JP2021101035A - Multi-component alloy excelling in balance of softening resistance, strength and elongation, and wear resistance - Google Patents
Multi-component alloy excelling in balance of softening resistance, strength and elongation, and wear resistance Download PDFInfo
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Abstract
Description
本発明は多成分系からなる合金に関するものである。 The present invention relates to an alloy composed of a multi-component system.
近年、合金材の一種として、ミディアムエントロピー合金（１．０Ｒ≦ΔＳmix≦１．５Ｒ）やハイエントロピー合金（ΔＳmix≧１．５Ｒ）と呼ばれる多成分系からなる合金が注目されている。（ΔＳmixは混合のエントロピー、Ｒは気体定数を示す。） In recent years, as a kind of alloy material, alloys composed of a multi-component system called a medium entropy alloy (1.0R ≤ ΔS mix ≤ 1.5R) and a high entropy alloy (ΔS mix ≥ 1.5R) have been attracting attention. (ΔS mix indicates the entropy of mixing, R indicates the gas constant.)
例えば、Ｔｉ、Ｖ、Ｆｅ、Ｎｉを含有するとともに、Ｃｕ、Ａｌ、Ｍｏ、Ｚｒ、Ｃｏ、Ｃｒ、Ｐｄから１種類以上選ばれた多元系合金が提案されている（特許文献１参照。）。この合金は、高硬度、高耐熱性、高耐食性の合金を提案している。 For example, a multi-element alloy containing Ti, V, Fe, Ni and one or more selected from Cu, Al, Mo, Zr, Co, Cr and Pd has been proposed (see Patent Document 1). As this alloy, we propose an alloy with high hardness, high heat resistance, and high corrosion resistance.
また、Ｃｏ、Ｃｒ、Ｆｅ、Ｎｉ、Ｔｉ、Ａｌ、Ｍｏを含んだ多元系合金が提案されている。この合金は、合金組成・微細組織の均質性に優れ、かつ形状制御性に優れた合金部材を提案している。（特許文献２参照。） Further, a multidimensional alloy containing Co, Cr, Fe, Ni, Ti, Al and Mo has been proposed. This alloy proposes an alloy member having excellent homogeneity of alloy composition and microstructure and excellent shape controllability. (See Patent Document 2.)
さらに、Ｃｏ、Ｃｒ、Ｆｅ、Ｎｉを含んだ多元系合金また、Ｃｏ、Ｃｒ、Ｆｅ、Ｎｉ、Ｃを含んだ多元系合金の鋳造材が提案されている。（非特許文献１参照。）この合金は、Ｃを添加することによる耐摩耗性に優れた合金を提案している。 Further, a multi-dimensional alloy containing Co, Cr, Fe and Ni, and a cast material of a multi-dimensional alloy containing Co, Cr, Fe, Ni and C have been proposed. (See Non-Patent Document 1.) As this alloy, an alloy having excellent wear resistance due to the addition of C has been proposed.
特許文献１に開示された多元系合金によると、高硬度が得られるものの、脆性相が析出しうる。脆性相が存在すると、破壊の起点となる。そこで、この多元系合金の伸びは不十分である。また、耐摩耗性についても考慮されていない。 According to the multidimensional alloy disclosed in Patent Document 1, although high hardness can be obtained, a brittle phase can be precipitated. The presence of a brittle phase is the starting point for fracture. Therefore, the elongation of this multidimensional alloy is insufficient. Also, wear resistance is not considered.
特許文献２に開示された多元系合金では、合金組成・微細組織の均質性に優れ、かつ形状制御性に優れた合金部材を提供しているが、金属間化合物であるＮｉ3（Ａｌ，Ｔｉ）が生成する。この金属間化合物は、破壊の起点となり得る。そこで、この多元系合金から得られた成形品の伸びは、十分ではない。 The multidimensional alloy disclosed in Patent Document 2 provides an alloy member having excellent homogeneity of alloy composition and microstructure and excellent shape controllability, but is an intermetallic compound Ni 3 (Al, Ti). ) Is generated. This intermetallic compound can be the starting point for fracture. Therefore, the elongation of the molded product obtained from this multidimensional alloy is not sufficient.
