JP6092615B2 - Thermal barrier coating materials - Google Patents
Thermal barrier coating materials Download PDFInfo
- Publication number
- JP6092615B2 JP6092615B2 JP2012283602A JP2012283602A JP6092615B2 JP 6092615 B2 JP6092615 B2 JP 6092615B2 JP 2012283602 A JP2012283602 A JP 2012283602A JP 2012283602 A JP2012283602 A JP 2012283602A JP 6092615 B2 JP6092615 B2 JP 6092615B2
- Authority
- JP
- Japan
- Prior art keywords
- barrier coating
- thermal barrier
- coating material
- compound
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012720 thermal barrier coating Substances 0.000 title claims description 43
- 239000000463 material Substances 0.000 title claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000010290 vacuum plasma spraying Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Description
本発明は、低熱伝導性に優れる皮膜等の形成に用いられる遮熱コーティング用材料に関する。 The present invention relates to a thermal barrier coating material used for forming a film having excellent low thermal conductivity.
従来、発電用ガスタービンエンジン、航空機用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、このイットリア安定化ジルコニアより低い熱伝導率を与える材料の探索が行われてきた。 2. Description of the Related Art Conventionally, in a gas turbine engine for power generation, an aircraft jet engine, and the like, since the combustion gas is high temperature, the surface of a high-temperature component such as a moving blade, stationary blade, or combustor is coated with a thermal barrier coating: A coating referred to as TBC) is applied. The surface of the thermal barrier coating is provided with corrosion resistance, oxidation resistance, heat resistance, and the like. Although materials containing yttria-stabilized zirconia are widely used for the formation of this film, in recent years, a search has been made for materials that give lower thermal conductivity than yttria-stabilized zirconia.
特許文献１には、Ａ２Ｂ２Ｏ７で表されるパイロクロール構造を有する化合物（Ｌａ２Ｚｒ２Ｏ７等）を含む皮膜を有する金属物体が開示されている。
特許文献２には、希土類安定化ジルコニア及び希土類安定化ジルコニア−ハフニアに、酸化ランタンを０．１〜１０ｍｏｌ％添加したセラミックスからなる遮熱層を有する遮熱コーティング部材が開示されている。
特許文献３には、Ｌｎ３Ｎｂ１−ｘＴａｘＯ７（０≦ｘ≦１、ＬｎはＳｃ、Ｙ及びランタノイドからなる群より選択される１種又は２種以上の原子）で表される化合物を主として含む遮熱コーティング用材料が開示されている。
特許文献４には、Ｌｎ１−ｘＭｘＯ１．５＋ｘ（０．１３≦ｘ≦０．２４、ＬｎはＳｃ、Ｙ及びランタノイドからなる群より選択される１種又は２種以上の原子、ＭはＴａ又はＮｂ）で表される化合物を主として含む遮熱コーティング用材料が開示されている。
また、特許文献５には、Ｌｎｘ＋ｙ−３ｘｙＴｉｘＴａｘＺｒ(１−３ｘ)（１−ｙ）Ｏ２＋１．５ｘｙ−０．５ｙ（０．０５≦ｘ≦０．２５、０≦ｙ≦０．１５、Ｌｎは、Ｙ、Ｓｍ、Ｙｂ及びＮｄからなる群より選択される１種又は２種以上の原子）を主として含む遮熱コーティング用材料が開示されている。
Patent Document 2 discloses a thermal barrier coating member having a thermal barrier layer made of a ceramic obtained by adding 0.1 to 10 mol% of lanthanum oxide to rare earth stabilized zirconia and rare earth stabilized zirconia-hafnia.
In Patent Document 3, it is represented by Ln 3 Nb 1-x Ta x O 7 (0 ≦ x ≦ 1, Ln is one or more atoms selected from the group consisting of Sc, Y and lanthanoid). A thermal barrier coating material mainly comprising a compound is disclosed.
In Patent Document 4, Ln 1-x M x O 1.5 + x (0.13 ≦ x ≦ 0.24, Ln is one or more atoms selected from the group consisting of Sc, Y and lanthanoids, A thermal barrier coating material mainly containing a compound represented by M being Ta or Nb) is disclosed.
Further, Patent Document 5, Ln x + y-3xy Ti x Ta x Zr (1-3x) (1-y) O 2 + 1.5xy-0.5y (0.05 ≦ x ≦ 0.25,0 ≦ y ≦ 0.15, Ln is a thermal barrier coating material mainly containing one or more atoms selected from the group consisting of Y, Sm, Yb and Nd).
本発明の目的は、低熱伝導性に優れる皮膜等の形成に用いられる遮熱コーティング用材料、及び、この材料を用いて形成された皮膜を備える物品を提供することである。 An object of the present invention is to provide a thermal barrier coating material used for forming a coating having excellent low thermal conductivity, and an article provided with the coating formed using this material.
