JP2005200226A - 耐環境性皮膜材料及びそれを利用した皮膜構造体並びにセラミック構造物 - Google Patents
耐環境性皮膜材料及びそれを利用した皮膜構造体並びにセラミック構造物 Download PDFInfo
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- JP2005200226A JP2005200226A JP2004005216A JP2004005216A JP2005200226A JP 2005200226 A JP2005200226 A JP 2005200226A JP 2004005216 A JP2004005216 A JP 2004005216A JP 2004005216 A JP2004005216 A JP 2004005216A JP 2005200226 A JP2005200226 A JP 2005200226A
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- 239000000919 ceramic Substances 0.000 title claims description 46
- 239000000463 material Substances 0.000 title abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 175
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims abstract description 164
- 241000588731 Hafnia Species 0.000 claims abstract description 159
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 159
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 94
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 46
- 229910000167 hafnon Inorganic materials 0.000 claims abstract description 40
- 229910004129 HfSiO Inorganic materials 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims description 160
- 238000000576 coating method Methods 0.000 claims description 75
- 239000011248 coating agent Substances 0.000 claims description 74
- 239000000758 substrate Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 27
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 23
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 23
- 230000007613 environmental effect Effects 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- 239000002344 surface layer Substances 0.000 claims description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 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 claims description 7
- 229910006501 ZrSiO Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 40
- 238000005260 corrosion Methods 0.000 abstract description 40
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000007789 gas Substances 0.000 description 37
- 238000012360 testing method Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000002585 base Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 230000035882 stress Effects 0.000 description 12
- 239000012535 impurity Substances 0.000 description 9
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 8
- 239000011225 non-oxide ceramic Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
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- 238000000608 laser ablation Methods 0.000 description 3
