JP2013155431A - Iron alloy - Google Patents
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Abstract
Description
本発明は、高強度で高延性な鉄合金に関する。 The present invention relates to an iron alloy having high strength and high ductility.
構造部材の多くは鉄系材料により形成されている。鉄系材料は、その仕様に応じて、成分が調整され、適当な熱処理や加工等が施されることにより、所望の強度や延性を発揮する。もっとも鉄系材料（特に鉄鋼材料）は、通常、強度と延性が背反関係にあり、両者を高次元で両立させものは殆どなかった。 Many of the structural members are made of an iron-based material. The iron-based material exhibits desired strength and ductility by adjusting the components according to the specifications and applying appropriate heat treatment or processing. However, iron-based materials (especially steel materials) usually have a contradictory relationship between strength and ductility, and there is hardly anything that can achieve both at a high level.
例えば、高強度な鉄系材料として周知のマルエージング鋼（Ｆｅ−Ｎｉ−Ｃｏ−Ｍｏ−Ｔｉ系合金）は、加工と熱処理を加えることにより、２０００ＭＰａを超える高強度（最大引張強さ：ＵＴＳ）を発揮する。しかし、その場合の延性（塑性変形能）は１０％以下に過ぎない。延性を２０％以上にするためには、強度を１５００ＭＰａ程度まで低下させなければならない。マルエージング鋼の場合、熱処理してできた微細析出物による転位運動抑制効果を利用して高強度化を図っている。これに強加工を加えると、転位が集積して微視的な亀裂が生じ、それが巨視的な亀裂へと成長して、破壊し易くなるため、延性の低下は避けがたかった。このように従来の高強度材では、強度が向上するにつれて、延性が低下する傾向にあった。 For example, maraging steel (Fe-Ni-Co-Mo-Ti alloy), which is well known as a high-strength iron-based material, has a high strength (maximum tensile strength: UTS) exceeding 2000 MPa by applying processing and heat treatment. Demonstrate. However, the ductility (plastic deformability) in that case is only 10% or less. In order to make the ductility 20% or more, the strength must be reduced to about 1500 MPa. In the case of maraging steel, high strength is achieved by utilizing the effect of suppressing dislocation motion by fine precipitates formed by heat treatment. When strong processing is applied to this, dislocations accumulate and microscopic cracks are formed, which grow into macroscopic cracks and become easy to break. Therefore, it is difficult to avoid a decrease in ductility. As described above, in the conventional high strength material, the ductility tends to decrease as the strength increases.
また特許文献１には、Ｆｅ−Ｎｉ−Ａｌ系合金からなる形状記憶合金が開示されている。形状記憶合金は、一般的に変態点以上で形状回復や超弾性を生じ、高延性を発揮する。しかし、その強度は必ずしも高くない。実際、特許文献１にあるＦｅ−Ｎｉ−Ａｌ系合金でも、マルテンサイト組織を得る溶体化処理後の引張強さが、高々７００ＭＰａ程度に留まっている。 Patent Document 1 discloses a shape memory alloy made of an Fe—Ni—Al alloy. Shape memory alloys generally exhibit shape recovery and superelasticity above the transformation point and exhibit high ductility. However, its strength is not necessarily high. In fact, even in the Fe—Ni—Al-based alloy disclosed in Patent Document 1, the tensile strength after solution treatment for obtaining a martensite structure remains at most about 700 MPa.
なお、特許文献１には、１質量％以下のＣを含有させることにより、Ｆｅ−Ｎｉ−Ａｌ系合金のＭｓが低下し、Ｎｉ量を低減させつつ形状記憶特性を向上させ得る旨が記載されている。しかし、そのような実施例は特許文献１に全く開示されておらず、Ｃ量と強度および延性との関係についても何ら言及されていない。 Patent Document 1 describes that the inclusion of 1% by mass or less of C reduces the Ms of the Fe—Ni—Al-based alloy and can improve the shape memory characteristics while reducing the amount of Ni. ing. However, such an example is not disclosed at all in Patent Document 1, and there is no mention of the relationship between the amount of C, strength, and ductility.
本発明はこのような事情に鑑みて為されたものであり、従来の鉄系材料とは異なる成分組成からなり、従来の鉄系材料では到達し得なかった高強度と高延性を両立させ得る鉄合金を提供することを目的とする。 The present invention has been made in view of such circumstances, and has a composition different from that of conventional iron-based materials, and can achieve both high strength and high ductility that cannot be achieved with conventional iron-based materials. An object is to provide an iron alloy.
本発明者はこの課題を解決すべく鋭意研究し、試行錯誤を重ねた結果、Ｆｅ、Ｎｉ、ＡｌおよびＣを特定の組成範囲に調整した素材に、適切な熱処理や加工を施すことにより、従来の鉄系材料とは格段に異なる高い強度および延性を発揮する鉄合金を得ることに成功した。この成果を発展させることにより、以降に述べる本発明を完成するに至った。 The present inventor has intensively studied to solve this problem, and as a result of repeated trial and error, by applying appropriate heat treatment and processing to a material in which Fe, Ni, Al and C are adjusted to a specific composition range, We succeeded in obtaining an iron alloy exhibiting high strength and ductility that is markedly different from other iron-based materials. By developing this result, the present invention described below has been completed.
