JP2016023367A - Manufacturing method of alloy structure - Google Patents
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- Powder Metallurgy (AREA)
Abstract
Description
本発明は、合金構造体の製造方法に関する。 The present invention relates to a method for manufacturing an alloy structure.
合金材は、構造物や機器の骨格を成す構造部材、各種の機構部材等をはじめとした種々の用途に用いられており、鉄鋼材やアルミニウム材を利用することが困難な過酷環境における用途に利用されることも多い。例えば、航空機や発電機等に備えられるタービン部材等に適用され、1000℃以上の超高熱環境にも適用し得るニッケル基合金、コバルト基合金等が開発されてきた。また、このような超高熱環境下においても高い耐食性や耐摩耗性を示すことができる高合金鋼等も開発されている。 Alloy materials are used in various applications including structural members that form the framework of structures and equipment, various mechanical members, etc., and for applications in harsh environments where it is difficult to use steel and aluminum materials. Often used. For example, nickel-based alloys, cobalt-based alloys, and the like have been developed that can be applied to turbine members and the like provided in aircrafts, generators, and the like and can be applied to an ultra-high heat environment of 1000 ° C. or higher. In addition, high alloy steels and the like that can exhibit high corrosion resistance and wear resistance even under such an ultra-high heat environment have been developed.
近年、合金材の一種として、高エントロピー合金(high-entropy alloys;HEAs)と呼ばれる多元合金が注目されている。高エントロピー合金は、一般に、5種類程度以上の複数元素で組成され、各元素を等原子比率乃至その近傍の原子比率で含有する合金であるとされている。原子拡散の速度が遅い特徴を有し、耐熱性、高温強度、耐腐食性等に優れるため、過酷環境における用途への応用が期待されている。 In recent years, multi-element alloys called high-entropy alloys (HEAs) have attracted attention as a kind of alloy material. High entropy alloys are generally composed of a plurality of elements of about five or more types and contain each element in an equiatomic ratio or an atomic ratio in the vicinity thereof. Since it has the characteristics of slow atomic diffusion and is excellent in heat resistance, high temperature strength, corrosion resistance, etc., it is expected to be applied to applications in harsh environments.
高エントロピー合金を応用した技術として、例えば、特許文献1には、超硬複合材料の製造方法であって、少なくとも1種のセラミック相粉末と多元高エントロピー合金粉末とを混合して混合物を形成する工程、前記混合物を圧粉する工程、および、前記混合物を焼結して超硬複合材料を形成する工程、を含み、前記多元高エントロピー合金粉末が5から11の主要元素からなり、各主要元素が前記多元高エントロピー合金粉末の5から35モル%を占める製造方法が開示されている。 As a technique applying a high entropy alloy, for example, Patent Document 1 discloses a method of manufacturing a cemented carbide composite material, in which at least one ceramic phase powder and a multi-element high entropy alloy powder are mixed to form a mixture. A step of compacting the mixture, and a step of sintering the mixture to form a cemented carbide composite material, wherein the multi-element high-entropy alloy powder is composed of 5 to 11 main elements, Discloses a production method comprising 5 to 35 mol% of the multi-element high-entropy alloy powder.
また、非特許文献1には、Al、Co、Cr、Fe、Niを等原子比率とした高エントロピー合金において、微細組織や機械的性質についての寸法効果を解析したことが開示されている。 Non-Patent Document 1 discloses that a high-entropy alloy having an equiatomic ratio of Al, Co, Cr, Fe, and Ni analyzed the dimensional effect on the microstructure and mechanical properties.
構造部材、機構部材等の構造体の材料として高エントロピー合金を応用し、その特性を活かした構造体を製造するためには、高エントロピー合金を組成する主成分元素を等原子比率で固溶させると共に、形状寸法が多岐にわたる構造体の全域で元素組成分布の均一性が高くなるように固溶相を形成させることが望まれる。 In order to manufacture high-entropy alloys as structural materials such as structural members and mechanism members, and to produce structures that take advantage of these properties, the main constituent elements of the high-entropy alloys are dissolved in an equiatomic ratio. At the same time, it is desired to form a solid solution phase so that the uniformity of the elemental composition distribution is high over the entire structure having a wide variety of shape dimensions.
しかしながら、特許文献1に開示されるメカニカルアロイング法や、非特許文献1に開示されるアーク溶解法等に例示される従来の高エントロピー合金の製造方法では、元素組成分布、溶融速度、冷却速度等にむらが生じ易く、均一な元素組成分布を有する凝固組織を形成することができず、各元素が実質的に等原子比率で固溶した固溶相を大型化させることが困難であった。例えば、非特許文献1に開示される合金材は、最大の試作材についても直径10mm×高さ70mm(体積5495mm3)の小片にすぎず、構造体の材料として適用することは難しい。 However, in the conventional high-entropy alloy manufacturing method exemplified in the mechanical alloying method disclosed in Patent Document 1 and the arc melting method disclosed in Non-Patent Document 1, the element composition distribution, the melting rate, and the cooling rate It was difficult to form a solidified structure having a uniform elemental composition distribution, and it was difficult to increase the size of a solid solution phase in which each element was substantially dissolved in an equiatomic ratio. . For example, the alloy material disclosed in Non-Patent Document 1 is only a small piece of diameter 10 mm × height 70 mm (volume 5495 mm 3 ) even for the largest prototype material, and it is difficult to apply it as a material for a structure.
特に、比較的大型の構造体を鋳造しようとする場合には、多量の地金を溶融させたり溶湯を凝固させたりする工程が必要となるため、元素組成分布、溶融速度、冷却速度等のむらの影響が強く表出することになり、高エントロピー合金の固溶相が形成され難くなるという問題がある。また、高エントロピー合金は、良好な高温強度と耐食性とを有するものの、原子拡散の速度が遅い特徴を有しているため、凝固後の熱処理によっては元素組成や機械的強度の均一性を確保することが困難である。また、難加工性であるため、凝固後の切り出し等によって任意形状の構造体とすることも困難であり、元素組成及び機械的強度の分布の均一性が高い高エントロピー合金の構造体を得るのが難しい現状がある。 In particular, when a relatively large structure is to be cast, a process of melting a large amount of metal or solidifying the molten metal is required. Therefore, unevenness in element composition distribution, melting rate, cooling rate, etc. There is a problem that the influence is strongly expressed and it is difficult to form a solid solution phase of the high entropy alloy. High-entropy alloys have good high-temperature strength and corrosion resistance, but have a slow atomic diffusion rate, so that uniformity of elemental composition and mechanical strength is ensured by heat treatment after solidification. Is difficult. In addition, since it is difficult to process, it is difficult to obtain a structure of arbitrary shape by cutting after solidification, etc., and a high entropy alloy structure with high uniformity of elemental composition and mechanical strength distribution can be obtained. There is a difficult current situation.
そこで、本発明は、元素組成及び機械的強度の分布の均一性が高く、良好な高温強度と耐食性とを有する任意の形状寸法の合金構造体を提供することを目的とする。 Therefore, an object of the present invention is to provide an alloy structure having an arbitrary shape and dimension having high uniformity in distribution of elemental composition and mechanical strength and having good high-temperature strength and corrosion resistance.
前記課題を解決するために本発明は、例えば特許請求の範囲に記載の構成を採用する。 In order to solve the above problems, the present invention employs, for example, the configurations described in the claims.
本発明によれば、元素組成及び機械的強度の分布の均一性が高く、良好な高温強度と耐食性とを有する任意の形状寸法の合金構造体を提供することができる。 According to the present invention, it is possible to provide an alloy structure having an arbitrary shape and dimension having high uniformity in distribution of elemental composition and mechanical strength and having good high-temperature strength and corrosion resistance.
以下、本発明の一実施形態に係る合金構造体について説明する。なお、各図において共通する構成については、同一の符号を付し、重複した説明を省略する。 Hereinafter, an alloy structure according to an embodiment of the present invention will be described. In addition, about the structure which is common in each figure, the same code | symbol is attached | subjected and the overlapping description is abbreviate | omitted.
本実施形態に係る合金構造体は、鉄(Fe)と、Feと固溶化する少なくとも4種以上の他の元素(以下、非Fe主成分元素ということがある。)とを主成分とする高エントロピー合金からなり、積層造形によって所望の形状寸法に造形された金属造形物である。この合金構造体は、非Fe主成分元素及びFeの元素を、個々の各元素についてそれぞれ5at%以上30at%以下の範囲の原子濃度で含有し、これらの元素のうちの少なくとも4種の元素が実質的に等原子比率となる元素組成を有している。そして、非Fe主成分元素及びFeの原子は、これら複数種の元素が多元的に固溶した固溶相を形成している。そのため、この合金構造体は、高エントロピー合金としての一般的性質として、高い耐熱性、高温強度、耐摩耗性、耐腐食性を有している。また、後記するように、積層造形によって形成される特有の凝固組織を有しており、元素組成及び機械的強度の分布の均一性が高い特徴を有している。 The alloy structure according to the present embodiment has a high content mainly composed of iron (Fe) and at least four or more other elements that solidify with Fe (hereinafter sometimes referred to as non-Fe main component elements). It is a metal shaped article made of an entropy alloy and shaped to a desired shape by additive manufacturing. This alloy structure contains a non-Fe main component element and an Fe element at an atomic concentration in the range of 5 at% or more and 30 at% or less for each element, and at least four kinds of these elements are contained. It has an elemental composition with a substantially equiatomic ratio. The non-Fe main component element and the Fe atom form a solid solution phase in which these plural types of elements are solidly dissolved. Therefore, this alloy structure has high heat resistance, high temperature strength, wear resistance, and corrosion resistance as general properties as a high entropy alloy. Further, as will be described later, it has a specific solidified structure formed by additive manufacturing, and has a feature of high uniformity of elemental composition and mechanical strength distribution.
本実施形態に係る合金構造体は、常温且つ常圧下において、主晶が実質的には柱状晶の集合からなる。柱状晶の存在割合は、凝固組織の任意断面における占有面積率で、少なくとも50%以上となっており、後記する製造方法における凝固組織の形成条件によって、90%以上としたり、95%以上とすることも可能である。また、柱状晶の平均結晶粒径は、100μm以下であり、さらに10μm以下にまで微細化させることも可能である。なお、平均結晶粒径は、JIS G 0551(2013)に規定される方法に準じて求めることができる。 The alloy structure according to the present embodiment is substantially composed of a collection of columnar crystals at a normal temperature and a normal pressure. The proportion of the columnar crystals is at least 50% or more in the area occupied by the solidified structure in an arbitrary cross section, and is 90% or more or 95% or more depending on the formation conditions of the solidified structure in the manufacturing method described later. It is also possible. The average crystal grain size of the columnar crystals is 100 μm or less, and can be further refined to 10 μm or less. The average crystal grain size can be determined according to the method defined in JIS G 0551 (2013).
合金材構造体の主晶は、常温且つ常圧下において、面心立方格子又は体心立方格子の結晶構造を有している。組成を選択設計することによって、面心立方格子の結晶構造の存在割合を、凝固組織の任意断面における占有面積率で、90%以上としたり、95%以上とすることも可能である。また、体心立方格子の結晶構造の存在割合を、凝固組織の任意断面における占有面積率で、90%以上としたり、95%以上とすることも可能である。 The main crystal of the alloy material structure has a face-centered cubic lattice or a body-centered cubic lattice crystal structure at normal temperature and normal pressure. By selectively designing the composition, the proportion of the crystal structure of the face-centered cubic lattice can be 90% or more, or 95% or more in terms of the occupied area ratio in an arbitrary cross section of the solidified structure. In addition, the proportion of the crystal structure of the body-centered cubic lattice can be 90% or more, or 95% or more in terms of the occupied area ratio in an arbitrary cross section of the solidified structure.
非Fe主成分元素としては、元素周期表の第3族から第16族(第3A族から第6B族)までに含まれる原子番号13から原子番号79の元素であって、Fe原子に対する原子半径の比率が0.83以上1.17以下であるFe以外の元素から少なくとも4種以上の元素が選択される。このような非Fe主成分元素としては、具体的には、Al、Si、P、Ti、V、Cr、Mn、Co、Ni、Cu、Zn、Ga、Ge、As、Se、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Sn、Sb、Te、Ta、W、Re、Os、Ir、Pt、Auが挙げられる。合金構造体をこのような元素組成とすることによって、原子容積効果が奏され、高エントロピー合金としての作用を示す安定した固溶相を形成させることができる。 The non-Fe main component element is an element of atomic number 13 to atomic number 79 included in groups 3 to 16 (groups 3A to 6B) of the periodic table, and has an atomic radius with respect to Fe atoms Is selected from elements other than Fe having a ratio of 0.83 to 1.17. As such non-Fe main component elements, specifically, Al, Si, P, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Nb, Mo, Examples include Tc, Ru, Rh, Pd, Ag, Sn, Sb, Te, Ta, W, Re, Os, Ir, Pt, and Au. By setting the alloy structure to such an elemental composition, an atomic volume effect is exerted, and a stable solid solution phase exhibiting an action as a high entropy alloy can be formed.
非Fe主成分元素としては、Fe原子に対する原子半径の比率が0.92以上1.08以下である元素を含有することがより好ましく、こうした元素のみをFeと共に含有することがさらに好ましい。Feと共に主成分元素となる非Fe主成分元素としては、具体的には、Si、V、Cr、Mn、Co、Ni、Cu、Zn、Ga、Ge、As、Se、Mo、Tc、Ru、Rh、Re、Os、Irが挙げられる。これらの中でさらに好ましい非Fe主成分元素は、V、Cr、Mn、Co、Ni、Cu、Ge、Moであり、Co、Cr及びNiを含有することが特に好ましい。 As the non-Fe main component element, it is more preferable to contain an element having an atomic radius ratio of 0.92 to 1.08, more preferably containing only such an element together with Fe. Specific examples of the non-Fe main component element which is a main component element together with Fe include Si, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Tc, Ru, Rh, Re, Os, Ir are mentioned. Among these, more preferable non-Fe main component elements are V, Cr, Mn, Co, Ni, Cu, Ge, and Mo, and it is particularly preferable to contain Co, Cr, and Ni.
合金構造体の元素組成としては、具体的には、CoCrFeNiAl、CoCrFeNiCu、CoCrFeNiCuAl、CoCrFeNiCuAlSi、MnCrFeNiCuAl、CoCrFeNiMnGe、CoCrFeNiMn、CoCrFeNiMnCu、TiCoCrFeNiCuAlV、TiCoCrFeNiAl、AlTiCoCrFeNiCuVMn、TiCrFeNiCuAl、TiCoCrFeNiCuAl、CoCrFeNiCuAlV、TiCoCrFeNiAl、TiCoCrFeNiCuAl、CoCrFeNiCuAl、CoFeNiCuV、CoCrFeNiCuAl、MnCrFeNiAl、MoCrFeNiCu、TiCoCrFeNi、TiCoCrFeNiMo、CoCrFeNiCuAlV、MnCrFeNiCu、TiCoCrFeNi、TiCoCrFeNiAl、CoCrFeNiMo、CoCrFeNiAlMo、TiCoCrFeNiCu、CoCrFeNiCuAlMn、TiCoCrFeNiMo、CoCrFeNiCuAlV、TiCoCrFeNiCuVMn、AlTiCoCrFeNiCuVMn、CoCrFeNiCuAlMn、CoCrFeNiAlMo、CoCrFeNiCuAlMo、TiCoCrFeNiCu等を例示することができる。なお、これらの元素組成において、各元素の原子濃度(原子のモル比)は、5at%以上30at%以下の範囲の原子濃度と、少なくとも4種の元素が実質的に等原子比率となる元素組成とが満たされる限りにおいて種々の値をとることができる。但し、成分元素としてTiを含有する場合は、Tiが成分元素中で最大原子濃度を持つ成分とならないようにし、好ましくは合金構造体あたりの原子濃度を5at%以上10at%未満とする。 The elemental composition of the alloy structure is specifically CoCrFeNiAl, CoCrFeNiCu, CoCrFeNiCuAl, CoCrFeNiCuAlSi, MnCrFeNiCu, CoCrFeNiMnGe, CoCrFeNiMn, CoCrFeNiMnCu, TiCoCrFeNiCuAlV, TiCoCrFeNiAl, AlTiCoCrFeNiCuVMn, TiCrCrNi. CoCrFeNiCuAl, MnCrFeNiAl, MoCrFeNiCu, TiCoCrFeNi, TiCoCrFeNiMo, CoCrFeNiCuAlV MnCrFeNiCu, it TiCoCrFeNi, TiCoCrFeNiAl, CoCrFeNiMo, CoCrFeNiAlMo, TiCoCrFeNiCu, CoCrFeNiCuAlMn, TiCoCrFeNiMo, CoCrFeNiCuAlV, TiCoCrFeNiCuVMn, AlTiCoCrFeNiCuVMn, CoCrFeNiCuAlMn, CoCrFeNiAlMo, CoCrFeNiCuAlMo, be illustrated TiCoCrFeNiCu like. In these elemental compositions, the atomic concentration (molar ratio) of each element is such that the atomic concentration is in the range of 5 at% or more and 30 at% or less, and at least four elements are substantially in the atomic ratio. As long as and are satisfied, various values can be taken. However, when Ti is contained as a component element, Ti is not a component having the maximum atomic concentration among the component elements, and preferably the atomic concentration per alloy structure is 5 at% or more and less than 10 at%.
合金構造体は、非Fe主成分元素及びFeのほか、他の不可避的不純物の元素を含有することが許容される。不可避的不純物の元素としては、例えば、P、Si、S、Sn、Sb、As、Mn、O、N等が挙げられる。但し、Pについては、好ましくは0.005wt%以下、より好ましくは0.002wt%以下に、Siについては、好ましくは0.040wt%以下、より好ましくは0.010wt%以下に、Sについては、好ましくは0.002wt%以下、より好ましくは0.001wt%以下に、Snについては、好ましくは0.005wt%以下、より好ましくは0.002wt%以下に、Sbについては、好ましくは0.002wt%以下、より好ましくは0.001wt%以下に、Asについては、好ましくは0.005wt%以下、より好ましくは0.001wt%以下に、Mnについては、好ましくは0.050wt%以下、より好ましくは0.020wt%以下に制限する。また、Oについては、好ましくは0.001wt%以下(10ppm以下)、より好ましくは0.0003wt%以下(3ppm以下)に、Nについては、好ましくは0.002wt%以下(20ppm以下)、より好ましくは0.001wt%以下(10ppm以下)に制限する。このように合金構造体に含まれる不可避的不純物の濃度を制限することによって、構造体の形状寸法に関わらず、元素組成及び機械的強度の分布の均一性をより高くすることができる。なお、P、Si、Sn、Sb、As又はMnの元素を非Fe主成分元素として合金構造体に含有させる場合には、元素の濃度をこのように制限する必要はない。 The alloy structure is allowed to contain elements of other inevitable impurities in addition to the non-Fe main component element and Fe. Examples of unavoidable impurity elements include P, Si, S, Sn, Sb, As, Mn, O, and N. However, for P, it is preferably 0.005 wt% or less, more preferably 0.002 wt% or less, for Si, preferably 0.040 wt% or less, more preferably 0.010 wt% or less, and for S, Preferably it is 0.002 wt% or less, more preferably 0.001 wt% or less, Sn is preferably 0.005 wt% or less, more preferably 0.002 wt% or less, and Sb is preferably 0.002 wt%. Or less, more preferably 0.001 wt% or less, As is preferably 0.005 wt% or less, more preferably 0.001 wt% or less, and Mn is preferably 0.050 wt% or less, more preferably 0 Limited to 020 wt% or less. Further, O is preferably 0.001 wt% or less (10 ppm or less), more preferably 0.0003 wt% or less (3 ppm or less), and N is preferably 0.002 wt% or less (20 ppm or less), more preferably Is limited to 0.001 wt% or less (10 ppm or less). Thus, by limiting the concentration of inevitable impurities contained in the alloy structure, the uniformity of the distribution of elemental composition and mechanical strength can be made higher regardless of the shape and size of the structure. In addition, when the P, Si, Sn, Sb, As, or Mn element is contained in the alloy structure as a non-Fe main component, the element concentration need not be limited in this way.