非特許文献１では、Ｃ無添加の合金を提案しているが、単相固溶体が形成されることで、高温域での軟化抵抗が小さくなる。また、Ｃ添加の合金ではＣ無添加の合金と比較し、耐摩耗性に優れた合金を提供しているが、炭化物が網状に析出しており、強度と伸びのバランスに劣っている。 Non-Patent Document 1 proposes an alloy without C added, but the softening resistance in a high temperature range is reduced by forming a single-phase solid solution. Further, the C-added alloy provides an alloy having excellent wear resistance as compared with the C-free alloy, but carbides are precipitated in a network, and the balance between strength and elongation is inferior.
そこで、本発明が解決しようとする課題は、軟化抵抗、強度と伸びのバランス、耐摩耗性が改善された優れた多元系合金を提供することである。 Therefore, an object to be solved by the present invention is to provide an excellent multidimensional alloy having improved softening resistance, balance between strength and elongation, and wear resistance.
本発明の課題を解決するための第１の手段は、Ｃｏ、Ｃｒ、Ｆｅ、Ｎｉの各元素をそれぞれ５原子％以上３５原子％以下の範囲で含み、Ｃを０．４７原子％以上８．７４原子％以下の範囲で含むことで、計１００原子％となる多元系合金であって（ただし不可避的不純物を含む。）、合金中の炭化物サイズが円相当径で１５μｍ以下であり、引張強度が７５０ＭＰａ以上かつ、伸びが５％以上であり、混合のエントロピーが１．１Ｒ以上であることを特徴とする多元系合金である。 The first means for solving the problem of the present invention contains each element of Co, Cr, Fe, and Ni in the range of 5 atomic% or more and 35 atomic% or less, and C is 0.47 atomic% or more and 8. It is a multi-element alloy with a total of 100 atomic% by including it in the range of 74 atomic% or less (however, it contains unavoidable impurities), the carbide size in the alloy is 15 μm or less in the equivalent circle diameter, and the tensile strength. Is a multi-element alloy characterized by having an elongation of 750 MPa or more, an elongation of 5% or more, and a mixed entropy of 1.1 R or more.
その第２の手段は、Ｃｏ、Ｃｒ、Ｆｅ、Ｎｉの各元素をそれぞれ５原子％以上３５原子％以下の範囲で含み、Ｃを０．４７原子％以上８．７４原子％以下の範囲で含み、
さらにＶ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌ、Ｍｎ、Ｓｉのいずれか１種以上をＶ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌ、Ｍｎについては２０原子％以下、Ｓｉについては１０原子％以下の範囲で含むことで、計１００原子％となる多元系合金であって（ただし不可避的不純物を含む。）、合金中の炭化物サイズが円相当径で１５μｍ以下であり、引張強度が７５０ＭＰａ以上かつ、伸びが５％以上であり、混合のエントロピーが１．１Ｒ以上であることを特徴とする多元系合金である。
The second means contains each element of Co, Cr, Fe, and Ni in the range of 5 atomic% or more and 35 atomic% or less, and C in the range of 0.47 atomic% or more and 8.74 atomic% or less. ,
Further, one or more of V, Mo, Nb, W, Ti, Zr, Cu, Al, Mn, and Si is used, and 20 atomic% or less is used for V, Mo, Nb, W, Ti, Zr, Cu, Al, and Mn. , Si is a multidimensional alloy with a total of 100 atomic% by including it in the range of 10 atomic% or less (however, it contains unavoidable impurities), and the carbide size in the alloy is 15 μm or less in the equivalent circle diameter. It is a multidimensional alloy characterized by having a tensile strength of 750 MPa or more, an elongation of 5% or more, and a mixed entropy of 1.1 R or more.
本発明の多成分系からなる合金によると、Ｃ無添加の合金に対して例えば８７０℃などの高温においても軟化抵抗が高く、強度と伸びのバランスが優れ、耐摩耗性に優れる合金を提供することができる。 According to the alloy composed of a multi-component system of the present invention, an alloy having high softening resistance even at a high temperature such as 870 ° C., an excellent balance between strength and elongation, and excellent wear resistance is provided as compared with an alloy without C added. be able to.
発明の実施の形態に先立って、各化学成分について規定する理由を説明する。
（Ｃｏ、Ｃｒ、Ｆｅ、Ｎｉをそれぞれ５原子％以上３５原子％以下の範囲で含むこと）
主要成分であるＣｏ、Ｃｒ、Ｆｅ、Ｎｉは添加量を等原子％に近づけるほど、混合のエントロピーが増大する。混合のエントロピーが増大することにより、混合状態の安定化、複雑な微細構造による緩和拡散、構成元素の原子半径の差による格子歪からなる高硬度化などの効果がみられる。
Prior to the embodiment of the invention, the reason for defining each chemical component will be described.
