している積層材料の断面について、実施例１と同様にして、ＥＤＳ分析による元素分布を測定した。図１４に積層界面を示す画像を、図１５にＥＤＳ分析結果（プロファイル）を、それぞれ、示す。図１５から、熱処理により、アルミナ膜に由来するＡｌ原子がＹ２Ｔｉ２Ｏ７基板の中に偏析したことが分かる。 Next, the element distribution by EDS analysis was measured in the same manner as in Example 1 for the cross section of the laminated material in which the alumina film remained. FIG. 14 shows an image showing a laminated interface, and FIG. 15 shows an EDS analysis result (profile). FIG. 15 shows that Al atoms derived from the alumina film were segregated in the Y 2 Ti 2 O 7 substrate by the heat treatment.
比較例２
Ａｌ原子が２原子％固溶しているＹ２Ｔｉ２Ｏ７焼結体を用いた以外は、実施例１と同様にして、図１の構造を有し、厚さ０．３μｍのアルミナ膜を有する積層材料（Ｍ３）を得た。そして、この積層材料を、モトヤマ社製電気炉の中に載置して、大気雰囲気中、１３００℃で１００時間熱処理を行い、実施例１と同様にして、積層材料の断面を観察した（図１６参照）。図１６から、熱処理により、界面にボイドが形成され、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７基板の内部にアルミナ粒子が析出したことが分かる。
Comparative Example 2
An alumina film having the structure of FIG. 1 and having a thickness of 0.3 μm in the same manner as in Example 1 except that a Y 2 Ti 2 O 7 sintered body in which 2 atomic% of Al atoms are solid-solved is used. A laminated material (M3) having Then, this laminated material was placed in an electric furnace manufactured by Motoyama, and subjected to heat treatment at 1300 ° C. for 100 hours in the atmosphere, and the cross section of the laminated material was observed in the same manner as in Example 1 (FIG. 16). From FIG. 16, it can be seen that voids are formed at the interface by the heat treatment, and alumina particles are precipitated inside the Al solid solution Y 2 Ti 2 O 7 substrate.
比較例３
Ａｌ原子が３原子％固溶しているＹ２Ｔｉ２Ｏ７焼結体を用いた以外は、実施例１と同様にして、図１の構造を有し、厚さ０．３μｍのアルミナ膜を有する積層材料（Ｍ４）を得た。そして、この積層材料を、モトヤマ社製電気炉の中に載置して、大気雰囲気中、１３００℃で１００時間熱処理を行い、実施例１と同様にして、積層材料の断面を観察した（図１７参照）。図１７から、熱処理により、界面にボイドが形成され、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７基板の内部に多数のアルミナ粒子が析出したことが分かる。
Comparative Example 3
An alumina film having the structure of FIG. 1 having a structure of FIG. 1 and having a thickness of 0.3 μm, as in Example 1, except that a Y 2 Ti 2 O 7 sintered body in which 3 atomic% of Al atoms are dissolved is used. A laminated material (M4) having Then, this laminated material was placed in an electric furnace manufactured by Motoyama, and subjected to heat treatment at 1300 ° C. for 100 hours in the atmosphere, and the cross section of the laminated material was observed in the same manner as in Example 1 (FIG. 17). From FIG. 17, it can be seen that voids are formed at the interface by heat treatment, and a large number of alumina particles are precipitated inside the Al solid solution Y 2 Ti 2 O 7 substrate.
実施例２
上記α−アルミナ微粒子に対して、一軸加圧の予備成形（２０ＭＰａ）を行った後、ＣＩＰ成形（２５０ＭＰａ）に供し、板体を得た。その後、この板体を、大気雰囲気下、１５００℃で５時間加熱し、焼結体を得て、表面を研磨して、鏡面を有するアルミナ焼結体基板（φ２３．５ｍｍ、厚さ０．２５ｍｍ）を作製した。
その後、このアルミナ焼結体基板を基材２７（図５）として用い、図５の噴射工程用装置２０内にセットし、下記の条件により、Ａｌ原子が１原子％固溶しているＹ２Ｔｉ２Ｏ７焼結体粉末を衝突させて、アルミナ焼結体基板の表面に、厚さ０．３μｍのＡｌ固溶Ｙ２Ｔｉ２Ｏ７粉末堆積膜を形成して、アルミナ基板１２の表面にＡｌ固溶Ｙ２Ｔｉ２Ｏ７膜１４を有する積層材料１０Ｂを得た（図２参照）。
＜製造条件＞
（１）エアロゾル発生機
Ａｌ固溶Ｙ２Ｔｉ２Ｏ７粉末の温度：１５０℃
Ａｌ固溶Ｙ２Ｔｉ２Ｏ７粉末の使用量：５０ｇ
微粒子撒き上げ用ヘリウムガスの流量：０．１Ｌ／分
エアロゾル搬送用ヘリウムガスの流量：４．９Ｌ／分
（２）製膜室
微粒子噴射用ノズルの開口サイズ：５ｍｍ×０．３ｍｍ
ノズルと、基板との距離（Ｌ）：７．０ｍｍ
基板に対するエアロゾルの吹き付け角度θ：６０度
基板の温度：２５℃
基板の移動速度：１５０ｍｍ／分
Example 2
The α-alumina fine particles were subjected to uniaxial pressurization (20 MPa) and then subjected to CIP molding (250 MPa) to obtain a plate. Thereafter, this plate body is heated at 1500 ° C. for 5 hours in an air atmosphere to obtain a sintered body, the surface is polished, and an alumina sintered body substrate having a mirror surface (φ23.5 mm, thickness 0.25 mm) ) Was produced.