合金構造体は、非Fe主成分元素及びFeのうちの少なくとも4種の元素を、5at%以上23.75at%以下の原子濃度の範囲で実質的に等原子比率で含有する。このとき、他の元素を、5at%以上30at%以下の原子濃度の範囲で含有し、残部が不可避的不純物によって組成される。このように少なくとも4種の元素を等原子比率で含有すると、自由エネルギの混合エントロピー項が増大するため、固溶相が安定化されるようになる。なお、本明細書においては、実質的に等原子比率であるとは、原子濃度の差が3at%未満の範囲にあることを意味するものとする。 The alloy structure contains a non-Fe main component element and at least four elements of Fe in an atomic concentration range of 5 at% to 23.75 at% in a substantially equiatomic ratio. At this time, other elements are contained in the atomic concentration range of 5 at% or more and 30 at% or less, and the remainder is composed of inevitable impurities. When at least four kinds of elements are contained in an equiatomic ratio in this way, the mixed entropy term of free energy increases, so that the solid solution phase is stabilized. In the present specification, “substantially equiatomic ratio” means that the difference in atomic concentration is in the range of less than 3 at%.
合金構造体を組成する元素種類及び原子比率は、例えば、生成エンタルピー、エントロピーないしギブスエネルギーを熱力学的計算で求めることによって、組成を選択設計することができる。例えば、等原子比率で含まれる少なくとも4種の元素と、他の元素との原子濃度の比率は、前記の原子濃度の範囲で適宜変えることができる。これら主成分元素の原子濃度の比率を変えることによって、合金構造体の結晶構造を変えることができ、機械的強度、展延性、硬度、密度等を調節することが可能である。熱力学的計算としては、第一原理計算法、Calphad(Calculation of phase diagrams)法、分子動力学法、Phase−Field法、有限要素法等を適宜組み合わせて用いることができる。 The element type and atomic ratio composing the alloy structure can be selected and designed by, for example, determining the formation enthalpy, entropy or Gibbs energy by thermodynamic calculation. For example, the ratio of atomic concentrations of at least four kinds of elements contained in an equiatomic ratio and other elements can be appropriately changed within the above-mentioned atomic concentration range. By changing the ratio of the atomic concentrations of these main component elements, the crystal structure of the alloy structure can be changed, and the mechanical strength, ductility, hardness, density, and the like can be adjusted. As the thermodynamic calculation, a first-principles calculation method, a Calphad (Calculation of phase diagrams) method, a molecular dynamics method, a phase-field method, a finite element method, or the like can be used in appropriate combination.
合金構造体は、例えば、Alを5at%以上30at%以下の原子濃度の範囲で含有すると共に、Co、Cr、Fe及びNiを15at%以上23.75at%以下の原子濃度の範囲で実質的に等原子比率で含有する元素組成とすることができる。合金構造体に含まれるAlの原子濃度を5at%以上30at%以下の範囲において低下させると、合金構造体の主相が面心立方格子の結晶構造で構成されるようにすることができる。その一方で、Alの原子濃度を5at%以上30at%以下の範囲において増大させると、合金構造体の主相が体心立方格子の結晶構造で構成されるようにすることができる。また、合金構造体に含まれるAlの原子濃度が5at%以上であると、合金構造体の機械的強度が過度に低下する恐れが低く、他方、合金構造体に含まれるAlの原子濃度が30at%以下であると、合金構造体の主相がAl系の金属間化合物になり難くなるため、合金材の延性が過度に低下する恐れが低い。 The alloy structure contains, for example, Al in an atomic concentration range of 5 at% to 30 at%, and substantially contains Co, Cr, Fe, and Ni in an atomic concentration range of 15 at% to 23.75 at%. It can be set as the element composition contained by an equiatomic ratio. When the atomic concentration of Al contained in the alloy structure is lowered in the range of 5 at% or more and 30 at% or less, the main phase of the alloy structure can be constituted by a crystal structure of a face-centered cubic lattice. On the other hand, when the atomic concentration of Al is increased in the range of 5 at% or more and 30 at% or less, the main phase of the alloy structure can be constituted by a body-centered cubic crystal structure. Further, if the atomic concentration of Al contained in the alloy structure is 5 at% or more, the mechanical strength of the alloy structure is less likely to be excessively reduced. On the other hand, the atomic concentration of Al contained in the alloy structure is 30 at%. % Or less, the main phase of the alloy structure is less likely to be an Al-based intermetallic compound, so that the ductility of the alloy material is less likely to deteriorate excessively.
同様にして、Coを5at%以上30at%以下、Al、Cr、Fe及びNiを15at%以上23.75at%以下の原子濃度の範囲で実質的に等原子比率で含有させたり、Crを5at%以上30at%以下、Al、Co、Fe及びNiを15at%以上23.75at%以下の原子濃度の範囲で実質的に等原子比率で含有させたり、Feを5at%以上30at%以下、Al、Co、Cr及びNiを15at%以上23.75at%以下の原子濃度の範囲で実質的に等原子比率で含有させたり、Niを5at%以上30at%以下、Al、Co、Cr及びFeを15at%以上23.75at%以下の原子濃度の範囲で実質的に等原子比率で含有させたりすることも可能である。 Similarly, Co is contained at a substantially equal atomic ratio within the atomic concentration range of 5 at% to 30 at%, Al, Cr, Fe and Ni at 15 at% to 23.75 at%, or Cr at 5 at%. 30 at% or less, Al, Co, Fe and Ni are contained in a substantially equiatomic ratio within the atomic concentration range of 15 at% or more and 23.75 at%, or Fe is 5 at% or more and 30 at% or less, Al, Co , Cr and Ni are contained in a substantially equiatomic ratio within the atomic concentration range of 15 at% to 23.75 at%, Ni is 5 at% to 30 at%, Al, Co, Cr and Fe are at least 15 at% It is also possible to contain it at a substantially equiatomic ratio within the atomic concentration range of 23.75 at% or less.
次に、本実施形態に係る合金構造体の製造方法について説明する。 Next, a method for manufacturing an alloy structure according to this embodiment will be described.
本実施形態に係る合金構造体は、合金粉末を用いた粉末積層造形によって製造することができる。合金粉末を溶融させた後に凝固させて凝固組織を形成し、多数の凝固組織を周囲と一体化させながら配列させることによって、所望の形状寸法の立体造形物として合金構造体を製造する方法である。本実施形態に係る合金構造体の製造方法は、積層造形に用いる合金粉末を調製する粉末調製工程と、調製された合金粉末を用いて合金構造体を造形する積層造形工程とを含んでなる。 The alloy structure according to the present embodiment can be manufactured by powder additive manufacturing using alloy powder. This is a method for producing an alloy structure as a three-dimensional object having a desired shape and size by melting and solidifying an alloy powder to form a solidified structure and arranging a number of solidified structures while being integrated with the surroundings. . The manufacturing method of the alloy structure which concerns on this embodiment comprises the powder preparation process which prepares the alloy powder used for additive manufacturing, and the additive manufacturing process which models an alloy structure using the prepared alloy powder.
粉末調製工程では、製造しようとする合金構造体と同じ主成分元素と添加元素とを含有し、主成分元素が実質的に等原子比率となる元素組成を有する合金粉末を調製する。合金粉末は、各粉末粒子が、製造しようとする合金構造体と略同じ元素組成となるような粒子集合とすることが好ましい。なお、凝固層造形工程において合金粉末を加熱する際に合金成分の一部が揮発して失われる場合があるため、こうした揮発による組成変化を考慮して原子濃度の範囲を高い範囲に設定してもよい。 In the powder preparation step, an alloy powder is prepared that contains the same main component elements and additive elements as the alloy structure to be manufactured and has an elemental composition in which the main component elements have a substantially equiatomic ratio. The alloy powder is preferably a particle aggregate in which each powder particle has substantially the same elemental composition as the alloy structure to be manufactured. In addition, when heating the alloy powder in the solidified layer forming process, some of the alloy components may volatilize and be lost, so the atomic concentration range is set to a high range in consideration of such volatilization of the composition change. Also good.
合金粉末の調製方法としては、従来から一般的に利用されている金属粉末の製造方法を用いることができる。例えば、合金の溶湯に流体を吹き付けて飛散させて凝固させるアトマイズ法、合金の溶湯を凝固させた後に機械的に粉砕する粉砕法、金属粉末を混合し圧接及び粉砕を繰り返して合金化させるメカニカルアロイング法、合金の溶湯を回転しているロール上に流下させて凝固させるメルトスピニング法等の適宜の方法を利用することができる。 As a method for preparing the alloy powder, a conventionally used method for producing metal powder can be used. For example, an atomizing method in which fluid is sprayed and dispersed by solidifying the molten alloy, a pulverizing method in which the molten alloy is solidified and then mechanically pulverized, or a mechanical alloy in which metal powder is mixed and repeatedly pressed and pulverized to form an alloy. An appropriate method such as an inging method or a melt spinning method in which a molten alloy is allowed to flow down on a rotating roll to be solidified can be used.
合金粉末の調製方法としては、アトマイズ法が好適であり、より好ましくはガスアトマイズ法、さらに好ましくは流体として不活性ガスを使用して不活性ガス雰囲気で行うガスアトマイズ法が用いられる。このような調製方法によると、真球度が高く、不純物の混入が少ない合金粉末を調製することが可能である。そして、合金粉末の真球度が高められると、積層造形において合金粉末を展延する際の抵抗が抑えられるため、合金粉末のむらを低減することができる。また、不活性ガスを使用することによって、酸化物不純物等の混入が抑制されるため、製造される合金材の金属組織をより均一なものとすることができる。 As a method for preparing the alloy powder, an atomizing method is preferable, a gas atomizing method is more preferable, and a gas atomizing method performed in an inert gas atmosphere using an inert gas as a fluid is more preferable. According to such a preparation method, it is possible to prepare an alloy powder having a high sphericity and a small amount of impurities. When the sphericity of the alloy powder is increased, the resistance at the time of spreading the alloy powder in additive manufacturing can be suppressed, so that the unevenness of the alloy powder can be reduced. In addition, by using an inert gas, mixing of oxide impurities and the like is suppressed, so that the metal structure of the manufactured alloy material can be made more uniform.
合金粉末は、積層造形において合金粉末を展延させる方式や、合金粉末を溶融させる熱源の出力等の溶融条件に応じて適宜の粒子径とすることができる。但し、通常は合金粉末の粒子径分布は、1μm以上500μm以下の範囲とすることが好ましい。合金粉末の粒子径が1μm以上であれば、合金粉末の巻き上がりや浮遊が抑制されたり、金属の酸化反応性が抑えられたりして、粉塵爆発等の恐れが低くなるためである。一方で、合金粉末の粒子径が500μm以下であれば、積層造形において形成される凝固層の表面が平滑になり易い点で有利である。また、合金粉末を溶融させるための加熱手段の出力を抑えることが可能になり、合金粉末の溶融速度や合金粉末を局所加熱する際の被加熱領域の範囲の制御が容易になるため、合金構造体の造形精度や凝固組織の均一性を確保し易くすることができる。 The alloy powder can have an appropriate particle size according to a melting condition such as a method of spreading the alloy powder in additive manufacturing and an output of a heat source for melting the alloy powder. However, normally, the particle size distribution of the alloy powder is preferably in the range of 1 μm to 500 μm. This is because if the particle diameter of the alloy powder is 1 μm or more, rolling-up or floating of the alloy powder is suppressed, or the oxidation reactivity of the metal is suppressed, and the risk of dust explosion or the like is reduced. On the other hand, if the particle diameter of the alloy powder is 500 μm or less, it is advantageous in that the surface of the solidified layer formed in the layered manufacturing tends to be smooth. In addition, it becomes possible to suppress the output of the heating means for melting the alloy powder, and it becomes easy to control the melting rate of the alloy powder and the range of the heated region when locally heating the alloy powder. It is possible to easily ensure the modeling accuracy of the body and the uniformity of the solidified structure.
図1は、本実施形態に係る合金構造体の製造方法の工程の一例を示す概念図である。 Drawing 1 is a key map showing an example of a process of a manufacturing method of an alloy structure concerning this embodiment.
本実施形態に係る合金構造体の製造方法では、図1(a)から(g)に順に示す積層造形工程を繰り返し行って合金構造体の立体造形を行う。積層造形工程は、従来から一般的に利用されている金属用の粉末積層造形装置を用いて行うことが可能であり、粉末調製工程で調製された合金粉末は、このような積層造形工程の原料粉末として用いられる。積層造形装置に備えられる加熱手段としては、例えば、電子線加熱、レーザー加熱、マイクロ波加熱、プラズマ加熱、集光加熱、高周波加熱等の適宜の加熱原理によるものが用いられる。これらの中では電子線加熱又はレーザー加熱による積層造形装置が特に好適である。電子線加熱又はレーザー加熱によると、熱源の出力や、合金粉末の被加熱領域の微小化や、合金構造体の造形精度等の制御を比較的容易に行えるためである。 In the manufacturing method of the alloy structure according to the present embodiment, the three-dimensional modeling of the alloy structure is performed by repeatedly performing the layered modeling process shown in order from FIGS. The additive manufacturing process can be performed using a metal additive manufacturing apparatus generally used for metal, and the alloy powder prepared in the powder preparation process is a raw material for such additive manufacturing process. Used as a powder. As the heating means provided in the layered manufacturing apparatus, for example, those based on an appropriate heating principle such as electron beam heating, laser heating, microwave heating, plasma heating, condensing heating, and high-frequency heating are used. Among these, an additive manufacturing apparatus using electron beam heating or laser heating is particularly suitable. This is because electron beam heating or laser heating makes it relatively easy to control the output of the heat source, miniaturization of the heated area of the alloy powder, and modeling accuracy of the alloy structure.
積層造形工程は、詳細には、粉末展延工程、凝固層造形工程を含んでなる。積層造形工程では、図1(a)から(g)に順に示されるような工程を経て、層状の凝固組織(凝固層)を形成し、層状の凝固組織(凝固層)の形成を繰り返すことで、凝固組織の集合からなる合金構造体を造形する。 In detail, the layered modeling process includes a powder spreading process and a solidified layer modeling process. In the additive manufacturing process, a layered solidified structure (solidified layer) is formed through steps as shown in order from FIGS. 1A to 1G, and the formation of the layered solidified structure (solidified layer) is repeated. Then, an alloy structure comprising a set of solidified structures is formed.
積層造形装置には、図1(a)に示すように、上端に基材載置台21を有する昇降可能なピストンが備えられている。この基材載置台21の周囲には、ピストンに連動しない加工テーブル22が備えられており、加工テーブル22上に原料粉末10を供給する不図示の粉末フィーダ、供給された原料粉末10を展延するリコータ23、原料粉末10を加熱する加熱手段24、加工テーブル22上の原料粉末10を除去する不図示のエアブラスト、不図示の調温器等が備えられている。加工テーブル22やこれらの機器類は、チャンバに収容されており、チャンバ内の雰囲気は、加熱手段24の種類に応じて真空雰囲気又はアルゴンガス等の不活性ガス雰囲気とされ、雰囲気圧力や温度が管理されるようになっている。積層造形を行うに際しては、基材載置台21にあらかじめ基材15が載置され、基材15の被造形面(上面)と加工テーブル22の上面とが面一となるように位置合わせされる。 As shown in FIG. 1A, the additive manufacturing apparatus is provided with a vertically movable piston having a substrate mounting table 21 at the upper end. A processing table 22 that does not interlock with the piston is provided around the substrate mounting table 21, and a powder feeder (not shown) that supplies the raw material powder 10 onto the processing table 22 and the supplied raw material powder 10 are spread. A recoater 23, a heating means 24 for heating the raw material powder 10, an air blast (not shown) for removing the raw material powder 10 on the processing table 22, a temperature controller (not shown), and the like. The processing table 22 and these devices are housed in a chamber, and the atmosphere in the chamber is a vacuum atmosphere or an inert gas atmosphere such as argon gas depending on the type of the heating means 24, and the atmospheric pressure and temperature are set. It has come to be managed. When performing layered modeling, the base material 15 is previously placed on the base material placing table 21 and aligned so that the surface to be shaped (upper surface) of the base material 15 and the upper surface of the processing table 22 are flush with each other. .
基材15としては、加熱手段24による加熱に対する耐熱性を備えていれば適宜の材料を用いることができる。この合金構造体の製造方法においては、基材15の被造形面上に対して合金構造体の積層造形が行われることで、基材15と合金構造体とが一体化した状態の造形物が得られることになる。そのため、基材15としては、切断加工等により合金構造体から分離することを想定して、平板状等の適宜の形状の基材15を用いることができる。或いは、基材15と合金構造体とを一体化した状態で機能させることを想定して、被造形面を有する任意形状の構造部材、機構部材等を基材15として用いることもできる。 As the base material 15, an appropriate material can be used as long as it has heat resistance against heating by the heating means 24. In this method for manufacturing an alloy structure, a modeled product in which the base material 15 and the alloy structure are integrated is obtained by performing layered modeling of the alloy structure on the surface to be modeled of the base material 15. Will be obtained. Therefore, as the base material 15, a base material 15 having an appropriate shape such as a flat plate shape can be used on the assumption that the base material 15 is separated from the alloy structure by cutting or the like. Alternatively, assuming that the base material 15 and the alloy structure are functioned in an integrated state, a structural member, a mechanism member or the like having an arbitrary shape can be used as the base material 15.
粉末展延工程では、調製された合金粉末10を被造形面上に展延する。すなわち、積層造形における初回の粉末展延工程では、積層造形装置に載置された基材15に合金粉末10を展延する。合金粉末10の展延は、図1(b)に示すように、不図示の粉末フィーダによって加工テーブル22上に供給された合金粉末10(図1(a)参照)を、リコータ23を被造形面(基材15)上を通過するように掃引して、合金粉末10を薄層状に敷き詰めることによって行うことができる。展延されて形成される合金粉末10の薄層の厚さは、合金粉末10を溶融させる加熱手段の出力や、合金粉末10の平均粒子径等に応じて適宜調節することができるが、好ましくは10μm以上1000μm以下程度の範囲とする。 In the powder spreading step, the prepared alloy powder 10 is spread on the surface to be shaped. That is, in the first powder spreading process in the layered modeling, the alloy powder 10 is spread on the base material 15 placed on the layered modeling apparatus. As shown in FIG. 1B, the spreading of the alloy powder 10 is performed by using the alloy powder 10 (see FIG. 1A) supplied on the processing table 22 by a powder feeder (not shown) and forming the recoater 23 on the model. It can be performed by sweeping over the surface (base material 15) and spreading the alloy powder 10 in a thin layer. The thickness of the thin layer of the alloy powder 10 formed by spreading can be appropriately adjusted according to the output of the heating means for melting the alloy powder 10, the average particle diameter of the alloy powder 10, etc. Is in the range of about 10 μm to 1000 μm.
凝固層造形工程では、展延された合金粉末10を局所加熱して溶融させた後に凝固させ、局所加熱による被加熱領域を合金粉末10が展延された平面に対して走査することによって凝固層40を造形する。後記の凝固層40(図1(e)参照)の造形は、製造しようとする合金構造体の立体形状を表す3次元形状情報(3D−CADデータ等)から得られる2次元形状情報にしたがって、加熱手段24による被加熱領域を走査することで行われる。2次元形状情報は、製造しようとする合金構造体の3次元形状を、仮想上、所定厚さ間隔でスライスして、複数の薄層の集合に分割した場合の各薄層の形状を特定する情報である。このような2次元形状情報にしたがって、所定の2次元形状と厚さとを有する凝固層40が形成される。 In the solidified layer forming step, the spread alloy powder 10 is locally heated and melted and then solidified, and the solidified layer is scanned by scanning the heated region by the local heating with respect to the plane on which the alloy powder 10 is spread. Model 40. The modeling of the solidified layer 40 (see FIG. 1E), which will be described later, is performed according to the two-dimensional shape information obtained from the three-dimensional shape information (3D-CAD data, etc.) representing the three-dimensional shape of the alloy structure to be manufactured. This is done by scanning the area to be heated by the heating means 24. The two-dimensional shape information specifies the shape of each thin layer when the three-dimensional shape of the alloy structure to be manufactured is virtually sliced at a predetermined thickness interval and divided into a plurality of thin layer sets. Information. According to such two-dimensional shape information, the solidified layer 40 having a predetermined two-dimensional shape and thickness is formed.