《鉄合金》
（１）本発明の鉄合金は、ニッケル（Ｎｉ）、アルミニウム（Ａｌ）、炭素（Ｃ）および残部が鉄（Ｆｅ）と不可避不純物からなる鉄合金であって、Ｆｅ、ＮｉおよびＡｌは、平均価電子濃度（ｅ／ａ）が７．５〜８．１となる組成範囲内にあり、Ｃは、全体を１００原子％（以下「％」という。）としたときに０．８〜４％であることを特徴とする。
《Iron alloy》
(1) The iron alloy of the present invention is an iron alloy composed of nickel (Ni), aluminum (Al), carbon (C) and the balance iron (Fe) and inevitable impurities, and Fe, Ni and Al are average The valence electron concentration (e / a) is in the composition range of 7.5 to 8.1, and C is 0.8 to 4% when the whole is 100 atomic% (hereinafter referred to as “%”). It is characterized by being.
（２）本発明の鉄合金によれば、従来の鉄系材料では不可能であった高強度および高延性の両立が可能となる。もっとも本発明の鉄合金が、何故、そのような高強度および高延性を発揮するのかは必ずしも定かではない。本発明者は、現在も、その理由を鋭意解明中である。いずれにしても、そのような高強度および高延性は、Ｆｅ、Ｎｉ、ＡｌおよびＣの必須元素が上述したように狭い組成範囲内にある鉄合金に生じる特異な現象であると考えられる。 (2) According to the iron alloy of the present invention, it is possible to achieve both high strength and high ductility, which is impossible with conventional iron-based materials. However, it is not always clear why the iron alloy of the present invention exhibits such high strength and high ductility. The present inventor is still elucidating the reason. In any case, such high strength and high ductility are considered to be unique phenomena that occur in iron alloys in which the essential elements of Fe, Ni, Al, and C are in the narrow composition range as described above.
《鉄合金の製造方法》
本発明の鉄合金は、その製造方法、加工の程度、熱処理の条件、形態等を問わない。例えば、本発明の鉄合金は、溶製材でも焼結材でもよいし、それらからなる素材に適当な熱処理や加工等が施された中間品でも最終品でもよい。要求仕様に応じて、組成、加工、熱処理等が適宜調整され、それにより所望する高強度および高延性な鉄合金（部材）が得られる。
《Method for producing iron alloy》
The iron alloy of the present invention is not limited by its production method, degree of processing, heat treatment conditions, form, and the like. For example, the iron alloy of the present invention may be a smelted material or a sintered material, and may be an intermediate product or a final product obtained by subjecting a material composed thereof to appropriate heat treatment or processing. Depending on the required specifications, the composition, processing, heat treatment, and the like are appropriately adjusted, thereby obtaining a desired high strength and high ductility iron alloy (member).
《その他》
（１）特に断らない限り本明細書でいう「ｘ〜ｙ」は下限値ｘおよび上限値ｙを含む。本明細書に記載した種々の数値または数値範囲に含まれる任意の数値を新たな下限値または上限値として、「ａ〜ｂ」のような範囲を新設し得る。
<Others>
(1) Unless otherwise specified, “x to y” in this specification includes a lower limit value x and an upper limit value y. A range such as “a to b” may be newly established with any numerical value included in various numerical values or numerical ranges described in the present specification as a new lower limit value or upper limit value.
（２）本発明の鉄合金は、その高強度および高延性が阻害されない範囲で、上述した必須元素（Ｆｅ、Ｎｉ、ＡｌおよびＣ）以外の元素を微量含み得る。例えば、鉄合金は、その特性を改善する元素として、不可避不純物とは別にＨ、Ｏ、Ｓｉ、Ｎ等を微量含み得る。なお、不可避不純物は、原料中に含まれる不純物や各工程時に混入等する不純物などであり、コスト的または技術的な理由等により除去困難な元素である。不可避不純物は通常微量であるが、その具体的な元素や含有量は問わない。 (2) The iron alloy of the present invention may contain a trace amount of elements other than the essential elements (Fe, Ni, Al, and C) described above as long as the high strength and high ductility are not hindered. For example, an iron alloy may contain a small amount of H, O, Si, N, etc., in addition to inevitable impurities, as an element that improves its characteristics. The inevitable impurities are impurities contained in the raw material, impurities mixed in at each step, etc., and are elements that are difficult to remove due to cost or technical reasons. Inevitable impurities are usually trace amounts, but their specific elements and contents are not limited.
（３）本発明でいう「鉄合金」は、その形態を問わず、例えば、素材（鋳塊、スラブ、ビレット、焼結体、圧延品、鍛造品、線材、棒材、角材、板材、箔材、繊維、織物等）であっても、その加工品（例えば、中間加工品、最終製品等）であっても良い。 (3) The “iron alloy” as used in the present invention is not limited to its form, for example, a raw material (ingot, slab, billet, sintered body, rolled product, forged product, wire, bar, square, plate, foil Material, fiber, woven fabric, etc.) or processed products thereof (for example, intermediate processed products, final products, etc.).
（４）本明細書でいう「強度」は、試験片の引張試験により求まる引張破断強さまたは最大引張強さ（ＵＴＳ）により指標される。また「延性」は、同引張試験により求まる破断伸び（ＥＬ）により指標される。また均一伸びも指標の一つである。均一伸びは、塑性不安定が生じるまでの伸びである。塑性不安定条件は、ｄσｔ／ｄεｔ ≦ εｔ （σｔ：真応力、εｔ：真ひずみ）で表されるくびれ開始の条件である。本発明の鉄合金が発揮する強度や延性は、その組成、熱処理、加工履歴等により変化するため、一概に特定することはできない。敢えていうならば、強度は１７００ＭＰａ以上、１８００ＭＰａ以上さらには１９００ＭＰａ以上であると好ましい。また延性は、２０％以上、２４％以上、さらには２８％以上であると好ましい。均一伸びでは、２０％以上、２２％以上さらには２５％以上であると好ましい。 (4) “Strength” as used herein is indicated by the tensile breaking strength or the maximum tensile strength (UTS) determined by a tensile test of a test piece. Further, “ductility” is indexed by elongation at break (EL) obtained by the tensile test. Uniform elongation is also an index. Uniform elongation is the elongation until plastic instability occurs. The plastic instability condition is a constriction start condition represented by dσ t / dε t ≦ ε t (σ t : true stress, ε t : true strain). Since the strength and ductility exhibited by the iron alloy of the present invention vary depending on its composition, heat treatment, processing history, etc., it cannot be specified unconditionally. In other words, the strength is preferably 1700 MPa or more, 1800 MPa or more, further 1900 MPa or more. The ductility is preferably 20% or more, 24% or more, and more preferably 28% or more. The uniform elongation is preferably 20% or more, 22% or more, and more preferably 25% or more.