(Co, Cr, Fe, and Ni should be included in the range of 5 atomic% or more and 35 atomic% or less, respectively)
The entropy of mixing of the main components Co, Cr, Fe, and Ni increases as the addition amount approaches the equiatomic%. By increasing the entropy of mixing, the effects of stabilizing the mixed state, relaxing diffusion due to the complicated fine structure, and increasing the hardness due to the lattice strain due to the difference in the atomic radii of the constituent elements can be seen.
そこで、この観点から、Ｃｏ、Ｃｒ、Ｆｅ、Ｎｉの４元素をそれぞれ５原子％以上３５原子％以下の範囲で含むものとする。さらに、これらの４元素を好ましくはそれぞれ１０原子％以上３０原子％以下の範囲で含むものとする。さらに、これらの４元素をより好ましくはそれぞれ１５原子％以上２５原子％以下の範囲で含むものとする。 Therefore, from this point of view, it is assumed that each of the four elements Co, Cr, Fe, and Ni is contained in the range of 5 atomic% or more and 35 atomic% or less. Further, each of these four elements is preferably contained in the range of 10 atomic% or more and 30 atomic% or less. Further, each of these four elements is more preferably contained in the range of 15 atomic% or more and 25 atomic% or less.
（Ｃを０．４７原子％以上８．７４原子％以下の範囲で含むこと）
Ｃは、Ｃｒと結合して炭化物を形成する元素である。この炭化物は、合金の高硬度に寄与する。この観点から、Ｃの含有率は０．４７原子％以上であることが好ましい。より好ましくは、Ｃは１．３９原子％以上である。さらに特に好ましくは、Ｃは２．３０原子％以上である。
他方、Ｃの含有率が過剰であると、合金の伸びが低下する。そこで、優れた伸びの観点からは、Ｃの含有率は８．７４原子％以下が好ましい。より好ましくは、Ｃは６．６７原子％以下であり、さらに特に好ましくは、Ｃは４．５３原子％以下である。
(C should be included in the range of 0.47 atomic% or more and 8.74 atomic% or less)
C is an element that combines with Cr to form carbides. This carbide contributes to the high hardness of the alloy. From this viewpoint, the C content is preferably 0.47 atomic% or more. More preferably, C is 1.39 atomic% or more. More preferably, C is 2.30 atomic% or more.
On the other hand, if the C content is excessive, the elongation of the alloy decreases. Therefore, from the viewpoint of excellent elongation, the C content is preferably 8.74 atomic% or less. More preferably, C is 6.67 atomic% or less, and even more preferably C is 4.53 atomic% or less.
（Ｖ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌ、Ｍｎ、Ｓｉのいずれか１種以上をＶ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌ、Ｍｎについては２０原子％以下、Ｓｉについては１０原子％以下の範囲で含むこと）
上記のＣｏ、Ｃｒ、Ｆｅ、Ｎｉ、Ｃに加えて、選択的添加成分として、さらに、Ｖ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌ、Ｍｎ、Ｓｉのいずれか１種以上を添加することができる。添加すると、合金中に微細析出物が生成し、高い軟化抵抗に寄与する。ただし、これらの添加元素の含有率が過剰であると、合金の伸びが低下する。
これらの観点から、Ｖ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌ、Ｍｎについては２０原子％以下、Ｓｉについては１０原子％以下の範囲で含むものとする。
(V, Mo, Nb, W, Ti, Zr, Cu, Al, Mn, Si at least one of V, Mo, Nb, W, Ti, Zr, Cu, Al, Mn is 20 atomic% or less. , Si should be included in the range of 10 atomic% or less)
In addition to the above Co, Cr, Fe, Ni, and C, one or more of V, Mo, Nb, W, Ti, Zr, Cu, Al, Mn, and Si are further added as selective additive components. can do. When added, fine precipitates are formed in the alloy, which contributes to high softening resistance. However, if the content of these additive elements is excessive, the elongation of the alloy will decrease.
From these viewpoints, V, Mo, Nb, W, Ti, Zr, Cu, Al, and Mn are included in the range of 20 atomic% or less, and Si is included in the range of 10 atomic% or less.