合金粉末10の局所加熱は、図1(c)に示すように、加熱手段24によって、展延された合金粉末10上の被加熱領域を限定して行い、展延された合金粉末10の一部を微小な溶融池(溶融部20)が形成されるように選択的に溶融させることにより行う。合金粉末10を溶融させて形成する溶融部20の大きさは、好ましくは直径1mm以下とする。溶融部20をこのような微小な大きさに制限することで、合金構造体の造形精度や、凝固組織における元素組成の均一性が高められるようになる。 As shown in FIG. 1C, the local heating of the alloy powder 10 is performed by limiting the heated region on the spread alloy powder 10 by the heating means 24, and one of the spread alloy powder 10. This is performed by selectively melting the part so that a small molten pool (melting part 20) is formed. The size of the melting part 20 formed by melting the alloy powder 10 is preferably 1 mm or less. By limiting the melted portion 20 to such a small size, the modeling accuracy of the alloy structure and the uniformity of the element composition in the solidified structure can be improved.
合金粉末10の局所加熱による被加熱領域は、図1(d)に示すように、被造形面に平行に移動するように走査させる。被加熱領域の走査は、加熱手段24の本体の走査のほか、ガルバノミラー等による熱源の照射スポットの走査により行うことも可能であり、ラスター走査のような適宜の方式で実施する。このとき、複数の線源によるオーバーラップ走査を行い、照射されるエネルギ密度を平坦化させてもよい。そして、被加熱領域の走査によって、合金粉末10が未だ溶融していない領域の局所加熱を新たに行うと共に、合金粉末10が既に溶融して溶融部20が形成された領域の加熱を止めて、溶融部20を雰囲気温度の下で冷却して凝固させる。溶融部20が凝固することで形成される凝固部30は、基材や既に形成されている凝固部30と一体化しつつ凝固部30の緻密な集合を形成することになる。 The area to be heated by local heating of the alloy powder 10 is scanned so as to move parallel to the surface to be shaped, as shown in FIG. Scanning of the heated region can be performed by scanning the irradiation spot of the heat source by a galvano mirror or the like in addition to scanning of the main body of the heating means 24, and is performed by an appropriate method such as raster scanning. At this time, overlapped scanning with a plurality of radiation sources may be performed to flatten the irradiated energy density. And by scanning the heated area, the local heating of the area where the alloy powder 10 has not yet melted is newly performed, and the heating of the area where the alloy powder 10 has already melted and the melted portion 20 is formed is stopped, The melting part 20 is cooled and solidified at ambient temperature. The solidified part 30 formed by the solidification of the melting part 20 forms a dense assembly of the solidified part 30 while being integrated with the base material and the already formed solidified part 30.
加熱手段24の走査速度、出力、エネルギ密度、走査幅は、合金粉末10の元素組成、粒度分布、基材15の材質、溶融部20と凝固部30との位置関係、チャンバ温度等から推定される熱伝導や熱放射に基いて適宜調整すればよい。また、溶融部20を冷却する冷却温度は、合金構造体の元素組成に応じて寸法変化、熱歪等を考慮して設定すればよい。溶融部20の大きさや、溶融速度や、冷却速度や、溶融及び冷却の時間間隔等を所定の範囲に維持して走査を行うことによって、造形される合金構造体の強度分布を均一化したり、残留応力や表面粗さを低減させたりすることが可能である。 The scanning speed, output, energy density, and scanning width of the heating means 24 are estimated from the elemental composition of the alloy powder 10, the particle size distribution, the material of the base material 15, the positional relationship between the molten portion 20 and the solidified portion 30, the chamber temperature, and the like. What is necessary is just to adjust suitably based on the heat conduction and heat radiation to be. Further, the cooling temperature for cooling the melting part 20 may be set in consideration of dimensional change, thermal strain, etc. according to the elemental composition of the alloy structure. By maintaining the size of the melting part 20, the melting rate, the cooling rate, the time interval of melting and cooling, etc. within a predetermined range, the strength distribution of the alloy structure to be shaped is made uniform, It is possible to reduce residual stress and surface roughness.
図1(c)から(e)に示すように、基材載置台21に載置された基材15上で、合金粉末10の溶融と凝固とを繰り返し凝固部30の集合を形成することで、所定の2次元形状と厚さとを有する凝固層40が形成される。形成された凝固層40の周囲や上面に残存している未溶融の合金粉末10をエアーブラストによって除去した後、図1(f)に示すように、基材載置台21を、形成された凝固層40の厚さに相当する高さ下降させて、凝固層40の上面の新たな被造形面と加工テーブル22の上面とが面一となるように位置合わせする。 As shown in FIGS. 1C to 1E, by forming a set of solidified portions 30 by repeatedly melting and solidifying the alloy powder 10 on the substrate 15 placed on the substrate placing table 21. The solidified layer 40 having a predetermined two-dimensional shape and thickness is formed. After the unmelted alloy powder 10 remaining around and on the upper surface of the formed solidified layer 40 is removed by air blasting, the substrate mounting table 21 is formed on the formed solidified plate as shown in FIG. The height corresponding to the thickness of the layer 40 is lowered, and the new surface to be formed on the upper surface of the solidified layer 40 is aligned with the upper surface of the processing table 22.
位置合わせを行った後、図1(a)から(b)と同様にして粉末展延工程を行い、図1(g)に示すように、既に形成されている凝固層40の上面に新たに供給された合金粉末10を展延する。その後、図1(c)から(e)と同様にして凝固層造形工程を行い、次層の凝固層40の積層を行う。積層される凝固部30は下層の凝固層40の一部と一体化して緻密に焼結することになる。以降、同様にして、形成された凝固層40の上面を被造形面とした粉末展延工程及び凝固層造形工程を繰り返すことで、所望の形状寸法の合金構造体を積層造形することができる。 After the alignment, a powder spreading process is performed in the same manner as in FIGS. 1A to 1B. As shown in FIG. 1G, a new surface is newly formed on the upper surface of the solidified layer 40 that has already been formed. The supplied alloy powder 10 is spread. Thereafter, the solidified layer forming process is performed in the same manner as in FIGS. 1C to 1E, and the next solidified layer 40 is laminated. The laminated solidified portion 30 is integrated with a part of the lower solidified layer 40 and sintered densely. Thereafter, in the same manner, by repeating the powder spreading process and the solidified layer modeling process in which the upper surface of the formed solidified layer 40 is the modeled surface, an alloy structure having a desired shape and dimension can be layered.
凝固層造形工程においては、合金粉末10が溶融した後、凝固部30が形成されるまでの高温の状態において、凝固部30乃至凝固層40の形状成形加工処理や表面加工処理を行うことができる。このような加工処理は、溶融部30乃至凝固部40の表面温度が500℃程度以上の状態、好ましくは合金の融点(Tm)の50%から75%の温度域で、例えば、金属製若しくは合金製の工具、又は、ダイヤモンド粉末、金属間化合物粉末、タングステンカーバイド等の圧粉体等による無機製若しくは無機複合材料製の工具を用いた加工を施すことによって行うことができる。このような加工処理によって、難加工性である合金構造体を、より高精度な形状寸法に成形したり、装飾したりすることが可能である。 In the solidified layer forming step, after the alloy powder 10 is melted, the solidified portion 30 to the solidified layer 40 can be shaped and surface-treated in a high temperature state until the solidified portion 30 is formed. . Such processing is performed in a state where the surface temperature of the melted part 30 to the solidified part 40 is about 500 ° C. or higher, preferably in a temperature range of 50% to 75% of the melting point (Tm) of the alloy, for example, metal or alloy It can be performed by processing using a tool made of an inorganic or inorganic composite material such as a diamond tool, an intermetallic compound powder, or a green compact such as tungsten carbide. By such processing, it is possible to form or decorate an alloy structure which is difficult to process into a more accurate shape and size.
粉末展延工程及び凝固層造形工程を繰り返すことで積層造形された合金構造体には、熱間等方圧加圧(Hot Isostatic Pressing;HIP)処理を別途実施してもよい。合金構造体を熱間等方圧加圧処理することによって、合金構造体の凝固組織をより緻密にしたり、凝固組織の欠陥を除去することができる場合があるためである。 A hot isostatic pressing (HIP) process may be separately performed on the alloy structure that has been layered by repeating the powder spreading process and the solidified layer modeling process. This is because by subjecting the alloy structure to hot isostatic pressing, the solidified structure of the alloy structure can be made denser or defects in the solidified structure can be removed.
このような積層造形工程を繰り返し行って立体造形を行う合金構造体の製造方法によれば、柱状晶を主晶とする合金構造体を微小な凝固組織の集合によって所望の形状寸法で製造することができる。また、微小な凝固組織(凝固部30)のそれぞれの元素組成は、用いた合金粉末の元素組成を良好に反映しているため、元素組成分布の均一性及び機械的強度の分布の均一性が高い固溶相を形成することができる。さらには、一方向からの加熱によって凝固組織(凝固部30)を形成し、結晶成長方向が略一方向に配向した凝固組織(凝固層40)を積層することができるため、異方性が高い合金構造体を形成することができる。 According to the method of manufacturing an alloy structure in which three-dimensional modeling is performed by repeatedly performing such a layered manufacturing process, an alloy structure having a columnar crystal as a main crystal is manufactured with a desired shape and size by a collection of minute solidification structures. Can do. In addition, each elemental composition of the minute solidified structure (solidified part 30) reflects the elemental composition of the alloy powder used well, so the uniformity of the elemental composition distribution and the mechanical strength distribution are A high solid solution phase can be formed. Furthermore, since a solidified structure (solidified portion 30) is formed by heating from one direction and a solidified structure (solidified layer 40) in which the crystal growth direction is oriented substantially in one direction can be laminated, the anisotropy is high. An alloy structure can be formed.
次に、積層造形によって形成される合金構造体の金属組織について説明する。 Next, the metal structure of the alloy structure formed by additive manufacturing will be described.
図2は、合金構造体が有する金属組織の概略を示した断面図である。(a)は、本実施形態に係る合金構造体の断面図、(b)は、(a)におけるA部の拡大断面図、(c)は、比較例に係る合金材が有する金属組織の概略を示した断面図である。 FIG. 2 is a cross-sectional view showing the outline of the metal structure of the alloy structure. (A) is sectional drawing of the alloy structure which concerns on this embodiment, (b) is an expanded sectional view of the A section in (a), (c) is the outline of the metal structure which the alloy material which concerns on a comparative example has It is sectional drawing which showed.
図2(a)に示すように、本実施形態に係る合金構造体1は、前記の積層造形による製造方法に由来する金属組織を有し溶融した合金が凝固して形成される凝固組織(凝固部30)の集合からなる。なお、図2(a)では、積層造形によって製造された合金構造体の一部分を抜き出して断面を示している。個々の凝固組織(凝固部30)は、局所加熱による溶融池(溶融部20)の輪郭形状に由来する略半球状の原形を有しており、周囲にある他の凝固部30と一体化して緻密な金属組織を形成する。また、各凝固部30は、円弧側を同じ方向に向けて2次元状に配列し、凝固部30の集合からなる層状の凝固層40を形成するようになる。そして、このようにして形成された凝固層40が多数積層されることで、凝固部30が3次元状に配列した金属組織が形成される。但し、積層造形における走査速度、走査幅等の造形条件によっては、凝固層40を形成する凝固部30が、同じ層の周囲の他の凝固部30と一体化したり、各凝固部30の弦側が、積層された他の凝固層40と一体化したりすることもあるため、凝固部の略半球状の原形や凝固部30同士の間の溶融境界100は、凝固組織中では観察されない場合があり得る。 As shown in FIG. 2 (a), the alloy structure 1 according to the present embodiment has a solidified structure (solidified) formed by solidification of a molten alloy having a metal structure derived from the manufacturing method by additive manufacturing. Part 30). In FIG. 2A, a cross section is shown by extracting a part of an alloy structure manufactured by additive manufacturing. Each solidified structure (solidified portion 30) has a substantially hemispherical original shape derived from the contour shape of the molten pool (molten portion 20) by local heating, and is integrated with other solidified portions 30 around it. A dense metal structure is formed. In addition, the solidified portions 30 are two-dimensionally arranged with the arc side facing in the same direction to form a layered solidified layer 40 that is a set of the solidified portions 30. A large number of solidified layers 40 formed in this way are stacked, thereby forming a metal structure in which the solidified portions 30 are arranged in a three-dimensional manner. However, depending on modeling conditions such as scanning speed and scanning width in the layered modeling, the solidified part 30 forming the solidified layer 40 may be integrated with other solidified parts 30 around the same layer, or the string side of each solidified part 30 may be In some cases, the solidified layer 40 may be integrated with the other solidified layers 40, so that the substantially hemispherical original shape of the solidified part and the melting boundary 100 between the solidified parts 30 may not be observed in the solidified structure. .
合金構造体1は、図2(b)に示すように、非Fe主成分元素及びFeが固溶した柱状晶を主晶としている。なお、図2(b)では、合金構造体の金属組織の断面を数百μmから数mmの視野角に拡大して示している。合金構造体の金属組織中に含まれる各結晶粒50は、結晶方位が凝固層40の積層方向に略沿うようにしてエピタキシャルに成長し、粒界110(大傾角粒界)が積層方向に向けて配向しながら、凝固部30同士の間の溶融境界100を超えて延びる構造が生じる。 As shown in FIG. 2B, the alloy structure 1 has a columnar crystal in which a non-Fe main component element and Fe are dissolved as a main crystal. In FIG. 2 (b), the cross section of the metal structure of the alloy structure is shown enlarged to a viewing angle of several hundred μm to several mm. Each crystal grain 50 included in the metal structure of the alloy structure is epitaxially grown so that the crystal orientation is substantially along the stacking direction of the solidified layer 40, and the grain boundary 110 (high tilt grain boundary) is directed in the stacking direction. A structure that extends beyond the melting boundary 100 between the solidified portions 30 is formed.
また、各結晶粒50は、平均結晶粒径が10μm以下にまで微細化していることがある。微細化した結晶粒50同士は結晶方位を維持しており、大傾角粒界110に区画される内側に小傾角粒界120が認められることがある。なお、小傾角粒界120は、傾角15°以下の粒界、大傾角粒界110は、傾角15°を超える粒界として定義される。微細化した結晶粒50は、傾角と共にねじれ角も小さい結晶粒の集合となる傾向がある。 Each crystal grain 50 may be refined to an average crystal grain size of 10 μm or less. The refined crystal grains 50 maintain the crystal orientation, and the small-angle grain boundary 120 may be recognized on the inner side partitioned by the large-angle grain boundary 110. Note that the low-inclination grain boundary 120 is defined as a grain boundary having an inclination angle of 15 ° or less, and the large-inclination grain boundary 110 is defined as a grain boundary having an inclination angle exceeding 15 °. The refined crystal grains 50 tend to be a collection of crystal grains having a small twist angle as well as an inclination angle.
これに対して、従来の高エントロピー合金材(比較例に係る合金材)は、鋳造による製造方法に由来する金属組織を有している。比較例に係る合金材では、図2(c)に示すように、等方的に延びる粒界110が認められ、平均結晶粒径が100μmを超える粗大な等軸晶の結晶粒が形成される傾向がある。なお、図2(c)では、合金材の金属組織の断面を数百μmから数mmの視野角に拡大して示している。比較例に係る合金材では、核成長に伴い偏析を生じ易く、組成分布の均一性は低くなったり、結晶粒が粗大であるために応力が分散され難く、劈開やすべりを生じる面が長尺となるため、機械的強度が十分なものとはならない。特に、固溶相が良好に成長することができないため、寸法が小さく複雑形状を形成することもできないという難がある。 On the other hand, the conventional high entropy alloy material (alloy material according to the comparative example) has a metal structure derived from a manufacturing method by casting. In the alloy material according to the comparative example, as shown in FIG. 2 (c), isotropic grain boundaries 110 are observed, and coarse equiaxed crystal grains having an average crystal grain size exceeding 100 μm are formed. Tend. In FIG. 2 (c), the cross section of the metal structure of the alloy material is shown enlarged to a viewing angle of several hundred μm to several mm. In the alloy material according to the comparative example, segregation is likely to occur due to the nucleus growth, the uniformity of the composition distribution is low, the stress is not easily dispersed because the crystal grains are coarse, and the surface that causes cleavage and slip is long. Therefore, the mechanical strength is not sufficient. In particular, since a solid solution phase cannot grow well, there is a difficulty that a complicated shape cannot be formed with a small size.
これに対して、本実施形態に係る合金構造体は、結晶方位が比較的揃った結晶がエピタキシャルに成長し、同等の環境で良好に成長した結晶粒50の集合からなるため、合金粉末について調整された元素組成が合金構造体の形状寸法に依らず維持され易く、組成分布の均一性が高くなる。また、結晶粒50が微細化され、応力による歪が局所的に集中し難く、機械的強度の均一性が高くなる利点がある。また、劈開やすべりを生じる面が短尺となるため、機械的強度が向上する点で有利である。さらには、結晶の成長方向が配向して、異方性が高くなるため、方向強度や磁気特性を利用する場合にも有効である。 On the other hand, the alloy structure according to the present embodiment is composed of a set of crystal grains 50 in which crystals having relatively uniform crystal orientations grow epitaxially and grow well in an equivalent environment. The elemental composition thus formed is easily maintained regardless of the shape and size of the alloy structure, and the uniformity of the composition distribution is increased. Further, there is an advantage that the crystal grains 50 are miniaturized, strain due to stress is hardly concentrated locally, and the uniformity of mechanical strength is increased. Moreover, since the surface that causes cleavage and slipping is short, it is advantageous in that the mechanical strength is improved. Furthermore, since the crystal growth direction is oriented and the anisotropy is increased, it is also effective in utilizing the direction strength and magnetic characteristics.
次に、本実施形態に係る合金構造体原料として用いられる合金粉末の製造方法の一例について説明する。 Next, an example of the manufacturing method of the alloy powder used as the alloy structure raw material according to the present embodiment will be described.
図3は、合金構造体の原料として用いられる合金粉末の製造方法の一例を示す概略流れ図である。 FIG. 3 is a schematic flow chart showing an example of a method for producing an alloy powder used as a raw material for an alloy structure.
前記のとおり本実施形態に係る合金構造体の諸特性は、積層造形において用いる合金粉末の元素組成の影響が反映され易い。したがって、原料として用いる合金粉末は、不可避的不純物の濃度が低減された元素組成とすることが好ましく、合金粉末の製造方法としては、清浄度が高い合金を製造することが可能な真空炭素脱酸法を利用した複合精錬による製造方法を利用するのが好適な形態となる。図3に示す合金粉末の製造方法は、取鍋を使用して炉外精錬を行い、粗金属を原料の地金として、真空炭素脱酸法を利用した複合製錬を行うことで清浄度が高い合金を精錬し、その合金を用いて合金粉末の調製を行う方法となっており、前記の合金粉末の調製工程として適用することができる方法となっている。 As described above, the effects of the elemental composition of the alloy powder used in additive manufacturing are easily reflected in the various characteristics of the alloy structure according to the present embodiment. Therefore, it is preferable that the alloy powder used as a raw material has an elemental composition in which the concentration of inevitable impurities is reduced. As a method for producing the alloy powder, a vacuum carbon deoxidation capable of producing an alloy having a high cleanliness is provided. It is preferable to use a manufacturing method by complex refining using the method. The method for producing the alloy powder shown in FIG. 3 performs cleansing outside the furnace using a ladle, and uses clean metal as raw metal to perform complex smelting using a vacuum carbon deoxidation method to achieve cleanliness. It is a method of refining a high alloy and preparing an alloy powder using the alloy, and is a method that can be applied as the preparation step of the alloy powder.