さらに本発明の鉄合金は、強度および延性のいずれか一方ではなく、それらが共に優れる点に大きな特徴を有する。これは、上述した強度（ＵＴＳ）と延性（ＥＬ）の積である強度延性バランス指標値（ＵＴＳ・ＥＬ）により指標される。これも一概には特定できないが、敢えていうならば、強度延性バランス指標値は３５０００ＭＰａ％以上、４００００ＭＰａ％以上さらには４５０００ＭＰａ％であると好ましい。 Furthermore, the iron alloy of the present invention has a great feature in that they are excellent in both strength and ductility. This is indicated by the strength ductility balance index value (UTS · EL), which is the product of the above-described strength (UTS) and ductility (EL). Although this cannot be specified unconditionally, the strength ductility balance index value is preferably 35000 MPa% or more, 40000 MPa% or more, and further 45000 MPa%.
本明細書で説明する内容は、本発明の鉄合金のみならず、その製造方法にも該当し得る。製造方法に関する構成要素は、プロダクトバイプロセスとして理解すれば物に関する構成要素ともなり得る。そして上述した本発明の構成要素に、本明細書中から任意に選択した一つまたは二つ以上の構成要素を付加し得る。いずれの実施形態が最良であるか否かは、対象、要求性能等によって異なる。 The contents described in this specification can be applied not only to the iron alloy of the present invention but also to the manufacturing method thereof. A component related to a manufacturing method can be a component related to an object if understood as a product-by-process. One or two or more components arbitrarily selected from the present specification can be added to the above-described components of the present invention. Which embodiment is the best depends on the target, required performance, and the like.
《鉄合金の組成》
（１）平均価電子濃度（ｅ／ａ）
本発明に係る平均価電子濃度（以下、単に「ｅ／ａ」という。）により、高強度および高延性を発揮し得る本発明の鉄合金を構成する必須金属元素（Ｆｅ、ＮｉおよびＡｌ）の組成範囲を規定できる理由は次のように考えられる。ＦＣＣ構造の相安定はｅ／ａに依存する。ｅ／ａは合金元素の価電子を組成で平均化したものであり、相安定と密接な関係にある。後述の適正範囲内において、冷間加工後に高強度化・高延性化に適した相安定性が得られる。
<Composition of iron alloy>
(1) Average valence electron concentration (e / a)
According to the average valence electron concentration (hereinafter simply referred to as “e / a”) according to the present invention, the essential metal elements (Fe, Ni and Al) constituting the iron alloy of the present invention capable of exhibiting high strength and high ductility. The reason why the composition range can be specified is considered as follows. The phase stability of the FCC structure depends on e / a. e / a is obtained by averaging the valence electrons of the alloy elements by the composition, and is closely related to phase stability. Phase stability suitable for high strength and high ductility can be obtained after cold working within an appropriate range described later.
ｅ／ａが最適範囲に対して過小になっても過大になっても、鉄合金の高強度と高延性は両立され難くなる。具体的には、ｅ／ａは７．５〜８．１さらには７．８５〜８．０５であると好ましい。後述するように、ｅ／ａがこのような範囲となる鉄合金の組成範囲は相当狭い範囲である。 Even if e / a is too small or too large with respect to the optimum range, it is difficult to achieve both high strength and high ductility of the iron alloy. Specifically, e / a is preferably 7.5 to 8.1, more preferably 7.85 to 8.05. As will be described later, the composition range of the iron alloy in which e / a falls within such a range is a considerably narrow range.
ｅ／ａで用いる価数電子数は、最外殻電子（当該元素よりも原子番号が小さい最初の希ガス原子（２Ｈｅ、１０Ｎｅ、１８Ａｒ等）の電子軌道より外側の軌道を回る電子）の数である。本明細書では、典型元素のみならず遷移金属についても同様に扱うため、必須金属元素の一原子あたりの価数電子数は次のようになる。 The number of valence electrons used in e / a is the number of outermost electrons (electrons that orbit around the outer orbital of the first rare gas atom ( 2 He, 10 Ne, 18 Ar, etc.) having an atomic number smaller than that of the element). ). In this specification, since not only typical elements but also transition metals are handled in the same manner, the number of valence electrons per atom of the essential metal element is as follows.
２６Ｆｅは、電子配置が［Ａｒ］３ｄ６ ４ｓ２ であるから、その価数電子数は一原子あたり８となる。同様に２８Ｎｉは、電子配置が［Ａｒ］３ｄ８ ４ｓ２ であるから、その価数電子数は一原子あたり１０となり、１３Ａｌは 電子配置が［Ｎｅ］３ｓ２ ３Ｐ１ であるから、その価数電子数は一原子あたり３となる。 Since 26 Fe has an [Ar] 3d 6 4s 2 electron configuration, its valence electron number is 8 per atom. Similarly, 28 Ni has an electron configuration of [Ar] 3d 8 4s 2 , so its valence electron number is 10 per atom, and 13 Al has an electron configuration of [Ne] 3s 2 3P 1 , The number of valence electrons is 3 per atom.