そして、Ｖ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌについては、好ましくは１原子％以上１６原子％以下とする。さらにより好ましくは３原子％以上９原子％以下とする。
また、Ｍｎについては、好ましくは１０原子％未満とする。より好ましくはＭｎは１原子％未満とする。
Ｓｉについては、好ましくはＳｉは０．５原子％以上８原子％以下とする。より好ましくはＳｉは１原子％以上５原子％以下とする。
The V, Mo, Nb, W, Ti, Zr, Cu, and Al are preferably 1 atomic% or more and 16 atomic% or less. Even more preferably, it is 3 atomic% or more and 9 atomic% or less.
The Mn is preferably less than 10 atomic%. More preferably, Mn is less than 1 atomic%.
Regarding Si, preferably Si is 0.5 atomic% or more and 8 atomic% or less. More preferably, Si is 1 atomic% or more and 5 atomic% or less.
（析出物の存在について）
ところで、本発明の多元系合金は、Ｃｏ、Ｃｒ、Ｆｅ、Ｎｉ、Ｃに加えて、さらに、Ｖ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌ、Ｍｎ、Ｓｉのいずれか１種以上を添加してもよい。添加すると、合金中に微細析出物が生成し、高い軟化抵抗に寄与する。
ただしこれらの添加元素の含有率が過剰であると、脆性相が生成し、合金の伸びが低下する。
この観点から、好ましくはＢＣＣ相・ＦＣＣ相・炭化物相以外で５μｍ以上の析出物が存在しないこととする。より好ましくはＢＣＣ相・ＦＣＣ相・炭化物相以外で１μｍ以上の析出物が存在しないことが望ましい。
(Regarding the presence of precipitates)
By the way, the multi-element alloy of the present invention is one or more of V, Mo, Nb, W, Ti, Zr, Cu, Al, Mn and Si in addition to Co, Cr, Fe, Ni and C. May be added. When added, fine precipitates are formed in the alloy, which contributes to high softening resistance.
However, if the content of these additive elements is excessive, a brittle phase is formed and the elongation of the alloy is lowered.
From this point of view, it is preferable that there is no precipitate of 5 μm or more other than the BCC phase, the FCC phase, and the carbide phase. More preferably, there is no precipitate of 1 μm or more other than the BCC phase, the FCC phase, and the carbide phase.
（不可避的不純物について）
本発明の多元系合金に含有されることが許容される不可避的不純物の元素について説明する。本発明の多元系合金に含有される不可避的不純物の元素としては、例えば、Ｐ、Ｓ、Ｓｎ、Ｓｂ、Ａｓ、Ｏ、Ｎ等が挙げられる（不可避不純物であれば、これら元素に限られるものではない。）。
ただし、Ｐについては、好ましくは０．００５質量％以下、より好ましくは０．００２質量％以下とする。
Ｓについては、好ましくは０．００２質量％以下、より好ましくは０．００１質量％以下とする。
Ｓｎについては、好ましくは０．００５質量％以下、より好ましくは０．００２質量％以下とする。
Ｓｂについては、好ましくは０．００２質量％以下、より好ましくは０．００１質量％以下とする。
Ａｓについては、好ましくは０．００５質量％以下、より好ましくは０．００１質量％以下とする。
また、Ｏについては、好ましくは０．００１質量％以下（１０ｐｐｍ以下）、より好ましくは０．０００３質量％以下（３ｐｐｍ以下）とする。
Ｎについては、好ましくは０．００２質量％以下（２０ｐｐｍ以下）、より好ましくは０．００１質量％以下（１０ｐｐｍ以下）とする。
(About unavoidable impurities)
The elements of unavoidable impurities that are allowed to be contained in the multidimensional alloy of the present invention will be described. Examples of the elements of the unavoidable impurities contained in the multidimensional alloy of the present invention include P, S, Sn, Sb, As, O, N and the like (if the unavoidable impurities are limited to these elements). is not it.).
However, P is preferably 0.005% by mass or less, more preferably 0.002% by mass or less.
S is preferably 0.002% by mass or less, more preferably 0.001% by mass or less.
Sn is preferably 0.005% by mass or less, more preferably 0.002% by mass or less.
Sb is preferably 0.002% by mass or less, more preferably 0.001% by mass or less.
As is preferably 0.005% by mass or less, and more preferably 0.001% by mass or less.
Further, O is preferably 0.001% by mass or less (10 ppm or less), more preferably 0.0003% by mass or less (3 ppm or less).