この製造方法では、図3(a)に示すように、はじめに、電気炉301によって、合金粉末の原料となる粗金属の金属塊302を溶融させる溶融処理を行う。なお、図3では、電気炉301が、炉内でアーク放電を発生させる炭素電極等の電極304と、炉内に酸素ガスを吹き込む酸素バーナ305とを備えた三相交流アーク炉とされているが、同等の構成を有する直流アーク炉や転炉等を使用することも可能である。 In this manufacturing method, as shown in FIG. 3 (a), first, a melting process is performed in which an electric furnace 301 melts a metal block 302 of a crude metal that is a raw material for alloy powder. In FIG. 3, the electric furnace 301 is a three-phase AC arc furnace including an electrode 304 such as a carbon electrode that generates arc discharge in the furnace and an oxygen burner 305 that blows oxygen gas into the furnace. However, it is also possible to use a DC arc furnace, a converter, or the like having an equivalent configuration.
金属塊302としては、金属スクラップ、鉄屑等を利用することができる。金属塊302の種類は、製造しようとする合金粉末に適合する元素組成となるように配合し、あらかじめ不純物元素が少ない種類を選定することが好ましい。非Fe主成分元素として含有させない場合には、Snについては0.005wt%以下、Sbについては0.002wt%以下、Asについては0.005wt%以下の範囲となるような種類を選定することが好ましい。 As the metal lump 302, metal scrap, iron scrap or the like can be used. It is preferable that the type of metal block 302 is blended so as to have an elemental composition compatible with the alloy powder to be manufactured, and a type with few impurity elements is selected in advance. When it is not contained as a non-Fe main component element, it is possible to select a type in which Sn is 0.005 wt% or less, Sb is 0.002 wt% or less, and As is 0.005 wt% or less. preferable.
溶融処理では、図3(a)に示すように、金属塊302を電気炉301の炉内に投入し、電極304と金属塊302との間でアーク放電303を発生させることによって、金属塊302を溶融させ、溶湯310とする。そして、図3(b)に示すように、溶湯310に、酸素バーナ305によって酸素ガス306を吹き込むことで、スラグを形成させる過酸化処理を行う。このように溶湯310に酸素を吹き込む過酸化処理を行うことによって、溶湯310に含まれているSi、Mn、P等の不純物元素を酸化物としてスラグ中に移行させることができる。また、酸素による燃焼熱で溶湯310を加熱するための電力量を削減することができるという利点もある。 In the melting process, as shown in FIG. 3A, the metal lump 302 is put into the furnace of the electric furnace 301, and an arc discharge 303 is generated between the electrode 304 and the metal lump 302, thereby causing the metal lump 302. To make a molten metal 310. And as shown in FIG.3 (b), the peroxidation process which forms slag by blowing oxygen gas 306 into the molten metal 310 with the oxygen burner 305 is performed. Thus, by performing the peroxidation process which blows oxygen into the molten metal 310, impurity elements, such as Si, Mn, and P contained in the molten metal 310, can be transferred into the slag as oxides. There is also an advantage that the amount of electric power for heating the molten metal 310 with the combustion heat of oxygen can be reduced.
溶湯310にスラグを形成させた後、図3(c)に示すように、溶湯310を電気炉301の出湯口308から出湯して取鍋309に移す。このとき、溶湯310の液面に浮上した不純物元素を多量に含むスラグが、取鍋309に移行しないようにして溶湯310とスラグとを分離し、Si、Mn、P等の不純物元素の濃度が低下した溶湯310を得る。 After slag is formed in the molten metal 310, the molten metal 310 is discharged from the outlet 308 of the electric furnace 301 and transferred to the ladle 309 as shown in FIG. At this time, the slag containing a large amount of impurity elements floating on the liquid surface of the molten metal 310 is separated from the molten metal 310 and the slag so as not to move to the ladle 309, and the concentration of impurity elements such as Si, Mn, and P is increased. A lowered molten metal 310 is obtained.
続いて、図3(d)に示すように、溶湯310を取鍋309の底部から出湯して取鍋精錬炉311に移す。取鍋精錬炉311は、底部にポーラスプラグ313を備えており、アルゴンガス314が不図示のガス供給器からポーラスプラグ313を通じて炉内に送気されることでアルゴンバブリングが行われるようになっている。アルゴンバブリングが行われることによって、取鍋精錬炉311に移された溶湯310は、撹拌により均一化されると共に、O、N等の不純物元素が脱気されることになる。 Subsequently, as shown in FIG. 3D, the molten metal 310 is discharged from the bottom of the ladle 309 and transferred to the ladle refining furnace 311. The ladle refining furnace 311 includes a porous plug 313 at the bottom, and argon bubbling is performed when argon gas 314 is fed into the furnace through a porous plug 313 from a gas supply (not shown). Yes. By performing argon bubbling, the molten metal 310 transferred to the ladle refining furnace 311 is homogenized by stirring, and impurity elements such as O and N are degassed.
取鍋精錬炉311では、図3(e)に示すように、はじめに、溶湯310の1次加熱処理を行う。取鍋精錬炉311に移された溶湯310を、電極304でアーク放電を発生させることによって加熱すると共に、ポーラスプラグ313を通じた底吹のアルゴンバブリングを継続して行うことで、元素成分や温度を均一化させることができる。 In the ladle refining furnace 311, as shown in FIG. 3E, first, the primary heat treatment of the molten metal 310 is performed. The molten metal 310 transferred to the ladle refining furnace 311 is heated by generating an arc discharge at the electrode 304, and the bottom blowing argon bubbling through the porous plug 313 is continuously performed, so that the elemental component and temperature can be adjusted. It can be made uniform.
続いて、図3(f)に示すように、溶湯310を真空脱ガス装置316を使用して脱ガス処理する。真空脱ガス装置316は、不図示の真空ポンプが接続された排気孔317を介して装置内が減圧され、取鍋精錬炉311に対して上下に相対運動することで溶湯310を吸上して、溶湯310に含まれるガスを脱ガス処理する装置となっている。なお、図3においては、真空脱ガス装置316として、1本の浸漬管を有するDH真空脱ガス炉(Dortmund Hoerde式)を模式的に示しているが、浸漬管を備えないシュラウドで取鍋製錬炉311を覆う形態としてもよいし、RH真空脱ガス炉(Ruhrstahl Heraeus式)や、RHインジェクション炉の形態とすることも可能である。 Subsequently, as shown in FIG. 3 (f), the molten metal 310 is degassed using a vacuum degasser 316. The vacuum degassing device 316 depressurizes the inside of the device through an exhaust hole 317 connected to a vacuum pump (not shown), and sucks up the molten metal 310 by moving up and down relative to the ladle refining furnace 311. In this apparatus, the gas contained in the molten metal 310 is degassed. In addition, in FIG. 3, although the DH vacuum degassing furnace (Dortmund Hoerde type | mold) which has one dip tube is shown typically as the vacuum degassing apparatus 316, it is a ladle made with the shroud which does not have a dip tube. The smelting furnace 311 may be covered, or an RH vacuum degassing furnace (Ruhrstahl Heraeus type) or an RH injection furnace may be used.
脱ガス処理では、真空脱ガス装置316によって装置内の気相雰囲気が減圧された状態で、アルゴンバブリングを行うことによって、溶湯310から脱気された不純物元素のガスを効率的に排気させることができる。脱ガス処理の間には、溶湯310を不図示のヒータで加熱して温度の低下を防止し、溶湯310には、適宜脱硫用粉体を注入する。溶湯310をこのような脱ガス処理に供することによって、S、O、H等の不純物元素の濃度が低下した溶湯310が得られる。 In the degassing treatment, the gas of the impurity element degassed from the molten metal 310 can be efficiently exhausted by performing argon bubbling in a state where the gas-phase atmosphere in the apparatus is decompressed by the vacuum degassing apparatus 316. it can. During the degassing process, the molten metal 310 is heated by a heater (not shown) to prevent the temperature from being lowered, and desulfurization powder is appropriately injected into the molten metal 310. By subjecting the molten metal 310 to such degassing treatment, the molten metal 310 in which the concentration of impurity elements such as S, O, and H is reduced is obtained.
続いて、取鍋精錬炉311では、図3(g)に示すように、溶湯310の2次加熱処理を行う。2次加熱処理では、溶湯310の元素組成と温度とを最終調整する。 Subsequently, in the ladle refining furnace 311, as shown in FIG. 3G, secondary heat treatment of the molten metal 310 is performed. In the secondary heat treatment, the elemental composition and temperature of the molten metal 310 are finally adjusted.
続いて、図3(h)に示すように、取鍋精錬炉311の溶湯310を鋳込み処理する。溶湯310は、取鍋精錬炉311の底部から出湯してタンディッシュ318に移し、タンディッシュ318において不純物元素をスラグとして分離させる。そして、溶湯310をタンディッシュ318の底部から出湯し、真空容器319内に設置された鋳型321に注湯する。真空容器319には、排気孔320を介して不図示の真空ポンプが接続され、鋳型321が設置された容器内部が減圧雰囲気とされるようになっている。このようにして、鋳型321に注湯された溶湯310が冷却されると、任意の形状の合金塊322が鋳造される。溶湯310を減圧雰囲気で鋳込み処理することによって、N、O、H等の不純物元素の濃度が低下した合金が得られる。 Then, as shown in FIG.3 (h), the molten metal 310 of the ladle refining furnace 311 is cast-processed. The molten metal 310 is discharged from the bottom of the ladle refining furnace 311 and transferred to the tundish 318, where the impurity elements are separated as slag. Then, the molten metal 310 is discharged from the bottom of the tundish 318 and poured into a mold 321 installed in the vacuum vessel 319. A vacuum pump (not shown) is connected to the vacuum container 319 through an exhaust hole 320 so that the inside of the container in which the mold 321 is installed is in a reduced pressure atmosphere. Thus, when the molten metal 310 poured into the mold 321 is cooled, an alloy lump 322 having an arbitrary shape is cast. By casting the molten metal 310 in a reduced-pressure atmosphere, an alloy having a reduced concentration of impurity elements such as N, O, and H can be obtained.
以上のような方法によって精錬された合金は、粉末調製工程において用いられる合金粉末を調製するための地金として用いることができる。真空炭素脱酸法を利用した複合製錬によって、不純物元素の濃度が低下した清浄度が高い合金となっているため、元素組成分布の均一性が高い粒子で構成され、粒子間の元素組成の均一性も高い合金粉末を調製するのに好適である。このようにして精錬された合金の清浄度を維持させる観点からは、合金粉末を調製するにあたって、真空炭素脱酸法を利用した粉末化処理を行うのが好ましい形態となる。 The alloy refined by the method as described above can be used as a bare metal for preparing the alloy powder used in the powder preparation step. Due to complex smelting using vacuum carbon deoxidation method, it has become a highly clean alloy with reduced impurity element concentration, so it is composed of particles with a high uniformity of elemental composition distribution, It is suitable for preparing an alloy powder having high uniformity. From the viewpoint of maintaining the cleanliness of the alloy refined as described above, it is preferable to perform a pulverization process using a vacuum carbon deoxidation method in preparing the alloy powder.
真空炭素脱酸法を利用した粉末化処理は、図3(i)に示すようにガスアトマイザが直結した真空炉324を利用して行うことができる。真空炉324は、炉内でアーク放電を発生させる電極304と、炉内にアルゴンガスを吹き込む不図示のガス注入ランスと、真空ポンプが接続される不図示の排気孔とを備えた電気炉とされる。真空炉324の底部には、ノズル328が設けられており、ノズル328の下方には、アトマイズチャンバ330がノズル328の出口を気密に覆うようにして備えられている。また、ノズル328の出口脇には、ノズル328から流下する溶湯326にアルゴンガス等の不活性ガスを吹き付けるガス噴射孔329が設けられている。 The powdering process using the vacuum carbon deoxidation method can be performed using a vacuum furnace 324 directly connected to a gas atomizer as shown in FIG. The vacuum furnace 324 includes an electric furnace having an electrode 304 for generating arc discharge in the furnace, a gas injection lance (not shown) for blowing argon gas into the furnace, and an exhaust hole (not shown) to which a vacuum pump is connected. Is done. A nozzle 328 is provided at the bottom of the vacuum furnace 324, and an atomizing chamber 330 is provided below the nozzle 328 so as to cover the outlet of the nozzle 328 in an airtight manner. Further, a gas injection hole 329 for blowing an inert gas such as argon gas to the molten metal 326 flowing down from the nozzle 328 is provided on the exit side of the nozzle 328.
真空炉324では、炉内に前記の複合精錬によって得られた合金が投入され、電極304と合金との間でアーク放電を発生させることによって、合金の溶湯326が形成される。なお、加熱される溶湯326の温度は、1600℃を超え2500℃以下の温度範囲である。溶湯326は、不図示の排気孔に接続される真空ポンプによって減圧雰囲気の下で、アルゴンバブリングが行われながら脱ガス処理されて、N、O、H等の不純物元素の濃度がさらに低減される。そして、脱ガス処理されて清浄度が維持された状態の溶湯326が、ノズル328から流下する。その後、流下した溶湯328は、ガス噴射孔329から噴射される不活性ガスが吹き付けられることによって微粒子化し、アトマイズチャンバ330内で凝固して粉末331となって底部に集積する。 In the vacuum furnace 324, the alloy obtained by the above-described composite refining is put into the furnace, and arc discharge is generated between the electrode 304 and the alloy, thereby forming a molten alloy 326 of the alloy. In addition, the temperature of the molten metal 326 to be heated is in a temperature range exceeding 1600 ° C. and not more than 2500 ° C. The molten metal 326 is degassed while performing argon bubbling under a reduced pressure atmosphere by a vacuum pump connected to an exhaust hole (not shown), and the concentration of impurity elements such as N, O, and H is further reduced. . Then, the molten metal 326 that has been degassed and in which the cleanliness is maintained flows down from the nozzle 328. Thereafter, the molten metal 328 that has flowed down is turned into fine particles by spraying an inert gas injected from the gas injection holes 329, solidifies in the atomizing chamber 330, and accumulates as powder 331 at the bottom.
真空炉324は、融点が比較的高い高エントロピー合金の溶融を行えるように耐熱且つ耐火性の加熱炉とすればよく、炉壁を水冷式等としてもよい。真空炉324の炉壁としては、例えば、黒鉛(グラファイト)、石英(SiO2)、アルミナ(Al2O3)、マグネシア(MgO)、Al2O3・SiO2・Fe2O3・Na2O等の混合焼結体からなるアルミナ質セラミックス、Al2O3・SiO2・Fe2O3・TiO2等の混合焼結体からなるムライト質セラミックス、Al2O3・MgO・SiO2・CaO・Fe2O3等の混合焼結体からなるマグネシア質セラミックス、Al2O3・MgO・ZrO2・SiO2・CaO・Fe2O3・TiO2等の混合焼結体からなるジルコニア質セラミックス、Al2O3・MgO・SiO2・CaO・Fe2O3等の混合焼結体からなるスピネル質セラミックス、Al2O3・MgO・SiO2・CaO・Fe2O3等の混合焼結体からなるカルシア質セラミックス、Al2O3・SiO2・Fe2O3・TiO2等の混合焼結体からなるシリカ質セラミックス等を適用することが好ましい。特に1000℃程度以上の超高温域の溶融を行う場合には、TiC、ZrC、HfC、NbC、TaC等の炭化物によるコーティングを行うことが好ましい。 The vacuum furnace 324 may be a heat-resistant and fire-resistant heating furnace so that a high-entropy alloy having a relatively high melting point can be melted, and the furnace wall may be a water-cooled type or the like. Examples of the furnace wall of the vacuum furnace 324 include graphite (graphite), quartz (SiO 2 ), alumina (Al 2 O 3 ), magnesia (MgO), Al 2 O 3 .SiO 2 .Fe 2 O 3 .Na 2. Alumina ceramics composed of mixed sintered bodies such as O, mullite ceramics composed of mixed sintered bodies such as Al 2 O 3 · SiO 2 · Fe 2 O 3 · TiO 2 , Al 2 O 3 · MgO · SiO 2 · magnesia ceramics consisting of a mixture sintered body such as CaO · Fe 2 O 3, Al 2 O 3 · MgO · ZrO 2 · SiO 2 · CaO · Fe 2 O 3 · TiO 2 zirconia comprising a mixed sintered body such as ceramic, Al 2 O 3 · MgO · SiO 2 · CaO · Fe 2 O 3 spinel ceramics consisting of a mixture sintered body such as, Al 2 O 3 · MgO · SiO 2 · CaO · Fe 2 O 3 mixed sintered such Calci consisting of union It is preferred to apply the quality ceramics, siliceous ceramics consisting of Al 2 O 3 · SiO 2 · Fe 2 O 3 · TiO 2 mixed sintered body such as. In particular, when melting in an ultrahigh temperature range of about 1000 ° C. or higher, it is preferable to perform coating with a carbide such as TiC, ZrC, HfC, NbC, and TaC.
図4は、真空炭素脱酸法を利用して調製された合金粉末における不純物元素の濃度変化の経過の一例を示した図である。 FIG. 4 is a diagram showing an example of a change in impurity element concentration in an alloy powder prepared using a vacuum carbon deoxidation method.
図4では、前記の真空炭素脱酸法を利用して合金を精錬し、その合金を粉末化処理して合金粉末を調製する過程において、合金粉末の地金に含まれる不純物元素の濃度変化を経時的に測定して示している。なお、経過時間1.5h〜2.8hに相当するA期間は、電気炉301における過酸化処理(図3(b)参照)に相当し、経過時間2.8h〜6hに相当するB1期間は、取鍋精錬炉311における1次加熱処理(図3(e)参照)に相当し、経過時間6h〜6.5hに相当するB2期間は、取鍋精錬炉311における脱ガス処理(図3(f)参照)に相当し、経過時間6.5h〜8.2hに相当するB3期間は、取鍋精錬炉311における2次加熱処理(図3(g)参照)に相当し、経過時間8.2h以降に相当するC期間は、真空炉324における脱ガス処理(図3(i)参照)に相当している。 In FIG. 4, in the process of refining an alloy using the vacuum carbon deoxidation method and preparing the alloy powder by pulverizing the alloy, the concentration change of the impurity element contained in the metal powder is shown. It is shown as measured over time. The period A corresponding to the elapsed time 1.5 h to 2.8 h corresponds to the peroxidation treatment in the electric furnace 301 (see FIG. 3B), and the period B1 corresponding to the elapsed time 2.8 h to 6 h is , Which corresponds to the primary heat treatment in the ladle refining furnace 311 (see FIG. 3E), and during the B2 period corresponding to the elapsed time 6h to 6.5h, the degassing process in the ladle refining furnace 311 (FIG. 3 ( The period B3 corresponding to the elapsed time 6.5h to 8.2h corresponds to the secondary heat treatment in the ladle refining furnace 311 (see FIG. 3G), and the elapsed time 8. The C period corresponding to 2h or later corresponds to the degassing process in the vacuum furnace 324 (see FIG. 3 (i)).
図4に示すように、真空炭素脱酸法を利用することによって、取鍋精錬炉311において2次加熱処理まで実施すると、Cについては、0.18wt%、Siについては0.01wt%、Mnについては0.019wt%、Pについては0.001wt%、Sについては0.001wt%まで濃度が低下し、真空炉324において脱ガス処理まで実施すると、Oについては0.0003wt%(3ppm)、Nについては0.001wt%(10ppm)まで濃度が低下し得ることが分かる。このように、真空炭素脱酸法を利用して合金粉末を調製する過程で、スラグ分離の回数、脱ガス処理の時間等を適宜調整することで、P、Si、S、Sn、Sb、As、Mn、O、N等の不純物元素の濃度を所望の範囲に制限することが可能である。なお、P、Si、Sn、Sb、As又はMnの元素を非Fe主成分元素として合金構造体に含有させる場合には、精錬の過程での濃度低下を見越して地金を選定したり、スラグ分離の回数等を適宜調整したりすればよい。 As shown in FIG. 4, by using the vacuum carbon deoxidation method, when performing the secondary heat treatment in the ladle refining furnace 311, 0.18 wt% for C, 0.01 wt% for Si, Mn The concentration decreases to 0.019 wt% for P, 0.001 wt% for P, 0.001 wt% for S, and when degassing treatment is performed in the vacuum furnace 324, 0.0003 wt% (3 ppm) for O, It can be seen that the concentration of N can be reduced to 0.001 wt% (10 ppm). As described above, in the process of preparing the alloy powder using the vacuum carbon deoxidation method, the number of slag separation, the time of degassing treatment, and the like are adjusted as appropriate, so that P, Si, S, Sn, Sb, As It is possible to limit the concentration of impurity elements such as Mn, O, and N to a desired range. In addition, when the P, Si, Sn, Sb, As, or Mn element is included in the alloy structure as a non-Fe main component, the metal is selected in anticipation of a decrease in concentration during the refining process, or slag What is necessary is just to adjust the frequency | count of isolation | separation etc. suitably.