本発明者らは、ＡＢ３Ｏ９で表される複合酸化物について検討を行い、本発明を完成するに至った。
本発明は、以下に示される。
１．下記一般式（１）で表される化合物を含む遮熱コーティング用材料。
Ｍ１Ｍ２ ３Ｏ９ （１）
（式中、Ｍ１は、イットリウム原子であり、Ｍ２は、タンタル原子である。）
２．上記１に記載の遮熱コーティング用材料を含む皮膜を備える物品。
The present inventors have studied a composite oxide represented by AB 3 O 9 and have completed the present invention.
The present invention is shown below.
1. A thermal barrier coating material comprising a compound represented by the following general formula (1).
M 1 M 2 3 O 9 (1)
(In the formula, M 1 is an yttrium atom, and M 2 is a tantalum atom .)
2 . An article comprising a coating containing the thermal barrier coating material according to 1 above.
本発明の遮熱コーティング用材料は、低熱伝導性に優れる皮膜等の形成に好適である。上記一般式（１）で表される化合物は、融点が１，４００℃以上と高く、熱的に安定であることから、遮熱コーティング用材料を用いて、金属、合金、耐熱性酸化物等からなる部材の表面に対して安定な皮膜形成を進めることができる。
本発明の物品は、好ましくは、基体と、その表面に、直接、又は、中間層を介して、遮熱コーティング材料を用いて形成された皮膜（遮熱コーティング）とを備える構成であり、１，４００℃〜１，７００℃程度の温度で、低熱伝導性、耐食性、耐酸化性、耐熱性、断熱性等における長寿命化の求められる用途に好適である。
The thermal barrier coating material of the present invention is suitable for forming a film having excellent low thermal conductivity. Since the compound represented by the general formula (1) has a high melting point of 1,400 ° C. or higher and is thermally stable, a metal, an alloy, a heat-resistant oxide, etc. are used using a thermal barrier coating material. A stable film can be formed on the surface of the member made of
The article of the present invention preferably comprises a substrate and a film (thermal barrier coating) formed on the surface thereof directly or via an intermediate layer using a thermal barrier coating material. , 400 ° C to 1,700 ° C, and suitable for applications requiring long life in low thermal conductivity, corrosion resistance, oxidation resistance, heat resistance, heat insulation, and the like.
本発明の遮熱コーティング用材料は、下記一般式（１）で表される化合物を含むことを特徴とする。
Ｍ１Ｍ２ ３Ｏ９ （１）
（式中、Ｍ１は、イットリウム原子であり、Ｍ２は、タンタル原子である。）
The thermal barrier coating material of the present invention is characterized by containing a compound represented by the following general formula (1).
M 1 M 2 3 O 9 (1)
(In the formula, M 1 is an yttrium atom, and M 2 is a tantalum atom.)
上記一般式（１）における原子Ｍ１は、イットリウム（Ｙ）である。 Atom M 1 in the general formula (1) is Ru yttrium (Y) der.
上記一般式（１）における原子Ｍ２は、タンタル原子である。 The atom M 2 in the general formula (1) is a tantalum atom .
上記一般式（１）で表される化合物は、カチオン欠損型の欠陥ペロブスカイト型複合酸化物（以下、「複合酸化物」ともいう。）であり、図１に示すような構造を有する。この構造は、Ａ３Ｂ３Ｏ９で表されるペロブスカイト構造から、２／３のＡイオン（図１における×印）が欠損した構造である。
本発明の遮熱コーティング用材料がこの構造を有する複合酸化物を含むことにより、低熱伝導性に優れた皮膜を得ることができる。
The compound represented by the general formula (1) is a cation-deficient defect perovskite complex oxide (hereinafter also referred to as “composite oxide”) and has a structure as shown in FIG. This structure is a structure in which 2/3 of the A ions (marked with x in FIG. 1) are missing from the perovskite structure represented by A 3 B 3 O 9 .
By including the composite oxide having this structure in the thermal barrier coating material of the present invention, a film excellent in low thermal conductivity can be obtained.
上記複合酸化物の融点は、通常、１，４００℃以上であり、ＪＩＳ Ｒ１６１１に準じて、レーザーフラッシュ法により測定される熱伝導度（測定温度：２０℃〜１，０００℃）が、好ましくは３．０Ｗ／（ｍ・Ｋ）未満、より好ましくは２．８Ｗ／（ｍ・Ｋ）未満である。 The melting point of the composite oxide is usually 1,400 ° C. or higher, and the thermal conductivity measured by the laser flash method according to JIS R1611 (measurement temperature: 20 ° C. to 1,000 ° C.) is preferably It is less than 3.0 W / (m · K), more preferably less than 2.8 W / (m · K).