After that, this alumina sintered body substrate is used as the base material 27 (FIG. 5) and set in the injection process apparatus 20 of FIG. 5, and Y 2 in which Al atom is dissolved at 1 atomic% under the following conditions. The Ti 2 O 7 sintered body powder is collided to form a 0.3 μm thick Al solid solution Y 2 Ti 2 O 7 powder deposition film on the surface of the alumina sintered body substrate. A laminated material 10B having an Al solid solution Y 2 Ti 2 O 7 film 14 was obtained (see FIG. 2).
<Production conditions>
(1) Aerosol generator Al solid solution Y 2 Ti 2 O 7 powder temperature: 150 ° C.
Amount used of Al solid solution Y 2 Ti 2 O 7 powder: 50 g
Flow rate of helium gas for fine particle lifting: 0.1 L / min Flow rate of helium gas for aerosol transfer: 4.9 L / min (2) Film forming chamber Opening size of nozzle for spraying fine particles: 5 mm × 0.3 mm
Distance between nozzle and substrate (L): 7.0 mm
Aerosol spray angle to substrate: 60 degrees Substrate temperature: 25 ° C
Substrate moving speed: 150 mm / min
比較例４
Ａｌ原子が１原子％固溶しているＹ２Ｔｉ２Ｏ７焼結体粉末に代えて、比較例１で合成したＡｌ未固溶のＹ２Ｔｉ２Ｏ７粉末を用いた以外は、実施例２と同様の操作を行った。そして、アルミナ焼結体基板の表面に厚さ１μｍのＡｌ未固溶Ｙ２Ｔｉ２Ｏ７粉末堆積膜を有する積層材料（Ｍ５）を得た。
Comparative Example 4
Except for using Y 2 Ti 2 O 7 powder in which Al atoms are not dissolved, instead of Y 2 Ti 2 O 7 sintered body powder in which 1 atom% of Al atoms is solid-dissolved, it was carried out. The same operation as in Example 2 was performed. Then, to obtain laminate material having Al undissolved Y 2 Ti 2 O 7 powder deposited film having a thickness of 1μm on the surface of the alumina sintered body substrate (M5).
得られた積層材料（Ｍ５）を、モトヤマ社製電気炉の中に載置して、大気雰囲気中、１３００℃で１００時間熱処理を行い、実施例１と同様にして、熱処理後の積層材料（Ｍ５）の表面及び断面を観察した（図１８及び図１９参照）。図１８及び図１９から、熱処理を行っても、積層材料（Ｍ５）の層構造に変化がないように見えた。しかしながら、Ａｌ未固溶Ｙ２Ｔｉ２Ｏ７膜が残存している積層材料（Ｍ５）の断面について、特に、図２０に示す積層界面を示す部分において、実施例１と同様にして、ＥＤＳ分析による元素分布を測定したところ、図２１に示すプロファイルを得た。図２１から、熱処理により、アルミナ焼結体基板に由来するＡｌ原子がＡｌ未固溶Ｙ２Ｔｉ２Ｏ７膜の中に偏析したことが分かる。 The obtained laminated material (M5) was placed in an electric furnace manufactured by Motoyama, and heat-treated at 1300 ° C. for 100 hours in an air atmosphere. In the same manner as in Example 1, the laminated material after heat treatment ( The surface and cross section of M5) were observed (see FIGS. 18 and 19). From FIG. 18 and FIG. 19, it seemed that the layer structure of the laminated material (M5) did not change even when the heat treatment was performed. However, with respect to the cross section of the laminated material (M5) in which the Al insoluble Y 2 Ti 2 O 7 film remains, particularly in the portion showing the laminated interface shown in FIG. When the element distribution according to was measured, the profile shown in FIG. 21 was obtained. FIG. 21 shows that Al atoms derived from the alumina sintered body substrate were segregated in the Al insoluble Y 2 Ti 2 O 7 film by the heat treatment.