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- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- -1 rare earth silicate Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- NAEKEHKTSNMBKE-UHFFFAOYSA-N [Si]([O-])([O-])([O-])O[Si]([O-])([O-])[O-].[Lu+3].[Lu+3] Chemical compound [Si]([O-])([O-])([O-])O[Si]([O-])([O-])[O-].[Lu+3].[Lu+3] NAEKEHKTSNMBKE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
【解決手段】 耐環境性皮膜材料は、ハフニア、ジルコニアを含むハフニア並びに希土類酸化物及び/又はシリカにより安定化されたハフニアまたはジルコニアを含むハフニアよりなる群から選ばれた1又は2以上を含む。更には、低熱膨張係数を有する基材を被覆する皮膜構造体において、ハフノン(HfSiO4)を基板1上に直接形成される第1層2とし、その上にハフニアを第2層3として皮膜するようにして耐環境性皮膜構造体を構成するようにしている。
【選択図】図1
Description
本発明の耐環境性皮膜材料は、ハフニア、ジルコニアを含むハフニア並びに希土類酸化物及び/又はシリカにより安定化されたハフニアあるいはジルコニアを含むハフニアの少なくともいずれか1つを主成分として含むものである。尚、本発明の耐環境性皮膜材料は、皮膜が複数層で構成されている場合には、少なくともトップコート層部分に、ハフニア、ジルコニアを含むハフニア並びに希土類酸化物及び/又はシリカにより安定化されたハフニアあるいはジルコニアを含むハフニアの少なくともいずれか1つを主成分として含むものであれば足りる。
以下に、ハフニアおよびジルコニアを含むハフニアについて静的な1500℃の環境下で水蒸気腐食試験を行ない、水蒸気の腐食に及ぼす影響、アルカリ成分の腐食に及ぼす影響が他の材料より優れることを実証した。また、実機相当の高速気流中においても(ハフニアおよび)ジルコニアを含むハフニアの耐食性が希土類シリケートよりも優れることを実証した。
Si3N4 + 3O2 → 3SiO2 + 2N2
SiO2 + HfO2 → HfSiO4
HfO2 + xSiO2 + 1/2xY2O3 → (SiO2,Y2O3)HfO2
HfO2 + xY2O3 → (Y2O3)HfO2
2 第1層
3 第2層
Claims (18)
- ハフニア、ジルコニアを含むハフニア並びに希土類酸化物及び/又はシリカにより安定化されたハフニアまたはジルコニアを含むハフニアよりなる群から選ばれた1又は2以上を含む耐環境性皮膜材料。
- 低熱膨張係数を有する基材を被覆する皮膜構造体において、ハフノン(HfSiO4)を前記基板上に直接形成される第1層とし、その上にハフニアを第2層として皮膜したことを特徴とする耐環境性皮膜構造体。
- 前記ハフニアは、ジルコニア(ZiO2)を含むものである請求項2記載の耐環境性皮膜構造体。
- 前記ハフニアは安定化されていることを特徴とする請求項3記載の耐環境性皮膜構造体。
- 前記ハフニアの安定化は希土類酸化物及びシリカよりなる群から選ばれた1つまたは2つによるものである請求項2から4のいずれかに記載の耐環境性皮膜構造体。
- 前記第2層は、ジルコニア含有率が前記第1層寄りの部分よりも表層寄りの部分の方が大きいものである請求項3から5のいずれかに記載の耐環境性皮膜構造体。
- 前記第2層は、前記第1層から離れるにしたがってジルコニア含有率が次第に増加するものである請求項6記載の耐環境性皮膜構造体。
- 前記第1層は、ハフノン(HfSiO4)を主成分とし、かつハフニア(HfO2)、ジルコニア(ZiO2)或いはシリカ(SiO2)の少なくともいずれか1つを含むハフニア−シリカ系酸化物層である請求項2から4のいずれかに記載の耐環境性皮膜構造体。
- 前記第2層としてジルコニアを含む希土類酸化物とシリカで安定化されたハフニアの層を成膜し、前記第2層のシリカ成分を前記第1層から皮膜表面に向けて徐々に減少するように傾斜させたことを特徴とする請求項4から8のいずれかに記載の耐環境性皮膜構造体。
- 前記第2層の前記第1層に最も近い部分にはシリカだけで安定化されたハフニアを、皮膜表面部分には希土類酸化物だけで安定化されたハフニアを形成するものである請求項9記載の耐環境性皮膜構造体。
- 前記第1層としてのハフニア−シリカ系酸化物層は、ハフニウムとシリコンの組成比が原子比で3:7から7:3の範囲の比率である請求項8,9または10のいずれかに記載の耐環境性皮膜構造体。
- 前記ハフニア−シリカ系酸化物層の膜厚は0.1μmから600μmである請求項11記載の耐環境性皮膜構造体。
- 前記第2層としての安定化ハフニア層は、副次相としてSiO2、Ln2Si2O7、Ln2SiO5、HfSiO4、ZrSiO4相のいずれか1つあるいは2つ以上を若干含むものである請求項4から11のいずれかに記載の耐環境性皮膜構造体。
- 前記安定化ハフニア層の膜厚は1μmから600μmである請求項13記載の耐環境性皮膜構造体。
- 前記安定化ハフニアは、希土類酸化物で立方晶系又は正方晶に安定化されており、ハフニアに対してモル比AO2(Aはハフニア):Ln2O3(Lnは希土類)が97:3から50:50の範囲とする請求項4から14のいずれかに記載の耐環境性皮膜構造体。
- 前記安定化ハフニアは、希土類酸化物とシリカで立方晶系又は正方晶に安定化されており、モル比AO2:Ln2O3及びSiO2が9:1から6:4の範囲とする請求項4から14のいずれかに記載の耐環境性皮膜構造体。
- 前記希土類酸化物は、Y2O3、La2O3、Nd2O3、Sm2O3、Gd2O3、Dy2O3、Ho2O3、Er2O3、Yb2O3、Lu2O3 よりなる群から選ばれた1又は2以上のハフニア安定化剤である請求項2記載の耐環境性皮膜構造体。
- 前記基材は窒化ケイ素セラミックス、炭化ケイ素セラミックス、或いはその複合体であり、その表面に請求項2〜17のいずれかに記載の前記皮膜セラミツク構造体を皮膜しているセラミック構造物。
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