本発明の遮熱コーティング用材料は、上記複合酸化物のみからなることが好ましい。 The thermal barrier coating material of the present invention preferably comprises only the above complex oxide.
本発明の遮熱コーティング用材料を、電子ビーム物理気相堆積（ＥＢ−ＰＶＤ）、プラズマ溶射、真空プラズマ溶射、フレーム溶射、高速溶射、焼結等の方法に供することにより、所望の材料からなる基体等の表面に、安定な皮膜を形成することができる。 The thermal barrier coating material of the present invention is made of a desired material by being subjected to methods such as electron beam physical vapor deposition (EB-PVD), plasma spraying, vacuum plasma spraying, flame spraying, high-speed spraying, and sintering. A stable film can be formed on the surface of a substrate or the like.
上記複合酸化物の製造方法は、一般式（１）における原子Ｍ１を含む化合物（以下、「化合物（ｍ１）」という。）と、原子Ｍ２を含む化合物（以下、「化合物（ｍ２）」という。）とを、原子Ｍ１及び原子Ｍ２のモル比が所定の割合となるように配合し、これを熱処理する方法が一般的である。更に、より均質な複合酸化物を得るために、例えば、尿素を含む混合物とした後、これを熱処理する方法もある。 The method for producing the composite oxide includes a compound containing the atom M 1 in the general formula (1) (hereinafter referred to as “compound (m1)”) and a compound containing the atom M 2 (hereinafter referred to as “compound (m2)”. Is generally blended so that the molar ratio of the atoms M 1 and M 2 is a predetermined ratio, and this is heat-treated. Furthermore, in order to obtain a more homogeneous composite oxide, for example, there is a method in which after making a mixture containing urea, this is heat-treated.
上記化合物（ｍ１）及び化合物（ｍ２）としては、酸化物、水酸化物、硫酸塩、炭酸塩、硝酸塩、リン酸塩、ハロゲン化物等を用いることができる。これらのうち、組成がより均一な複合酸化物を得る場合には、水溶性化合物が好ましいが、水不溶性化合物を用いることもできる。 As the compound (m1) and the compound (m2), oxides, hydroxides, sulfates, carbonates, nitrates, phosphates, halides, and the like can be used. Among these, when obtaining a complex oxide having a more uniform composition, a water-soluble compound is preferable, but a water-insoluble compound can also be used.
上記複合酸化物の好ましい製造方法は、以下の通りである。
初めに、原子Ｍ１及び原子Ｍ２のモル比が１：３となるように配合した、化合物（ｍ１）及び化合物（ｍ２）と、尿素とを含む水溶液又は水分散液（懸濁液）を調製する。この混合液に含まれる化合物（ｍ１）、化合物（ｍ２）及び尿素の濃度は、それぞれ、好ましくは０．０２〜０．１ｍｏｌ／ｌ、０．０２〜０．１ｍｏｌ／ｌ及び２〜１０ｍｏｌ／ｌ、より好ましくは０．０２〜０．０５ｍｏｌ／ｌ、０．０２〜０．０５ｍｏｌ／ｌ及び２〜５ｍｏｌ／ｌである。
次に、混合液を、還流冷却下、８０℃〜９５℃の温度で加熱して尿素加水分解反応を行う。反応時間は、通常、１０〜２０時間である。
その後、反応系に含まれる反応生成物の形態によって、必要に応じて、遠心分離等を行い、反応生成物を回収する。そして、水、アルコール等を用いて洗浄し、乾燥させ、必要に応じて、粉砕することにより、第１前駆化合物からなる粉体を得る。
次に、第１前駆化合物からなる粉体を整粒し、必要に応じて、プレス成形等に供して、板状、塊状等の成形物を作製する。そして、この成形物を、酸素ガスを含む雰囲気下、１，２００℃〜１，５００℃の温度で、１〜３時間程度の熱処理（仮焼）を行い、第２前駆化合物からなる仮焼物を得る。この第２前駆化合物は、単一化合物ではなく、Ｍ１Ｍ２ ３Ｏ９、Ｍ１Ｍ２ ７Ｏ１９等の混合物と推定される。
その後、得られた仮焼物を、必要に応じて、粉砕、整粒する。そして、必要に応じて、プレス成形等に供して、板状、塊状等の成形物を作製し、この成形物を、酸素ガスを含む雰囲気下、１，４００℃〜１，７００℃の温度で、１〜３時間程度の熱処理を行い、上記一般式（１）で表される複合酸化物を得る。
A preferred method for producing the composite oxide is as follows.