本発明の積層材料は、プラント関係（製造プラント、エネルギー供給プラント等）、輸送機器関係（車両、船舶、航空機、宇宙機器等）、その他の施設、設備、機器等における内燃機関、ボイラー、蒸気タービン、ガスタービン等において、例えば、１４００℃を上限とする高い温度環境における部材（炉壁材等）等に利用することができる。 The laminated material of the present invention is an internal combustion engine, boiler, steam turbine in plant-related (manufacturing plant, energy supply plant, etc.), transportation equipment-related (vehicle, ship, aircraft, space equipment, etc.), other facilities, equipment, equipment, etc. In a gas turbine or the like, it can be used for a member (furnace wall material or the like) in a high temperature environment having an upper limit of 1400 ° C., for example.
１０Ａ，１０Ｂ，１０Ｃ：積層材料
１２：アルミナ系材料からなる層又は膜又は基部
１４：Ａｌ固溶Ｙ２Ｔｉ２Ｏ７からなる層又は膜又は基部
１６：他の材料からなる層又は基部
２０：噴射工程用装置
２１：エアロゾル発生機
２２：エアロゾル搬送用配管
２３：製膜室
２５：微粒子噴射用ノズル
２７：基材
２９：真空ポンプ
３１：微粒子容器
３３：α−アルミナ結晶微粒子（α−アルミナ微粒子）
３５：微粒子撒き上げ用ガス供給部
３７：エアロゾル搬送用ガス供給部
３９：ヒーター
10A, 10B, 10C: Laminate material 12: Layer or film or base portion made of alumina material 14: Layer or film or base portion 16 made of Al solid solution Y 2 Ti 2 O 7 16: Layer or base portion 20 made of another material Injection process device 21: aerosol generator 22: aerosol transport pipe 23: film forming chamber 25: fine particle injection nozzle 27: base material 29: vacuum pump 31: fine particle container 33: α-alumina crystal fine particle (α-alumina fine particle )
35: Gas supply unit for lifting fine particles 37: Gas supply unit for aerosol transport 39: Heater
Claims (5)
前記層（Ｂ）を構成する前記Ａｌ固溶Ｙ２Ｔｉ２Ｏ７におけるＡｌ原子の含有割合は、Ａｌ原子、Ｙ原子及びＴｉ原子の合計量を１００原子％とした場合に、０．５〜１．８原子％であることを特徴とする積層材料。 A layered material comprising a layer (A) made of an alumina-based material and a layer (B) made of Y 2 Ti 2 O 7 bonded to the layer (A) and in which Al atoms are dissolved,
The content ratio of Al atoms in the Al solid solution Y 2 Ti 2 O 7 constituting the layer (B) is 0.5 to 0.5 when the total amount of Al atoms, Y atoms and Ti atoms is 100 atomic%. A laminated material characterized by being 1.8 atomic%.
アルミナ系材料からなる微粒子を含むエアロゾルを、Ａｌ固溶Ｙ２Ｔｉ２Ｏ７からなる基材の表面に噴射して、前記微粒子を前記基材の表面に堆積させる噴射工程を備え、
前記基材を構成する前記Ａｌ固溶Ｙ２Ｔｉ２Ｏ７におけるＡｌ原子の含有割合は、Ａｌ原子、Ｙ原子及びＴｉ原子の合計量を１００原子％とした場合に、０．５〜１．８原子％であることを特徴とする積層材料の製造方法。 It is a manufacturing method of the lamination material according to claim 2,
An injection step of spraying an aerosol containing fine particles made of an alumina-based material onto the surface of a base material made of Al solid solution Y 2 Ti 2 O 7 and depositing the fine particles on the surface of the base material;
The content ratio of Al atoms in the Al solid solution Y 2 Ti 2 O 7 constituting the substrate is 0.5 to 1. When the total amount of Al atoms, Y atoms and Ti atoms is 100 atomic%. A method for producing a laminated material, characterized in that the content is 8 atomic%.
Ａｌ固溶Ｙ２Ｔｉ２Ｏ７からなる微粒子を含むエアロゾルを、アルミナ系材料からなる基材の表面に噴射して、前記微粒子を前記基材の表面に堆積させる噴射工程を備え、
前記微粒子を構成する前記Ａｌ固溶Ｙ２Ｔｉ２Ｏ７におけるＡｌ原子の含有割合は、Ａｌ原子、Ｙ原子及びＴｉ原子の合計量を１００原子％とした場合に、０．５〜１．８原子％であることを特徴とする積層材料の製造方法。 It is a manufacturing method of the lamination material according to claim 3,
An injection step of spraying an aerosol containing fine particles of Al solid solution Y 2 Ti 2 O 7 on the surface of a substrate made of an alumina-based material and depositing the fine particles on the surface of the substrate;
The content ratio of Al atoms in the Al solid solution Y 2 Ti 2 O 7 constituting the fine particles is 0.5 to 1.8 when the total amount of Al atoms, Y atoms and Ti atoms is 100 atomic%. A method for producing a laminated material, characterized in that it is atomic%.
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