N is preferably 0.002% by mass or less (20 ppm or less), more preferably 0.001% by mass or less (10 ppm or less).
（合金中の炭化物サイズが円相当径で１５μｍ以下であること）
合金中に炭化物が存在することで、高温域での軟化抵抗の向上、耐摩耗性の向上に寄与する。もっとも、合金中の炭化物サイズが過剰に大きくなると、合金の伸びが低下する。そこで、合金中の炭化物サイズは、１５μｍ以下とする。好ましくは、合金中の炭化物サイズは、１３μｍ以下とする。さらにより好ましくは、合金中の炭化物サイズは、１０μｍ以下とする。
(The size of carbides in the alloy must be 15 μm or less with a diameter equivalent to a circle)
The presence of carbides in the alloy contributes to the improvement of softening resistance and wear resistance in the high temperature range. However, if the carbide size in the alloy becomes excessively large, the elongation of the alloy decreases. Therefore, the carbide size in the alloy is set to 15 μm or less. Preferably, the carbide size in the alloy is 13 μm or less. Even more preferably, the carbide size in the alloy is 10 μm or less.
（混合のエントロピーが１．１Ｒ以上であること）
まず、本発明の混合のエントロピーは以下の式（１）で求めることができる。
(The entropy of mixing is 1.1R or more)
First, the entropy of mixing of the present invention can be obtained by the following formula (1).
上記の式（１）に従って計算すると、例えば、Ｃを１原子％添加したＣｏＣｒＦｅＮｉ等原子量合金の場合の混合のエントロピーは１．４３Ｒであり、ステンレス鋼であるＳＵＳ３０４（Ｆｅ−１８Ｃｒ−８Ｎｉ）の場合の混合のエントロピーは０．７４Ｒとなる。混合のエントロピーが増大することにより、混合状態の安定化、複雑な微細構造による緩和拡散、構成元素の原子半径の差による格子歪からなる高硬度化などの効果がみられる。この観点から、混合のエントロピーは１．１Ｒ以上とする。好ましくは、混合のエントロピーは１．２Ｒ以上とする。より好ましくは、混合のエントロピーは１．３Ｒ以上とする。 When calculated according to the above formula (1), for example, the entropy of mixing in the case of an atomic weight alloy such as CoCrFeNi to which 1 atomic% of C is added is 1.43R, and in the case of SUS304 (Fe-18Cr-8Ni) which is a stainless steel. The entropy of mixing of is 0.74R. By increasing the entropy of mixing, the effects of stabilizing the mixed state, relaxing diffusion due to the complicated fine structure, and increasing the hardness due to the lattice strain due to the difference in the atomic radii of the constituent elements can be seen. From this point of view, the entropy of mixing is 1.1R or more. Preferably, the entropy of mixing is 1.2R or higher. More preferably, the entropy of mixing is 1.3R or higher.
以下、本発明について実施例および比較例によって具体的に説明する。
表１に、本発明の実施例および比較例の各多元系合金の化学成分を原子％で示す。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
Table 1 shows the chemical composition of each of the multiple alloys of Examples and Comparative Examples of the present invention in atomic%.
[バルクの製造について]
まず、実施例、比較例として、表１に示す組成のように、等モル組成のＣｏＣｒＦｅＮｉをベースとしてＣ量を振った原料、加えて等モル組成のＣｏＣｒＦｅＮｉに１元素添加してＣ量を振った原料、Ｃｏ、Ｃｒ、Ｆｅ、Ｎｉの添加量がそれぞれ異なる原料について、それぞれガスアトマイズ法により所定の成分の粉末を作製し、３００μｍ以下に分級した。
ガスアトマイズは、アルミナ製坩堝を溶解に用い、坩堝下の直径５ｍｍ のノズルから合金溶湯を出湯し、これに高圧アルゴンを噴霧することで実施した。その後、１１７０℃でＨＩＰ処理して固化成形し、１１００℃で鍛造加工を行ったのち、空冷した。
さらに、比較例として、上記の作製法のほかに、等モル組成のＣｏＣｒＦｅＮｉをベースとしてＣ量を振った原料に対して、アーク溶解法によって鋳造材を作製した。
[About bulk manufacturing]
First, as an example and a comparative example, as shown in Table 1, a raw material in which the amount of C was shaken based on CoCrFeNi having an equimolar composition, and in addition, one element was added to CoCrFeNi having an equimolar composition and the amount of C was shaken. For raw materials with different amounts of Co, Cr, Fe, and Ni, powders having predetermined components were prepared by the gas atomization method and classified to 300 μm or less.