First , an aqueous solution or aqueous dispersion (suspension) containing the compound (m1) and the compound (m2) and urea, blended so that the molar ratio of the atoms M 1 and the atoms M 2 is 1: 3. Prepare. The concentrations of compound (m1), compound (m2) and urea contained in this mixed solution are preferably 0.02 to 0.1 mol / l, 0.02 to 0.1 mol / l and 2 to 10 mol / l, respectively. More preferably, they are 0.02-0.05 mol / l, 0.02-0.05 mol / l, and 2-5 mol / l.
Next, the mixed liquid is heated at a temperature of 80 ° C. to 95 ° C. under reflux cooling to perform a urea hydrolysis reaction. The reaction time is usually 10 to 20 hours.
Thereafter, depending on the form of the reaction product contained in the reaction system, centrifugation or the like is performed as necessary to collect the reaction product. And it wash | cleans using water, alcohol, etc., it is made to dry, and the powder which consists of a 1st precursor compound is obtained by grind | pulverizing as needed.
Next, the powder composed of the first precursor compound is sized and, if necessary, subjected to press molding or the like to produce a molded product such as a plate or lump. And this molded product is heat-treated (calcination) for about 1 to 3 hours at a temperature of 1,200 ° C. to 1,500 ° C. in an atmosphere containing oxygen gas, and a calcined product made of the second precursor compound is obtained. obtain. This second precursor compound is not a single compound, but a mixture of M 1 M 2 3 O 9 , M 1 M 2 7 O 19 and the like.
Thereafter, the obtained calcined product is pulverized and sized as necessary. Then, if necessary, it is subjected to press molding or the like to produce a molded product such as a plate or a lump, and this molded product is subjected to a temperature of 1,400 ° C. to 1,700 ° C. in an atmosphere containing oxygen gas. Then, heat treatment is performed for about 1 to 3 hours to obtain a composite oxide represented by the general formula (1).
本発明の遮熱コーティング用材料を用いて、金属、合金等の材料からなる基体の表面に、直接、又は、間接的に、遮熱コーティング（皮膜）を形成し、一体化された物品（遮熱コーティング付き物品）を得ることができる。本発明の物品の概略断面を図５及び図６に示す。
図５は、基体１５と、この基体１５の表面に配された遮熱コーティング（皮膜）１１とを備える物品（遮熱コーティング付き物品）１を示す。図６は、基体１５と、中間層１３と、遮熱コーティング（皮膜）１１とを、順次、備える物品（遮熱コーティング付き物品）１を示す。この構成により、１，４００℃〜１，７００℃程度の温度で、低熱伝導性、耐食性、耐酸化性、耐熱性、断熱性等における長寿命化の求められる用途に好適である。
Using the thermal barrier coating material of the present invention, a thermal barrier coating (film) is formed directly or indirectly on the surface of a substrate made of a material such as a metal or an alloy, and an integrated article (shield) is formed. Articles with thermal coating can be obtained. A schematic cross section of the article of the present invention is shown in FIGS.
FIG. 5 shows an article (article with a thermal barrier coating) 1 including a
遮熱コーティング（皮膜）１１の形成方法は、上記例示した方法等とすることができる。また、遮熱コーティング（皮膜）１１の厚さは、目的、用途等に応じて、適宜、選択され、低熱伝導性、耐食性、耐酸化性、耐熱性、断熱性、基体又は中間層の保護効果等の観点から、下限値は、通常、３００μｍである。尚、遮熱コーティング（皮膜）１１の厚さが大きいほど、上記性質に優れることは言うまでもないが、大型の物品に適用する場合には、その膜厚を、公知の場合より小さくすることも可能である。そして、軽量化を実現した遮熱コーティング付き物品を得ることができる。 The method for forming the thermal barrier coating (film) 11 may be the method exemplified above. In addition, the thickness of the thermal barrier coating (film) 11 is appropriately selected according to the purpose, application, etc., and has low thermal conductivity, corrosion resistance, oxidation resistance, heat resistance, heat insulation, and protective effect on the base or intermediate layer. From such a viewpoint, the lower limit value is usually 300 μm. It goes without saying that the larger the thickness of the thermal barrier coating (film) 11 is, the better the above properties are. However, when applied to a large article, the film thickness can be made smaller than in the known case. It is. And the article with the thermal barrier coating which implement | achieved weight reduction can be obtained.