ここで、鉄合金を構成する総原子数に対する必須金属元素の各原子数の割合をそれぞれ、Ｎｉ：ｘ、Ａｌ：ｙ、Ｆｅ：ｚとする（０＜ｘ、ｙ、ｚ＜１）と、ｅ／ａ＝１０ｘ＋３ｙ＋８ｚとなる。ここで、鉄合金に含まれるＣの原子割合をｃとし、鉄合金がＦｅ、Ｎｉ、ＡｌおよびＣの４元素のみからなるとすると、ｚ＝１−ｃ−ｘ−ｙとなり、ｅ／ａ＝２ｘ−５ｙ＋８−８ｃとなる。 Here, the ratio of the number of each of the essential metal elements to the total number of atoms constituting the iron alloy is Ni: x, Al: y, Fe: z (0 <x, y, z <1), e / a = 10x + 3y + 8z. Here, assuming that the atomic ratio of C contained in the iron alloy is c, and the iron alloy is composed of only four elements of Fe, Ni, Al, and C, z = 1−c−xy, and e / a = 2x -5y + 8-8c.
α≦ｅ／ａ≦βとすると、α−８＋８ｃ≦２ｘ−５ｙ≦β−８＋８ｃとなる。また本発明は鉄合金に関するものであるから、０．５≦ｚ（つまりｘ＋ｙ≦０．５−ｃ）とすると、ＮｉおよびＡｌの組成範囲は、図４に示す斜線範囲となる。 When α ≦ e / a ≦ β, α−8 + 8c ≦ 2x−5y ≦ β−8 + 8c. Since the present invention relates to an iron alloy, when 0.5 ≦ z (that is, x + y ≦ 0.5−c), the composition range of Ni and Al is a hatched range shown in FIG.
本発明の場合、α＝７．５、β＝８．１、ｃ：０．００８〜０．０４であることを考慮すると、上記の斜線部分が実質的に非常に狭い特異な範囲であることがわかる。 In the case of the present invention, in consideration of α = 7.5, β = 8.1, and c: 0.008 to 0.04, the shaded portion is a very narrow and unique range. I understand.
（２）Ｃ量
Ｃは、鉄合金の固溶元素であり鉄合金の強度向上に寄与する。その含有量（固溶限）は上記のｅ／ａにより変化するが、鉄合金全体を１００％としたときに０．８〜４％さらには１〜２％であると好ましい。Ｃが過少では効果が乏しく、Ｃが過多になると延性が低下して好ましくない。
(2) Amount of C C is a solid solution element of the iron alloy and contributes to improving the strength of the iron alloy. The content (solid solubility limit) varies depending on the above e / a, but is preferably 0.8 to 4%, more preferably 1 to 2% when the entire iron alloy is 100%. When C is too small, the effect is poor, and when C is excessive, the ductility is lowered, which is not preferable.
なお、質量％でいうと、Ｃ量は０．１〜１質量％、０．１５〜０．８質量％さらには０．２〜０．７質量％であると好ましい。 In terms of mass%, the C content is preferably 0.1 to 1 mass%, 0.15 to 0.8 mass%, and further 0.2 to 0.7 mass%.
（３）Ｎｉ量
Ｎｉは、鉄合金中においてＦＣＣ構造をもつ相を安定化させる元素である。その含有量はｅ／ａにより規定されるが、敢えていうと、鉄合金全体を１００％としたときに１８〜２５％、１９〜２４％さらには２０〜２３％であると好ましい。Ｎｉが過少では効果が乏しく、Ｎｉが過多になると冷間加工により高強度化に適した相安定性が得られなくなり好ましくない。
(3) Ni content Ni is an element that stabilizes a phase having an FCC structure in an iron alloy. Although the content is prescribed | regulated by e / a, when it dares to say, when the whole iron alloy is made into 100%, it is preferable in it being 18-25%, 19-24%, and also 20-23%. If Ni is too small, the effect is poor, and if Ni is excessive, phase stability suitable for high strength cannot be obtained by cold working, which is not preferable.
なお、質量％でいうと、Ｎｉ量は２０〜２８質量％、２１〜２７質量％さらには２２．５〜２６．５質量％であると好ましい。 In terms of mass%, the amount of Ni is preferably 20 to 28 mass%, 21 to 27 mass%, and further 22.5 to 26.5 mass%.
（４）Ａｌ量
Ａｌは、鉄合金中においてＦＣＣ構造をもつ相を安定化させる元素である。その含有量はｅ／ａにより規定されるが、敢えていうと、鉄合金全体を１００％としたときに４〜１９％、５〜１５％さらには６〜１２％であると好ましい。Ａｌが過少では効果が乏しく、Ａｌが過多になると冷間加工により高強度化に適した相安定性が得られなくなり好ましくない。
(4) Al content Al is an element that stabilizes a phase having an FCC structure in an iron alloy. The content is defined by e / a, but daringly, it is preferably 4 to 19%, 5 to 15%, and more preferably 6 to 12% when the entire iron alloy is 100%. If the amount of Al is too small, the effect is poor, and if the amount of Al is excessive, the phase stability suitable for increasing the strength cannot be obtained by cold working, which is not preferable.