Gas atomization was carried out by using an alumina crucible for melting, discharging an alloy molten metal from a nozzle with a diameter of 5 mm under the crucible, and spraying it with high-pressure argon. Then, it was subjected to HIP treatment at 1170 ° C., solidified and molded, forged at 1100 ° C., and then air-cooled.
Further, as a comparative example, in addition to the above-mentioned production method, a cast material was produced by an arc melting method with respect to a raw material in which the amount of C was shaken based on CoCrFeNi having an equimolar composition.
[炭化物サイズについて]
炭化物サイズは、鍛造後の試料から、縦１０ｍｍ、横１０ｍｍ、長さ１０ｍｍの角材を切り出し、走査型電子顕微鏡（ＳＥＭ）にて４０００倍の反射電子像を確認し、画像解析ソフトにより円相当径の炭化物のサイズを算出した。
なお、比較例１５〜１８のように炭化物の形状が編み目状のものは塊状ではないのでサイズが観念できないものとして、評価外とした。
[About carbide size]
For the carbide size, cut out a square piece with a length of 10 mm, a width of 10 mm, and a length of 10 mm from the forged sample, confirm a 4000 times reflected electron image with a scanning electron microscope (SEM), and use image analysis software to confirm the equivalent circle diameter. The size of the carbide was calculated.
It should be noted that the carbides having a stitch-like shape as in Comparative Examples 15 to 18 were not evaluated because they were not lumpy and the size could not be considered.
[混合のエントロピー]
各実施例、比較例の混合のエントロピー（ΔＳmix）は、表１の化学成分と式（１）に基づいて算出した。
[Entropy of mixing]
The entropy of mixing (ΔS mix ) of each Example and Comparative Example was calculated based on the chemical composition in Table 1 and the formula (1).
表２にロックウェル硬さ試験、引張試験、大越式摩耗試験の結果、析出物のサイズを示す。 Table 2 shows the size of the precipitate as a result of the Rockwell hardness test, the tensile test, and the Ogoshi type wear test.
[硬さ]
硬さの評価方法として、鍛造後もしくは鋳造後の各試料についてロックウェル硬さ試験を行った。試験は鍛造後もしくは鋳造後熱処理なしの試料と、鍛造後もしくは鋳造後８７０℃、１時間熱処理後の試料に対して試験を行った。表２では、室温でのロックウェル硬さと８７０℃熱処理後のロックウェル硬さの差分の値を「室温と８７０℃熱処理後のロックウェル硬さの差分」として示している。
[Hardness]
As a method for evaluating hardness, a Rockwell hardness test was performed on each sample after forging or casting. The test was carried out on a sample after forging or after casting without heat treatment and a sample after forging or casting at 870 ° C. for 1 hour after heat treatment. In Table 2, the value of the difference between the Rockwell hardness at room temperature and the Rockwell hardness after the 870 ° C. heat treatment is shown as "the difference between the Rockwell hardness at room temperature and the Rockwell hardness after the 870 ° C. heat treatment".
なお、各実施例におけるロックウェル硬さの値を具体的に摘示すると、例えば、実施例Ｎｏ．４の合金の室温でのロックウェル硬さは、１００．７ＨＲＢであり、８７０℃熱処理後のロックウェル硬さは９９．６ＨＲＢであった。
また、実施例Ｎｏ．１０の合金の室温でのロックウェル硬さは、１０３．４ＨＲＢであり、８７０℃熱処理後のロックウェル硬さは１０３．１ＨＲＢであった。
実施例Ｎｏ．１５の合金の室温でのロックウェル硬さは、１０４．０ＨＲＢであり、８７０℃熱処理後のロックウェル硬さは１０１．４ＨＲＢであった。
In addition, when the value of Rockwell hardness in each Example is concretely shown, for example, Example No. The Rockwell hardness of the alloy of No. 4 at room temperature was 100.7 HRB, and the Rockwell hardness after the heat treatment at 870 ° C. was 99.6 HRB.
In addition, Example No. The Rockwell hardness of the 10 alloys at room temperature was 103.4 HRB, and the Rockwell hardness after heat treatment at 870 ° C. was 103.1 HRB.