本発明を、航空機用ジェットエンジンにおける燃焼器、及び、発電用ガスタービンにおける高温部品に適用する場合、例えば、Ｎｉを含む合金からなる基体１５の表面に配された、ＭＣｒＡｌＹ合金（Ｍ：Ｃｏ、Ｎｉ、Ｆｅ）等からなる耐酸化性中間層１３、そして、この中間層１３の表面に配された、本発明の遮熱コーティング用材料を含む皮膜１１を備えるものとすることができる（図６参照）。この構成において、本発明に係る遮熱コーティング（皮膜）を備えることにより、１，４００℃〜１，７００℃程度の高い温度で耐久性を得ることができる。
When the present invention is applied to a combustor in an aircraft jet engine and a high-temperature component in a power generation gas turbine, for example, an MCrAlY alloy (M: Co, arranged on the surface of a
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。尚、下記において、部及び％は、特に断らない限り、質量基準である。
遮熱コーティング用材料の製造に係る中間生成物（仮焼物）及び最終生成物（複合酸化物）について、Ｘ線回折測定を行った。
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. In the following, “part” and “%” are based on mass unless otherwise specified.
X-ray diffraction measurement was performed on the intermediate product (calcined product) and the final product (composite oxide) related to the production of the thermal barrier coating material.
実施例１（ＹＴａ３Ｏ９を含む遮熱コーティング用材料の製造）
フッ素樹脂製の反応器に収容した蒸留水９００グラムに、純度９９．９９％以上のＹ（ＮＯ３）３・６Ｈ２Ｏ粉末（関東化学社製）１０グラム（０．０２５モル）を入れて、室温（２５℃）で１時間撹拌し、無色透明の水溶液を得た。次いで、この水溶液に、尿素１９０グラム（３モル）を投入し、室温（２５℃）で１時間撹拌した。その後、得られた無色透明の水溶液に、純度９９．９％以上のＴａ２Ｏ５粉末（レアメタリック社製）１７グラム（０．０３８モル）を投入し、室温（２５℃）で７時間撹拌し、懸濁液を得た。
次に、懸濁液を加熱して９５℃とし、還流冷却しながら、攪拌下、反応（尿素加水分解反応）させた（反応時間：１５時間）。その後、得られた反応液を、２５℃、４，８００ｒｐｍで３０分間遠心分離し、下層のゲルを回収した。このゲルを、大量の蒸留水に投入し、十分に撹拌したところで、上記と同じ条件で遠心分離し、下層のゲルを回収した。そして、このゲルを、大量のイソプロピルアルコールに投入し、十分に撹拌したところで、上記と同じ条件で遠心分離し、沈殿物を回収した。
その後、沈殿物を、大気雰囲気中、１２０℃で２４時間加熱し、乾燥粉末とした。次いで、この乾燥粉末をふるい（１００メッシュ）にかけて、微粉末を回収した。そして、この微粉末を、プレス成形（圧力５ＭＰａ）に供し、円板形状の成形体を作製した。その後、この成形体を、大気雰囲気中、１，４００℃で１時間熱処理（仮焼）し、仮焼成形体を得た。得られた仮焼成形体を、室温（２５℃）で、乳鉢により乾式粉砕し、そのＸ線回折測定を行ったところ、仮焼物は、ＹＴａ７Ｏ１９を主として含むことが分かった（図２（Ａ）参照）。
次いで、乾式粉砕物をふるい（１００メッシュ）にかけて、微粉末を回収した。そして、この微粉末を、プレス成形（圧力２５ＭＰａ）に供し、更に、冷間等方静水圧加圧（荷重２．５トン）を行って、円板形状の成形体を作製した。その後、この成形体を大気雰囲気中、１，６５０℃で１時間熱処理した。得られた焼成体を、室温（２５℃）で、乳鉢により乾式粉砕し、そのＸ線回折測定を行ったところ、焼成物は、実質的にＹＴａ３Ｏ９からなる単斜晶系であることが分かった（図２（Ｂ）参照）。また、焼成物を目視観察したところ、１，６５０℃における高温熱処理により、溶融等を伴っていないことを確認した。密度ρは６．９４ｇ／ｃｍ３であった。
上記のようにして得られた焼成物を、そのまま遮熱コーティング用材料とした。
Example 1 (Production of thermal barrier coating material containing YTa 3 O 9 )
Distilled water 900 g were housed in a fluororesin-made reactor, purity of 99.99% or higher Y (NO 3) 3 · 6H ( Kanto Chemical) 2 O powder placed for 10 grams (0.025 moles) The mixture was stirred at room temperature (25 ° C.) for 1 hour to obtain a colorless and transparent aqueous solution. Next, 190 g (3 mol) of urea was added to the aqueous solution, and the mixture was stirred at room temperature (25 ° C.) for 1 hour. Thereafter, 17 g (0.038 mol) of Ta 2 O 5 powder (manufactured by Rare Metallic) having a purity of 99.9% or more was added to the obtained colorless and transparent aqueous solution and stirred at room temperature (25 ° C.) for 7 hours. To obtain a suspension.