なお、質量％でいうと、Ａｌ量は２〜１２質量％、２．５〜１１質量％さらには３〜１０．５質量％であると好ましい。 In terms of mass%, the amount of Al is preferably 2 to 12 mass%, 2.5 to 11 mass%, and more preferably 3 to 10.5 mass%.
（５）全体組成
上述した組成をまとめると、鉄合金は、全体を１００原子％としたとき、Ｎｉ：１８〜２５％、Ａｌ：４〜１９％、Ｃ：０．８〜４％、残部：Ｆｅおよび不可避不純物であると好ましい。また鉄合金は、全体を１００質量％としたとき、Ｎｉ：２０〜２８質量％、Ａｌ：２〜１２質量％、Ｃ：０．１〜１質量％、残部：Ｆｅおよび不可避不純物であると好ましい。
(5) Overall composition Summarizing the above-described composition, the iron alloy has Ni: 18 to 25%, Al: 4 to 19%, C: 0.8 to 4%, and the balance: 100% by atom. Fe and inevitable impurities are preferable. The iron alloy is preferably Ni: 20 to 28% by mass, Al: 2 to 12% by mass, C: 0.1 to 1% by mass, balance: Fe and inevitable impurities when the whole is 100% by mass. .
《鉄合金の組織》
（１）オーステナイト組織
本発明の鉄合金は、温度により変態し得るが、常温域でオーステナイト組織からなり、高強度および高延性を発揮する。このオーステナイト組織中に、Ｃは固溶状態となっていると好ましいが、ナノ炭化物として存在しても良い。またＦｅ、ＮｉおよびＡｌの一部は、そのオーステナイト組織中において金属間化合物を形成していてもよい。この金属間化合物は塑性不安定性を抑制する第二相として機能し、本発明の鉄合金の高強度および高延性に寄与する。
《Iron alloy structure》
(1) Austenitic structure Although the iron alloy of the present invention can be transformed by temperature, it is composed of an austenitic structure in a normal temperature range and exhibits high strength and high ductility. In this austenite structure, C is preferably in a solid solution state, but may exist as nanocarbides. Further, part of Fe, Ni and Al may form an intermetallic compound in the austenite structure. This intermetallic compound functions as a second phase for suppressing plastic instability, and contributes to the high strength and high ductility of the iron alloy of the present invention.
（２）冷間加工組織
本発明の鉄合金は、冷間加工組織からなると、高次元で両立した強度および延性を発揮する。冷間加工の具体的な加工温度、加工方法、加工程度等は問わない。一般的に、冷間加工は、再結晶温度未満でなされる塑性加工であり、再結晶温度以上でなされる塑性加工である熱間加工とは区別される。もっとも本発明に係る冷間加工は、通常は室温域で行われる。
(2) Cold-worked structure When the iron alloy of the present invention is made of a cold-worked structure, it exhibits high-strength strength and ductility. The specific processing temperature, processing method, processing level, etc. of the cold processing are not limited. Generally, the cold working is a plastic working performed at a temperature lower than the recrystallization temperature, and is distinguished from a hot working which is a plastic working performed at a temperature higher than the recrystallization temperature. However, the cold working according to the present invention is usually performed at room temperature.
冷間加工は、周知の方法でなされ、例えば、スウェージング加工、圧延加工、鍛造加工等によりなされる。冷間加工は、高強度・高延性な素材を製造するためになされても、最終的な製品を製造するためになされてもよい。 The cold working is performed by a known method, for example, swaging, rolling, forging, or the like. The cold working may be performed to produce a material having high strength and high ductility, or may be made to produce a final product.
冷間加工の程度は、鉄合金の塑性変形により導入される相当（塑性）ひずみが１．５以上、３以上さらには４以上となると好ましい。なお、相当ひずみは、３軸応力状態において鉄合金に生じる各向の塑性ひずみを、単軸応力状態の塑性ひずみに換算して評価したものである。本明細書に係る相当ひずみは、フォン・ミーゼスの降伏条件に基づき算出される。 The degree of cold working is preferably when the equivalent (plastic) strain introduced by plastic deformation of the iron alloy is 1.5 or more, 3 or more, or 4 or more. The equivalent strain is evaluated by converting the plastic strain in each direction generated in the iron alloy in the triaxial stress state into the plastic strain in the uniaxial stress state. The equivalent strain according to the present specification is calculated based on the von Mises yield condition.
上述したことから、本発明の鉄合金は、オーステナイト組織かつ冷間加工組織であるときに高強度および高延性を発揮する。従って本発明の鉄合金の組織は、例えば、集合組織である層状オーステナイト組織であると好ましい。ここでいう「層状」とは、鉄合金の鋳塊を構成する結晶粒等が冷間加工されて形成される。具体的には、加工によって形成された微細な結晶粒の集合体として特定される。その結晶粒の平均粒径は１μｍ以下さらには２００ｎｍ以下であると好ましい。このときの平均粒径は、ＴＥＭ写真（１０万倍）の観察結果を画像処理して求めることができる。 From the above, the iron alloy of the present invention exhibits high strength and high ductility when it has an austenite structure and a cold work structure. Therefore, the structure of the iron alloy of the present invention is preferably, for example, a layered austenite structure that is a texture. The term “layered” as used herein is formed by cold-working the crystal grains constituting the iron alloy ingot. Specifically, it is specified as an aggregate of fine crystal grains formed by processing. The average grain size of the crystal grains is preferably 1 μm or less, more preferably 200 nm or less. The average particle size at this time can be obtained by image processing the observation result of the TEM photograph (100,000 times).