Example No. The Rockwell hardness of the 15 alloys at room temperature was 104.0 HRB, and the Rockwell hardness after heat treatment at 870 ° C. was 101.4 HRB.
このように、実施例Ｎｏ．１から実施例Ｎｏ．１８において、室温でのロックウェル硬さは、９８．１ＨＲＢ〜１０５．２ＨＲＢ、８７０℃熱処理後のロックウェル硬さは、９０．２ＨＲＢ〜１０３．８ＨＲＢの範囲にあった。 In this way, Example No. From 1 to Example No. At 18, the Rockwell hardness at room temperature was in the range of 98.1 HRB to 105.2 HRB, and the Rockwell hardness after 870 ° C. heat treatment was in the range of 90.2 HRB to 103.8 HRB.
そして、本発明においては、室温と８７０℃熱処理後のロックウェル硬さの差分（ＨＲＢ）が１０ＨＲＢ以下であることを、軟化抵抗が高いものとする。 Then, in the present invention, the softening resistance is high when the difference (HRB) between the room temperature and the Rockwell hardness after the heat treatment at 870 ° C. is 10 HRB or less.
[引張試験]
強度と伸びの評価方法として、鍛造後もしくは鋳造後の試料において、ＪＩＳ１４Ａ号 φ５試験片（φ５×ＧＬ２５ｍｍ）を作製し、室温引張試験を行った。
[Tensile test]
As a method for evaluating strength and elongation, a JIS14A φ5 test piece (φ5 × GL25 mm) was prepared in a sample after forging or casting, and a room temperature tensile test was performed.
本発明においては、引張強さが７５０ＭＰａ以上であって、かつ伸びが５％以上であることを、強度と伸びのバランスが優れているものとする。 In the present invention, when the tensile strength is 750 MPa or more and the elongation is 5% or more, the balance between the strength and the elongation is considered to be excellent.
[大越式摩耗試験]
耐摩耗性の評価方法として、鍛造後もしくは鋳造後の試料において、大越式摩耗試験を行った。なお、大越式摩耗試験の条件は、縦１９ｍｍ、横４１ｍｍ、厚さ６ｍｍの試験片に対し、相手材リングＳＣＭ４２０、荷重６．３ｋｇ、摩耗距離２００ｍ、摩耗速度２．３８ｍ／ｓ、および乾式とした。
[Ogoshi type wear test]
As a method for evaluating wear resistance, an Ogoshi-type wear test was performed on a sample after forging or casting. The conditions of the Ogoshi type wear test are as follows: a mating material ring SCM420, a load of 6.3 kg, a wear distance of 200 m, a wear speed of 2.38 m / s, and a dry type for a test piece having a length of 19 mm, a width of 41 mm, and a thickness of 6 mm. did.
本発明においては、比摩耗量が４．０×１０-6ｍｍ2／ｋｇ以下であることを、耐摩耗性に優れているものとする。 In the present invention, it is assumed that the specific wear amount is 4.0 × 10 -6 mm 2 / kg or less, which is excellent in wear resistance.
[析出物サイズ]
析出物サイズは、鍛造後の試料から、縦１０ｍｍ、横１０ｍｍ、長さ１０ｍｍの角材を切り出し、走査型電子顕微鏡（ＳＥＭ）にて４０００倍の反射電子像を確認した。
[Precipitate size]
As for the size of the precipitate, a square material having a length of 10 mm, a width of 10 mm, and a length of 10 mm was cut out from the forged sample, and a 4000-fold reflected electron image was confirmed with a scanning electron microscope (SEM).
実施例Ｎｏ．１から実施例Ｎｏ．１８に係る合金は、いずれも室温と８７０℃熱処理後のロックウェル硬さの差分（ＨＲＢ）が１０ＨＲＢ以下であって、引張強さが７５０ＭＰａ以上かつ伸びが５％以上であって、比摩耗量が４．０ｍｍ2／ｋｇ以下であった。なお、析出物サイズは、検出限界以下であった。
これらの結果から、本発明の多元系合金は、例えば８７０℃などの高温における軟化抵抗が高いこと、強度と伸びのバランスが優れていること、耐摩耗性に優れていることが確認された。
Example No. From 1 to Example No. All of the alloys according to 18 have a Rockwell hardness difference (HRB) of 10 HRB or less, a tensile strength of 750 MPa or more and an elongation of 5% or more after heat treatment at room temperature and 870 ° C., and a specific wear amount. Was 4.0 mm 2 / kg or less. The precipitate size was below the detection limit.