Next, the suspension was heated to 95 ° C. and reacted (urea hydrolysis reaction) with stirring while cooling under reflux (reaction time: 15 hours). Thereafter, the obtained reaction solution was centrifuged at 25 ° C. and 4,800 rpm for 30 minutes to recover the lower layer gel. When this gel was poured into a large amount of distilled water and sufficiently stirred, it was centrifuged under the same conditions as above to recover the lower layer gel. The gel was poured into a large amount of isopropyl alcohol, and when sufficiently stirred, the gel was centrifuged under the same conditions as described above to collect the precipitate.
Thereafter, the precipitate was heated in an air atmosphere at 120 ° C. for 24 hours to obtain a dry powder. The dried powder was then sieved (100 mesh) to collect a fine powder. And this fine powder was used for press molding (pressure 5MPa), and the disk-shaped molded object was produced. Then, this molded object was heat-processed (calcination) for 1 hour at 1,400 degreeC in air | atmosphere atmosphere, and the temporary baking molded object was obtained. The obtained calcined shape was dry-ground with a mortar at room temperature (25 ° C.) and subjected to X-ray diffraction measurement. As a result, it was found that the calcined product mainly contains YTa 7 O 19 (FIG. 2 ( A)).
Next, the dry pulverized product was sieved (100 mesh) to collect a fine powder. The fine powder was subjected to press molding (pressure 25 MPa), and further subjected to cold isostatic pressing (load 2.5 tons) to produce a disk-shaped molded body. Thereafter, the compact was heat-treated at 1,650 ° C. for 1 hour in an air atmosphere. The obtained fired product was dry-ground with a mortar at room temperature (25 ° C.) and subjected to X-ray diffraction measurement. As a result, the fired product was substantially monoclinic composed of YTa 3 O 9. (See FIG. 2B). Further, when the fired product was visually observed, it was confirmed that it was not melted by high-temperature heat treatment at 1,650 ° C. The density ρ was 6.94 g / cm 3 .
The fired product obtained as described above was directly used as a thermal barrier coating material.
上記焼成物を、超音波パルス法（ＪＩＳ Ｒ１６０２に準拠）に供して、２５℃における弾性率Ｅを計測し、下記式（５）により、最小熱伝導率κｍｉｎを算出し、０．９７Ｗ／（ｍ・Ｋ）を得た（表１参照）。
κｍｉｎ＝０．８７ｋＢ・Ωａ −２／３・（Ｅ／ρｉ）１／２ （５）
（式中、ｋＢはボルツマン定数、Ωａは有効原子体積でありΩａ＝Ｍ／（ｍ・ρｉ・ＮＡ）、Ｅは弾性率、ρｉは理論密度、Ｍは分子量、ｍは原子数／分子、ＮＡはアボガドロ数である。）
The fired product is subjected to an ultrasonic pulse method (based on JIS R1602), the elastic modulus E at 25 ° C. is measured, and the minimum thermal conductivity κ min is calculated by the following equation (5), 0.97 W / (M · K) was obtained (see Table 1).
κ min = 0.87k B · Ω a -2/3 · (E / ρ i) 1/2 (5)
(Where B is the Boltzmann constant, Ω a is the effective atomic volume and Ω a = M / (m · ρ i · N A ), E is the elastic modulus, ρ i is the theoretical density, M is the molecular weight, and m is atoms / molecules, N a is Avogadro's number.)
更に、上記焼成物を、レーザーフラッシュ法（ＪＩＳ Ｒ１６１１に準拠）に供して、２５℃、２００℃、４００℃、６００℃、８００℃及び１，０００℃における熱伝導率を測定した。その結果を図４に示す。 Furthermore, the fired product was subjected to a laser flash method (based on JIS R1611), and the thermal conductivity at 25 ° C., 200 ° C., 400 ° C., 600 ° C., 800 ° C. and 1,000 ° C. was measured. The result is shown in FIG.
参考例（ＬａＴａ３Ｏ９を含む遮熱コーティング用材料の製造）
出発原料であるＹ（ＮＯ３）３・６Ｈ２Ｏ粉末に代えて、純度９９．９９％以上のＬａ（ＮＯ３）３・６Ｈ２Ｏ粉末（関東化学社製）を用いた以外は、実施例１と同様にして、ＬａＴａ３Ｏ９を含む遮熱コーティング用材料を得た。仮焼物のＸ線回折像は、図３における（Ａ）であり、ＬａＴａ３Ｏ９及びＬａＴａ７Ｏ１９を主として含むことが分かる。また、焼成物のＸ線回折像は、図３における（Ｂ）であり、実質的にＬａＴａ３Ｏ９からなる正方晶系であることが分かった。また、焼成物を目視観察したところ、１，６５０℃における高温熱処理により、溶融等を伴っていないことを確認した。密度ρは７．２５ｇ／ｃｍ３であった。
また、実施例１と同様にして得られた、２５℃、２００℃、４００℃、６００℃、８００℃及び１，０００℃における熱伝導率を図４に示すとともに、これらの計測値と、最小熱伝導率κｍｉｎ等とを表１に示した。
Reference example (production of a thermal barrier coating material containing LaTa 3 O 9 )
Instead of Y (NO 3) 3 · 6H 2 O powder as a starting material, except for using 99.99% pure or more La (NO 3) 3 · 6H 2 O powder (manufactured by Kanto Chemical Co., Inc.) is performed In the same manner as in Example 1, a thermal barrier coating material containing LaTa 3 O 9 was obtained. The X-ray diffraction image of the calcined product is (A) in FIG. 3, and it can be seen that it mainly includes LaTa 3 O 9 and LaTa 7 O 19 . Further, the X-ray diffraction image of the fired product is (B) in FIG. 3, and was found to be a tetragonal system substantially composed of LaTa 3 O 9 . Further, when the fired product was visually observed, it was confirmed that it was not melted by high-temperature heat treatment at 1,650 ° C. The density ρ was 7.25 g / cm 3 .