《鉄合金の製造方法》
（１）素材
本発明の鉄合金に係る素材は、溶解、鋳造を経る溶製法、金属粉末（原料粉末）を焼結させる焼結法等、いずれの方法で製造されても良い。溶製法は、例えば、アーク溶解法、プラズマ溶解法、インダクションスカル法、浮遊溶解法等がある。焼結法には、原料粉末を成形用金型に充填し（充填工程）、それを加圧成形して得た粉末成形体を（成形工程）、加熱して焼結（焼結工程）させる通常の焼結法の他、ＣＩＰ法（冷間静水圧成形法）またはＲＩＰ法（ゴム型静水圧成形法）により成形した粉末成形体を焼結させたり、ＨＩＰ法（熱間静水圧成形法）により金属粉末を成形焼結させる方法等を用いることができる。
《Method for producing iron alloy》
(1) Material The material according to the iron alloy of the present invention may be manufactured by any method such as a melting method through melting and casting, and a sintering method in which metal powder (raw material powder) is sintered. Examples of the melting method include an arc melting method, a plasma melting method, an induction skull method, and a floating melting method. In the sintering method, a raw material powder is filled in a molding die (filling step), and a powder molded body obtained by pressure molding (molding step) is heated and sintered (sintering step). In addition to the usual sintering method, powder molded bodies molded by CIP method (cold isostatic pressing method) or RIP method (rubber type isostatic pressing method) are sintered, or HIP method (hot isostatic pressing method). ) And the like can be used.
（２）熱間加工
溶製材等からなる素材に、前述した冷間加工を施す前に、熱間加工を施してもよい。熱間加工は、冷間加工前の組成、組織の均質化のために行う。この熱間加工も、その具体的な加工温度、加工方法、加工程度等は問わない。熱間加工は、前述したように、再結晶温度以上でなされる塑性加工であるが、本発明に係る熱間加工は、鉄合金が安定したオーステナイト相となる温度（例えば１１００℃）以上で加工されると好ましい。
(2) Hot working Hot working may be performed on the material made of melted material before the cold working described above. Hot working is performed to homogenize the composition and structure before cold working. This hot working is not limited to specific working temperature, working method, working degree or the like. As described above, the hot working is a plastic working performed at a temperature higher than the recrystallization temperature. However, the hot working according to the present invention is performed at a temperature higher than the temperature at which the iron alloy becomes a stable austenite phase (for example, 1100 ° C.). It is preferred if
熱間加工も、スウェージング加工、圧延加工、鍛造加工等により行える。熱間加工は鉄合金の安定したオーステナイト相となる温度でなされると好ましい。 Hot working can also be performed by swaging, rolling, forging and the like. The hot working is preferably performed at a temperature at which a stable austenite phase of the iron alloy is obtained.
（３）熱処理
溶製材等からなる素材に、前述した冷間加工を施す前に、熱処理を施してもよい。熱処理には、例えば、均質化処理、溶体化処理（焼入れ）、焼戻し、時効処理などがある。鉄合金が、高強度および高延性を安定して発現するように、加熱温度、加熱時間さらには加熱後の冷却速度等は、適宜調整される。処理温度は１０５０〜１２００℃さらには１１００〜１１５０℃で、６０〜１４４０分加熱した後、１００℃／秒以上で冷却すると好ましい。
(3) Heat treatment Before the cold working described above is performed on the material made of the melted material, etc., heat treatment may be performed. Examples of the heat treatment include homogenization treatment, solution treatment (quenching), tempering, and aging treatment. The heating temperature, the heating time, the cooling rate after heating, and the like are appropriately adjusted so that the iron alloy stably exhibits high strength and high ductility. The treatment temperature is preferably 1050 to 1200 ° C., more preferably 1100 to 1150 ° C., and after heating for 60 to 1440 minutes, cooling is preferably performed at 100 ° C./second or more.
なお、冷間加工後に熱間加工および熱処理を行うと、その冷間加工により鉄合金内に導入された塑性ひずみが加熱により喪失される。このため冷間加工を行う場合は、少なくとも熱間加工や熱処理の後に冷間加工を行うと好ましい。 When hot working and heat treatment are performed after cold working, the plastic strain introduced into the iron alloy by the cold working is lost by heating. For this reason, when performing cold working, it is preferable to perform cold working at least after hot working or heat treatment.
《鉄合金の用途》
本発明の鉄合金は、高強度および高延性であるから、各種の構造部材に用いることができる。また本発明の鉄合金は、高延性であり、強加工がなされても割れ等を生じないため、塑性加工品に好適である。
<Applications of iron alloys>
Since the iron alloy of the present invention has high strength and high ductility, it can be used for various structural members. In addition, the iron alloy of the present invention is highly ductile and does not cause cracking or the like even when subjected to strong processing, and therefore is suitable for plastic processed products.
具体的にいうと、本発明の鉄合金は、各種構造部材、高強度ボルト、シール材、弾性材（スプリング、ダイアフラム、トーションバー等）、補強材、動力伝動用ベルト材、各種ワイヤ類、装飾品、自動車部品、スポーツ用品、燃料電池部品、航空機器、宇宙船および人工衛星等の各種部材、原子炉用部品、核融合炉用部品等、各種分野の各種製品に利用することができる。 Specifically, the iron alloy of the present invention includes various structural members, high-strength bolts, sealing materials, elastic materials (springs, diaphragms, torsion bars, etc.), reinforcing materials, power transmission belt materials, various wires, and decorations. It can be used for various products in various fields such as products, automobile parts, sports equipment, fuel cell parts, aircraft equipment, spacecrafts and satellites, nuclear reactor parts, fusion reactor parts, etc.
実施例を挙げて本発明をより具体的に説明する。 The present invention will be described more specifically with reference to examples.