以上の本実施形態に係る合金構造体は、構造部材、機構部材等として適用することができる。積層造形可能な範囲で、任意の形状とすることができ、長さ寸法が70mmを超え、体積が5495mm3を超える任意の寸法とすることができる。常環境における用途の他、高温環境、高放射線量環境、高腐食性環境等の過酷環境における用途に用いることが可能である。また、高温下における原子拡散の速度が遅く、物性を安定して維持できることから、高温環境に長期間おかれる用途にも好適に用いることができる。より具体的には、例えば、ケーシング、配管、バルブ等を含めたプラント用構造材、発電機用構造材、原子炉用構造材、航空宇宙用構造材、油圧機器用部材、タービンブレード等を含むタービン用部材、ボイラ用部材、エンジン用部材、ノズル用部材、軸受やピストン等の各種機器の機構部材等の用途に利用することが可能である。また、本実施形態に係る合金構造体は、金属製又は合金製の構造部材、機構部材等の構造体の表面を被覆するように適用することによって、耐熱コーティング、耐腐食コーティング、耐摩耗コーティング、原子拡散の障壁となる拡散バリア層等として利用することも可能である。また、摩擦撹拌溶接(Friction Stir Welding;FSW)用加工具等の工具類にも適用することができ、高い高温強度や耐摩耗性が要求される鉄系材料の摩擦撹拌溶接を含む広い用途について好適に利用することができる。 The alloy structure according to this embodiment can be applied as a structural member, a mechanism member, or the like. As long as the layered manufacturing is possible, the shape can be any shape, and the length can be any dimension exceeding 70 mm and the volume exceeding 5495 mm 3 . In addition to applications in normal environments, it can be used in applications in severe environments such as high temperature environments, high radiation dose environments, and highly corrosive environments. Further, since the atomic diffusion rate under high temperature is slow and the physical properties can be stably maintained, it can be suitably used for applications that are left in a high temperature environment for a long time. More specifically, for example, plant structural materials including casings, piping, valves, etc., generator structural materials, nuclear reactor structural materials, aerospace structural materials, hydraulic equipment members, turbine blades, etc. It can be used for applications such as turbine members, boiler members, engine members, nozzle members, and mechanical members of various devices such as bearings and pistons. In addition, the alloy structure according to the present embodiment is applied so as to cover the surface of a structure such as a metal or alloy structural member or mechanism member, thereby providing a heat resistant coating, a corrosion resistant coating, an abrasion resistant coating, It can also be used as a diffusion barrier layer or the like serving as an atomic diffusion barrier. It can also be applied to tools such as Friction Stir Welding (FSW) processing tools, and it can be used for a wide range of applications including friction stir welding of ferrous materials that require high-temperature strength and wear resistance. It can be suitably used.
以下、本発明の実施例を用いて本発明をより詳細に説明するが、本発明の技術的範囲はこれに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using the Example of this invention, the technical scope of this invention is not limited to this.
本発明の実施例として、実施例1−1〜実施例1−4及び実施例2−1〜実施例2−3に係る合金構造体を製造し、凝固組織の観察、元素組成分布、機械的特性の評価を行った。また、実施例の対照として、比較例1−1〜比較例1−4及び比較例2−1〜比較例2−4に係る合金構造体を製造し、併せて評価を行った。 As examples of the present invention, alloy structures according to Examples 1-1 to 1-4 and Examples 2-1 to 2-3 are manufactured, and observation of solidified structure, elemental composition distribution, mechanical The characteristics were evaluated. Moreover, the alloy structure which concerns on Comparative Example 1-1-Comparative Example 1-4 and Comparative Example 2-1-Comparative Example 2-4 as a control | contrast of an Example was manufactured, and also evaluated.
[実施例1−1]
実施例1−1として、元素組成がAl0.3CoCrFeNiで表わされる合金構造体を積層造形により製造した。原子濃度比率は、Alの原子濃度が約7at%、Co、Cr、Fe及びNiの原子濃度が約23.3at%である。
[Example 1-1]
As Example 1-1, an alloy structure whose element composition is represented by Al 0.3 CoCrFeNi was manufactured by additive manufacturing. The atomic concentration ratio is such that the atomic concentration of Al is about 7 at%, and the atomic concentrations of Co, Cr, Fe, and Ni are about 23.3 at%.
はじめに、Alの原子濃度が約7at%、Co、Cr、Fe及びNiの原子濃度が約23.3at%である合金を地金として用いて、ガスアトマイズ法によって、合金粉末を調製した。そして、得られた合金粉末を分級し、粒子径分布を50μm以上100μm以下の範囲に限定すると共に、体積基準の平均粒子径が約70μmとなるようにした。 First, an alloy powder was prepared by a gas atomizing method using an alloy having an atomic concentration of Al of about 7 at% and an atomic concentration of Co, Cr, Fe, and Ni of about 23.3 at% as a bare metal. The obtained alloy powder was classified so that the particle size distribution was limited to a range of 50 μm or more and 100 μm or less, and the volume-based average particle size was about 70 μm.
続いて、積層造形装置を使用して、基材上に合金構造体を造形した。基材としては、100mm×100mm×10mmの板状の機械構造用炭素鋼「S45C」を用いた。また、積層造形装置としては、熱源を電子ビームとした電子ビーム溶融積層造形装置「A2X」(Arcam社製)を使用した。積層造形装置では、真空雰囲気下において、基材上に、粉末展延工程及び凝固層造形工程を繰り返し行うことによって、直径10mm、高さ50mmの円柱形状の合金構造体を製造した。このとき、合金粉末の溶融は、合金の融点(Tm)の50%から80%の温度の予備加熱を事前に行いながら実施し、展延された合金粉末の飛散を抑制した。その後、合金構造体を基材から切り離した。 Subsequently, an alloy structure was modeled on the base material using an additive manufacturing apparatus. As the base material, a plate-like carbon steel for mechanical structure “S45C” of 100 mm × 100 mm × 10 mm was used. Further, as the additive manufacturing apparatus, an electron beam melt additive manufacturing apparatus “A2X” (manufactured by Arcam) using an electron beam as a heat source was used. In the layered manufacturing apparatus, a cylindrical alloy structure having a diameter of 10 mm and a height of 50 mm was manufactured by repeatedly performing a powder spreading process and a solidified layer modeling process on a base material in a vacuum atmosphere. At this time, the melting of the alloy powder was performed while preheating at a temperature of 50% to 80% of the melting point (Tm) of the alloy was performed in advance to suppress the spread of the spread alloy powder. Thereafter, the alloy structure was separated from the substrate.
[実施例1−2]
実施例1−2として、元素組成がAlCoCrFeNiで表わされる合金構造体を積層造形により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。
[Example 1-2]
As Example 1-2, an alloy structure having an element composition represented by AlCoCrFeNi was manufactured by additive manufacturing. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%.
実施例1−2に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例1−1と同様にして製造した。 The alloy structure according to Example 1-2 was manufactured in the same manner as Example 1-1 except that the composition of the metal used for preparing the alloy powder was changed.
[比較例1−1]
比較例1−1として、元素組成がAl0.3CoCrFeNiで表わされる合金構造体を鋳造により製造した。原子濃度比率は、Alの原子濃度が約7at%、Co、Cr、Fe及びNiの原子濃度が約23.3at%である。
[Comparative Example 1-1]
As Comparative Example 1-1, an alloy structure having an elemental composition represented by Al 0.3 CoCrFeNi was manufactured by casting. The atomic concentration ratio is such that the atomic concentration of Al is about 7 at%, and the atomic concentrations of Co, Cr, Fe, and Ni are about 23.3 at%.
はじめに、Alの原子濃度が約7at%、Co、Cr、Fe及びNiの原子濃度が約23.3at%である合金を地金として用いて、ガスアトマイズ法によって、合金粉末を調製した。そして、得られた合金粉末を分級し、粒子径分布を50μm以上100μm以下の範囲に限定すると共に、体積基準の平均粒子径が約70μmとなるようにした。 First, an alloy powder was prepared by a gas atomizing method using an alloy having an atomic concentration of Al of about 7 at% and an atomic concentration of Co, Cr, Fe, and Ni of about 23.3 at% as a bare metal. The obtained alloy powder was classified so that the particle size distribution was limited to a range of 50 μm or more and 100 μm or less, and the volume-based average particle size was about 70 μm.
続いて、得られた合金粉末を、アルミナ製の坩堝に投入し、真空雰囲気下において、高周波誘導加熱によって溶解させた後、銅製の水冷鋳型に注湯し、冷却して凝固させることによって、直径10mm、高さ50mmの円柱形状の合金構造体を製造した。 Subsequently, the obtained alloy powder was put into an alumina crucible, dissolved in a vacuum atmosphere by high frequency induction heating, poured into a copper water-cooled mold, cooled and solidified to obtain a diameter. A cylindrical alloy structure having a size of 10 mm and a height of 50 mm was manufactured.
[比較例1−2]
比較例1−2として、元素組成がAl0.2CoCrFeNiで表わされる合金構造体を積層造形により製造した。原子濃度比率は、Alの原子濃度が約4.8at%、Co、Cr、Fe及びNiの原子濃度が約23.8at%である。
[Comparative Example 1-2]
As Comparative Example 1-2, an alloy structure having an element composition represented by Al 0.2 CoCrFeNi was manufactured by additive manufacturing. The atomic concentration ratio is such that the atomic concentration of Al is about 4.8 at%, and the atomic concentrations of Co, Cr, Fe, and Ni are about 23.8 at%.
比較例1−2に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例1−1と同様にして製造した。 The alloy structure according to Comparative Example 1-2 was manufactured in the same manner as in Example 1-1 except that the composition of the metal used for preparing the alloy powder was changed.
[実施例1−3]
実施例1−3として、元素組成がAl1.5CoCrFeNiで表わされる合金構造体を積層造形により製造した。原子濃度比率は、Alの原子濃度が約27.2at%、Co、Cr、Fe及びNiの原子濃度が約18.2at%である。
[Example 1-3]
As Example 1-3, an alloy structure having an element composition represented by Al 1.5 CoCrFeNi was manufactured by additive manufacturing. The atomic concentration ratio is such that the atomic concentration of Al is about 27.2 at%, and the atomic concentrations of Co, Cr, Fe, and Ni are about 18.2 at%.
はじめに、Alの原子濃度が約27.2at%、Co、Cr、Fe及びNiの原子濃度が約18.2at%である合金を地金として用いて、ガスアトマイズ法によって、合金粉末を調製した。そして、得られた合金粉末を分級し、粒子径分布を20μm以上50μm以下の範囲に限定すると共に、体積基準の平均粒子径が約30μmとなるようにした。 First, an alloy powder was prepared by a gas atomization method using an alloy having an atomic concentration of Al of about 27.2 at% and an atomic concentration of Co, Cr, Fe, and Ni of about 18.2 at% as a bare metal. The obtained alloy powder was classified so that the particle size distribution was limited to a range of 20 μm or more and 50 μm or less, and the volume-based average particle size was about 30 μm.
続いて、積層造形装置を使用して、基材上に合金材を造形した。基材としては、直径10mm、高さ50mmの円柱形状の機械構造用炭素鋼「S45C」を用いた。また、積層造形装置としては、熱源をレーザー光としたレーザー溶融積層造形装置「EOSINT M270」(EOS社製)を使用した。積層造形装置では、窒素雰囲気下において、基材上に、粉末展延工程及び凝固層造形工程を繰り返し行うことによって、200μmの多層膜状の合金材を製造した。 Subsequently, an alloy material was modeled on the base material using an additive manufacturing apparatus. As a base material, carbon steel “S45C” having a diameter of 10 mm and a height of 50 mm and having a cylindrical shape for mechanical structure was used. Further, as the additive manufacturing apparatus, a laser melt additive manufacturing apparatus “EOSINT M270” (manufactured by EOS) using a laser beam as a heat source was used. In the layered modeling apparatus, a 200 μm multilayer alloy material was manufactured by repeatedly performing a powder spreading process and a solidified layer modeling process on a substrate in a nitrogen atmosphere.
[比較例1−3]
比較例1−3として、元素組成がAlCoCrFeNiで表わされる合金構造体を溶射により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。
[Comparative Example 1-3]
As Comparative Example 1-3, an alloy structure having an element composition represented by AlCoCrFeNi was manufactured by thermal spraying. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%.
はじめに、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%となるように、Al、Co、Cr、Fe及びNiの各金属粉を混合した。なお、各金属粉は分級し、粒子径分布を50μm以上150μm以下の範囲に限定すると共に、体積基準の平均粒子径が約70μmとなるようにした。 First, each metal powder of Al, Co, Cr, Fe, and Ni was mixed so that the atomic concentration of Al, Co, Cr, Fe, and Ni was about 20.0 at%. Each metal powder was classified so that the particle size distribution was limited to the range of 50 μm or more and 150 μm or less, and the volume-based average particle size was about 70 μm.
続いて、混合した金属粉末を、窒素雰囲気下において、基材上に、プラズマ溶射法によって溶射することによって、200μmの膜状の合金構造体を製造した。基材としては、直径100mm、高さ10mmの円柱形状の機械構造用炭素鋼「S45C」を用いた。 Subsequently, the mixed metal powder was sprayed on a base material by a plasma spraying method in a nitrogen atmosphere to produce a 200 μm film-like alloy structure. As the base material, a carbon steel “S45C” having a diameter of 100 mm and a height of 10 mm and having a cylindrical shape for mechanical structure was used.
[比較例1−4]
比較例1−4として、元素組成がAl2.0CoCrFeNiで表わされる合金構造体を積層造形により製造した。原子濃度比率は、Alの原子濃度が約33.3at%、Co、Cr、Fe及びNiの原子濃度が約16.7at%である。
[Comparative Example 1-4]
As Comparative Example 1-4, an alloy structure having an elemental composition represented by Al 2.0 CoCrFeNi was manufactured by additive manufacturing. The atomic concentration ratio is such that the atomic concentration of Al is about 33.3 at%, and the atomic concentrations of Co, Cr, Fe, and Ni are about 16.7 at%.
比較例1−4に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例1−2と同様にして製造した。 The alloy structure according to Comparative Example 1-4 was manufactured in the same manner as in Example 1-2, except that the composition of the metal used for preparing the alloy powder was changed.
[実施例1−4]
実施例1−4として、元素組成がAlCoCrFeNiMo0.5で表わされる合金構造体を積層造形により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約18.2at%、Moの原子濃度が約9.1at%である。
[Example 1-4]
As Example 1-4, an alloy structure having an element composition represented by AlCoCrFeNiMo 0.5 was manufactured by additive manufacturing. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 18.2 at%, and the atomic concentration of Mo is about 9.1 at%.
はじめに、Al、Co、Cr、Fe及びNiの原子濃度が約18.2at%、Moの原子濃度が約9.1at%である合金を地金として用いて、ガスアトマイズ法によって、合金粉末を調製した。そして、得られた合金粉末を分級し、粒子径分布を50μm以上100μm以下の範囲に限定すると共に、体積基準の平均粒子径が約70μmとなるようにした。 First, an alloy powder was prepared by a gas atomization method using an alloy having an atomic concentration of Al, Co, Cr, Fe, and Ni of about 18.2 at% and an atomic concentration of Mo of about 9.1 at% as a bare metal. . The obtained alloy powder was classified so that the particle size distribution was limited to a range of 50 μm or more and 100 μm or less, and the volume-based average particle size was about 70 μm.
続いて、積層造形装置を使用して、基材上に合金構造体を造形した。基材としては、直径300mm、高さ10mmの円柱形状の機械構造用炭素鋼「S45C」を用いた。また、積層造形装置としては、熱源を電子ビームとした電子ビーム溶融積層造形装置「A2X」(Arcam社製)を使用した。積層造形装置では、真空雰囲気下において、基材上に、粉末展延工程及び凝固層造形工程を繰り返し行うことによって、直径300mm、高さ100mmの略円柱の羽根車形状の合金構造体を製造した。このとき、合金粉末の溶融は、合金の融点(Tm)の50%から80%の温度の予備加熱を事前に行いながら実施し、展延された合金粉末の飛散を抑制した。その後、羽根車形状の合金構造体を基材から切り離した。 Subsequently, an alloy structure was modeled on the base material using an additive manufacturing apparatus. As the base material, a carbon steel for structural use “S45C” having a diameter of 300 mm and a height of 10 mm was used. Further, as the additive manufacturing apparatus, an electron beam melt additive manufacturing apparatus “A2X” (manufactured by Arcam) using an electron beam as a heat source was used. In the additive manufacturing apparatus, an approximately cylindrical impeller-shaped alloy structure having a diameter of 300 mm and a height of 100 mm was manufactured by repeatedly performing a powder spreading process and a solidified layer forming process on a base material in a vacuum atmosphere. . At this time, the melting of the alloy powder was performed while preheating at a temperature of 50% to 80% of the melting point (Tm) of the alloy was performed in advance to suppress the spread of the spread alloy powder. Thereafter, the impeller-shaped alloy structure was cut off from the base material.
[実施例2−1]
実施例2−1として、元素組成がAl0.3CoCrFeNiで表わされ、不可避的不純物の濃度を制限した合金構造体を積層造形により製造した。原子濃度比率は、Alの原子濃度が約7at%、Co、Cr、Fe及びNiの原子濃度が約23.3at%である。また、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した。
[Example 2-1]
As Example 2-1, an alloy structure in which the elemental composition was expressed by Al 0.3 CoCrFeNi and the concentration of inevitable impurities was limited was manufactured by additive manufacturing. The atomic concentration ratio is such that the atomic concentration of Al is about 7 at%, and the atomic concentrations of Co, Cr, Fe, and Ni are about 23.3 at%. Further, the P concentration is 0.002 wt% or less, the Si concentration is 0.010 wt% or less, the S concentration is 0.001 wt% or less, the Sn concentration is 0.002 wt% or less, and the Sb concentration is 0.001 wt%. Hereinafter, the As concentration was limited to 0.001 wt% or less, the Mn concentration was 0.020 wt% or less, the O concentration was 0.0003 wt% or less, and the N concentration was 0.001 wt% or less.
実施例2−1に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例1−1と同様にして製造した。 The alloy structure according to Example 2-1 was manufactured in the same manner as in Example 1-1 except that the composition of the metal used for preparing the alloy powder was changed.
[実施例2−2]
実施例2−2として、元素組成がAlCoCrFeNiで表わされ、不可避的不純物の濃度を制限した合金構造体を積層造形により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。また、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した。
[Example 2-2]
As Example 2-2, an alloy structure in which the elemental composition is expressed by AlCoCrFeNi and the concentration of inevitable impurities is limited is manufactured by additive manufacturing. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%. Further, the P concentration is 0.002 wt% or less, the Si concentration is 0.010 wt% or less, the S concentration is 0.001 wt% or less, the Sn concentration is 0.002 wt% or less, and the Sb concentration is 0.001 wt%. Hereinafter, the As concentration was limited to 0.001 wt% or less, the Mn concentration was 0.020 wt% or less, the O concentration was 0.0003 wt% or less, and the N concentration was 0.001 wt% or less.
実施例2−2に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例1−1と同様にして製造した。 The alloy structure according to Example 2-2 was manufactured in the same manner as in Example 1-1 except that the composition of the metal used for preparing the alloy powder was changed.