From these results, it was confirmed that the multidimensional alloy of the present invention has a high softening resistance at a high temperature such as 870 ° C., an excellent balance between strength and elongation, and an excellent wear resistance.
他方、比較例Ｎｏ．１、比較例Ｎｏ．２に係る合金は、Ｃが過小なので、炭化物の体積率が小さく、高い軟化抵抗、優れた耐摩耗性が得られなかった。 On the other hand, Comparative Example No. 1. Comparative Example No. Since C is too small in the alloy according to No. 2, the volume fraction of carbides is small, and high softening resistance and excellent wear resistance cannot be obtained.
比較例Ｎｏ．３に係る合金は、Ｃが過剰なので炭化物の体積率が大きく、十分な伸びが得られなかった。 Comparative Example No. In the alloy according to No. 3, since C was excessive, the volume fraction of carbides was large, and sufficient elongation could not be obtained.
比較例Ｎｏ．４に係る合金は、混合のエントロピーが小さく、十分な強度が得られなかった。 Comparative Example No. The alloy according to No. 4 had a small entropy of mixing, and sufficient strength could not be obtained.
比較例Ｎｏ．５〜比較例Ｎｏ．１４に係る合金は、添加元素量が過剰なので、脆性相が生成し、十分な伸びが得られなかった。 Comparative Example No. 5-Comparative Example No. In the alloy according to No. 14, since the amount of added elements was excessive, a brittle phase was formed and sufficient elongation could not be obtained.
比較例Ｎｏ．１５〜比較例Ｎｏ．１８に係る合金は、非特許文献１のＣを添加したＣｏＣｒＦｅＮｉ合金に相当する。析出した炭化物は事実上円形でもなく、網状に析出していたため、強度と伸びのバランスが劣った。 Comparative Example No. 15-Comparative Example No. The alloy according to 18 corresponds to the CoCrFeNi alloy to which C of Non-Patent Document 1 is added. The precipitated carbide was not substantially circular and was precipitated in a net shape, so that the balance between strength and elongation was poor.
Claims (2)
合金中の炭化物サイズが円相当径で１５μｍ以下であり、引張強度が７５０ＭＰａ以上かつ、伸びが５％以上であり、混合のエントロピーが１．１Ｒ以上であることを特徴とする多元系合金。 By containing each element of Co, Cr, Fe, and Ni in the range of 5 atomic% or more and 35 atomic% or less, and C in the range of 0.47 atomic% or more and 8.74 atomic% or less, a total of 100 atomic% It is a multi-element alloy (but contains unavoidable impurities).
A multidimensional alloy characterized in that the carbide size in the alloy is 15 μm or less in a circle equivalent diameter, the tensile strength is 750 MPa or more, the elongation is 5% or more, and the entropy of mixing is 1.1 R or more.
さらにＶ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌ、Ｍｎ、Ｓｉのいずれか１種以上をＶ、Ｍｏ、Ｎｂ、Ｗ、Ｔｉ、Ｚｒ、Ｃｕ、Ａｌ、Ｍｎについては２０原子％以下、Ｓｉについては１０原子％以下の範囲で含むことで、計１００原子％となる多元系合金であって（ただし不可避的不純物を含む。）、
合金中の炭化物サイズが円相当径で１５μｍ以下であり、引張強度が７５０ＭＰａ以上かつ、伸びが５％以上であり、混合のエントロピーが１．１Ｒ以上であることを特徴とする多元系合金。 Each element of Co, Cr, Fe, and Ni is contained in the range of 5 atomic% or more and 35 atomic% or less, and C is contained in the range of 0.47 atomic% or more and 8.74 atomic% or less.
Further, one or more of V, Mo, Nb, W, Ti, Zr, Cu, Al, Mn, and Si is used, and 20 atomic% or less is used for V, Mo, Nb, W, Ti, Zr, Cu, Al, and Mn. , Si is a multi-element alloy with a total of 100 atomic% by including it in the range of 10 atomic% or less (however, it contains unavoidable impurities).
A multidimensional alloy characterized in that the carbide size in the alloy is 15 μm or less in a circle equivalent diameter, the tensile strength is 750 MPa or more, the elongation is 5% or more, and the entropy of mixing is 1.1 R or more.
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| JP4190720B2 (en) | 2000-11-29 | 2008-12-03 | 國立清華大學 | Multi-component alloy |
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