《試料の製造》
（１）鋳造工程
原料となる母合金として、市販されている純鉄、Ｆｅ−４．３％Ｃ合金（単位：質量％、以下同様）、Ａｌ−１０％Ｆｅ合金を用意した。これらをアルゴン雰囲気下で溶解した。得られた溶湯を金型に注湯して凝固させた（冷却速度：５０℃／秒）。こうして表１に示す各組成からなるφ５０×１５０ｍｍの鋳塊を得た。表１に示した組成値は分析値であり、残部は鉄と不純物である。また表１には、質量％で表示した組成値と原子％で表示した両方を示した。なお、組成分析は、Ｆｅ、Ｎｉ、Ａｌについては誘導結合プラズマ（ＩＣＰ）発光分析法により、Ｃについては酸素中燃焼−赤外線吸収法により行った。
<Production of sample>
(1) Casting Step As commercially available mother alloys, commercially available pure iron, Fe-4.3% C alloy (unit: mass%, the same applies hereinafter), and Al-10% Fe alloy were prepared. These were dissolved under an argon atmosphere. The obtained molten metal was poured into a mold and solidified (cooling rate: 50 ° C./second). Thus, ingots of φ50 × 150 mm having the respective compositions shown in Table 1 were obtained. The composition values shown in Table 1 are analytical values, with the balance being iron and impurities. Table 1 shows both the composition value expressed in mass% and the atomic value expressed in atomic%. The composition analysis was performed by inductively coupled plasma (ICP) emission analysis for Fe, Ni, and Al, and by combustion in oxygen-infrared absorption for C.
（２）熱間加工工程
得られた各鋳塊に、熱間鍛造加工を施した。具体的には、予め１１５０℃に加熱しておいたガス炉へ鋳塊を入れて十分に加熱保持した。この加熱した鋳塊を大気中で鍛造して、φ５０ｍｍ→φ１５ｍｍとした。この際、タップ径を１２回に分けて変化させ、その都度、上記の加熱と鍛造を繰り返し行った。そして１２回目の鍛造後に空冷して、鍛造片を得た。
(2) Hot working process Hot forging was performed on each ingot obtained. Specifically, the ingot was put into a gas furnace that had been heated to 1150 ° C. in advance and sufficiently heated and held. This heated ingot was forged in the atmosphere to make φ50 mm → φ15 mm. At this time, the tap diameter was changed to 12 times, and the above heating and forging were repeated each time. And after forging for the 12th time, it air-cooled and the forge piece was obtained.
（３）熱処理工程
得られた各鍛造片を加熱炉内にいれて、１１００℃×２４時間の均質化処理を施した。これに続いて、加熱された鍛造片を水冷した。こうして均質化処理および水焼入れされた熱処理片を得た。
(3) Heat treatment step Each forged piece obtained was placed in a heating furnace and subjected to a homogenization treatment at 1100 ° C for 24 hours. Following this, the heated forged pieces were water cooled. Thus, a heat-treated piece homogenized and water-quenched was obtained.
（４）冷間加工工程
得られた熱処理片から切り出したφ１１×１３０ｍｍの棒材に、冷間加工を施した。具体的には、各棒材に、室温で、冷間スウェージング加工を施して、φ１１ｍｍ→φ４ｍｍとした。この際、ダイス径を１０回に分けて変化させた。こうして得られた各冷間加工片を機械加工して、平行部φ２．４ｍｍ×１４ｍｍ、全長４０ｍｍの試験片を製造した。ちなみに、この試験片に導入された相当ひずみは、既述した方法で算出すると２．０となる。
(4) Cold working step Cold working was performed on a rod of φ11 × 130 mm cut out from the obtained heat-treated piece. Specifically, each bar was subjected to cold swaging at room temperature to obtain φ11 mm → φ4 mm. At this time, the die diameter was changed in 10 steps. Each cold-worked piece thus obtained was machined to produce a test piece having a parallel part φ2.4 mm × 14 mm and a total length of 40 mm. Incidentally, the equivalent strain introduced into the test piece is 2.0 when calculated by the method described above.
《測定・観察》
（１）引張試験
上記の各試験片を用いて引張試験を行った。引張試験は、ひずみ速度：５×１０−４／ｓ、室温、大気中で、株式会社島津製作所製オートグラフを用いて行った。各試験片の平行部のゲージ長さは１０ｍｍとした。
<Measurement / Observation>
(1) Tensile test A tensile test was performed using each of the above test pieces. The tensile test was performed using an autograph manufactured by Shimadzu Corporation in a strain rate of 5 × 10 −4 / s, room temperature, and air. The gauge length of the parallel part of each test piece was 10 mm.
引張試験から得られた公称応力−公称ひずみ線図に基づき求めた各試験片の最大引張強さ（ＵＴＳ）と延性（ＥＬ）を表１にそれぞれ示した。最大引張強さは、公称応力−公称ひずみ線図上に現れた引張強さの最大値（ＭＰａ）とし、延性は株式会社島津製作所製オートグラフのビデオ伸び計の測定値を公称応力−公称ひずみ線上に現し、伸び値を測定した。なお、ビデオ伸び計の感度は±３μｍである。一例である試料Ｎｏ．６に係る公称応力−公称ひずみ線図を図１に、真応力（σｔ）−真ひずみ（εｔ）線図とｄσｔ／ｄεｔ−εｔ線図を図２に併せて示した。 Table 1 shows the maximum tensile strength (UTS) and ductility (EL) of each test piece obtained based on the nominal stress-nominal strain diagram obtained from the tensile test. The maximum tensile strength is the maximum value (MPa) of the tensile strength appearing on the nominal stress-nominal strain diagram, and the ductility is the value measured by Shimadzu Autograph's autograph video extensometer. It appeared on the line and the elongation value was measured. The sensitivity of the video extensometer is ± 3 μm. Sample No. as an example. The nominal stress-nominal strain diagram according to FIG. 6 is shown in FIG. 1, and the true stress (σ t ) -true strain (ε t ) diagram and the dσ t / dε t -ε t diagram are shown in FIG.