Moreover, while showing the thermal conductivity in 25 degreeC, 200 degreeC, 400 degreeC, 600 degreeC, 800 degreeC, and 1,000 degreeC obtained similarly to Example 1, these measured values and minimum The thermal conductivity κ min and the like are shown in Table 1.
尚、図４には、従来、遮熱コーティング用材料として知られているイットリア安定化ジルコニア（ＹＳＺ）の熱伝導率を示した。このデータは、Ｍ．Ｒ．Ｗｉｎｔｅｒら、Ｊ．Ａｍ．Ｃｅｒａｍ．Ｓｏｃ． ９０（２００７） ５３３−５４０から引用したものである。図４から明らかなように、実施例１及び参考例の熱伝導率は、いずれも、イットリア安定化ジルコニア（ＹＳＺ）の熱伝導率よりも低く、遮熱性に優れることが分かる。 FIG. 4 shows the thermal conductivity of yttria-stabilized zirconia (YSZ), which is conventionally known as a thermal barrier coating material. This data is from R. Winter et al. Am. Ceram. Soc. 90 (2007) 533-540. As is clear from FIG. 4, the thermal conductivity of Example 1 and the reference example are both lower than the thermal conductivity of yttria-stabilized zirconia (YSZ), and it can be seen that the thermal conductivity is excellent.
本発明の遮熱コーティング用材料によれば、低熱伝導性に優れる皮膜を、従来、公知の溶射等の方法により、金属、合金等からなる部材又はその表面に配された層（中間層用の層）の表面に効率よく形成することができる。そして、この構成は、航空機用ジェットエンジンにおける燃焼器、発電用ガスタービンにおける高温部品、その他、各種プラントにおける高温部品等への適用に好適である。 According to the material for thermal barrier coating of the present invention, a film excellent in low thermal conductivity is conventionally formed by a known method such as thermal spraying or the like, or a layer disposed on the surface thereof (for intermediate layer) Can be efficiently formed on the surface of the layer. This configuration is suitable for application to a combustor in an aircraft jet engine, a high-temperature component in a power generation gas turbine, and other high-temperature components in various plants.
１：遮熱コーティング付き物品
１１：遮熱コーティング層
１３：中間層
１５：基体
1: Article with thermal barrier coating 11: Thermal barrier coating layer 13: Intermediate layer 15: Substrate
Claims (2)
Ｍ１Ｍ２ ３Ｏ９ （１）
（式中、Ｍ１は、イットリウム原子であり、Ｍ２は、タンタル原子である。） A thermal barrier coating material comprising a compound represented by the following general formula (1).
