JP2017210658A - HEAT-RESISTANT Ti ALLOY AND HEAT-RESISTANT Ti ALLOY MATERIAL - Google Patents
HEAT-RESISTANT Ti ALLOY AND HEAT-RESISTANT Ti ALLOY MATERIAL Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 139
- 239000000956 alloy Substances 0.000 title claims description 15
- 229910052718 tin Inorganic materials 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 3
- 238000000576 coating method Methods 0.000 claims 3
- 230000003647 oxidation Effects 0.000 abstract description 63
- 238000007254 oxidation reaction Methods 0.000 abstract description 63
- 239000000523 sample Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 14
- 238000009826 distribution Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Abstract
Description
本発明は、ＡｌおよびＳｎの少なくとも１種を含む耐熱Ｔｉ合金および耐熱Ｔｉ合金材に関する。 The present invention relates to a heat resistant Ti alloy and a heat resistant Ti alloy material containing at least one of Al and Sn.
Ｔｉ合金は、軽量、高強度で耐腐食性に優れるため、化学や電力分野、航空機産業等の様々な技術分野において使用されている。近年では、部品の軽量化への要望や、Ｔｉ合金の低コスト製造技術開発の進展等の要因により、Ｔｉ合金を四輪車や二輪車等の車両用の排気系部品（例えばマフラー）に適用する動きが活発化している。 Ti alloys are lightweight, high-strength and excellent in corrosion resistance, and are therefore used in various technical fields such as the chemical and power fields and the aircraft industry. In recent years, Ti alloy is applied to exhaust system parts for vehicles such as four-wheeled vehicles and two-wheeled vehicles (for example, mufflers) due to factors such as demand for weight reduction of parts and progress in development of low-cost manufacturing technology for Ti alloys. The movement is becoming active.
一般的なＴｉ合金の使用温度可能域は６００℃以下とされているが、航空機エンジンや車両用の排気系部品では６００℃を超える高温度域で使用可能な耐熱Ｔｉ合金が求められている。そこで、特許文献１、２では、高温度域７５０℃−８００℃で使用可能な耐熱Ｔｉ合金が提案されている。 The usable temperature range of a general Ti alloy is set to 600 ° C. or less, but a heat-resistant Ti alloy that can be used in a high temperature range exceeding 600 ° C. is required for an exhaust system part for an aircraft engine or a vehicle. Therefore, Patent Documents 1 and 2 propose heat-resistant Ti alloys that can be used in a high temperature range of 750 ° C. to 800 ° C.
しかしながら、車両用の排気系部品では一時的に８００℃を超える温度に曝されることがある。このため、８００℃を超える高温度域において耐熱Ｔｉ合金の耐酸化性を向上することが望まれている。 However, exhaust parts for vehicles may be temporarily exposed to temperatures exceeding 800 ° C. For this reason, it is desired to improve the oxidation resistance of the heat-resistant Ti alloy in a high temperature range exceeding 800 ° C.
本発明の目的は、８００℃を超える高温度域における耐酸化性を向上できる耐熱Ｔｉ合金および耐熱Ｔｉ合金材を提供することにある。 An object of the present invention is to provide a heat-resistant Ti alloy and a heat-resistant Ti alloy material that can improve oxidation resistance in a high temperature range exceeding 800 ° C.
上述の課題を解決するために、第１の発明は、８００℃を超える高温度域にて使用される耐熱Ｔｉ合金であって、ＡｌおよびＳｎの少なくとも１種と、Ｓｉとを含み、Ｓｉの含有量が、０．１質量％を超え１０質量％未満である耐熱Ｔｉ合金である。 In order to solve the above-described problems, a first invention is a heat-resistant Ti alloy used in a high temperature range exceeding 800 ° C., and includes at least one of Al and Sn, and Si. It is a heat-resistant Ti alloy having a content exceeding 0.1% by mass and less than 10% by mass.
第２の発明は、耐熱Ｔｉ合金からなる基材と、基材の表面に設けられた被膜とを備え、耐熱Ｔｉ合金は、ＡｌおよびＳｎの少なくとも１種と、Ｓｉとを含み、Ｓｉの含有量が、０．１質量％を超え１０質量％未満である耐熱Ｔｉ合金材である。 2nd invention is equipped with the base material which consists of a heat-resistant Ti alloy, and the film provided in the surface of the base material, and heat-resistant Ti alloy contains at least 1 sort (s) of Al and Sn, and Si containing It is a heat-resistant Ti alloy material whose amount is more than 0.1% by mass and less than 10% by mass.
本発明によれば、８００℃を超える高温度域における耐熱Ｔｉ合金の耐酸化性を向上できる。 According to the present invention, the oxidation resistance of a heat-resistant Ti alloy in a high temperature range exceeding 800 ° C. can be improved.
［耐熱Ｔｉ合金の組成］
本発明の一実施形態に係る耐熱Ｔｉ合金は、８００℃を超える高温度域にて使用される耐熱Ｔｉ合金であり、Ｔｉと、ＡｌおよびＳｎの少なくとも１種と、Ｓｉと、不可避的不純物とからなる。耐熱Ｔｉ合金が、高温強度向上、耐クリープ性または疲労強度向上等の観点から、必要に応じて、Ｏ（酸素）、Ｎ（窒素）、Ｃ（炭素）、Ｖ、Ｎｂ、Ｔａ、Ｍｏ、Ｚｒ、Ｃｒ、Ｆｅ、Ｗ、Ｈｆ、Ｇａ、Ｃｕ、Ｍｎ、Ｐｄ、Ｙ、ＬａおよびＣｅ等からなる群より選ばれる少なくとも１種をさらに含んでいてもよい。耐熱Ｔｉ合金が使用される高温度域の上限値は、例えば１０００℃以下、好ましくは９００℃以下である。本実施形態に係る耐熱Ｔｉ合金では、８００℃を超え９００℃以下の高温度域において特に優れた耐酸化性が得られるからである。
[Composition of heat-resistant Ti alloy]
A heat-resistant Ti alloy according to an embodiment of the present invention is a heat-resistant Ti alloy used in a high temperature range exceeding 800 ° C., and includes Ti, at least one of Al and Sn, Si, and inevitable impurities. Consists of. The heat-resistant Ti alloy is O (oxygen), N (nitrogen), C (carbon), V, Nb, Ta, Mo, Zr as necessary from the viewpoint of improving high temperature strength, creep resistance or fatigue strength. , Cr, Fe, W, Hf, Ga, Cu, Mn, Pd, Y, La, Ce, and the like may further be included. The upper limit of the high temperature range in which the heat-resistant Ti alloy is used is, for example, 1000 ° C. or less, preferably 900 ° C. or less. This is because the heat-resistant Ti alloy according to the present embodiment provides particularly excellent oxidation resistance in a high temperature range exceeding 800 ° C. and 900 ° C. or less.
耐熱Ｔｉ合金は、α＋β型Ｔｉ合金であってもよいし、α型またはβ型Ｔｉ合金であってもよい。耐熱Ｔｉ合金は、航空機エンジン、四輪車や二輪車用等の車両用の排気系部品に適用して好適なものである。排気系部品としては、例えば、エキゾーストマニホールド、エキゾーストパイプ、触媒マフラーまたはメインマフラー等が挙げられるが、これに限定されるものではない。 The heat-resistant Ti alloy may be an α + β-type Ti alloy, or an α-type or β-type Ti alloy. The heat-resistant Ti alloy is suitable for application to exhaust system parts for vehicles such as aircraft engines, automobiles, and motorcycles. Examples of the exhaust system parts include, but are not limited to, exhaust manifolds, exhaust pipes, catalyst mufflers, main mufflers, and the like.
耐熱Ｔｉ合金中におけるＳｉの含有量は、０．１質量％を超え１０質量％未満、より好ましくは０．２質量％以上２質量％以下、さらにより好ましくは０．５質量％以上１質量％以下、最も好ましくは約１質量％である。Ｓｉの含有量が０．１質量％以下であると、Ｓｉの含有量が少なすぎて、耐酸化性向上の効果が低下する。一方、Ｓｉの含有量が１０質量％以上であると、耐熱Ｔｉ合金の成形加工性が低下する。 The content of Si in the heat-resistant Ti alloy is more than 0.1% by mass and less than 10% by mass, more preferably 0.2% by mass to 2% by mass, and even more preferably 0.5% by mass to 1% by mass. Hereinafter, it is most preferably about 1% by mass. If the Si content is 0.1% by mass or less, the Si content is too small, and the effect of improving oxidation resistance is reduced. On the other hand, if the Si content is 10% by mass or more, the moldability of the heat-resistant Ti alloy is lowered.
耐熱Ｔｉ合金がＡｌおよびＳｎの少なくとも１種を含むことで、耐高温特性等が向上する。耐熱Ｔｉ合金中におけるＡｌの含有量は、例えば１質量％以上９質量％以下である。耐熱Ｔｉ合金中におけるＳｎの含有量は、例えば２質量％以上８質量％以下である。 When the heat resistant Ti alloy contains at least one of Al and Sn, the high temperature resistance and the like are improved. The Al content in the heat-resistant Ti alloy is, for example, 1% by mass or more and 9% by mass or less. The Sn content in the heat-resistant Ti alloy is, for example, 2% by mass or more and 8% by mass or less.
上記のＳｉ、ＡｌおよびＳｎの含有量は、誘導結合プラズマ発光分光分析法（ＩＣＰ−ＡＥＳ）を用いて元素分析を行うことにより求めることが可能である。 The contents of Si, Al, and Sn can be obtained by performing elemental analysis using inductively coupled plasma emission spectroscopy (ICP-AES).
耐熱Ｔｉ合金は、ＡｌおよびＳｎの少なくとも１種を含む既存のＴｉ合金と、Ｓｉとを含むものであってもよい。既存のＴｉ合金に上記範囲のＳｉを含ませることで、８００℃を超える高温度域における耐酸化性を向上できる。 The heat resistant Ti alloy may include an existing Ti alloy containing at least one of Al and Sn, and Si. By including Si in the above range in the existing Ti alloy, oxidation resistance in a high temperature range exceeding 800 ° C. can be improved.
Ａｌを含む既存のＴｉ合金としては、例えば、Ｔｉ−６Ａｌ−４Ｖ（以下「Ｔｉ−６４」という。）、Ｔｉ−３Ａｌ−２．５Ｖ、Ｔｉ−６Ａｌ−２Ｎｂ−１Ｔａ−０．８Ｍｏ、Ｔｉ−８Ａｌ−１Ｍｏ−１Ｖ、Ｔｉ−７Ａｌ−４Ｍｏ、Ｔｉ−４．５Ａｌ−３Ｖ−２Ｍｏ−２Ｆｅ、Ｔｉ−６Ａｌ−７Ｎｂ、Ｔｉ−４Ａｌ−３Ｍｏ−１Ｖ、Ｔｉ−４．５Ａｌ−５Ｍｏ−１．５Ｃｒ、Ｔｉ−５Ａｌ−１．５Ｆｅ−１．４Ｃｒ−１．２Ｍｏ、Ｔｉ−５Ａｌ−２．５Ｆｅ、Ｔｉ−６．４Ａｌ−１．２Ｆｅ、Ｔｉ−３Ａｌ−８Ｖ−６Ｃｒ−４Ｍｏ−４Ｚｒ、Ｔｉ−１０Ｖ−２Ｆｅ−３Ａｌ、Ｔｉ−１３Ｖ−１１Ｃｒ−３Ａｌ、Ｔｉ−１．５Ａｌ−５．５Ｆｅ−６．８Ｍｏ、Ｔｉ−８Ｍｏ−８Ｖ−２Ｆｅ−３Ａｌ、Ｔｉ−１５Ｍｏ−５Ｚｒ−３Ａｌ、Ｔｉ−８Ｖ−５Ｆｅ−１Ａｌ、Ｔｉ−１６Ｖ−２．５Ａｌ等を用いることができる。これらを単独で用いてもよいし、２種以上組み合わせて用いてもよい。 Examples of the existing Ti alloy containing Al include Ti-6Al-4V (hereinafter referred to as “Ti-64”), Ti-3Al-2.5V, Ti-6Al-2Nb-1Ta-0.8Mo, Ti— 8Al-1Mo-1V, Ti-7Al-4Mo, Ti-4.5Al-3V-2Mo-2Fe, Ti-6Al-7Nb, Ti-4Al-3Mo-1V, Ti-4.5Al-5Mo-1.5Cr, Ti-5Al-1.5Fe-1.4Cr-1.2Mo, Ti-5Al-2.5Fe, Ti-6.4Al-1.2Fe, Ti-3Al-8V-6Cr-4Mo-4Zr, Ti-10V- 2Fe-3Al, Ti-13V-11Cr-3Al, Ti-1.5Al-5.5Fe-6.8Mo, Ti-8Mo-8V-2Fe-3Al, Ti-15Mo-5Zr-3Al, Ti-8 -5Fe-1Al, can be used Ti-16V-2.5Al like. These may be used alone or in combination of two or more.
Ｓｎを含む既存のＴｉ合金、およびＡｌおよびＳｎを含む既存のＴｉ合金としては、例えば、Ｔｉ−５Ａｌ−２Ｓｎ−２Ｚｒ−４Ｍｏ−４Ｃｒ（以下「Ｔｉ−１７」という。）、Ｔｉ−５Ａｌ−２．５Ｓｎ、Ｔｉ−６Ａｌ−２Ｓｎ−４Ｚｒ−６Ｍｏ、Ｔｉ−６Ａｌ−６Ｖ−２Ｓｎ、Ｔｉ−１１．５Ｍｏ−６Ｚｒ−４．５Ｓｎ、Ｔｉ−１５Ｖ−３Ａｌ−３Ｃｒ−３Ｓｎ、Ｔｉ−５Ａｌ−２Ｓｎ−４Ｚｒ−４Ｍｏ−２Ｃｒ−１Ｆｅ、Ｔｉ−１１．５Ｖ−２Ａｌ−２Ｓｎ−１１Ｚｒ、Ｔｉ−１２Ｖ−２．５Ａｌ−２Ｓｎ−６Ｚｒ、Ｔｉ−１３Ｖ−２．７Ａｌ−７Ｓｎ−２Ｚｒを用いることができる。これらを単独で用いてもよいし、２種以上組み合わせて用いてもよい。 Examples of the existing Ti alloy containing Sn and the existing Ti alloy containing Al and Sn include, for example, Ti-5Al-2Sn-2Zr-4Mo-4Cr (hereinafter referred to as “Ti-17”), Ti-5Al-2. .5Sn, Ti-6Al-2Sn-4Zr-6Mo, Ti-6Al-6V-2Sn, Ti-11.5Mo-6Zr-4.5Sn, Ti-15V-3Al-3Cr-3Sn, Ti-5Al-2Sn-4Zr -4Mo-2Cr-1Fe, Ti-11.5V-2Al-2Sn-11Zr, Ti-12V-2.5Al-2Sn-6Zr, Ti-13V-2.7Al-7Sn-2Zr can be used. These may be used alone or in combination of two or more.
不可避的不純物としては、例えば、Ｏ、Ｎ、Ｃ、Ｈ（水素）、Ｎｉ、Ｃｌ、Ｍｇ、Ｍｎ、Ｎａ、Ｃｕ、Ｖ、Ｐｂ、Ｒｕ、Ｃｏ、Ｓ等が挙げられる。 Examples of inevitable impurities include O, N, C, H (hydrogen), Ni, Cl, Mg, Mn, Na, Cu, V, Pb, Ru, Co, and S.
［Ｓｉ添加による耐酸化性向上のメカニズム］
ＡｌおよびＳｎの少なくとも１種を含むＴｉ合金に０．１質量％を超え１０質量％未満のＳｉを添加することで、８００℃を超える高温度域において耐酸化性を向上できる。この効果の発現のメカニズムは、以下に示すように、（ａ）耐熱Ｔｉ合金がＡｌを含む場合と、（ｂ）耐熱Ｔｉ合金がＳｎを含む、もしくはＡｌおよびＳｎの両方を含む場合とで異なる。
[Mechanism for improving oxidation resistance by adding Si]
By adding more than 0.1 mass% and less than 10 mass% of Si to a Ti alloy containing at least one of Al and Sn, oxidation resistance can be improved in a high temperature range exceeding 800 ° C. The mechanism of manifestation of this effect is different between (a) the case where the heat-resistant Ti alloy contains Al and (b) the case where the heat-resistant Ti alloy contains Sn or contains both Al and Sn as shown below. .
（ａ）耐熱Ｔｉ合金がＡｌを含む場合
８００℃を超える高温度域にて耐熱Ｔｉ合金を使用すると、図１に示すように、耐熱Ｔｉ合金からなる基材１１の表面に酸化被膜１２が形成される。この際、上記含有量のＳｉを耐熱Ｔｉ合金が含んでいることで、基材１１と酸化被膜１２との間にＡｌ濃化層１３が形成される。Ａｌ濃化層１３は、Ｔｉ3Ａｌを含んでいる。このようなＡｌ濃化層１３の形成により、基材１１の耐酸化性が向上する。放物線速度定数を低減し、耐酸化性を向上する観点からすると、Ａｌ濃化層１３は、連続膜であることが好ましい。なお、基材１１と酸化被膜１２とＡｌ濃化層１３とにより耐熱Ｔｉ合金材が構成される。
(A) When the heat-resistant Ti alloy contains Al When a heat-resistant Ti alloy is used in a high temperature range exceeding 800 ° C., an oxide film 12 is formed on the surface of the substrate 11 made of the heat-resistant Ti alloy as shown in FIG. Is done. At this time, the Al-enriched layer 13 is formed between the base material 11 and the oxide film 12 because the heat-resistant Ti alloy contains Si having the above content. The Al concentrated layer 13 contains Ti 3 Al. By forming the Al concentrated layer 13 as described above, the oxidation resistance of the substrate 11 is improved. From the viewpoint of reducing the parabolic rate constant and improving the oxidation resistance, the Al concentrated layer 13 is preferably a continuous film. The base material 11, the oxide film 12, and the Al concentrated layer 13 constitute a heat resistant Ti alloy material.
Ａｌ濃化層１３の平均膜厚は、好ましくは２μｍ以上、より好ましくは４μｍ以上１００μｍ以下、更により好ましくは５μｍ以上５０μｍ以下である。Ａｌ濃化層１３の平均膜厚が２μｍ以上であると、特に優れた耐酸化性が得られる。一方、Ａｌ濃化層１３の平均膜厚が１００μｍを超えると、耐熱Ｔｉ合金材全体の機械的特性が低下する虞がある。Ａｌ濃化層１３の平均膜厚は、以下のようにして求められる。まず、耐熱Ｔｉ合金の断面をＥＰＭＡ（Electron Probe Micro Analyzer）等により観察する。次に、観察した断面像から無作為に１０箇所のＡｌ濃化層１３の位置を選び出し、それらの各位置においてＡｌ濃化層１３の膜厚を測定する。次に、これらの測定値を単純に平均（算術平均）してＡｌ濃化層１３の平均膜厚を求める。 The average film thickness of the Al concentrated layer 13 is preferably 2 μm or more, more preferably 4 μm or more and 100 μm or less, and even more preferably 5 μm or more and 50 μm or less. When the average film thickness of the Al concentrated layer 13 is 2 μm or more, particularly excellent oxidation resistance is obtained. On the other hand, when the average film thickness of the Al concentrated layer 13 exceeds 100 μm, the mechanical properties of the entire heat resistant Ti alloy material may be deteriorated. The average film thickness of the Al concentrated layer 13 is obtained as follows. First, the cross section of the heat-resistant Ti alloy is observed with an EPMA (Electron Probe Micro Analyzer) or the like. Next, ten positions of the Al concentrated layer 13 are selected at random from the observed cross-sectional image, and the film thickness of the Al concentrated layer 13 is measured at each of these positions. Next, these measured values are simply averaged (arithmetic average) to determine the average film thickness of the Al concentrated layer 13.
（ｂ）耐熱Ｔｉ合金がＳｎを含む、もしくはＡｌおよびＳｎの両方を含む場合
８００℃を超える高温度域にて耐熱Ｔｉ合金を使用すると、図２に示すように、耐熱Ｔｉ合金からなる基材２１の表面に、内側層（Inner層）２２ａと外側層（Outer層）２２ｂとからなる酸化被膜２２が形成される。この際、内側層２２ａと外側層２２ｂとの界面にＡｌ2Ｏ3リッチ層（酸化アルミニウム含有層）２２ｃが形成されるが、上記含有量のＳｉを耐熱Ｔｉ合金が含んでいることで、Ａｌ2Ｏ3リッチ層２２ｃが安定化する。また、基材２１と内側層２２ａとの界面にＴｉＮ層２３が形成されるが、上記含有量のＳｉを耐熱Ｔｉ合金が含んでいることで、このＴｉＮ層２３の形成が抑制される。このようなＡｌ2Ｏ3リッチ層２２ｃの安定化とＴｉＮ層２３の形成抑制とにより、基材２１の耐酸化性が向上する。なお、基材２１と酸化被膜２２とにより耐熱Ｔｉ合金材が構成されるか、もしくは基材２１と酸化被膜２２とＴｉＮ層２３とにより耐熱Ｔｉ合金材が構成される。
(B) When the heat-resistant Ti alloy contains Sn or contains both Al and Sn When the heat-resistant Ti alloy is used in a high temperature range exceeding 800 ° C., as shown in FIG. An oxide film 22 composed of an inner layer (Inner layer) 22 a and an outer layer (Outer layer) 22 b is formed on the surface of 21. At this time, an Al 2 O 3 rich layer (aluminum oxide-containing layer) 22c is formed at the interface between the inner layer 22a and the outer layer 22b. The heat-resistant Ti alloy contains Si having the above content, so that Al The 2 O 3 rich layer 22c is stabilized. Moreover, although the TiN layer 23 is formed at the interface between the base material 21 and the inner layer 22a, the formation of the TiN layer 23 is suppressed because the heat-resistant Ti alloy contains the above-described content of Si. By stabilizing the Al 2 O 3 rich layer 22c and suppressing the formation of the TiN layer 23, the oxidation resistance of the substrate 21 is improved. The base material 21 and the oxide film 22 constitute a heat resistant Ti alloy material, or the base material 21, the oxide film 22 and the TiN layer 23 constitute a heat resistant Ti alloy material.
［耐熱Ｔｉ合金の製造方法］
まず、ＡｌおよびＳｎの少なくとも１種を含む既存のＴｉ合金を準備する。次に、準備したＴｉ合金をＳｉと共に溶解し、Ｔｉ合金を作製する。この際、Ｓｉは、Ｔｉ合金中のＳｉの含有量が０．１質量％を超え１０質量％未満となるように添加される。次に、Ｔｉ合金を熱間鍛造することにより、目的とする耐熱Ｔｉ合金が得られる。
[Method for producing heat-resistant Ti alloy]
First, an existing Ti alloy containing at least one of Al and Sn is prepared. Next, the prepared Ti alloy is melted together with Si to produce a Ti alloy. At this time, Si is added so that the content of Si in the Ti alloy is more than 0.1 mass% and less than 10 mass%. Next, the target heat-resistant Ti alloy is obtained by hot forging the Ti alloy.
なお、耐熱Ｔｉ合金の製造方法は上記の製造方法に限定されるものではなく、例えば、粉末冶金を用いて、以下のようにして耐熱Ｔｉ合金を製造してもよい。まず、原料となる粉末を準備する。粉末としては、目的の耐熱Ｔｉ合金と同様の組成を有するＴｉ合金粉末であってもよいし、目的の耐熱Ｔｉ合金と同様の組成となるように複数の素粉末が混合されたものであってもよい。次に、粉末をプレス機等に入れて所定の形状に成形することにより、成形体を得る。最後に、成形体を焼結させることにより、目的とする耐熱Ｔｉ合金が得られる。 In addition, the manufacturing method of a heat resistant Ti alloy is not limited to said manufacturing method, For example, you may manufacture a heat resistant Ti alloy as follows using powder metallurgy. First, a raw material powder is prepared. The powder may be a Ti alloy powder having the same composition as the target heat-resistant Ti alloy, or a mixture of a plurality of elementary powders so as to have the same composition as the target heat-resistant Ti alloy. Also good. Next, the powder is put into a press machine or the like and molded into a predetermined shape to obtain a molded body. Finally, the target heat-resistant Ti alloy is obtained by sintering the compact.
［効果］
本実施形態に係る耐熱Ｔｉ合金は、Ｔｉと、ＡｌおよびＳｎの少なくとも１種と、Ｓｉと、不可避的不純物とからなる。耐熱Ｔｉ合金中におけるＳｉの含有量は、０．１質量％を超え１０質量％未満である。これにより、８００℃を超える高温度域における耐酸化性を向上できる。
[effect]
The heat-resistant Ti alloy according to this embodiment includes Ti, at least one of Al and Sn, Si, and inevitable impurities. The Si content in the heat-resistant Ti alloy is more than 0.1% by mass and less than 10% by mass. Thereby, the oxidation resistance in the high temperature range exceeding 800 degreeC can be improved.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.
＜Ａｌを含むＴｉ合金にＳｉを添加したサンプル＞
［サンプル１〜４］
まず、原料としてＴｉ−６４ＥＬＩおよびＳｉフレーク（１１Ｎ）を準備し、アーク溶製によりＴｉ合金を作製した。この際、Ｓｉフレークの添加量は、Ｔｉ合金中におけるＳｉの含有量が０．０１質量％（サンプル１）、０．１質量％（サンプル２）、１質量％（サンプル３）、１０質量％（サンプル４）となるように調整した。次に、Ｔｉ合金を熱間鍛造（１１７３Ｋ）し、α＋β型の耐熱Ｔｉ合金を得た。次に、この耐熱Ｔｉ合金の両面を鏡面研磨することにより、平板状（１２ｍｍ×１２ｍｍ×２ｍｍ）のサンプル１〜４を得た。
<Sample with Si added to Ti alloy containing Al>
[Samples 1 to 4]
First, Ti-64ELI and Si flakes (11N) were prepared as raw materials, and a Ti alloy was produced by arc melting. At this time, the amount of Si flake added was 0.01 mass% (sample 1), 0.1 mass% (sample 2), 1 mass% (sample 3), 10 mass% of the Si content in the Ti alloy. It adjusted so that it might become (sample 4). Next, the Ti alloy was hot forged (1173K) to obtain an α + β type heat-resistant Ti alloy. Next, both surfaces of this heat-resistant Ti alloy were mirror-polished to obtain flat plate-shaped (12 mm × 12 mm × 2 mm) samples 1 to 4.
［サンプル５］
Ｓｉフレーク（１１Ｎ）を添加しないこと以外はサンプル１と同様にしてサンプル５を得た。
[Sample 5]
Sample 5 was obtained in the same manner as Sample 1 except that Si flakes (11N) were not added.
［評価］
上述のようにして得られたサンプル１〜３、５について以下の評価を行った。なお、サンプル４では鍛造時に割れが発生したため、以下の評価を行わなかった。
[Evaluation]
The following evaluations were performed on samples 1 to 3 and 5 obtained as described above. In sample 4, cracks occurred during forging, so the following evaluation was not performed.
（質量増加）
サンプルをアルミナボードに置き、マッフル炉にてサンプルを酸化させて、酸化による質量増加を評価した。以下に、酸化の条件を示す。
雰囲気：大気
温度：８１０Ｋ（５３６．８５℃）、９１０Ｋ（６３６．８５℃）、１０１０Ｋ（７３６．８５℃）、１１１０Ｋ（８３６．８５℃）、１２１０Ｋ（９３６．８５℃）（室温から昇温［１５Ｋ／ｍｉｎ］、空冷）
時間：〜１４４ｈ（８１０Ｋ：〜２８８ｈ）
(Mass increase)
The sample was placed on an alumina board, the sample was oxidized in a muffle furnace, and the mass increase due to oxidation was evaluated. The oxidation conditions are shown below.
Atmosphere: Air Temperature: 810K (536.85 ° C), 910K (636.85 ° C), 1010K (736.85 ° C), 1110K (836.85 ° C), 1210K (936.85 ° C) 15K / min], air cooling)
Time: ~ 144h (810K: ~ 288h)
（断面分析）
サンプルをアルミナボードに置き、マッフル炉にてサンプルを酸化させた後、断面をＥＰＭＡにより観察した。以下に、酸化の条件を示す。
雰囲気：大気
温度：１２１０Ｋ（室温から昇温［１５Ｋ／ｍｉｎ］、空冷）
時間：４８ｈ
次に、断面像からＴｉ合金基板と酸化被膜との界面（Ｔｉ合金基板側の界面）に、連続膜としてのＡｌ濃化層が形成されているか否かを確認した。そして、連続膜としてのＡｌ濃化層が形成されていた場合には、その平均膜厚を断面像から求めた。なお、平均膜厚の求め方は、上述した通りである。
(Cross section analysis)
After placing the sample on an alumina board and oxidizing the sample in a muffle furnace, the cross section was observed with EPMA. The oxidation conditions are shown below.
Atmosphere: Air Temperature: 1210K (temperature rise from room temperature [15K / min], air cooling)
Time: 48h
Next, it was confirmed from the cross-sectional image whether or not an Al concentrated layer as a continuous film was formed at the interface between the Ti alloy substrate and the oxide film (the interface on the Ti alloy substrate side). And when Al concentration layer as a continuous film was formed, the average film thickness was calculated | required from the cross-sectional image. The method for obtaining the average film thickness is as described above.
（Ａｌ濃化層の組成）
上記断面分析により連続膜としてのＡｌ濃化層が確認されたサンプルについて、Ｘ線回折（X‐ray diffraction：ＸＲＤ）によりＡｌ濃化層の構成成分を同定した。その結果、Ａｌ濃化層はＴｉ3Ａｌにより構成されていることがわかった。
(Composition of Al concentrated layer)
About the sample by which the Al concentrated layer as a continuous film was confirmed by the said cross-sectional analysis, the component of Al concentrated layer was identified by X-ray diffraction (XRD). As a result, it was found that the Al concentrated layer was composed of Ti 3 Al.
［結果］
図３Ａ〜４Ｂは、質量増加と酸化時間（１／２乗）との関係を示す。図３Ａ〜４Ｂにおいて、放物線則領域を実線にて示している。
[result]
3A-4B show the relationship between mass increase and oxidation time (1/2 power). 3A to 4B, the parabolic law region is indicated by a solid line.
表１は、図３Ａ〜４Ｂに示した直線の傾き（放物線速度定数Ｋｐ）を示す。
図３Ａ〜４Ｂ、表１から以下のことがわかる。ＳｉをＴｉ−６４に添加することにより、酸化時間の増加に対する質量増加が抑制されている。したがって、酸化被膜の厚さが低減され、酸化被膜の剥離が抑制されているので、耐酸化性が向上している。また、Ｓｉ添加量が多いほど、直線の傾きが小さくなり、耐酸化性が向上する傾向がある。直線の傾きが小さくなるのは、Ｔｉ合金側の最表面（酸化被膜直下のＴｉ合金基板）において、Ｔｉ−６４から、より高い耐酸化性を有するＴｉ3Ａｌに変化するためと考えられる。直線の傾きが小さくなることは、酸化被膜の厚さが薄くなることを意味している。酸化被膜が薄くなると、酸化被膜の剥離が抑制される。また、直線の傾きが小さくなると、放物線則領域が拡大される傾向がある。 3A-4B and Table 1 show the following. By adding Si to Ti-64, an increase in mass with respect to an increase in oxidation time is suppressed. Therefore, since the thickness of the oxide film is reduced and the peeling of the oxide film is suppressed, the oxidation resistance is improved. Also, the greater the Si addition amount, the smaller the slope of the straight line and the better the oxidation resistance. The reason why the inclination of the straight line becomes smaller is considered to be that Ti-64 changes to Ti 3 Al having higher oxidation resistance on the outermost surface (Ti alloy substrate immediately below the oxide film) on the Ti alloy side. The smaller slope of the straight line means that the thickness of the oxide film becomes thinner. When the oxide film becomes thin, peeling of the oxide film is suppressed. Moreover, when the inclination of the straight line becomes small, the parabolic law region tends to be enlarged.
図５Ａ〜６Ｂは、図３Ａ〜４Ｂにて放物線則に従う酸化時間をｘ軸とし、温度をｙ軸としたグラフである。図７は、図５Ａ〜６Ｂをまとめて表した３次元の棒グラフである。図５Ａ〜６Ｂ、７から、ＳｉをＴｉ−６４に添加することにより、放物線則領域が広がっていることがわかる。Ｓｉの含有量が１質量％である場合、放物線則領域が特に広がっていることがわかる。 5A to 6B are graphs in which the oxidation time according to the parabolic law in FIGS. 3A to 4B is taken as the x axis and the temperature is taken as the y axis. FIG. 7 is a three-dimensional bar graph that collectively represents FIGS. 5A to 6B and 7, it can be seen that the parabolic law region is expanded by adding Si to Ti-64. When the Si content is 1% by mass, it can be seen that the parabolic law region is particularly widened.
図８は、１２１０Ｋ、４８ｈの酸化試験後のＴｉ合金（Ｓｉ：０質量％）の断面ＥＰＭＡマッピング結果を示す。図９は、１２１０Ｋ、４８ｈの酸化試験後のＴｉ合金（Ｓｉ：１質量％）の断面ＥＰＭＡマッピング結果を示す。 FIG. 8 shows a cross-sectional EPMA mapping result of a Ti alloy (Si: 0 mass%) after an oxidation test at 1210 K for 48 hours. FIG. 9 shows a cross-sectional EPMA mapping result of a Ti alloy (Si: 1% by mass) after an oxidation test at 1210K for 48 hours.
表２は、サンプル１〜３、５のＡｌ濃化層の観察結果を示す。
図８、９、表２から以下のことがわかる。Ｓｉの含有量が１質量％であるサンプル３では、１０１０Ｋ以上１２１０Ｋ以下の範囲の高温度域においてＴｉ合金基板と酸化被膜との界面に連続膜としてのＡｌ濃化層が形成されている。一方、Ｓｉの含有量が０、０．０１、０．１質量％であるサンプル５、１、２では、１０１０Ｋ以上１２１０Ｋ以下の範囲の高温度域においてＴｉ合金基板と酸化被膜との界面に連続膜としてのＡｌ濃化層が形成されていない。但し、サンプル５、１、２では、１２１０Ｋの高温度域においてＴｉ合金基板と酸化被膜との界面に非常に薄い島状膜（不連続膜）の形成が確認された（図８参照）。この島状膜もＴｉ3Ａｌにより構成されていると推測される。 8 and 9 and Table 2 show the following. In sample 3 having a Si content of 1 mass%, an Al concentrated layer as a continuous film is formed at the interface between the Ti alloy substrate and the oxide film in a high temperature range of 1010K to 1210K. On the other hand, in Samples 5, 1, and 2 having Si contents of 0, 0.01, and 0.1% by mass, continuous to the interface between the Ti alloy substrate and the oxide film in a high temperature range of 1010K to 1210K. An Al concentrated layer as a film is not formed. However, in Samples 5, 1, and 2, formation of a very thin island film (discontinuous film) was confirmed at the interface between the Ti alloy substrate and the oxide film in a high temperature range of 1210K (see FIG. 8). It is presumed that this island film is also composed of Ti 3 Al.
１２１０Ｋの高温度域では、上述のように、Ｓｉの含有量が０、０．０１、０．１質量％であるサンプル５、１、２でも島状膜が形成されているため、図７に示すように、１２１０Ｋの高温度域において、Ｓｉの含有量が１質量％であるサンプル３と同程度の放物線則領域の広さとなっていると考えられる。しかしながら、１２１０Ｋの高温度域において、サンプル３の直線の傾き（放物線速度定数Ｋｐ）は、図４Ｂに示すように、サンプル５、１、２に比べて著しく抑制されている。したがって、Ｓｉの含有量が１質量％であるサンプル３が、耐酸化性の観点で最も優れている。 In the high temperature range of 1210 K, as described above, since the island-like films are formed even in the samples 5, 1, and 2 having the Si content of 0, 0.01, and 0.1 mass%, FIG. As shown, in the high temperature range of 1210K, it is considered that the width of the parabola law region is about the same as that of the sample 3 in which the Si content is 1% by mass. However, in the high temperature range of 1210 K, the slope of the straight line of sample 3 (parabolic rate constant Kp) is significantly suppressed as compared to samples 5, 1 and 2, as shown in FIG. 4B. Therefore, the sample 3 having a Si content of 1% by mass is most excellent in terms of oxidation resistance.
＜ＡｌおよびＳｎを含むＴｉ合金にＳｉを添加したサンプル＞
［サンプル６〜９］
まず、原料としてＴｉ−１７およびＳｉフレーク（１１Ｎ）を準備し、アーク溶製によりＴｉ合金を作製した。この際、Ｓｉフレークの添加量は、Ｔｉ合金中におけるＳｉの含有量が０．０１質量％（サンプル６）、０．１質量％（サンプル７）、１質量％（サンプル８）、１０質量％（サンプル９）となるように調整した。次に、Ｔｉ合金を熱間鍛造（１３７３Ｋ）し、ｎｅａｒ−β型の耐熱Ｔｉ合金を得た。次に、この耐熱Ｔｉ合金の両面を鏡面研磨することにより、平板状（１２ｍｍ×１２ｍｍ×２ｍｍ）のサンプル１〜４を得た。
<Sample in which Si is added to Ti alloy containing Al and Sn>
[Samples 6-9]
First, Ti-17 and Si flakes (11N) were prepared as raw materials, and a Ti alloy was produced by arc melting. At this time, the amount of Si flake added was 0.01 mass% (sample 6), 0.1 mass% (sample 7), 1 mass% (sample 8), 10 mass% of the Si content in the Ti alloy. It adjusted so that it might become (sample 9). Next, the Ti alloy was hot forged (1373K) to obtain a near-β type heat-resistant Ti alloy. Next, both surfaces of this heat-resistant Ti alloy were mirror-polished to obtain flat plate-shaped (12 mm × 12 mm × 2 mm) samples 1 to 4.
［サンプル１０］
Ｓｉフレーク（１１Ｎ）を添加しないこと以外はサンプル６と同様にしてサンプル１０を得た。
[Sample 10]
Sample 10 was obtained in the same manner as Sample 6 except that Si flakes (11N) were not added.
［評価］
上述のようにして得られたサンプル６〜８、１０について以下の評価を行った。なお、サンプル９では鍛造時に割れが発生したため、以下の評価を行わなかった。
[Evaluation]
The samples 6 to 8 and 10 obtained as described above were evaluated as follows. In sample 9, cracks occurred during forging, so the following evaluation was not performed.
（質量増加）
サンプルをアルミナボードに置き、マッフル炉にてサンプルを酸化させて、酸化による質量増加を評価した。以下に、酸化の条件を示す。
雰囲気：大気
温度：９２３Ｋ（６４９．８５℃）、１０２３Ｋ（７４９．８５℃）、１１２３Ｋ（８４９．８５℃）、１２２３Ｋ（９４９．８５℃）（室温から昇温［５０Ｋ／ｍｉｎ］、空冷）
時間：〜１４４ｈ
(Mass increase)
The sample was placed on an alumina board, the sample was oxidized in a muffle furnace, and the mass increase due to oxidation was evaluated. The oxidation conditions are shown below.
Atmosphere: Air Temperature: 923K (649.85 ° C), 1023K (749.85 ° C), 1123K (849.85 ° C), 1223K (949.85 ° C) (temperature rise from room temperature [50K / min], air cooling)
Time: ~ 144h
（断面分析（１））
サンプルをアルミナボードに置き、マッフル炉にてサンプルを酸化させた後、断面をＥＰＭＡにより観察した。以下に、酸化の条件を示す。
雰囲気：大気
温度：１１２３Ｋ（室温から昇温［５０Ｋ／ｍｉｎ］、空冷）
時間：２４ｈ（８６．４ｋｓ）、１４４ｈ（５１８．４ｋｓ）
次に、断面像から内側層と外側層の厚さを測定した。また、断面像から酸化時間に対するＡｌ2Ｏ3リッチ層の安定性を確認した。
(Cross section analysis (1))
After placing the sample on an alumina board and oxidizing the sample in a muffle furnace, the cross section was observed with EPMA. The oxidation conditions are shown below.
Atmosphere: Air Temperature: 1123K (temperature rise from room temperature [50K / min], air cooling)
Time: 24h (86.4ks), 144h (518.4ks)
Next, the thickness of the inner layer and the outer layer was measured from the cross-sectional image. The stability of the Al 2 O 3 rich layer with respect to the oxidation time was confirmed from the cross-sectional image.
（断面分析（２））
サンプルをアルミナボードに置き、マッフル炉にてサンプルを酸化させた後、断面をＥＰＭＡにより観察し、ＴｉＮ層を観察した。以下に、酸化の条件を示す。
雰囲気：大気
温度：１２２３Ｋ（室温から昇温［５０Ｋ／ｍｉｎ］、空冷）
時間：１４４ｈ
次に、断面像から内側層の厚さｄin、外側層の厚さｄoutおよびＴｉＮ層の厚さｄTiNを測定した。
(Cross section analysis (2))
After placing the sample on an alumina board and oxidizing the sample in a muffle furnace, the cross section was observed with EPMA and the TiN layer was observed. The oxidation conditions are shown below.
Atmosphere: Air Temperature: 1223K (temperature rise from room temperature [50K / min], air cooling)
Time: 144h
Next, from the cross-sectional image, the thickness d in of the inner layer, the thickness d out of the outer layer, and the thickness d TiN of the TiN layer were measured.
［結果］
図１０Ａ〜１１Ｂは、酸化における質量増加と酸化時間（１／２乗）との関係を示す。図１０Ａ〜１１Ｂにおいて、放物線則領域を実線にて示している。図１０Ａ〜１１Ｂから、ＳｉをＴｉ−１７に添加することにより、酸化時間の増加に対する質量増加が抑制されている。したがって、酸化被膜の厚さが低減され、酸化被膜の剥離が抑制されているので、耐酸化性が向上している。
[result]
10A to 11B show the relationship between mass increase in oxidation and oxidation time (1/2 power). 10A to 11B, the parabolic law region is indicated by a solid line. From FIG. 10A-11B, the mass increase with respect to the increase in oxidation time is suppressed by adding Si to Ti-17. Therefore, since the thickness of the oxide film is reduced and the peeling of the oxide film is suppressed, the oxidation resistance is improved.
図１２は、図１０Ａ〜１１Ｂにて放物線則に従う酸化時間をｚ軸とし、Ｓｉ添加量、温度をそれぞれｘ軸、ｙ軸とする３次元の棒グラフである。図１２から、ＳｉをＴｉ−１７に添加することにより、放物線則領域が広がっていることがわかる。Ｓｉの含有量が１質量％である場合、放物線則領域が特に広がっていることがわかる。 FIG. 12 is a three-dimensional bar graph in which the oxidation time according to the parabolic law in FIGS. 10A to 11B is the z axis, and the Si addition amount and temperature are the x axis and the y axis, respectively. From FIG. 12, it can be seen that the parabolic law region is expanded by adding Si to Ti-17. When the Si content is 1% by mass, it can be seen that the parabolic law region is particularly widened.
図１３は、内側層および外側層の厚さと酸化時間との関係を示す。図１３から、ＳｉをＴｉ−１７に添加することにより、内側層および外側層の厚さが低減されていることがわかる。 FIG. 13 shows the relationship between the thickness of the inner and outer layers and the oxidation time. FIG. 13 shows that the thickness of the inner layer and the outer layer is reduced by adding Si to Ti-17.
図１４Ａは、１１２３Ｋ、８６．４ｋｓの酸化試験後のＴｉ合金（Ｓｉ：０質量％）断面のＡｌ分布を示す。図１４Ｂは、１１２３Ｋ、５１８．４ｋｓの酸化試験後のＴｉ合金（Ｓｉ：０質量％）断面のＡｌ分布を示す。図１５Ａは、１１２３Ｋ、８６．４ｋｓの酸化試験後のＴｉ合金（Ｓｉ：１質量％）断面のＡｌ分布を示す。図１５Ｂは、１１２３Ｋ、５１８．４ｋｓの酸化試験後のＴｉ合金（Ｓｉ：１質量％）断面のＡｌ分布を示す。図１４Ａ〜１５Ｂから、Ｔｉ合金がＳｉを１質量％含有することで、内側層と外側層との間に形成されるＡｌ2Ｏ3リッチ層の安定性が向上していることがわかる。これは、内側層中に存在するＳｉがＡｌ2Ｏ3リッチ層の安定性に寄与しているためと考えられる。 FIG. 14A shows an Al distribution of a cross section of a Ti alloy (Si: 0 mass%) after an oxidation test of 1123 K and 86.4 ks. FIG. 14B shows an Al distribution of a cross section of a Ti alloy (Si: 0 mass%) after an oxidation test of 1123K and 518.4 ks. FIG. 15A shows an Al distribution of a cross section of a Ti alloy (Si: 1% by mass) after an oxidation test of 1123K and 86.4 ks. FIG. 15B shows an Al distribution of a Ti alloy (Si: 1% by mass) cross section after an oxidation test of 1123K and 518.4 ks. 14A to 15B, it can be seen that the stability of the Al 2 O 3 rich layer formed between the inner layer and the outer layer is improved when the Ti alloy contains 1% by mass of Si. This is presumably because Si present in the inner layer contributes to the stability of the Al 2 O 3 rich layer.
図１６は、１２２３Ｋ、１４４時間の酸化試験後のＴｉ合金（Ｓｉ：０質量％）断面の元素分布を示す。図１７は、１２２３Ｋ、１４４時間の酸化試験後のＴｉ合金（Ｓｉ：１質量％）断面の元素分布を示す。図１８は、１２２３Ｋ、１４４時間の酸化試験後の内側層、外側層、ＴｉＮ層の厚さ（ｄin、ｄout、ｄTiN）の測定結果を示す。図１６、１７、１８から、内側層とＴｉ合金基板との界面にＴｉＮ層が形成されていることがわかる。また、Ｔｉ合金がＳｉを１質量％含有することで、ＴｉＮ層の膜厚が低減されていることがわかる。 FIG. 16 shows an element distribution of a cross section of a Ti alloy (Si: 0 mass%) after an oxidation test at 1223K for 144 hours. FIG. 17 shows an element distribution of a cross section of a Ti alloy (Si: 1% by mass) after an oxidation test at 1223K for 144 hours. FIG. 18 shows the measurement results of the thicknesses (d in , d out , d TiN ) of the inner layer, the outer layer, and the TiN layer after the oxidation test at 1223K for 144 hours. 16, 17, and 18 that a TiN layer is formed at the interface between the inner layer and the Ti alloy substrate. Moreover, it turns out that the film thickness of a TiN layer is reduced because Ti alloy contains 1 mass% of Si.
以上、本発明の実施形態および実施例について具体的に説明したが、本発明は、上述の実施形態および実施例に限定されるものではなく、本発明の技術的思想に基づく各種の変形が可能である。 Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments and examples, and various modifications based on the technical idea of the present invention are possible. It is.
例えば、上述の実施形態および実施例において挙げた構成、方法、工程、形状、材料および数値等はあくまでも例に過ぎず、必要に応じてこれと異なる構成、方法、工程、形状、材料および数値等を用いてもよい。 For example, the configurations, methods, steps, shapes, materials, numerical values, and the like given in the above-described embodiments and examples are merely examples, and different configurations, methods, steps, shapes, materials, numerical values, and the like, as necessary May be used.
また、上述の実施形態および実施例の構成、方法、工程、形状、材料および数値等は、本発明の主旨を逸脱しない限り、互いに組み合わせることが可能である。 The configurations, methods, processes, shapes, materials, numerical values, and the like of the above-described embodiments and examples can be combined with each other without departing from the gist of the present invention.
また、耐熱Ｔｉ合金をユーザに提供する前に、予め８００℃を超える高温度域にて耐熱Ｔｉ合金を熱処理し、耐酸化性を向上しておくようにしてもよい。 In addition, before providing the heat-resistant Ti alloy to the user, the heat-resistant Ti alloy may be heat-treated in advance in a high temperature range exceeding 800 ° C. to improve the oxidation resistance.
１１、２１ 基材
１２、２２ 酸化被膜（被膜）
１３ Ａｌ濃化層
２２ａ 内側層
２２ｂ 外側層
２２ｃ Ａｌ2Ｏ3リッチ層（酸化アルミニウム含有層）
２３ ＴｉＮ層
11, 21 Base material 12, 22 Oxide film (film)
13 Al concentrated layer 22a Inner layer 22b Outer layer 22c Al 2 O 3 rich layer (aluminum oxide-containing layer)
23 TiN layer
Claims (10)
ＡｌおよびＳｎの少なくとも１種と、
Ｓｉと
を含み、
前記Ｓｉの含有量が、０．１質量％を超え１０質量％未満である耐熱Ｔｉ合金。 A heat-resistant Ti alloy used in a high temperature range exceeding 800 ° C,
At least one of Al and Sn;
Si and
A heat-resistant Ti alloy having a Si content of more than 0.1% by mass and less than 10% by mass.
前記基材の表面に設けられた被膜と
を備え、
耐熱Ｔｉ合金は、
ＡｌおよびＳｎの少なくとも１種と、
Ｓｉと
を含み、
前記Ｓｉの含有量が、０．１質量％を超え１０質量％未満である耐熱Ｔｉ合金材。 A base material made of a heat-resistant Ti alloy;
A coating provided on the surface of the base material,
The heat-resistant Ti alloy
At least one of Al and Sn;
Si and
A heat-resistant Ti alloy material having a Si content of more than 0.1% by mass and less than 10% by mass.
前記耐熱Ｔｉ合金層と前記被膜との界面に設けられたＡｌ濃化層をさらに備える請求項６に記載の耐熱Ｔｉ合金材。 The heat-resistant Ti alloy is a heat-resistant Ti alloy containing Al and Si,
The heat resistant Ti alloy material according to claim 6, further comprising an Al concentrated layer provided at an interface between the heat resistant Ti alloy layer and the coating.
前記被膜は、
内側層と、
外側層と、
前記内側層と前記外側層との間に設けられた安定な酸化アルミニウム含有層と
を備える請求項６に記載の耐熱Ｔｉ合金材。 The heat-resistant Ti alloy is a heat-resistant Ti alloy containing Sn and Si, or a heat-resistant Ti alloy containing Al, Sn and Si,
The coating is
An inner layer,
An outer layer,
The heat-resistant Ti alloy material according to claim 6, comprising a stable aluminum oxide-containing layer provided between the inner layer and the outer layer.
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