[比較例2−1]
比較例2−1として、元素組成がAlCoCrFeNiで表わされ、不可避的不純物の濃度を制限した合金構造体を鋳造により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。また、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した。
[Comparative Example 2-1]
As Comparative Example 2-1, an alloy structure having an element composition represented by AlCoCrFeNi and limiting the concentration of inevitable impurities was manufactured by casting. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%. Further, the P concentration is 0.002 wt% or less, the Si concentration is 0.010 wt% or less, the S concentration is 0.001 wt% or less, the Sn concentration is 0.002 wt% or less, and the Sb concentration is 0.001 wt%. Hereinafter, the As concentration was limited to 0.001 wt% or less, the Mn concentration was 0.020 wt% or less, the O concentration was 0.0003 wt% or less, and the N concentration was 0.001 wt% or less.
比較例2−1に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、比較例1−1と同様にして製造した。 The alloy structure according to Comparative Example 2-1 was manufactured in the same manner as Comparative Example 1-1 except that the composition of the metal used for preparing the alloy powder was changed.
[比較例2−2]
比較例2−2として、元素組成がAl0.2CoCrFeNiで表わされ、不可避的不純物の濃度を制限した合金構造体を鋳造により製造した。原子濃度比率は、Alの原子濃度が約4.8at%、Co、Cr、Fe及びNiの原子濃度が約23.8at%である。また、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した。
[Comparative Example 2-2]
As Comparative Example 2-2, an alloy structure having an elemental composition represented by Al 0.2 CoCrFeNi and limiting the concentration of inevitable impurities was manufactured by casting. The atomic concentration ratio is such that the atomic concentration of Al is about 4.8 at%, and the atomic concentrations of Co, Cr, Fe, and Ni are about 23.8 at%. Further, the P concentration is 0.002 wt% or less, the Si concentration is 0.010 wt% or less, the S concentration is 0.001 wt% or less, the Sn concentration is 0.002 wt% or less, and the Sb concentration is 0.001 wt%. Hereinafter, the As concentration was limited to 0.001 wt% or less, the Mn concentration was 0.020 wt% or less, the O concentration was 0.0003 wt% or less, and the N concentration was 0.001 wt% or less.
比較例2−2に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例1−1と同様にして製造した。 The alloy structure according to Comparative Example 2-2 was manufactured in the same manner as Example 1-1, except that the composition of the metal used for preparing the alloy powder was changed.
[実施例2−3]
実施例2−3として、元素組成がAl1.5CoCrFeNiで表わされ、不可避的不純物の濃度を制限した合金構造体を積層造形により製造した。原子濃度比率は、Alの原子濃度が約27.2at%、Co、Cr、Fe及びNiの原子濃度が約18.2at%である。また、Pの濃度を0.005wt%以下、Siの濃度を0.040wt%以下、Sの濃度を0.002wt%以下、Snの濃度を0.005wt%以下、Sbの濃度を0.002wt%以下、Asの濃度を0.005wt%以下、Mnの濃度を0.050wt%以下、Oの濃度を0.001wt%以下、Nの濃度を0.002wt%以下に制限した。
[Example 2-3]
As Example 2-3, an alloy structure in which the elemental composition is expressed by Al 1.5 CoCrFeNi and the concentration of inevitable impurities is limited is manufactured by additive manufacturing. The atomic concentration ratio is such that the atomic concentration of Al is about 27.2 at%, and the atomic concentrations of Co, Cr, Fe, and Ni are about 18.2 at%. Further, the P concentration is 0.005 wt% or less, the Si concentration is 0.040 wt% or less, the S concentration is 0.002 wt% or less, the Sn concentration is 0.005 wt% or less, and the Sb concentration is 0.002 wt%. Hereinafter, the As concentration was limited to 0.005 wt% or less, the Mn concentration was 0.050 wt% or less, the O concentration was 0.001 wt% or less, and the N concentration was 0.002 wt% or less.
はじめに、Alの原子濃度が約27.2at%、Co、Cr、Fe及びNiの原子濃度が約18.2at%であり、Pの濃度を0.005wt%以下、Siの濃度を0.040wt%以下、Sの濃度を0.002wt%以下、Snの濃度を0.005wt%以下、Sbの濃度を0.002wt%以下、Asの濃度を0.005wt%以下、Mnの濃度を0.050wt%以下、Oの濃度を0.001wt%以下、Nの濃度を0.002wt%以下に制限した合金を地金として用いて、ガスアトマイズ法によって、合金粉末を調製した。そして、得られた合金粉末を分級し、粒子径分布を20μm以上50μm以下の範囲に限定すると共に、体積基準の平均粒子径が約30μmとなるようにした。 First, the atomic concentration of Al is about 27.2 at%, the atomic concentration of Co, Cr, Fe and Ni is about 18.2 at%, the P concentration is 0.005 wt% or less, and the Si concentration is 0.040 wt%. Hereinafter, the S concentration is 0.002 wt% or less, the Sn concentration is 0.005 wt% or less, the Sb concentration is 0.002 wt% or less, the As concentration is 0.005 wt% or less, and the Mn concentration is 0.050 wt%. Hereinafter, an alloy powder was prepared by a gas atomization method using an alloy in which the concentration of O was limited to 0.001 wt% or less and the concentration of N was limited to 0.002 wt% or less as a bare metal. The obtained alloy powder was classified so that the particle size distribution was limited to a range of 20 μm or more and 50 μm or less, and the volume-based average particle size was about 30 μm.
続いて、積層造形装置を使用して、基材上に合金材を造形した。基材としては、直径100mm、高さ10mmの円柱形状の機械構造用炭素鋼「S45C」を用いた。また、積層造形装置としては、熱源をレーザー光としたレーザー溶融積層造形装置「EOSINT M270」(EOS社製)を使用した。積層造形装置では、窒素雰囲気下において、基材上に、粉末展延工程及び凝固層造形工程を繰り返し行うことによって、200μmの多層膜状の合金材を製造した。 Subsequently, an alloy material was modeled on the base material using an additive manufacturing apparatus. As the base material, a carbon steel “S45C” having a diameter of 100 mm and a height of 10 mm and having a cylindrical shape for mechanical structure was used. Further, as the additive manufacturing apparatus, a laser melt additive manufacturing apparatus “EOSINT M270” (manufactured by EOS) using a laser beam as a heat source was used. In the layered modeling apparatus, a 200 μm multilayer alloy material was manufactured by repeatedly performing a powder spreading process and a solidified layer modeling process on a substrate in a nitrogen atmosphere.
[比較例2−3]
比較例2−3として、元素組成がAlCoCrFeNiで表わされ、不可避的不純物の濃度を制限した合金構造体を溶射により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。また、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した。
[Comparative Example 2-3]
As Comparative Example 2-3, an alloy structure having an element composition represented by AlCoCrFeNi and limiting the concentration of inevitable impurities was manufactured by thermal spraying. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%. Further, the P concentration is 0.002 wt% or less, the Si concentration is 0.010 wt% or less, the S concentration is 0.001 wt% or less, the Sn concentration is 0.002 wt% or less, and the Sb concentration is 0.001 wt%. Hereinafter, the As concentration was limited to 0.001 wt% or less, the Mn concentration was 0.020 wt% or less, the O concentration was 0.0003 wt% or less, and the N concentration was 0.001 wt% or less.
はじめに、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%となり、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した、Al、Co、Cr、Fe及びNiの各金属粉を混合した。なお、各金属粉は分級し、粒子径分布を50μm以上150μm以下の範囲に限定すると共に、体積基準の平均粒子径が約70μmとなるようにした。 First, the atomic concentration of Al, Co, Cr, Fe, and Ni is about 20.0 at%, the P concentration is 0.002 wt% or less, the Si concentration is 0.010 wt% or less, and the S concentration is 0.001 wt%. Hereinafter, the Sn concentration is 0.002 wt% or less, the Sb concentration is 0.001 wt% or less, the As concentration is 0.001 wt% or less, the Mn concentration is 0.020 wt% or less, and the O concentration is 0.0003 wt%. Hereafter, each metal powder of Al, Co, Cr, Fe, and Ni in which the concentration of N was limited to 0.001 wt% or less was mixed. Each metal powder was classified so that the particle size distribution was limited to the range of 50 μm or more and 150 μm or less, and the volume-based average particle size was about 70 μm.
続いて、混合した金属粉末を、窒素雰囲気下において、基材上に、プラズマ溶射法によって溶射することによって、200μmの膜状の合金構造体を製造した。基材としては、直径100mm、高さ10mmの円柱形状の機械構造用炭素鋼「S45C」を用いた。 Subsequently, the mixed metal powder was sprayed on a base material by a plasma spraying method in a nitrogen atmosphere to produce a 200 μm film-like alloy structure. As the base material, a carbon steel “S45C” having a diameter of 100 mm and a height of 10 mm and having a cylindrical shape for mechanical structure was used.
[比較例2−4]
比較例2−4として、元素組成がAl2.0CoCrFeNiで表わされ、不可避的不純物の濃度を制限した合金構造体を積層造形により製造した。原子濃度比率は、Alの原子濃度が約33.3at%、Co、Cr、Fe及びNiの原子濃度が約16.7at%である。また、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した。
[Comparative Example 2-4]
As Comparative Example 2-4, an alloy structure in which the elemental composition was expressed by Al 2.0 CoCrFeNi and the concentration of inevitable impurities was limited was manufactured by additive manufacturing. The atomic concentration ratio is such that the atomic concentration of Al is about 33.3 at%, and the atomic concentrations of Co, Cr, Fe, and Ni are about 16.7 at%. Further, the P concentration is 0.002 wt% or less, the Si concentration is 0.010 wt% or less, the S concentration is 0.001 wt% or less, the Sn concentration is 0.002 wt% or less, and the Sb concentration is 0.001 wt%. Hereinafter, the As concentration was limited to 0.001 wt% or less, the Mn concentration was 0.020 wt% or less, the O concentration was 0.0003 wt% or less, and the N concentration was 0.001 wt% or less.
比較例2−4に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例2−2と同様にして製造した。 The alloy structure according to Comparative Example 2-4 was manufactured in the same manner as Example 2-2 except that the composition of the metal used for preparing the alloy powder was changed.
次に、製造した実施例1−1〜実施例1−4及び実施例2−1〜実施例2−3に係る合金構造体、及び、比較例1−1〜比較例1−4及び比較例2−1〜比較例2−4に係る合金構造体について、凝固組織の観察、ニッケル濃度分布の解析、硬度測定を行った。なお、凝固組織の観察は、高分解能の透過型電子顕微鏡によって、結晶構造と平均結晶粒径を確認することによって行った。また、ニッケル濃度分布の解析は、走査型電子顕微鏡−エネルギー分散型X線分光(Scanning Electron Microscope - Energy Dispersive X-ray Detector;SEM−EDX)によって、任意に抽出した10箇所の領域についてニッケル濃度を計測することによって行った。また、硬度測定は、合金材の任意に抽出した10点についてビッカース硬度(Hv)を計測することによって行った。試験荷重は100gfとし、保持時間は10秒とした。 Next, the manufactured alloy structures according to Example 1-1 to Example 1-4 and Example 2-1 to Example 2-3, and Comparative Example 1-1 to Comparative Example 1-4 and Comparative Example The alloy structure according to 2-1 to Comparative Example 2-4 was subjected to observation of a solidified structure, analysis of nickel concentration distribution, and hardness measurement. The solidified structure was observed by confirming the crystal structure and average crystal grain size with a high-resolution transmission electron microscope. In addition, the nickel concentration distribution is analyzed by using a scanning electron microscope-energy dispersive X-ray detector (SEM-EDX) to determine the nickel concentration of 10 regions arbitrarily extracted. Done by measuring. Moreover, the hardness measurement was performed by measuring Vickers hardness (Hv) about 10 points | pieces extracted arbitrarily of the alloy material. The test load was 100 gf and the holding time was 10 seconds.
凝固組織の観察、ニッケル濃度分布の解析、硬度測定の結果を表1に示す。表1において元素組成の欄は、主成分元素と添加元素の原子濃度比を示している。また、不純物の欄は、「±」が不可避的不純物を制限していない例、「−」が不可避的不純物をやや制限した例、「−−」が不可避的不純物をより制限した例を示している。また、「結晶構造」の欄は、主晶の結晶構造を示している。「硬度」の欄における「*」は、割れが生じたことを示している。 Table 1 shows the results of observation of solidified structure, analysis of nickel concentration distribution, and hardness measurement. In Table 1, the element composition column indicates the atomic concentration ratio between the main component element and the additive element. In the impurity column, “±” indicates an example in which inevitable impurities are not restricted, “−” indicates an example in which inevitable impurities are somewhat restricted, and “−−” indicates an example in which inevitable impurities are more restricted. Yes. The column “Crystal structure” indicates the crystal structure of the main crystal. “*” In the “Hardness” column indicates that a crack occurred.
表1に示されるように、実施例1−1〜実施例1−4及び実施例2−1〜実施例2−3に係る合金構造体は、面心立方格子の結晶構造又は体心立方格子の結晶構造のいずれかを有していることが確認された。また、ニッケル濃度分布及び硬度の値からは、標準偏差が小さく、元素組成及び機械的強度の分布の均一性が高いことが分かる。また、凝固組織の観察からは、図2(a)及び(b)に示されるような凝固組織と結晶構造とが確認された。羽根車形状とした実施例1−4に係る合金構造体については、塩水(人工海水)腐食試験時における腐食減肉量が、オーステナイト系ステンレス鋼(SUS304)よりも抑制されることが別途確認され、耐腐食用構造部材、耐腐食用機構部材等として好適であることも確認された。 As shown in Table 1, the alloy structures according to Example 1-1 to Example 1-4 and Example 2-1 to Example 2-3 have a face-centered cubic lattice crystal structure or a body-centered cubic lattice. It was confirmed to have any one of the following crystal structures. Moreover, it can be seen from the nickel concentration distribution and hardness values that the standard deviation is small and the uniformity of the distribution of elemental composition and mechanical strength is high. Further, from the observation of the solidified structure, a solidified structure and a crystal structure as shown in FIGS. 2A and 2B were confirmed. For the alloy structure according to Example 1-4 having an impeller shape, it was separately confirmed that the amount of corrosion thinning during the salt water (artificial seawater) corrosion test is suppressed more than that of austenitic stainless steel (SUS304). It was also confirmed that it is suitable as a corrosion-resistant structural member, a corrosion-resistant mechanism member, and the like.
これに対して、比較例1−1〜比較例1−4及び比較例2−1〜比較例2−4に係る合金構造体は、ニッケル濃度分布及び硬度の値は、標準偏差が大きく、元素組成及び機械的強度の分布の均一性は低いことが分かる。また、結晶構造は、元素組成の均一性の低さが反映されて、複相組織が形成されていることが認められた。特に、Alの原子濃度を低下させると、硬度が軟鋼よりも低い値に留まり、構造部材、機構部材等として不適であることが判明した。また、Alの原子濃度を増大させると、B2型金属間化合物が生じ、試験時において割れが生じてしまい、構造部材、機構部材等として不適であることが判明した。 On the other hand, the alloy structures according to Comparative Example 1-1 to Comparative Example 1-4 and Comparative Example 2-1 to Comparative Example 2-4 have a large standard deviation in the nickel concentration distribution and hardness values. It can be seen that the uniformity of composition and mechanical strength distribution is low. In addition, it was recognized that the crystal structure reflects the low uniformity of the elemental composition and a multiphase structure is formed. In particular, when the atomic concentration of Al is lowered, it has been found that the hardness remains lower than that of mild steel and is unsuitable as a structural member, a mechanism member, or the like. Further, when the atomic concentration of Al was increased, a B2 type intermetallic compound was formed, and cracks were generated during the test, which proved unsuitable as a structural member, a mechanism member, or the like.
一般に、構造部材、機構部材等においては、熱劣化、摩耗、腐食等が、耐性が低い領域を起点として進展するため、圧延等を考慮すると構造部材、機構部材等においては硬度と延性を両立することが望まれるといえる。また、これらの性質の偏差も極小化されることが求められるといえる。このような観点からは、実施例1−1〜実施例1−4及び実施例2−1〜実施例2−3に係る合金構造体と比較例1−1〜比較例1−4及び比較例2−1〜比較例2−4に係る合金構造体との結果から、本発明が有する元素組成及び機械的強度の分布の均一性が、構造部材、機構部材等の特性を向上させる場合において極めて有利に働くことが確認できたといえる。 In general, in structural members, mechanism members, etc., heat deterioration, wear, corrosion, etc. progress from a low-resistance region, so considering rolling, etc., both structural members, mechanism members, etc. have both hardness and ductility. It can be said that it is desirable. It can also be said that the deviation of these properties is required to be minimized. From such a viewpoint, the alloy structures according to Example 1-1 to Example 1-4 and Example 2-1 to Example 2-3, Comparative Example 1-1 to Comparative Example 1-4, and Comparative Example From the results with the alloy structure according to 2-1 to Comparative Example 2-4, the uniformity of the distribution of the elemental composition and the mechanical strength of the present invention is extremely high when the characteristics of the structural member, the mechanism member, and the like are improved. It can be said that it was confirmed that it works favorably.
次に、本発明の実施例として、実施例3−1及び実施例3−2に係る合金構造体を製造し、応力−歪特性の評価を行った。 Next, as examples of the present invention, alloy structures according to Example 3-1 and Example 3-2 were manufactured, and stress-strain characteristics were evaluated.
図5は、実施例3に係る合金構造体の形状寸法を示す図である。 FIG. 5 is a diagram showing the shape and dimensions of the alloy structure according to Example 3.
[実施例3−1]
実施例3−1として、元素組成がAlCoCrFeNiで表わされ、不可避的不純物の濃度を制限した図5に示す合金構造体を積層造形により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。また、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した。
[Example 3-1]
As Example 3-1, the alloy structure shown in FIG. 5 in which the elemental composition was expressed by AlCoCrFeNi and the concentration of inevitable impurities was limited was manufactured by additive manufacturing. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%. Further, the P concentration is 0.002 wt% or less, the Si concentration is 0.010 wt% or less, the S concentration is 0.001 wt% or less, the Sn concentration is 0.002 wt% or less, and the Sb concentration is 0.001 wt%. Hereinafter, the As concentration was limited to 0.001 wt% or less, the Mn concentration was 0.020 wt% or less, the O concentration was 0.0003 wt% or less, and the N concentration was 0.001 wt% or less.
はじめに、Alの原子濃度が約7at%、Co、Cr、Fe及びNiの原子濃度が約23.3at%であり、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した合金を地金として用いて、ガスアトマイズ法によって、合金粉末を調製した。そして、得られた合金粉末を分級し、粒子径分布を45μm以上105μm以下の範囲に限定すると共に、体積基準の平均粒子径が約70μmとなるようにした。 First, the atomic concentration of Al is about 7 at%, the atomic concentration of Co, Cr, Fe and Ni is about 23.3 at%, the concentration of P is 0.002 wt% or less, the concentration of Si is 0.010 wt% or less, S concentration is 0.001 wt% or less, Sn concentration is 0.002 wt% or less, Sb concentration is 0.001 wt% or less, As concentration is 0.001 wt% or less, Mn concentration is 0.020 wt% or less, An alloy powder was prepared by a gas atomization method using an alloy in which the concentration of O was limited to 0.0003 wt% or less and the concentration of N was limited to 0.001 wt% or less as a bare metal. The obtained alloy powder was classified so that the particle size distribution was limited to a range of 45 μm or more and 105 μm or less, and the volume-based average particle size was about 70 μm.
続いて、積層造形装置を使用して、基材上に合金材を造形した。基材としては、200mm×200mm×10mmの板状の機械構造用炭素鋼「S45C」を用いた。また、積層造形装置としては、熱源を電子ビームとした電子ビーム溶融積層造形装置「A2X」(Arcam社製)を使用した。積層造形装置では、真空雰囲気下において、基材上に、粉末展延工程及び凝固層造形工程を繰り返し行うことによって、図5に示すように、150mm×150mm×30mmの板状造形物(板状部)を形成し、その上に28mm×28mm×20mmの直方体造形物(直方体部)を縦横6mmの間隔を空けて計16個造形した。このとき、合金粉末の溶融は、合金粉末の融点(Tm)の50%から80%の温度の予備加熱を事前に行いながら実施し、展延された合金粉末の飛散を抑制した。なお、造形物全体の体積は、925880mm3であった。 Subsequently, an alloy material was modeled on the base material using an additive manufacturing apparatus. As the substrate, a plate-like carbon steel for mechanical structure “S45C” of 200 mm × 200 mm × 10 mm was used. Further, as the additive manufacturing apparatus, an electron beam melt additive manufacturing apparatus “A2X” (manufactured by Arcam) using an electron beam as a heat source was used. In the layered manufacturing apparatus, by repeatedly performing the powder spreading process and the solidified layer modeling process on a base material in a vacuum atmosphere, as shown in FIG. 5, a plate-shaped model (plate shape) of 150 mm × 150 mm × 30 mm is used. Part) was formed, and a total of 16 cuboid shaped objects (cuboid parts) of 28 mm × 28 mm × 20 mm were formed at intervals of 6 mm in length and width. At this time, the melting of the alloy powder was performed while preheating at a temperature of 50% to 80% of the melting point (Tm) of the alloy powder was performed in advance, and scattering of the spread alloy powder was suppressed. In addition, the volume of the whole molded article was 925880 mm 3 .
[実施例3−2]
実施例3−2として、元素組成がAlCoCrFeNiで表わされ、不可避的不純物の濃度を制限していない図5に示す合金構造体を積層造形により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。
[Example 3-2]
As Example 3-2, the alloy structure shown in FIG. 5 in which the elemental composition is expressed by AlCoCrFeNi and the concentration of inevitable impurities is not limited was manufactured by additive manufacturing. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%.
実施例3−2に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例3−1と同様にして製造した。なお、合金粉末における不可避的不純物の濃度は、Pの濃度が0.008wt%、Siの濃度が0.040wt%、Sの濃度が0.012wt%、Snの濃度が0.006wt%、Sbの濃度が0.002wt%、Asの濃度が0.006wt%、Mnの濃度が0.300wt%、Oの濃度が0.002wt%、Nの濃度が0.003wt%であった。 The alloy structure according to Example 3-2 was manufactured in the same manner as in Example 3-1, except that the composition of the metal used for preparing the alloy powder was changed. The concentration of inevitable impurities in the alloy powder is as follows: P concentration is 0.008 wt%, Si concentration is 0.040 wt%, S concentration is 0.012 wt%, Sn concentration is 0.006 wt%, and Sb. The concentration was 0.002 wt%, the As concentration was 0.006 wt%, the Mn concentration was 0.300 wt%, the O concentration was 0.002 wt%, and the N concentration was 0.003 wt%.
次に、製造した実施例3−1及び実施例3−2に係る合金構造体について、ニッケル濃度分布の解析を行った。ニッケル濃度分布の解析は、計16個の各直方体部について、走査型電子顕微鏡−エネルギー分散型X線分光(Scanning Electron Microscope - Energy Dispersive X-ray Detector;SEM−EDX)によって、任意に抽出した10箇所の領域についてニッケル濃度を計測することによって行った。計16個の各直方体部についての、Ni濃度分布の平均値と標準偏差の結果を表2に示す。 Next, nickel concentration distribution was analyzed about the manufactured alloy structure which concerns on Example 3-1 and Example 3-2. The analysis of the nickel concentration distribution was performed by arbitrarily extracting a total of 16 rectangular parallelepiped portions by a scanning electron microscope-energy dispersive X-ray detector (SEM-EDX) 10 This was done by measuring the nickel concentration in the area of the location. Table 2 shows the results of the average value and standard deviation of the Ni concentration distribution for a total of 16 rectangular parallelepiped parts.
表2に示すように、不可避的不純物をより制限した実施例3−1に係る合金構造体では、各直方体部についてのニッケル濃度分布の偏差が、実施例3−2に係る合金構造体よりも小さい傾向が現れており、合金粉末の不可避的不純物をより制限することで、合金構造体の元素組成分布の均一性が高められていることが分かる。 As shown in Table 2, in the alloy structure according to Example 3-1 in which inevitable impurities are further restricted, the deviation of the nickel concentration distribution for each rectangular parallelepiped part is larger than that in the alloy structure according to Example 3-2. A small tendency appears, and it can be seen that the uniformity of the elemental composition distribution of the alloy structure is enhanced by further limiting the inevitable impurities of the alloy powder.
次に、図5に示す合金構造体の計16個の各直方体部について積層方向に沿って試験片を採取し、単軸圧縮試験を行った。試験片は、合金構造体における積層方向を長軸とするダンベル状試験片を各直方体部から板状部にかけて切り出したものとし、平行部の寸法は、直径4mm×高さ30mmとしたものを用いた。室温における圧縮真応力―圧縮真歪線図の測定結果を、計16個の各直方体部についての平均として図6に示す。 Next, test pieces were sampled along the stacking direction for a total of 16 rectangular parallelepiped portions of the alloy structure shown in FIG. 5 and subjected to a uniaxial compression test. For the test piece, a dumbbell-shaped test piece having a major axis in the stacking direction in the alloy structure is cut out from each rectangular parallelepiped part to a plate-like part, and the dimension of the parallel part is 4 mm in diameter and 30 mm in height. It was. The measurement result of the compression true stress-compression true strain diagram at room temperature is shown in FIG. 6 as an average of a total of 16 rectangular parallelepiped parts.
図6は、実施例3に係る合金構造体における圧縮真応力―圧縮真歪線図である。 6 is a compression true stress-compression true strain diagram in an alloy structure according to Example 3. FIG.
図6に示すように真応力―真歪線図のばらつきは、実施例3−1及び実施例3−2のいずれにおいてもほとんど認められず、図6に示す線幅の線図を描くことができた。すなわち、非特許文献2に示される合金材よりも約160倍以上大きな体積の合金構造体において、造形物の全域に亘り、機械的特性の均一性が高められることが確認できた。特に、実施例3−2では、引張強度は約2800MPa、全伸びは約38%であるのに対し、実施例3−1では、引張強度は約3850MPa、全伸びは約43%であり、引張強度が約1.37倍、全伸びが約1.1倍増加していることが分かる。よって、不可避的不純物の濃度を低減することにより、より機械的特性を向上させることが可能であることが認められる。 As shown in FIG. 6, the variation of the true stress-true strain diagram is hardly recognized in any of Example 3-1 and Example 3-2, and the diagram of the line width shown in FIG. 6 can be drawn. did it. That is, it was confirmed that the uniformity of the mechanical characteristics was enhanced over the entire area of the shaped object in the alloy structure having a volume about 160 times larger than the alloy material shown in Non-Patent Document 2. In particular, in Example 3-2, the tensile strength is about 2800 MPa and the total elongation is about 38%, whereas in Example 3-1, the tensile strength is about 3850 MPa and the total elongation is about 43%. It can be seen that the strength is increased by about 1.37 times and the total elongation is increased by about 1.1 times. Therefore, it is recognized that the mechanical characteristics can be further improved by reducing the concentration of inevitable impurities.
次に、本発明の実施例として、実施例4−1〜実施例4−3に係る合金構造体を製造し、引張特性の評価を行った。 Next, as examples of the present invention, alloy structures according to Example 4-1 to Example 4-3 were manufactured, and tensile properties were evaluated.
[実施例4−1]
実施例4−1として、元素組成がAlCoCrFeNiで表わされ、不可避的不純物の濃度を制限した合金構造体を積層造形により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。また、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した。
[Example 4-1]
As Example 4-1, an alloy structure in which the elemental composition is expressed by AlCoCrFeNi and the concentration of inevitable impurities is limited is manufactured by additive manufacturing. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%. Further, the P concentration is 0.002 wt% or less, the Si concentration is 0.010 wt% or less, the S concentration is 0.001 wt% or less, the Sn concentration is 0.002 wt% or less, and the Sb concentration is 0.001 wt%. Hereinafter, the As concentration was limited to 0.001 wt% or less, the Mn concentration was 0.020 wt% or less, the O concentration was 0.0003 wt% or less, and the N concentration was 0.001 wt% or less.
はじめに、Alの原子濃度が約7at%、Co、Cr、Fe及びNiの原子濃度が約23.3at%であり、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した合金を地金として用いて、ガスアトマイズ法によって、合金粉末を調製した。そして、得られた合金粉末を分級し、粒子径分布を45μm以上105μm以下の範囲に限定すると共に、体積基準の平均粒子径が約70μmとなるようにした。 First, the atomic concentration of Al is about 7 at%, the atomic concentration of Co, Cr, Fe and Ni is about 23.3 at%, the concentration of P is 0.002 wt% or less, the concentration of Si is 0.010 wt% or less, S concentration is 0.001 wt% or less, Sn concentration is 0.002 wt% or less, Sb concentration is 0.001 wt% or less, As concentration is 0.001 wt% or less, Mn concentration is 0.020 wt% or less, An alloy powder was prepared by a gas atomization method using an alloy in which the concentration of O was limited to 0.0003 wt% or less and the concentration of N was limited to 0.001 wt% or less as a bare metal. The obtained alloy powder was classified so that the particle size distribution was limited to a range of 45 μm or more and 105 μm or less, and the volume-based average particle size was about 70 μm.
続いて、積層造形装置を使用して、基材上に合金構造体を造形した。基材としては、200mm×200mm×10mmの板状の機械構造用炭素鋼「S45C」を用いた。また、積層造形装置としては、熱源を電子ビームとした電子ビーム溶融積層造形装置「A2X」(Arcam社製)を使用した。積層造形装置では、真空雰囲気下において、基材上に、粉末展延工程及び凝固層造形工程を繰り返し行うことによって、凝固層の積層方向を水平軸とするダンベル状試験片を合金構造体として造形した。このとき、合金粉末の溶融は、合金粉末の融点(Tm)の50%から80%の温度の予備加熱を事前に行いながら実施し、展延された合金粉末の飛散を抑制した。なお、ダンベル状試験片は、試験片本体を支持する支持部材と共に基材上に横置きの状態で造形し、平行部の寸法を直径4mm×高さ30mmとした。 Subsequently, an alloy structure was modeled on the base material using an additive manufacturing apparatus. As the substrate, a plate-like carbon steel for mechanical structure “S45C” of 200 mm × 200 mm × 10 mm was used. Further, as the additive manufacturing apparatus, an electron beam melt additive manufacturing apparatus “A2X” (manufactured by Arcam) using an electron beam as a heat source was used. In the additive manufacturing apparatus, a dumbbell-shaped test piece having the horizontal direction of the solidified layer as a horizontal axis is formed as an alloy structure by repeatedly performing a powder spreading process and a solidified layer forming process on a substrate in a vacuum atmosphere. did. At this time, the melting of the alloy powder was performed while preheating at a temperature of 50% to 80% of the melting point (Tm) of the alloy powder was performed in advance, and scattering of the spread alloy powder was suppressed. In addition, the dumbbell-shaped test piece was modeled in a state of being placed horizontally on the base material together with the support member that supports the test piece main body, and the dimensions of the parallel portion were 4 mm in diameter and 30 mm in height.
[実施例4−2]
実施例4−2として、元素組成がAlCoCrFeNiで表わされ、不可避的不純物の濃度を制限した合金構造体を積層造形により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。また、Pの濃度を0.002wt%〜0.005wt%、Siの濃度を0.010wt%〜0.040wt%、Sの濃度を0.001wt%〜0.002wt%、Snの濃度を0.002wt%〜0.005wt%、Sbの濃度を0.001wt%〜0.002wt%、Asの濃度を0.001wt%〜0.005wt%、Mnの濃度を0.020wt%〜0.050wt%、Oの濃度を0.0003wt%〜0.001wt%、Nの濃度を0.001wt%〜0.002wt%とした。
[Example 4-2]
As Example 4-2, an alloy structure whose element composition is expressed by AlCoCrFeNi and in which the concentration of inevitable impurities is limited was manufactured by additive manufacturing. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%. Further, the concentration of P is 0.002 wt% to 0.005 wt%, the concentration of Si is 0.010 wt% to 0.040 wt%, the concentration of S is 0.001 wt% to 0.002 wt%, and the concentration of Sn is 0.00. 002 wt% to 0.005 wt%, Sb concentration 0.001 wt% to 0.002 wt%, As concentration 0.001 wt% to 0.005 wt%, Mn concentration 0.020 wt% to 0.050 wt%, The O concentration was 0.0003 wt% to 0.001 wt%, and the N concentration was 0.001 wt% to 0.002 wt%.
実施例4−2に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例4−1と同様にして製造した。 The alloy structure according to Example 4-2 was manufactured in the same manner as in Example 4-1, except that the composition of the metal used for preparing the alloy powder was changed.
[実施例4−3]
実施例4−3として、元素組成がAlCoCrFeNiで表わされ、不可避的不純物の濃度を制限していない合金構造体を積層造形により製造した。原子濃度比率は、Al、Co、Cr、Fe及びNiの原子濃度が約20.0at%である。
[Example 4-3]
As Example 4-3, an alloy structure in which the elemental composition is expressed by AlCoCrFeNi and the concentration of inevitable impurities is not limited is manufactured by additive manufacturing. As for the atomic concentration ratio, the atomic concentration of Al, Co, Cr, Fe and Ni is about 20.0 at%.
実施例4−3に係る合金構造体は、合金粉末の調製に用いる地金の組成を変えた点を除いて、実施例4−1と同様にして製造した。なお、合金粉末における不可避的不純物の濃度は、Pの濃度が0.008wt%、Siの濃度が0.040wt%、Sの濃度が0.012wt%、Snの濃度が0.006wt%、Sbの濃度が0.002wt%、Asの濃度が0.006wt%、Mnの濃度が0.300wt%、Oの濃度が0.002wt%、Nの濃度が0.003wt%であった。 The alloy structure according to Example 4-3 was manufactured in the same manner as in Example 4-1, except that the composition of the metal used for preparing the alloy powder was changed. The concentration of inevitable impurities in the alloy powder is as follows: P concentration is 0.008 wt%, Si concentration is 0.040 wt%, S concentration is 0.012 wt%, Sn concentration is 0.006 wt%, and Sb. The concentration was 0.002 wt%, the As concentration was 0.006 wt%, the Mn concentration was 0.300 wt%, the O concentration was 0.002 wt%, and the N concentration was 0.003 wt%.
次に、製造した実施例4−1〜実施例4−3に係る合金構造体について、引張試験を行った。引張試験は、0℃から900℃の温度にかけて行い、引張強度を計測した。引張試験の測定結果を図7に示す。 Next, a tensile test was performed on the manufactured alloy structures according to Example 4-1 to Example 4-3. The tensile test was performed from 0 ° C. to 900 ° C., and the tensile strength was measured. The measurement result of the tensile test is shown in FIG.
図7は、実施例4に係る合金構造体における引張強度の試験温度依存性を示す図である。 FIG. 7 is a diagram showing the test temperature dependence of the tensile strength in the alloy structure according to Example 4.
図7に示すように、不可避的不純物を制限した実施例4−1〜実施例4−2に係る合金構造体では、不可避的不純物を制限していない実施例4−3に係る合金構造体に対して、引張強度が向上していることが判る。また、不可避的不純物をより制限した実施例4−1に係る合金構造体では、広い温度域で引張強度が向上していることが判る。よって、不可避的不純物の濃度を低減することにより、さらに機械的特性を向上させることが有効であることが確認された。 As shown in FIG. 7, in the alloy structure according to Example 4-1 to Example 4-2 in which inevitable impurities are limited, the alloy structure according to Example 4-3 in which inevitable impurities are not limited. On the other hand, it can be seen that the tensile strength is improved. Moreover, in the alloy structure which concerns on Example 4-1 which restricted the inevitable impurity more, it turns out that the tensile strength is improving in a wide temperature range. Therefore, it was confirmed that it is effective to further improve the mechanical characteristics by reducing the concentration of inevitable impurities.
次に、本発明の実施例として、主成分元素の元素種類を変えて実施例5、実施例6、実施例7及び実施例8に係る合金構造体を製造し、その評価を行った。 Next, as examples of the present invention, the alloy structures according to Example 5, Example 6, Example 7, and Example 8 were manufactured by changing the element type of the main component, and evaluated.
はじめに、鉄(Fe)とその他の複数元素とを主成分として、高エントロピー合金の固溶相を形成することが可能か否かを熱力学的計算によって推定した。なお、熱力学的計算は、Feを含めて5種類以上の元素を等原子比率となる元素組成で含有する場合を仮定して第一原理計算法を使用して行い、そのような元素組成において常温且つ常圧下で固溶相が形成され得るか否かを確認した。主成分の元素は、Feのほか、元素周期律表の第3族から第16族までに含まれる原子番号3から原子番号83の元素群から複数種づつ選択した。 First, it was estimated by thermodynamic calculation whether or not a solid solution phase of a high entropy alloy can be formed with iron (Fe) and other plural elements as main components. The thermodynamic calculation is performed using the first principle calculation method assuming that five or more elements including Fe are contained in an element composition having an equiatomic ratio, and in such an element composition, It was confirmed whether a solid solution phase could be formed at normal temperature and normal pressure. In addition to Fe, a plurality of main elements were selected from element groups of atomic number 3 to atomic number 83 contained in groups 3 to 16 of the periodic table.
図8は、合金構造体において固溶相を形成することができる主成分元素の範囲を示す図である。 FIG. 8 is a diagram showing a range of main component elements capable of forming a solid solution phase in the alloy structure.
図8において、縦軸は、元素の原子番号、横軸は、Fe原子に対する原子半径の比率(各元素の原子半径/Feの原子半径)を示している。また、各プロットの形状は、常温且つ常圧下での結晶構造を示している。二重四角は面心立方格子、二重丸は体心立方格子、六角は六方細密充填、四角はその他の結晶格子である。 In FIG. 8, the vertical axis represents the atomic number of the element, and the horizontal axis represents the ratio of the atomic radius to the Fe atom (atomic radius of each element / atomic radius of Fe). Moreover, the shape of each plot shows the crystal structure at normal temperature and normal pressure. Double squares are face-centered cubic lattices, double circles are body-centered cubic lattices, hexagons are hexagonal close packed, and squares are other crystal lattices.
主成分の元素の種々の組合せについて熱力学的計算を行ったところ、図8において鎖線で囲まれた領域の元素を等原子比率で含有する元素組成について、固溶相を形成することが可能であることが判明した。具体的には、Feと共に固溶化が可能であることが認められた元素(非Fe主成分元素)は、原子番号13のAlから原子番号79のAuまでのうち、Fe原子に対する原子半径の比率が0.83以上1.17以下である元素、すなわち、Al、Si、P、Ti、V、Cr、Mn、Co、Ni、Cu、Zn、Ga、Ge、As、Se、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Sn、Sb、Te、Ta、W、Re、Os、Ir、Pt、Auである。また、その組合せによる成分組成としては、CoCrFeNiAl、CoCrFeNiCu、CoCrFeNiCuAl、CoCrFeNiCuAlSi、MnCrFeNiCuAl、CoCrFeNiMnGe、CoCrFeNiMn、CoCrFeNiMnCu、TiCoCrFeNiCuAlV、TiCoCrFeNiAl、AlTiCoCrFeNiCuVMn、TiCrFeNiCuAl、TiCoCrFeNiCuAl、CoCrFeNiCuAlV、TiCoCrFeNiAl、TiCoCrFeNiCuAl、CoCrFeNiCuAl、CoFeNiCuV、CoCrFeNiCuAl、MnCrFeNiAl、MoCrFeNiCu、TiCoCrFeNi、TiCoCrFeNiMo、CoCrFeNiCuAlV、MnCrFeNiCu、TiCoCrFeNi、TiCoCrFeNiAl、CoCrFeNiMo、CoCrFeNiAlMo、TiCoCrFeNiCu、CoCrFeNiCuAlMn、TiCoCrFeNiMo、CoCrFeNiCuAlV、TiCoCrFeNiCuVMn、AlTiCoCrFeNiCuVMn、CoCrFeNiCuAlMn、CoCrFeNiAlMo、CoCrFeNiCuAlMo、TiCoCrFeNiCu等が確認された。これらのうち、AlTiCoCrFeNiCuVMnの9元高エントロピー合金を、実施例5、実施例6、実施例7及び実施例8に係る合金構造体の造形に応用した。 As a result of thermodynamic calculations for various combinations of the main component elements, it is possible to form a solid solution phase for the elemental composition containing the elements in the region surrounded by the chain line in FIG. It turned out to be. Specifically, the element (non-Fe main component element) that was found to be soluble with Fe is the ratio of the atomic radius to the Fe atom among the atomic number 13 Al to the atomic number 79 Au. Elements having a value of 0.83 or more and 1.17 or less, that is, Al, Si, P, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Nb, Mo, Tc , Ru, Rh, Pd, Ag, Sn, Sb, Te, Ta, W, Re, Os, Ir, Pt, and Au. Further, as the component composition according to the combination, CoCrFeNiAl, CoCrFeNiCu, CoCrFeNiCuAl, CoCrFeNiCuAlSi, MnCrFeNiCuAl, CoCrFeNiMnGe, CoCrFeNiMn, CoCrFeNiMnCu, TiCoCrFeNiCuAlV, TiCoCrFeNiAl, AlTiCoCrFeNiCuVMn, TiCrFeNiCuAl, TiCoCrFeNiCuAl, CoCrFeNiCuAlV, TiCoCrFeNiAl, TiCoCrFeNiCuAl, CoCrFeNiCuAl, CoFeNiCuV, CoCrFeNiCuAl, MnCrFeNiAl, MoCrFeNiCu, TiCoCrFeNi, TiCoCrFeNiMo, CoCrFeNiCuAlV, nCrFeNiCu, TiCoCrFeNi, TiCoCrFeNiAl, CoCrFeNiMo, CoCrFeNiAlMo, TiCoCrFeNiCu, CoCrFeNiCuAlMn, TiCoCrFeNiMo, CoCrFeNiCuAlV, TiCoCrFeNiCuVMn, AlTiCoCrFeNiCuVMn, CoCrFeNiCuAlMn, CoCrFeNiAlMo, CoCrFeNiCuAlMo, TiCoCrFeNiCu, etc. was confirmed. Among these, a 9-element high-entropy alloy of AlTiCoCrFeNiCuVMn was applied to modeling of the alloy structures according to Example 5, Example 6, Example 7, and Example 8.
[実施例5]
実施例5として、元素組成をAlTiCoCrFeNiCuVMnとし、不可避的不純物の濃度を制限した図5に示す合金構造体を積層造形により製造した。原子濃度比率は、Al、Ti、Co、Cr、Fe、Ni、Cu、V及びMnの原子濃度については、原子濃度の差を±3%以内の範囲に揃えて略等原子比率とした。また、Pの濃度を0.005wt%〜0.002wt%、Siの濃度を0.040wt%〜0.010wt%、Sの濃度を0.002wt%〜0.001wt%、Snの濃度を0.005wt%〜0.002wt%、Sbの濃度を0.002wt%〜0.001wt%、Asの濃度を0.005wt%〜0.001wt%、Mnの濃度を0.050wt%〜0.020wt%、Oの濃度を0.001wt%〜0.0003wt%、Nの濃度を0.002wt%〜0.001wt%の範囲に制限した。
[Example 5]
As Example 5, the alloy structure shown in FIG. 5 in which the elemental composition was AlTiCoCrFeNiCuVMn and the concentration of inevitable impurities was limited was manufactured by additive manufacturing. The atomic concentration ratios of Al, Ti, Co, Cr, Fe, Ni, Cu, V, and Mn were set to be approximately equiatomic ratios by making the difference in atomic concentration within a range of ± 3%. Further, the concentration of P is 0.005 wt% to 0.002 wt%, the concentration of Si is 0.040 wt% to 0.010 wt%, the concentration of S is 0.002 wt% to 0.001 wt%, and the concentration of Sn is 0.00. 005 wt% to 0.002 wt%, Sb concentration from 0.002 wt% to 0.001 wt%, As concentration from 0.005 wt% to 0.001 wt%, Mn concentration from 0.050 wt% to 0.020 wt%, The O concentration was limited to the range of 0.001 wt% to 0.0003 wt%, and the N concentration was limited to the range of 0.002 wt% to 0.001 wt%.
はじめに、Al、Ti、Co、Cr、Fe、Ni、Cu、V及びMnの原子濃度が、略等原子比率であり、Pの濃度を0.002wt%以下、Siの濃度を0.010wt%以下、Sの濃度を0.001wt%以下、Snの濃度を0.002wt%以下、Sbの濃度を0.001wt%以下、Asの濃度を0.001wt%以下、Mnの濃度を0.020wt%以下、Oの濃度を0.0003wt%以下、Nの濃度を0.001wt%以下に制限した合金を地金として用いて、ガスアトマイズ法によって、合金粉末を調製した。そして、得られた合金粉末を分級し、粒子径分布を45μm以上105μm以下の範囲に限定すると共に、体積基準の平均粒子径が約70μmとなるようにした。 First, the atomic concentrations of Al, Ti, Co, Cr, Fe, Ni, Cu, V, and Mn are substantially equiatomic ratios, the P concentration is 0.002 wt% or less, and the Si concentration is 0.010 wt% or less. The concentration of S is 0.001 wt% or less, the concentration of Sn is 0.002 wt% or less, the concentration of Sb is 0.001 wt% or less, the concentration of As is 0.001 wt% or less, and the concentration of Mn is 0.020 wt% or less. An alloy powder was prepared by a gas atomization method using an alloy in which the concentration of O was limited to 0.0003 wt% or less and the concentration of N was limited to 0.001 wt% or less as a bare metal. The obtained alloy powder was classified so that the particle size distribution was limited to a range of 45 μm or more and 105 μm or less, and the volume-based average particle size was about 70 μm.
続いて、積層造形装置を使用して、基材上に合金材を造形した。基材としては、200mm×200mm×10mmの板状の機械構造用炭素鋼「S45C」を用いた。また、積層造形装置としては、熱源を電子ビームとした電子ビーム溶融積層造形装置「A2X」(Arcam社製)を使用した。積層造形装置では、真空雰囲気下において、基材上に、粉末展延工程及び凝固層造形工程を繰り返し行うことによって造形した。このとき、合金粉末の溶融は、合金粉末の融点(Tm)の50%から80%の温度の予備加熱を事前に行いながら実施し、展延された合金粉末の飛散を抑制した。製造された実施例5に係る合金構造体は、図5に示す合金構造体と略同形状を有し、造形物全体の体積は、856700mm3であった。 Subsequently, an alloy material was modeled on the base material using an additive manufacturing apparatus. As the substrate, a plate-like carbon steel for mechanical structure “S45C” of 200 mm × 200 mm × 10 mm was used. Further, as the additive manufacturing apparatus, an electron beam melt additive manufacturing apparatus “A2X” (manufactured by Arcam) using an electron beam as a heat source was used. In the layered modeling apparatus, modeling was performed by repeatedly performing a powder spreading process and a solidified layer modeling process on a base material in a vacuum atmosphere. At this time, the melting of the alloy powder was performed while preheating at a temperature of 50% to 80% of the melting point (Tm) of the alloy powder was performed in advance, and scattering of the spread alloy powder was suppressed. The manufactured alloy structure according to Example 5 had substantially the same shape as the alloy structure shown in FIG. 5, and the volume of the entire shaped article was 856700 mm 3 .
次に、実施例5に係る合金構造体の計16個の各直方体部について積層方向に沿って試験片を採取し、単軸圧縮試験を行った。試験片は、合金構造体における積層方向を長軸とするダンベル状試験片を各直方体部から板状部にかけて切り出したものとし、平行部の寸法は、直径8mm×高さ12mmとしたものを用いた。また、製造された実施例5に係る合金構造体について、Fe濃度分布の解析を行った。Fe濃度分布の解析は、計16個の各直方体部について、走査型電子顕微鏡−エネルギー分散型X線分光によって、任意に抽出した10箇所の領域について鉄濃度を計測することによって行った。 Next, test pieces were sampled along the stacking direction for a total of 16 rectangular parallelepiped portions of the alloy structure according to Example 5, and a uniaxial compression test was performed. For the test piece, a dumbbell-shaped test piece having a major axis in the stacking direction in the alloy structure is cut out from each rectangular parallelepiped part to a plate-like part, and the parallel part has a diameter of 8 mm × height of 12 mm. It was. Moreover, Fe concentration distribution was analyzed about the manufactured alloy structure based on Example 5. FIG. The analysis of the Fe concentration distribution was performed by measuring the iron concentration in 10 regions arbitrarily extracted by scanning electron microscope-energy dispersive X-ray spectroscopy for a total of 16 cuboid portions.
その結果、各直方体部についての平均では、真応力―真歪線図のばらつきと、Fe濃度分布とが、いずれも1〜3%以内の差の範囲内にあることが確認された。また、標準偏差は、1.20%以下という結果が得られ、元素組成の分布の均一性が高められることが確認できた。また、実施例5に係る合金構造体の元素組成は、用いた合金粉末の元素組成と略同一で、成分濃度の誤差が凡そ±3%以内に収まっており、元素組成分布、溶融速度、冷却速度等に起因するむらが解消されると共に、元素組成及び機械的強度の分布の均一性も確保できることが確認された。 As a result, it was confirmed that on average for each rectangular parallelepiped part, the variation in the true stress-true strain diagram and the Fe concentration distribution were both within the range of the difference of 1 to 3%. Moreover, the result that the standard deviation was 1.20% or less was obtained, and it was confirmed that the uniformity of the distribution of the element composition was improved. Further, the elemental composition of the alloy structure according to Example 5 is substantially the same as the elemental composition of the alloy powder used, and the error in the component concentration is within about ± 3%, and the elemental composition distribution, melting rate, cooling It was confirmed that the unevenness caused by the speed and the like was eliminated and the uniformity of the distribution of the element composition and the mechanical strength could be secured.
[実施例6]
実施例6として、元素組成をAlTiCoCrFeNiCuVMnとし、不可避的不純物の濃度を制限した円弧状の形状を有する合金構造体(図9参照)を積層造形により製造した。
[Example 6]
As Example 6, an alloy structure (see FIG. 9) having an arc-shaped shape in which the elemental composition was AlTiCoCrFeNiCuVMn and the concentration of inevitable impurities was limited was manufactured by additive manufacturing.
図9は、実施例6に係る合金構造体の形状寸法を示す図である。 FIG. 9 is a diagram illustrating the shape dimensions of the alloy structure according to Example 6.
図9に示すように、実施例6に係る合金構造体1Aは、横断面が円弧状の形状を有する柱状体であり、タービンブレード等に適用できる形状となっている。このような形状の合金構造体1Aを、積層造形される立体形状を変えた点を除いて、実施例5と同様にして製造し、幅(W)149mm×奥行き(D)110mm×高さ(H)153mmの円弧状造形物として造形した。製造された実施例6に係る合金構造体は、造形物全体の体積が、184480mm3、表面積が、60470mm2であり、非特許文献2に示される合金材の約33倍の体積で形成することができた。 As shown in FIG. 9, the alloy structure 1 </ b> A according to Example 6 is a columnar body having a circular cross section, and has a shape applicable to a turbine blade or the like. An alloy structure 1A having such a shape is manufactured in the same manner as in Example 5 except that the three-dimensional shape to be layered is changed, and the width (W) 149 mm × depth (D) 110 mm × height ( H) Modeled as a 153 mm arc shaped model. The manufactured alloy structure according to Example 6 has a total volume of 184480 mm 3 and a surface area of 60470 mm 2 , and is formed with a volume approximately 33 times that of the alloy material shown in Non-Patent Document 2. I was able to.
次に、実施例6に係る合金構造体について、Fe濃度分布の解析を行った。Fe濃度分布の解析は、走査型電子顕微鏡−エネルギー分散型X線分光によって、任意に抽出した10箇所の領域について鉄濃度を計測することによって行った。 Next, the Fe concentration distribution of the alloy structure according to Example 6 was analyzed. The analysis of the Fe concentration distribution was performed by measuring the iron concentration in 10 arbitrarily extracted regions by scanning electron microscope-energy dispersive X-ray spectroscopy.
その結果、実施例6に係る合金構造体の元素組成は、用いた合金粉末の元素組成と略同一で、成分濃度の誤差が凡そ±3%以内に収まっており、元素組成分布、溶融速度、冷却速度等に起因するむらが解消されると共に、元素組成及び機械的強度の分布の均一性も確保できることが確認された。 As a result, the elemental composition of the alloy structure according to Example 6 is substantially the same as the elemental composition of the alloy powder used, and the component concentration error is within about ± 3%, and the elemental composition distribution, melting rate, It was confirmed that the unevenness due to the cooling rate and the like was eliminated and the uniformity of the distribution of the element composition and the mechanical strength could be secured.
[実施例7]
実施例7として、元素組成をAlTiCoCrFeNiCuVMnとし、不可避的不純物の濃度を制限したダンベル状の形状を有する合金構造体を積層造形により製造した。
[Example 7]
As Example 7, an alloy structure having an element composition of AlTiCoCrFeNiCuVMn and a dumbbell-shaped shape in which the concentration of inevitable impurities was limited was manufactured by additive manufacturing.
実施例7に係る合金構造体は、合金粉末の調製に用いる地金の組成と、積層造形される立体形状とを変えた点を除いて、実施例4−1と同様にして製造し、凝固層の積層方向を水平軸とするダンベル状の造形物とした。 The alloy structure according to Example 7 was manufactured in the same manner as in Example 4-1, except that the composition of the bare metal used for the preparation of the alloy powder and the three-dimensional shape to be layered were changed, and solidified. It was set as the dumbbell-shaped shaped object which makes the lamination direction of a layer a horizontal axis.
その結果、実施例7に係る合金構造体の元素組成は、用いた合金粉末の元素組成と略同一で、成分濃度の誤差が凡そ±3%以内に収まっており、元素組成分布、溶融速度、冷却速度等に起因するむらが解消されると共に、元素組成及び機械的強度の分布の均一性も確保できることが確認された。また、実施例4−1に係る合金構造体と比較して、表面が平滑になり、金属光沢が強く発現することが確認され、合金構造体の元素組成を多元化することによって、表面性状を改質する効果が得られることが分かった。 As a result, the elemental composition of the alloy structure according to Example 7 is substantially the same as the elemental composition of the alloy powder used, and the component concentration error is within about ± 3%, and the elemental composition distribution, melting rate, It was confirmed that the unevenness due to the cooling rate and the like was eliminated and the uniformity of the distribution of the element composition and the mechanical strength could be secured. Moreover, compared with the alloy structure which concerns on Example 4-1, it was confirmed that the surface became smooth and a metallic luster was strongly expressed, and surface properties were improved by diversifying the elemental composition of the alloy structure. It was found that the effect of reforming can be obtained.
[実施例8]
実施例8として、元素組成をAlTiCoCrFeNiCuVMnとし、不可避的不純物の濃度を制限したロッド状の形状を有する合金構造体を積層造形により製造した。
[Example 8]
As Example 8, an alloy structure having an element composition of AlTiCoCrFeNiCuVMn and having a rod-like shape in which the concentration of inevitable impurities was limited was manufactured by additive manufacturing.
実施例8に係る合金構造体は、合金粉末の調製に用いる地金の組成と、積層造形される立体形状とを変えた点を除いて、実施例4−1と同様にして造形した。 The alloy structure according to Example 8 was modeled in the same manner as in Example 4-1, except that the composition of the metal used for preparing the alloy powder and the three-dimensional shape to be layered were changed.
その結果、実施例8に係る合金構造体の元素組成は、用いた合金粉末の元素組成と略同一で、成分濃度の誤差が凡そ±3%以内に収まっており、元素組成分布、溶融速度、冷却速度等に起因するむらが解消されると共に、元素組成及び機械的強度の分布の均一性も確保できることが確認された。製造された実施例8に係る合金構造体を摩擦撹拌用ツールとして使用して、厚さ10mm以下の軟鉄製の板材について摩擦撹拌接合による接合を行った。その結果、接合部に欠陥を生じることなく接合することができ、反りがほとんど見られない良好な接合を行うことができた。すなわち、多元化された実施例8に係る合金構造体は、高温強度や耐摩耗性が要求され、従来困難であったFeを主体とした材料の摩擦撹拌接合に適用可能であることが確認された。また、凝固層造形工程で、凝固部が形成されるまでの高温の状態において、凝固部乃至凝固層の形状成形加工や表面加工を行うことによって、適切に加工が施された造形物を得ることができることも確認された。 As a result, the elemental composition of the alloy structure according to Example 8 is substantially the same as the elemental composition of the used alloy powder, and the error of the component concentration is within about ± 3%, the elemental composition distribution, the melting rate, It was confirmed that the unevenness due to the cooling rate and the like was eliminated and the uniformity of the distribution of the element composition and the mechanical strength could be secured. Using the manufactured alloy structure according to Example 8 as a friction stir tool, a soft iron plate having a thickness of 10 mm or less was joined by friction stir welding. As a result, it was possible to perform bonding without causing defects in the bonded portion, and it was possible to perform good bonding with almost no warping. That is, the multi-component alloy structure according to Example 8 was required to have high-temperature strength and wear resistance, and was confirmed to be applicable to friction stir welding of Fe-based materials, which was difficult in the past. It was. In addition, in a solidified layer forming process, in a high temperature state until the solidified portion is formed, by performing shape forming processing or surface processing of the solidified portion or the solidified layer, a molded object that has been appropriately processed is obtained. It was also confirmed that
1 合金構造体
10 合金粉末
15 基材
20 溶融部
21 基材載置台
22 加工テーブル
23 リコータ
24 加熱手段
30 凝固部
40 凝固層
50 結晶粒
100 溶融境界
110 粒界(大傾角粒界)
120 小傾角粒界
301 電気炉
302 金属塊
303 アーク放電
304 電極
305 酸素バーナ
306 酸素ガス
309 取鍋
310 溶湯
311 取鍋製錬炉
313 ポーラスプラグ
314 アルゴンガス
316 真空装置
317 排気孔
318 タンディッシュ
319 真空容器
320 排気孔
324 電気炉
326 合金溶湯
330 チャンバ
DESCRIPTION OF SYMBOLS 1 Alloy structure 10 Alloy powder 15 Base material 20 Melting part 21 Base material mounting base 22 Processing table 23 Recoater 24 Heating means 30 Solidification part 40 Solidified layer 50 Crystal grain 100 Melting boundary 110 Grain boundary (Large angle grain boundary)
120 Low-angle grain boundary 301 Electric furnace 302 Metal lump 303 Arc discharge 304 Electrode 305 Oxygen burner 306 Oxygen gas 309 Ladle 310 Molten metal 311 Ladle smelting furnace 313 Porous plug 314 Argon gas 316 Vacuum device 317 Exhaust hole 318 Tundish 319 Vacuum Vessel 320 Exhaust hole 324 Electric furnace 326 Molten alloy 330 Chamber
Claims (9)
展延された前記合金粉末を局所加熱して溶融させた後に凝固させて凝固組織を形成し、前記局所加熱による被加熱領域を前記合金粉末が展延された面に対して平行に移動させて凝固層を形成する凝固層造形工程と、を備え、
前記粉末展延工程と前記凝固層造形工程とを交互に繰り返すことで複数の層状の凝固層を形成することを特徴とする合金構造体の製造方法。 At least four elements selected from the group consisting of atoms 13 to 79 contained in groups 3 to 16 of the periodic table and having a ratio of atomic radii to Fe atoms of 0.83 to 1.17 And at least 4 elements of Fe, and the difference in atomic concentration of at least 4 elements of Fe is less than 3 at%. As unavoidable impurities, P is 0.005 wt% or less, Si is 0.040 wt% or less, S is 0.002 wt% or less, Sn is 0.005 wt% or less, Sb is 0.002 wt% or less, and As is An alloy powder containing 0.005 wt% or less, Mn 0.050 wt% or less, O 0.001 wt% or less, and N in an atomic concentration range of 0.002 wt% or less is spread in layers. Powder spreading step that,
The spread alloy powder is locally heated and melted and then solidified to form a solidified structure, and a region to be heated by the local heating is moved parallel to the surface on which the alloy powder is spread. A solidified layer forming step for forming a solidified layer,
A method for producing an alloy structure, wherein a plurality of layered solidified layers are formed by alternately repeating the powder spreading step and the solidified layer forming step.
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