（２）金属組織
試料Ｎｏ．６に係る冷間加工片の金属組織を光学顕微鏡で観察した。その顕微鏡写真を図３に示した。
(2) Metal structure Sample No. The metal structure of the cold-worked piece according to 6 was observed with an optical microscope. The photomicrograph is shown in FIG.
《評価》
（１）強度および延性
表１および図１からわかるように、本発明に係る組成範囲にある鉄合金は、高強度であると共に高延性であることがわかる。逆に、組成範囲、特に平均価電子濃度が本発明に係る範囲から逸脱すると、強度および延性が共に急減することがわかる。これは、最大引張強さ（ＵＴＳ）と延性（ＥＬ）の積である強度延性バランス指標値（ＵＴＳ＊ＥＬ）が、本発明に係る試料では非常に大きいが、それ以外の試料では小さいことからもわかる。
<Evaluation>
(1) Strength and ductility As can be seen from Table 1 and FIG. 1, it can be seen that the iron alloy in the composition range according to the present invention has high strength and high ductility. On the contrary, when the composition range, particularly the average valence electron concentration, deviates from the range according to the present invention, it can be seen that both the strength and the ductility rapidly decrease. This is because the strength ductility balance index value (UTS * EL), which is the product of maximum tensile strength (UTS) and ductility (EL), is very large in the samples according to the present invention, but small in other samples. I understand.
（２）金属組織
図３からわかるように、本発明に係る組成範囲にある鉄合金（試料Ｎｏ．６）は、層状組織となっている。この組織がオーステナイト（γ）組織であることはＸ線回折実験（ＸＲＤ）により確認している。
(2) Metal structure As can be seen from FIG. 3, the iron alloy (sample No. 6) in the composition range according to the present invention has a layered structure. It has been confirmed by an X-ray diffraction experiment (XRD) that this structure is an austenite (γ) structure.
Claims (9)
Ｆｅ、ＮｉおよびＡｌは、平均価電子濃度（ｅ／ａ）が７．５〜８．１となる組成範囲内にあり、
Ｃは、全体を１００原子％（以下「％」という。）としたときに０．８〜４％であることを特徴とする鉄合金。 Nickel (Ni), aluminum (Al), carbon (C) and the balance is iron alloy consisting of iron (Fe) and inevitable impurities,
Fe, Ni and Al are in the composition range where the average valence electron concentration (e / a) is 7.5 to 8.1,
C is 0.8-4% when the whole is 100 atomic% (hereinafter referred to as “%”).
Ｎｉ：１８〜２５％、
Ａｌ：４〜１９％、
である請求項１に記載の鉄合金。 When the whole is 100%,
Ni: 18-25%,
Al: 4 to 19%
The iron alloy according to claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016031958A1 (en) * | 2014-08-28 | 2016-03-03 | 国立大学法人豊橋技術科学大学 | Metal material and processing/treatment method |
| JP5994951B2 (en) * | 2014-03-31 | 2016-09-21 | 日立金属株式会社 | Method for producing Fe-Ni base superalloy |
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|---|---|---|---|---|
| JPH03257141A (en) * | 1990-03-07 | 1991-11-15 | Natl Res Inst For Metals | Fe-ni-co-al-c alloy |
| JPH0931605A (en) * | 1995-04-20 | 1997-02-04 | Philip Morris Prod Inc | Iron aluminide useful for electric resistance heating element |
| JP2001129655A (en) * | 1999-11-04 | 2001-05-15 | Ykk Corp | Method ad apparatus for manufacturing casting product having small mole |
| JP2003268501A (en) * | 2002-03-13 | 2003-09-25 | Kiyohito Ishida | SHAPE MEMORY Fe ALLOY AND PRODUCTION METHOD THEREOF |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03257141A (en) * | 1990-03-07 | 1991-11-15 | Natl Res Inst For Metals | Fe-ni-co-al-c alloy |
| JPH0931605A (en) * | 1995-04-20 | 1997-02-04 | Philip Morris Prod Inc | Iron aluminide useful for electric resistance heating element |
| JP2001129655A (en) * | 1999-11-04 | 2001-05-15 | Ykk Corp | Method ad apparatus for manufacturing casting product having small mole |
| JP2003268501A (en) * | 2002-03-13 | 2003-09-25 | Kiyohito Ishida | SHAPE MEMORY Fe ALLOY AND PRODUCTION METHOD THEREOF |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5994951B2 (en) * | 2014-03-31 | 2016-09-21 | 日立金属株式会社 | Method for producing Fe-Ni base superalloy |
| US10196723B2 (en) | 2014-03-31 | 2019-02-05 | Hitachi Metals, Ltd. | Production method for Fe-Ni based heat-resistant superalloy |
| WO2016031958A1 (en) * | 2014-08-28 | 2016-03-03 | 国立大学法人豊橋技術科学大学 | Metal material and processing/treatment method |
| JPWO2016031958A1 (en) * | 2014-08-28 | 2017-09-07 | 国立大学法人豊橋技術科学大学 | Metal material and processing method |
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| JP5929251B2 (en) | 2016-06-01 |
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