JP4853952B2 - 炭素ドープ酸化ジルコニウム層を有する多機能材 - Google Patents
炭素ドープ酸化ジルコニウム層を有する多機能材 Download PDFInfo
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- JP4853952B2 JP4853952B2 JP2006100515A JP2006100515A JP4853952B2 JP 4853952 B2 JP4853952 B2 JP 4853952B2 JP 2006100515 A JP2006100515 A JP 2006100515A JP 2006100515 A JP2006100515 A JP 2006100515A JP 4853952 B2 JP4853952 B2 JP 4853952B2
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims description 95
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims description 95
- 239000007777 multifunctional material Substances 0.000 title claims description 33
- 239000010410 layer Substances 0.000 claims description 127
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 76
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 45
- 229910052726 zirconium Inorganic materials 0.000 claims description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 28
- 239000002344 surface layer Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 description 39
- 238000005253 cladding Methods 0.000 description 31
- 238000002485 combustion reaction Methods 0.000 description 29
- 239000000446 fuel Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
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- 239000004215 Carbon black (E152) Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
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- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- 239000011941 photocatalyst Substances 0.000 description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
- 239000003758 nuclear fuel Substances 0.000 description 3
- -1 oxygen Chemical compound 0.000 description 3
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910002076 stabilized zirconia 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
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000007545 Vickers hardness test Methods 0.000 description 2
- 229910000946 Y alloy Inorganic materials 0.000 description 2
- NDUKHFILUDZSHZ-UHFFFAOYSA-N [Fe].[Zr] Chemical compound [Fe].[Zr] NDUKHFILUDZSHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000012467 final product Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012857 radioactive material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910000711 U alloy Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical class [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910021652 non-ferrous alloy Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- 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
本発明の多機能材を発電用、航空機用のガスタービン翼に応用した一例を示す。
図3は、本発明の多機能材を適用した自動車エンジンのリフターの一例を模式的に示す断面図である。
ジルコニウム又はジルコニウム合金からなる坩堝や容器の所望の部位に化学的な反応性が小さく、電気抵抗が大きい等の特性を有する炭素ドープ酸化ジルコニウム層を設けることにより、種々の分野での利用が可能となる。
熱中性子が吸収されにくいというジルコニウムの特性を利用し、ジルコニウム合金は軽水炉の被覆管に用いられるが、被覆管の内面及び外面の少なくとも一方に炭素ドープ酸化ジルコニウム層を形成することにより、多くの効果を得ることができる。
アセチレンの燃焼炎を用い、厚さ0.50mmのジルコニウム板((株)ニラコ製:ZR−493402、純度99.2%)をその表面温度が約400℃となるように360分間加熱処理することにより、表面層として炭素ドープ酸化ジルコニウム層を有するジルコニウム板を形成した。
加熱処理の表面温度及び加熱処理時間を下記表1の通りに変更した以外は実施例1と同様にして、実施例2〜6の炭素ドープ酸化ジルコニウム層を有するジルコニウム板を形成した。
メタンガスの燃焼炎を用い、実施例1と同様なジルコニウム板をその表面温度が約900℃となるように30分間加熱処理することにより、実施例7の炭素ドープジルコニウム層を有するジルコニウム板を形成した。
加熱処理していないジルコニウム板を比較例1のジルコニウム板とした。
比較例1と同一のジルコニウム板を加熱炉で所定の加熱処理温度及び加熱処理時間で大気酸化して表面に酸化ジルコニウム層を形成した。加熱処理温度及び加熱処理時間は表1に示すとおりであり、室温から加熱温度に達するまでの時間は加熱時間に換算しないで加熱処理時間を設定した。
市販のジルコニウム合金(ジルカロイ−2)製のジルカロイ管(内径10mm、外径12mm)を実施例1と同様にアセチレンの燃焼炎を用いて、表1の加熱処理の表面温度及び加熱処理時間で加熱処理し、実施例8〜10の炭素ドープジルカロイ酸化物層を有するジルカロイ管を得た。
市販のジルカロイ管そのものを未処理品として比較例8とした。
各実施例及び比較例の表面硬度を、マイクロビッカース硬度計により、圧子:ダイヤモンド圧子、試験力:245.2mN、荷重保持時間:15secの条件下で皮膜硬度を測定したところ、表1の結果が得られた。
実施例4の炭素ドープ酸化ジルコニウム層についてXRD(X線回折分析)をした結果を図5に示す。比較のために比較例5の大気酸化による酸化ジルコニウム層の分析結果も併せて示す。なお、測定条件は以下の通りである。
管球:Cu
出力:40kV−50mA
スキャン速度:1°/min
スキャン範囲:2θ= 2〜80°
スリット:DS・SS; 照射範囲が15mm一定となるよう自動調整
mask; 10mm
1M硫酸水溶液および1M水酸化ナトリウム水溶液それぞれについて、実施例2、5及び比較例3、6のジルコニウム板を室温で1週間浸漬した後、ビッカース硬度試験を行なった。これらの結果を表2及び表3に示す。
実施例4(700℃、120分)の炭素ドープ酸化ジルコニウム層及び比較例5(700℃、120分)の酸化ジルコニウム皮膜の短波長用ランプ照射による自然浸漬電位を測定した。具体的には、それぞれの皮膜に対し、0.05M硫酸ナトリウム水溶液(飽和溶存酸素、常温)中で、参照電極として飽和銀−塩化銀を用いて、電位を測定した。その結果を図7に示す。
実施例8〜10で形成したジルカロイ管を切断し、切断面の組織の観察をキーエンス社製SEM装置VE7800を用いて行った。この結果、各試料とも最上部に炭素ドープ酸化ジルコニウム層である酸化皮膜が形成され、特に、加熱処理温度が1050℃及び1100℃の実施例9、10のサンプルについては、酸化皮膜が柱状結晶の層であることが観察され、さらに、酸化皮膜の下側に、炭素が拡散したと思われる拡散層が観察された。
実施例8及び9にジルカロイ管を3mmの長さに切断し、その切断面の外側面について、深さ方向にビッカース試験を実施した。この結果を図8及び図9に示す。
Claims (4)
- 基体の少なくとも表面層が炭素ドープ酸化ジルコニウム層又は炭素ドープジルコニウム合金酸化物層からなる多機能層とジルコニウム、ジルコニウム合金、ジルコニウム合金酸化物又は酸化ジルコニウムの何れかで構成されている下層とを具備し、前記炭素ドープ酸化ジルコニウム層又は炭素ドープジルコニウム合金酸化物層が前記下層から連続して一体的に形成された柱状結晶であることを特徴とする多機能材。
- 請求項1記載の多機能材において、
前記多機能層中の炭素がZr−C結合した状態でドープされていることを特徴とする多機能材。 - 請求項1又は2記載の多機能材において、
前記多機能層が、ジルコニウム、ジルコニウム合金、酸化ジルコニウム又はジルコニウム合金酸化物以外の材質からなる基体の表面に設けられていることを特徴とする多機能材。 - 請求項1〜3の何れかに記載の多機能材において、
多機能材が粉末状であることを特徴とする多機能材。
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