M 1 M 2 3 O 9 (1)
(In the formula, M 1 is an yttrium atom, and M 2 is a tantalum atom.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012283602A JP6092615B2 (en) | 2012-12-26 | 2012-12-26 | Thermal barrier coating materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012283602A JP6092615B2 (en) | 2012-12-26 | 2012-12-26 | Thermal barrier coating materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014125656A JP2014125656A (en) | 2014-07-07 |
| JP6092615B2 true JP6092615B2 (en) | 2017-03-08 |
Family
ID=51405406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012283602A Active JP6092615B2 (en) | 2012-12-26 | 2012-12-26 | Thermal barrier coating materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6092615B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6173778B2 (en) * | 2013-06-05 | 2017-08-02 | 一般財団法人ファインセラミックスセンター | Thermal barrier coating materials |
| WO2019168174A1 (en) | 2018-03-02 | 2019-09-06 | 一般財団法人ファインセラミックスセンター | Thermal barrier coating |
| JP2019151927A (en) * | 2018-03-02 | 2019-09-12 | 一般財団法人ファインセラミックスセンター | Thermal barrier coating material and article |
| WO2020050227A1 (en) | 2018-09-03 | 2020-03-12 | 一般財団法人ファインセラミックスセンター | Thermal barrier coating material, and article |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58161924A (en) * | 1982-03-16 | 1983-09-26 | Agency Of Ind Science & Technol | Manufacture of transparent thin strip of crystalline oriented lanthanum niobate |
| US6117560A (en) * | 1996-12-12 | 2000-09-12 | United Technologies Corporation | Thermal barrier coating systems and materials |
| JP4481027B2 (en) * | 2003-02-17 | 2010-06-16 | 財団法人ファインセラミックスセンター | Thermal barrier coating member and manufacturing method thereof |
| JP2005154885A (en) * | 2003-03-26 | 2005-06-16 | Mitsubishi Heavy Ind Ltd | Material for thermal barrier coating |
| US20050129869A1 (en) * | 2003-12-12 | 2005-06-16 | General Electric Company | Article protected by a thermal barrier coating having a group 2 or 3/group 5 stabilization-composition-enriched surface |
| JP2006124734A (en) * | 2004-10-26 | 2006-05-18 | Mitsubishi Heavy Ind Ltd | Film material |
| JP4511987B2 (en) * | 2005-04-20 | 2010-07-28 | 三菱重工業株式会社 | Thermal barrier coating material |
| EP1862568A1 (en) * | 2006-05-30 | 2007-12-05 | Siemens Aktiengesellschaft | Thermal barrier coating with tungsten-bronze structure |
| JP2009221551A (en) * | 2008-03-17 | 2009-10-01 | Mitsubishi Heavy Ind Ltd | Thermal barrier coating material |
| JP2009191297A (en) * | 2008-02-12 | 2009-08-27 | Mitsubishi Heavy Ind Ltd | Thermal barrier coating material |
| JP2010235415A (en) * | 2009-03-31 | 2010-10-21 | Mitsubishi Heavy Ind Ltd | Material for thermal barrier coating, thermal barrier coating, turbine member, and gas turbine and method for producing material for thermal barrier coating |
-
2012
- 2012-12-26 JP JP2012283602A patent/JP6092615B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014125656A (en) | 2014-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7597971B2 (en) | Thermal barrier coating material | |
| Yuan et al. | SrCeO3 as a novel thermal barrier coating candidate for high–temperature applications | |
| Ma et al. | The thermal cycling behavior of Lanthanum–Cerium Oxide thermal barrier coating prepared by EB–PVD | |
| EP1862568A1 (en) | Thermal barrier coating with tungsten-bronze structure | |
| JP4511987B2 (en) | Thermal barrier coating material | |
| EP2186919B1 (en) | Heat-shielding coating material | |
| JP6092615B2 (en) | Thermal barrier coating materials | |
| JP2010235415A (en) | Material for thermal barrier coating, thermal barrier coating, turbine member, and gas turbine and method for producing material for thermal barrier coating | |
| JP2005501174A (en) | Thermal insulation layer for high temperature based on La2Zr2O7 | |
| JP2010255121A (en) | Film material | |
| JP5117372B2 (en) | Insulating material and its manufacturing method and application | |
| JP5610698B2 (en) | Thermal barrier coating material, thermal barrier coating, turbine component and gas turbine | |
| JP5285486B2 (en) | Thermal barrier coating material, thermal barrier coating, turbine component and gas turbine | |
| JP6173778B2 (en) | Thermal barrier coating materials | |
| Xu et al. | Infrared radiation and thermal cyclic performance of a high-entropy rare-earth hexaaluminate coating prepared by atmospheric plasma spraying | |
| JP7061099B2 (en) | Materials and articles for thermal barrier coating | |
| JP6941634B2 (en) | Thermal barrier coating | |
| Wang et al. | The hot corrosion behavior in vanadate environment and thermal cycling behaviors of YTZ and 2GYTZ for thermal barrier coating applications | |
| JP6216219B2 (en) | Thermal insulation structure | |
| JP2019151927A (en) | Thermal barrier coating material and article | |
| CN115010506A (en) | RE-Zr (Hf) co-doped gadolinium zirconate material, preparation method and thermal barrier coating | |
| CN114835488A (en) | Zirconia-based ceramic material without phase change and preparation method thereof | |
| Ryu et al. | Improvement of thermal insulating performance via entropy-stabilization in rare-earth zirconate structures | |
| Cao et al. | Hot corrosion behaviour of Gd2O3 doped LaMgAl11O19 thermal barrier coating exposed to molten V2O5 at 900° C | |
| Wang et al. | Preparation and thermo-physical properties of La2AlTaO7 ceramic for thermal barrier coating application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20140617 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20151021 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160905 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160913 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161018 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170131 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170209 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6092615 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |