JP2009068031A - HIGH STRENGTH FeNi-BASED ALLOY - Google Patents
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本発明は、γ′相強化型ＦｅＮｉ基合金に係り、特に、高圧水素環境で使用される部材である耐水素脆化特性に優れた高強度ＦｅＮｉ基合金に関する。 The present invention relates to a γ 'phase strengthened FeNi base alloy, and more particularly to a high strength FeNi base alloy having excellent hydrogen embrittlement resistance, which is a member used in a high pressure hydrogen environment.
近年、７０ＭＰａ級の高圧水素ステーションの開発が進められている。環境は現状の３５ＭＰａ級と比較して非常に過酷となるため、高圧水素機器部材には、優れた耐水素脆化特性だけでなく、機器のコンパクト化の要求に対応した高強度な材料が必要とされている。 In recent years, development of a 70 MPa class high-pressure hydrogen station has been underway. The environment is much harsh compared to the current 35 MPa class, so high-pressure hydrogen equipment members need not only excellent hydrogen embrittlement resistance but also high-strength materials that meet the demands for compact equipment. It is said that.
タービン材料として実績のある１５Ｃｒ−２６Ｎｉ−１.３Ｍｏ合金（以下、Ａ２８６と呼称する）は、水素環境中での強度劣化がほとんどないため、高圧水素環境において高強度が必要とされる部位に使用されている。 15Cr-26Ni-1.3Mo alloy (hereinafter referred to as A286), which has a proven track record as a turbine material, has almost no deterioration in strength in a hydrogen environment, so it is used for parts that require high strength in a high-pressure hydrogen environment. Has been.
Ａ２８６は、γ′相（Ｎｉ3[Ａｌ，Ｔｉ]）析出強化型のＦｅＮｉ基合金で、強度は１０００ＭＰａ級であることが非特許文献１に開示されているが、機器のコンパクト化の要求に対しては強度不足である。
A286 is a γ ′ phase (Ni 3 [Al, Ti]) precipitation strengthened type FeNi-based alloy, and it is disclosed in
また、高圧水素ステーション機器は、一般に常温で使用されるため、タービン材料で重要な高温強度よりも、常温での強度と耐水素脆化特性が必要とされ、かつコスト低減のためにも安価であることが望ましい。 In addition, since high-pressure hydrogen station equipment is generally used at room temperature, it requires strength at room temperature and resistance to hydrogen embrittlement rather than high-temperature strength, which is important for turbine materials, and is also inexpensive for cost reduction. It is desirable to be.
本発明は、上記のような事情に鑑みてなされたものであり、その目的は耐水素脆化特性に優れた１２００ＭＰａ以上の高強度ＦｅＮｉ基合金を提供するものである。 This invention is made | formed in view of the above situations, The objective is providing the high strength FeNi base alloy of 1200 Mpa or more excellent in the hydrogen embrittlement resistance.
本発明の高強度ＦｅＮｉ基合金は、γ′相強化型ＦｅＮｉ基合金であって、γ相，γ′相，炭化物相（α）の化学組成（重量％）を、それぞれ
Ｃγ（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）、
Ｃγ′（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）、
Ｃα（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）
とし、ｘ，ｙ，ｚを、それぞれγ，γ′，αの相分率としたとき、溶体化熱処理及び時効熱処理後の合金の化学組成
Ｃ（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）
が、式（１）で表され、残部は不可避不純物とする成分から成ることを特徴とする。
The high-strength FeNi base alloy of the present invention is a γ 'phase strengthened FeNi base alloy, and the chemical composition (wt%) of the γ phase, γ' phase, and carbide phase (α) is set to Cγ (Ni, Al, Cr, Fe, Mo, Si, Ti, C),
Cγ ′ (Ni, Al, Cr, Fe, Mo, Si, Ti, C),
Cα (Ni, Al, Cr, Fe, Mo, Si, Ti, C)
Where x, y, z are the phase fractions of γ, γ ′, α, respectively, and the chemical composition of the alloy after solution heat treatment and aging heat treatment C (Ni, Al, Cr, Fe, Mo, Si, Ti, C)
Is represented by the formula (1), and the balance consists of components that are inevitable impurities.
式（１）は、以下のとおりである。 Formula (1) is as follows.
Ｃ（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）＝ｘＣγ（２１.５，０.０２ ，１６.５，５９.９，１.４３，０.５４，０.１３，０）＋ｙＣγ′（７１.９，
１.９８，０.３０，７.６８，０.０１，０.０８，１８.１，０）＋ｚＣα（０，０ ，０.０６，０，０.０５，０，８１.３，１８.６） 式（１）
ただし、ｘ＋ｙ＋ｚ＝１，０.１２＜ｙ＜０.２３，０＜ｚ＜０.０１であり、式（１）の合金組成に対して、Ｎｉ：±２.０重量％，Ａｌ：±０.１重量％，Ｃｒ：±１.０重量％，Ｆｅ：±３.０重量％，Ｍｏ：±０.１重量％，Ｓｉ：±０.１重量％，Ｔｉ：±０.１重量％，Ｃ：±０.０３重量％以内とする。
C (Ni, Al, Cr, Fe, Mo, Si, Ti, C) = xCγ (21.5, 0.02, 16.5, 59.9, 1.43, 0.54, 0.13, 0 ) + YCγ ′ (71.9,
1.98, 0.30, 7.68, 0.01, 0.08, 18.1, 0) + zCα (0,0,0.06,0,0.05,0,81.3,18. 6) Formula (1)
However, x + y + z = 1, 0.12 <y <0.23, 0 <z <0.01, and with respect to the alloy composition of the formula (1), Ni: ± 2.0% by weight, Al: ± 0 0.1 wt%, Cr: ± 1.0 wt%, Fe: ± 3.0 wt%, Mo: ± 0.1 wt%, Si: ± 0.1 wt%, Ti: ± 0.1 wt%, C: Within ± 0.03% by weight.
また、本発明のＦｅＮｉ基合金において、更に、Ｍｎ：０〜１.０重量％，Ｂ：０〜０.０２重量％，Ｍｇ：０.００１〜０.０１重量％，Ｖ：０.０１〜０.５０重量％，Ｃｏ：０〜１.０重量％，Ｗ：０〜１.０重量％のうち少なくとも一種類以上を含むことも好ましい。 Further, in the FeNi-based alloy of the present invention, Mn: 0 to 1.0 wt%, B: 0 to 0.02 wt%, Mg: 0.001 to 0.01 wt%, V: 0.01 to It is also preferable to include at least one of 0.50 wt%, Co: 0 to 1.0 wt%, and W: 0 to 1.0 wt%.
また、本発明のＦｅＮｉ基合金において、γ′相の平均粒径が１５〜２５ｎｍであることが好ましい。 In the FeNi-based alloy of the present invention, the average particle size of the γ ′ phase is preferably 15 to 25 nm.
また、本発明の高強度ＦｅＮｉ基合金を部材として高圧水素流量計，高圧水素配管等の高圧水素機器に用いることが好ましい。 The high-strength FeNi-based alloy of the present invention is preferably used as a member for high-pressure hydrogen equipment such as a high-pressure hydrogen flow meter and high-pressure hydrogen piping.
本発明により、γ相，γ′相，α相の化学組成を変えずにＦｅＮｉ基合金の高強度化が可能となり、耐水素脆化特性に優れた高強度化ＦｅＮｉ基合金の提供が可能となった。 According to the present invention, it is possible to increase the strength of the FeNi base alloy without changing the chemical composition of the γ phase, γ ′ phase, and α phase, and it is possible to provide a high strength FeNi base alloy having excellent hydrogen embrittlement resistance. became.
以下に、本発明における耐水素脆化性高強度ＦｅＮｉ基合金の特徴を示す。 The characteristics of the hydrogen embrittlement resistant high strength FeNi base alloy in the present invention will be described below.
ＦｅＮｉ基合金は、主にマトリクスであるγ相と析出物であるγ′（Ｎｉ3[Ａｌ，Ｔｉ]）相，γ″（Ｎｉ3Ｎｂ）相，α（ＴｉＣ，ＮｂＣ）相等からなる合金であり、γ′相あるいはγ″相、またはその両者を主な析出強化相としている。 An FeNi-based alloy is an alloy mainly composed of a γ phase as a matrix and a γ ′ (Ni 3 [Al, Ti]) phase, a γ ″ (Ni 3 Nb) phase, an α (TiC, NbC) phase and the like as precipitates. In other words, the γ ′ phase or the γ ″ phase, or both, is the main precipitation strengthening phase.
高強度化するためにＮｂを添加することは有効であるが、γ″相強化型のＦｅＮｉ基合金は水素脆化し、機械的特性が低下することが知られている。この理由として、γ″相は完全整合析出物であるものの、格子ミスフィットが大きく、水素をトラップするためであると考えられる。 Although it is effective to add Nb to increase the strength, it is known that the γ ″ phase strengthened FeNi base alloy becomes hydrogen embrittled and the mechanical properties are lowered. Although the phase is a perfectly matched precipitate, the lattice misfit is large, which is considered to trap hydrogen.
また、本発明者らは、これまでにＮｂＣを含むＦｅＮｉ基合金が水素脆化することを確認しているため、炭化物相はＴｉＣであることが好ましい。 Moreover, since the present inventors have confirmed that an FeNi-based alloy containing NbC has been hydrogen embrittled so far, the carbide phase is preferably TiC.
ＦｅＮｉ基合金においては、Ｆｅが多過ぎるとフェライトが生成し、一方、Ｎｉが多過ぎるとニッケル水素化物が生成するため、それぞれ水素脆化することになる。 In an FeNi-based alloy, if too much Fe is formed, ferrite is generated. On the other hand, if too much Ni is formed, nickel hydride is formed, and each of them becomes hydrogen embrittled.
本発明者らは、水素感受性が低く、かつ、高強度化が可能な合金として、ＦｅとＮｉとのバランスが良く、水素脆化因子になる可能性があるγ″相およびＮｂＣを含まないγ′相強化型ＦｅＮｉ基合金に着目し、その水素脆化特性について検討した。 As an alloy having low hydrogen sensitivity and high strength, the present inventors have a good balance between Fe and Ni and a γ ″ phase that may become a hydrogen embrittlement factor and a γ that does not contain NbC. Focusing on the phase strengthened FeNi-based alloy, its hydrogen embrittlement characteristics were examined.
その結果、γ相とγ′相とα（ＴｉＣ）相の化学組成が、それぞれ式（２），式（３），式（４）に示す重量％のときに、耐水素脆化特性が優れていることを見出した。 As a result, the hydrogen embrittlement resistance is excellent when the chemical composition of the γ phase, γ ′ phase and α (TiC) phase is the weight% shown in the formulas (2), (3) and (4), respectively. I found out.
Ｃγ（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）＝Ｃγ（２１.５，０.０２ ，１６.５，５９.９，１.４３，０.５４，０.１３，０） 式（２）
Ｃγ′（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）＝Ｃγ′（７１.９，
１.９８，０.３０，７.６８，０.０１，０.０８，１８.１，０） 式（３）
Ｃα（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）＝Ｃα（０，０，０.０６ ，０，０.０５，０，８１.３，１８.６） 式（４）
これらの化学組成のγ相，γ′相及びα相のみにより構成されるＦｅＮｉ基合金は、式（１）で表すことができ、どの相分率においてもＮｉ3ＮｂやＮｂＣのような水素脆化因子になりうる相が析出しないため、優れた耐水素脆化特性を示す。
Cγ (Ni, Al, Cr, Fe, Mo, Si, Ti, C) = Cγ (21.5, 0.02, 16.5, 59.9, 1.43, 0.54, 0.13, 0 Formula (2)
Cγ ′ (Ni, Al, Cr, Fe, Mo, Si, Ti, C) = Cγ ′ (71.9,
(1.98, 0.30, 7.68, 0.01, 0.08, 18.1, 0) Equation (3)
Cα (Ni, Al, Cr, Fe, Mo, Si, Ti, C) = Cα (0, 0, 0.06, 0, 0.05, 0, 81.3, 18.6) Equation (4)
An FeNi-based alloy composed only of γ phase, γ ′ phase and α phase having these chemical compositions can be expressed by the formula (1), and hydrogen embrittlement such as Ni 3 Nb or NbC is obtained at any phase fraction. Since a phase that can be a forming factor does not precipitate, it exhibits excellent hydrogen embrittlement resistance.
γ相，γ′相及びα相の化学組成が式（２），式（３），式（４）から外れた場合には、析出物であるγ′相，α相とマトリクスであるγ相との格子ミスフィットが増加し、これらが水素トラップサイトになりうるため、各構成相の化学組成を変えると耐水素脆化性が損なわれる可能性が高くなる。 When the chemical composition of the γ phase, γ ′ phase, and α phase deviates from the equations (2), (3), and (4), the precipitates are the γ ′ phase, the α phase, and the γ phase that is the matrix. Since the lattice misfits of these components can be increased and these can become hydrogen trap sites, the hydrogen embrittlement resistance is likely to be impaired when the chemical composition of each constituent phase is changed.
一方、強度特性に関して、本発明者らは、γ相，γ′相及びα相の化学組成を式（２），式（３），式（４）の状態に維持したままγ′相を増量することにより、耐水素脆化特性を損なうことなく高強度化できると考え、本発明に至った。 On the other hand, regarding the strength characteristics, the present inventors increased the amount of γ ′ phase while maintaining the chemical composition of the γ phase, γ ′ phase, and α phase in the state of Formula (2), Formula (3), and Formula (4). By doing so, it was considered that the strength could be increased without impairing the hydrogen embrittlement resistance, and the present invention was achieved.
ここで、γ′相分率（ｙ）の下限は、引張強さの下限値を１２００ＭＰａとして、その強度に相当する値である０.１２（１２重量％）とした。 Here, the lower limit of the γ ′ phase fraction (y) was set to 0.12 (12 wt%), which is a value corresponding to the strength, with the lower limit of the tensile strength being 1200 MPa.
一方、γ′相分率の増加に伴いγ′相の固溶温度が上昇するため、γ′量が多過ぎると製造性が低下する。従って、γ′相分率の上限は鍛造可能なγ′相分率の上限、即ちγ′相の固溶温度が９９８℃となる０.２３（２３重量％）とした。 On the other hand, since the solid solution temperature of the γ ′ phase increases with an increase in the γ ′ phase fraction, if the amount of γ ′ is too large, the productivity decreases. Therefore, the upper limit of the γ ′ phase fraction is set to 0.23 (23 wt%) at which the solid solution temperature of the γ ′ phase becomes 998 ° C., that is, the upper limit of the γ ′ phase fraction that can be forged.
α相分率（ｚ）は、ＴｉＣを過度に析出させるとγ′相の析出に寄与するＴｉ量が減少するため、最大で０.０１（１重量％）とした。 The α phase fraction (z) was set to 0.01 (1 wt%) at the maximum because Ti content contributing to the precipitation of the γ ′ phase decreased when TiC was excessively precipitated.
γ相分率（ｘ）は、γ相分率及びα相分率を決めることにより、ｘ＋ｙ＋ｚ＝１から決定される。 The γ phase fraction (x) is determined from x + y + z = 1 by determining the γ phase fraction and the α phase fraction.
式（１）の各組成において、Ｎｉ：±２.０重量％，Ａｌ：±０.１重量％，Ｃｒ：±１.０重量％，Ｆｅ：±３.０重量％，Ｍｏ：±０.１重量％，Ｓｉ：±０.１重量％，Ｔｉ：±０.１重量％，Ｃ：±０.０３重量％以内であっても本発明合金の耐水素脆化特性が大幅に損なわれることはないため、各元素をこれらの範囲に限定した。 In each composition of formula (1), Ni: ± 2.0% by weight, Al: ± 0.1% by weight, Cr: ± 1.0% by weight, Fe: ± 3.0% by weight, Mo: ± 0.0%. Even if it is within 1% by weight, Si: ± 0.1% by weight, Ti: ± 0.1% by weight, C: ± 0.03% by weight, the hydrogen embrittlement resistance of the alloy of the present invention is greatly impaired. Therefore, each element was limited to these ranges.
また、（１）式に含まれない元素として、Ｍｎ：０〜１.０重量％，Ｂ：０〜０.０２重量％，Ｍｇ：０.００１〜０.０１重量％，Ｖ：０.０１〜０.５０重量％，Ｃｏ：０〜１.０重量％，Ｗ：０〜１.０重量％を含有しても良い。 Further, as elements not included in the formula (1), Mn: 0 to 1.0 wt%, B: 0 to 0.02 wt%, Mg: 0.001 to 0.01 wt%, V: 0.01 ˜0.50 wt%, Co: 0 to 1.0 wt%, W: 0 to 1.0 wt% may be contained.
本発明の合金は、γ相，γ′相，α相の相分率により合金組成が決定するため、成分ごとに分けて範囲を限定するものではなく、上記の成分範囲を外れると、格子ミスフィットが増加することにより、耐水素脆化特性が損なわれることを示している。 In the alloy of the present invention, the alloy composition is determined by the phase fraction of the γ phase, the γ ′ phase, and the α phase. Therefore, the range is not limited separately for each component. This shows that the hydrogen embrittlement resistance is impaired by increasing the fit.
γ′相強化型ＦｅＮｉ基合金を高強度化するには、γ′相を微細かつ多量に析出させることが有効である。本発明合金におけるγ′相の平均粒径は、１５〜２５ｎｍであることが好ましい。 In order to increase the strength of the γ 'phase strengthened FeNi base alloy, it is effective to precipitate the γ' phase in a fine and large amount. The average particle size of the γ ′ phase in the alloy of the present invention is preferably 15 to 25 nm.
熱処理は、溶体化処理を９００℃〜９８０℃で１〜２時間行った後、水冷し、次に時効処理を７００℃〜７６０℃で１６時間以上行った後、室温まで炉冷することが望ましく、この熱処理によって、上記に記載の平均粒径を有する鍛造可能な耐水素性高強度ＦｅＮｉ基合金を作製することができる。 As for the heat treatment, it is desirable that the solution treatment is performed at 900 ° C. to 980 ° C. for 1 to 2 hours, followed by water cooling, and then the aging treatment is performed at 700 ° C. to 760 ° C. for 16 hours or more, followed by furnace cooling to room temperature. By this heat treatment, a forgeable hydrogen-resistant high-strength FeNi-based alloy having the above-described average particle diameter can be produced.
本発明の合金は、上記の通りの特徴を持つものであり、以下、本発明の実施の形態について説明するが、本発明はこれらの実施例に限定されるものではない。 The alloy of the present invention has the characteristics as described above. Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these examples.
表１に、本発明合金及び従来材の化学組成の例を示す。 Table 1 shows examples of chemical compositions of the alloys of the present invention and the conventional materials.
従来材Ａは、Ａ２８６の代表組成、また従来材ＢはＮｂ添加により高強度化したγ′相強化型高強度ＦｅＮｉ基合金の一例であり、それぞれ比較材として使用した。 The conventional material A is an example of a representative composition of A286, and the conventional material B is an example of a γ ′ phase strengthened high strength FeNi base alloy that has been strengthened by adding Nb, and was used as a comparative material.
従来材Ａ及び発明材Ａ〜Ｄは、真空誘導溶解及び真空アーク再溶解による真空二重溶解で１０kgのインゴットを作製し、鍛造により３０×３０mm断面の角材とした。 For the conventional material A and the inventive materials A to D, a 10 kg ingot was prepared by vacuum double melting by vacuum induction melting and vacuum arc remelting, and a square material having a cross section of 30 × 30 mm was formed by forging.
熱処理については、９８０℃で２時間保持して溶体化熱処理した後、水冷し、次に７２０℃で２４時間保持して時効熱処理した後、室温まで炉冷した。従来材Ｂは、高周波真空溶解により１０kgのインゴットを作製し、鍛造により３０×３０mm断面の角材とした。熱処理は９８０℃で２時間保持して溶体化熱処理した後、空冷し、次に８４０℃で８時間保持した後，７３０℃で２４時間保持して二段時効処理を行い、室温まで炉冷した。 With respect to the heat treatment, solution heat treatment was carried out by holding at 980 ° C. for 2 hours, followed by water cooling, followed by aging heat treatment at 720 ° C. for 24 hours, and then furnace cooling to room temperature. For the conventional material B, a 10 kg ingot was prepared by high-frequency vacuum melting, and a square material having a 30 × 30 mm cross section was formed by forging. The heat treatment was held at 980 ° C. for 2 hours, followed by solution heat treatment, then air cooling, then held at 840 ° C. for 8 hours, then held at 730 ° C. for 24 hours, and then subjected to two-stage aging treatment, and the furnace was cooled to room temperature .
図１は、γ′相分率と引張強さの関係を示す。また、従来材Ａ及び本発明材におけるそれぞれのγ′相分率も同図中に示した。この結果、γ′相分率の増加に伴い高強度化されていることが確認された。 FIG. 1 shows the relationship between the γ ′ phase fraction and the tensile strength. In addition, the γ ′ phase fractions in the conventional material A and the material of the present invention are also shown in FIG. As a result, it was confirmed that the strength was increased as the γ ′ phase fraction increased.
図２は、陰極チャージ時間と引張強さとの関係を示す。強度特性に及ぼす水素の影響を調べる目的で、各材料について、陰極チャージ法により水素チャージした後、引張試験を実施した。陰極チャージは０.０５ＭのＨ2ＳＯ4と０.０１ＭのＫＳＣＮを有する電解液に、試験片とＰｔ電極及び熱電対を入れ、試験片を陰極（−）、Ｐｔ電極を陽極（＋）として５５℃で２００ｍＡの定電流を６時間，１０時間流して実施した。 FIG. 2 shows the relationship between cathode charge time and tensile strength. In order to investigate the influence of hydrogen on strength properties, each material was charged with hydrogen by the cathodic charging method and then subjected to a tensile test. Cathode charge is placed in an electrolyte solution containing 0.05 M H 2 SO 4 and 0.01 M KSCN, and a test piece, a Pt electrode and a thermocouple are placed, and the test piece is used as a cathode (−) and the Pt electrode is used as an anode (+). A constant current of 200 mA was flowed at 55 ° C. for 6 hours and 10 hours.
引張試験は、２.５×１０-4のひずみ速度で行った。 The tensile test was performed at a strain rate of 2.5 × 10 −4 .
その結果、従来材及び発明材とも大幅な強度の低下は見られなかった。 As a result, neither the conventional material nor the inventive material showed a significant decrease in strength.
図３は、陰極チャージ時間と水素脆化指標の関係を示す。ここで、耐水素脆化特性を表す指標として、式（５）を定義して比較した。 FIG. 3 shows the relationship between the cathode charge time and the hydrogen embrittlement index. Here, equation (5) was defined and compared as an index representing the hydrogen embrittlement resistance.
[水素脆化指標]＝[水素チャージ後の伸び率]／[水素チャージ前の伸び率] 式（５）
水素脆化指標は、１に近いほど耐水素脆化特性が高い材料であり、水素脆化の少ない材料であることを示す。この結果、Ｎｂ添加により高強度化した従来材Ｂが最も水素脆化指標の低下が顕著であった。
[Hydrogen embrittlement index] = [Elongation after hydrogen charge] / [Elongation before hydrogen charge] Formula (5)
The hydrogen embrittlement index is closer to 1, indicating that the material has higher hydrogen embrittlement resistance and less hydrogen embrittlement. As a result, the decrease in the hydrogen embrittlement index was most remarkable in the conventional material B which was strengthened by adding Nb.
次に、水素脆化指標が低い材料は従来材Ａであり、発明材の耐水素脆化特性が従来材Ａ及びＢと比較して優れていることが確認された。 Next, the material having a low hydrogen embrittlement index is the conventional material A, and it was confirmed that the hydrogen embrittlement resistance of the inventive material is superior to the conventional materials A and B.
表２は、本発明合金及び従来材Ａの熱処理後のγ′相の平均粒径及び面積率を示す。 Table 2 shows the average grain size and area ratio of the γ ′ phase after heat treatment of the alloy of the present invention and the conventional material A.
γ′相の平均粒径は、一つの視野について２０個以上測定した。 The average particle diameter of the γ ′ phase was measured by 20 or more for one visual field.
その結果、平均粒径は従来材と発明材で大差なかったが、面積率の増加に伴い粒子間距離が減少していた。合金の強度を増すには微細なγ′相が析出することが好ましく、平均粒径は１５〜２５ｎｍであることが好ましい。 As a result, the average particle size did not differ greatly between the conventional material and the invention material, but the interparticle distance decreased with an increase in the area ratio. In order to increase the strength of the alloy, it is preferable that a fine γ 'phase is precipitated, and the average particle size is preferably 15 to 25 nm.
図４は、本発明の実施の一例として、高圧水素環境機器の一つである高圧水素流量計の模式図を示す。 FIG. 4 shows a schematic diagram of a high-pressure hydrogen flow meter that is one of high-pressure hydrogen environmental equipment as an example of the implementation of the present invention.
水素流量計１は、Ｕ字状のセンサチューブ２と、センサチューブを加振する加振器３と、流入側及び流出側のセンサチューブの振動による変位を検出するピックアップ４と、センサチューブが固定されたベース５を有する。
The
本実施例では、センサチューブ２に高強度な本発明材Ａ〜Ｄを適用することによって、センサチューブ２の外径が従来材よりも減少する。
In the present embodiment, the high-strength invention materials A to D are applied to the
従って、流体による振動が従来よりも容易となり測定ノイズが減少する。その結果、機器のコンパクト化と所定の性能を達成することが可能となった。 Therefore, vibration due to the fluid is easier than before, and measurement noise is reduced. As a result, it has become possible to achieve a compact device and a predetermined performance.
本実施例では高圧水素流量計を示したが、その他にも高圧水素配管等の耐水素脆化特性と高強度を要する機器部材として、本発明合金は適用可能である。 Although the high-pressure hydrogen flowmeter is shown in this embodiment, the alloy of the present invention can be applied to other equipment members that require hydrogen embrittlement resistance and high strength such as high-pressure hydrogen piping.
本発明は、耐水素脆化特性に優れた高強度化ＦｅＮｉ基合金を提供することが可能となるため、高圧水素流量計や高圧水素配管等の耐水素脆化特性と高強度を要する高圧水素機器用の部材として、利用可能である。 The present invention makes it possible to provide a high-strength FeNi-based alloy having excellent hydrogen embrittlement resistance, so that high-pressure hydrogen that requires hydrogen embrittlement resistance and high strength, such as a high-pressure hydrogen flow meter and a high-pressure hydrogen pipe. It can be used as a member for equipment.
１ 水素流量計
２ センサチューブ
３ 加振器
４ ピックアップ
５ ベース
1
Claims (5)
γ相，γ′相，炭化物相（α）の化学組成（重量％）を、それぞれ
Ｃγ（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）、
Ｃγ′（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）、
Ｃα（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）
とし、ｘ，ｙ，ｚを、それぞれγ，γ′，αの相分率としたとき、
溶体化熱処理及び時効熱処理後の合金の化学組成
Ｃ（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）
が、式（１）で表され、残部は不可避不純物とする成分から成ることを特徴とする高強度ＦｅＮｉ基合金。
Ｃ（Ｎｉ，Ａｌ，Ｃｒ，Ｆｅ，Ｍｏ，Ｓｉ，Ｔｉ，Ｃ）＝ｘＣγ（２１.５，０.０２ ，１６.５，５９.９，１.４３，０.５４，０.１３，０）＋ｙＣγ′（７１.９，
１.９８，０.３０，７.６８，０.０１，０.０８，１８.１，０）＋ｚＣα（０，０ ，０.０６，０，０.０５，０，８１.３，１８.６） 式（１）
ただし、ｘ＋ｙ＋ｚ＝１，０.１２＜ｙ＜０.２３，０＜ｚ＜０.０１であり、式（１）の合金組成に対して、Ｎｉ：±２.０重量％，Ａｌ：±０.１重量％，Ｃｒ：±１.０重量％，Ｆｅ：±３.０重量％，Ｍｏ：±０.１重量％，Ｓｉ：±０.１重量％，Ｔｉ：±０.１重量％，Ｃ：±０.０３重量％以内とする。 In the γ ′ phase strengthened FeNi base alloy,
The chemical composition (% by weight) of the γ phase, γ ′ phase, and carbide phase (α) is expressed as Cγ (Ni, Al, Cr, Fe, Mo, Si, Ti, C),
Cγ ′ (Ni, Al, Cr, Fe, Mo, Si, Ti, C),
Cα (Ni, Al, Cr, Fe, Mo, Si, Ti, C)
And x, y, z are phase fractions of γ, γ ′, α, respectively,
Chemical composition of the alloy after solution heat treatment and aging heat treatment C (Ni, Al, Cr, Fe, Mo, Si, Ti, C)
Is a high-strength FeNi-base alloy represented by the formula (1), with the balance being components that are inevitable impurities.
C (Ni, Al, Cr, Fe, Mo, Si, Ti, C) = xCγ (21.5, 0.02, 16.5, 59.9, 1.43, 0.54, 0.13, 0 ) + YCγ ′ (71.9,
1.98, 0.30, 7.68, 0.01, 0.08, 18.1, 0) + zCα (0,0,0.06,0,0.05,0,81.3,18. 6) Formula (1)
However, x + y + z = 1, 0.12 <y <0.23, 0 <z <0.01, and with respect to the alloy composition of the formula (1), Ni: ± 2.0% by weight, Al: ± 0 0.1 wt%, Cr: ± 1.0 wt%, Fe: ± 3.0 wt%, Mo: ± 0.1 wt%, Si: ± 0.1 wt%, Ti: ± 0.1 wt%, C: Within ± 0.03% by weight.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011068919A (en) * | 2009-09-24 | 2011-04-07 | Hitachi Ltd | Fe-ni based alloy with high-strength hydrogen embrittlement resistant |
| WO2014030705A1 (en) | 2012-08-24 | 2014-02-27 | 株式会社日本製鋼所 | Ni-based alloy having excellent hydrogen embrittlement resistance, and method for producing ni-based alloy material |
| JP2014047409A (en) * | 2012-09-03 | 2014-03-17 | Nippon Steel & Sumitomo Metal | High-strength austenitic stainless steel for high-pressure hydrogen gas |
| CN116891984A (en) * | 2023-09-11 | 2023-10-17 | 成都先进金属材料产业技术研究院股份有限公司 | Fe-Cr-Ni intermediate alloy for hydrogen-resistant stainless steel and preparation method thereof |
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2007
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011068919A (en) * | 2009-09-24 | 2011-04-07 | Hitachi Ltd | Fe-ni based alloy with high-strength hydrogen embrittlement resistant |
| WO2014030705A1 (en) | 2012-08-24 | 2014-02-27 | 株式会社日本製鋼所 | Ni-based alloy having excellent hydrogen embrittlement resistance, and method for producing ni-based alloy material |
| KR20150034282A (en) | 2012-08-24 | 2015-04-02 | 더 재팬 스틸 워크스 엘티디 | Ni-based alloy having excellent hydrogen embrittlement resistance, and method for producing ni-based alloy material |
| JP2014047409A (en) * | 2012-09-03 | 2014-03-17 | Nippon Steel & Sumitomo Metal | High-strength austenitic stainless steel for high-pressure hydrogen gas |
| CN116891984A (en) * | 2023-09-11 | 2023-10-17 | 成都先进金属材料产业技术研究院股份有限公司 | Fe-Cr-Ni intermediate alloy for hydrogen-resistant stainless steel and preparation method thereof |
| CN116891984B (en) * | 2023-09-11 | 2024-02-02 | 成都先进金属材料产业技术研究院股份有限公司 | Fe-Cr-Ni intermediate alloy for hydrogen-resistant stainless steel and preparation method thereof |
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