JP7484875B2 - Method for producing melting raw material, and melting raw material - Google Patents
Method for producing melting raw material, and melting raw material Download PDFInfo
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- 238000002844 melting Methods 0.000 title claims description 118
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- 239000000843 powder Substances 0.000 claims description 144
- 238000000034 method Methods 0.000 claims description 78
- 229910045601 alloy Inorganic materials 0.000 claims description 52
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- 239000002184 metal Substances 0.000 claims description 32
- 239000011812 mixed powder Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052776 Thorium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- -1 tectinium Chemical compound 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Description
本発明は、溶解原料の製造方法と溶解原料に関するものであり、特に高融点元素を含む溶解原料の製造方法と溶解原料に関するものである。 The present invention relates to a method for producing a melting raw material and the melting raw material, and in particular to a method for producing a melting raw material containing a high melting point element and the melting raw material.
金属粉末は素形材分野においては圧粉成型、粉末冶金、金属射出成型（Ｍｅｔａｌ Ｉｎｊｅｃｔｉｏｎ Ｍｏｌｄｉｎｇ、 ＭＩＭ）などの素材として重要な基礎材料である。金属粉末を用いるこれらの素形材技術は強度と量産性に優れるために、各種工業製品に好適に用いられる。また、近年では金属積層造形（金属三次元プリンティング）の原料にも用いられるようになって型レスでの素形材製造も可能となり、その重要度が増している。 In the field of basic materials, metal powder is an important basic material used in processes such as powder compaction, powder metallurgy, and metal injection molding (MIM). These basic material technologies that use metal powder are excellent in strength and mass production, making them ideal for use in a variety of industrial products. In recent years, metal powder has also come to be used as a raw material for metal additive manufacturing (metal three-dimensional printing), making it possible to manufacture basic materials without molds, and its importance is increasing.
このような素形材技術に用いられる金属粉末としてはこれまでに鉄鋼、アルミ合金、銅合金、ニッケル基合金、チタン合金など数多くの合金が用いられてきた。さらには、タングステン、モリブデン、ニオブなどの高融点元素（金属）を加えることで耐熱性などを飛躍的に向上させる試みがなされている。 To date, numerous alloys have been used as metal powders in this type of material forming technology, including steel, aluminum alloys, copper alloys, nickel-based alloys, and titanium alloys. Furthermore, attempts have been made to dramatically improve heat resistance by adding high-melting point elements (metals) such as tungsten, molybdenum, and niobium.
特許文献１には、チタン粉末とアルミ粉末を混合した原料粉末を冷間成形によって圧粉体の棒状原料とし、その棒状原料をガスアトマイズ法により粉末化する手法が開示されている。 Patent Document 1 discloses a method in which a raw powder mixture of titanium powder and aluminum powder is cold-formed into a rod-shaped raw material for a green compact, and the rod-shaped raw material is then powdered by a gas atomization method.
しかしながら、特許文献１に開示されている手法では、冷間での加工性に乏しい材料、例えば、高融点元素（高融点金属）を含む場合には、冷間成形された成形体の内部に空隙が生じやすい。そして、成形体を溶解させる際に、空隙が起点となって成形体が損傷したり、空隙中に残存する空気が成形体の溶解を不安定にしてしまうことで、安定的に合金粉末を製造することが困難であった。 However, in the method disclosed in Patent Document 1, when the material contains a material that is poorly workable in cold working, such as a high-melting point element (high-melting point metal), voids are likely to form inside the cold-formed compact. When the compact is melted, the voids can cause damage to the compact, and the air remaining in the voids can make the melting of the compact unstable, making it difficult to stably produce alloy powder.
以上のことより、本発明の目的は、高融点元素を含む合金粉末について、例えば、金属積層造形、圧粉成型、粉末冶金、金属射出成型等に用いる合金粉末を安定的に製造できる溶解原料とその製造方法を提供することにある。 In view of the above, the object of the present invention is to provide a melting material and a manufacturing method thereof that can stably produce alloy powder containing a high melting point element for use in, for example, metal additive manufacturing, powder compaction, powder metallurgy, metal injection molding, etc.
本発明は、溶解・噴霧させて合金粉末を得るための溶解原料であって、複数種の原料粉末からなる混合粉末を、前記原料粉末を構成する元素の中で最も融点が低い元素の融点をＭＰｍｉｎ（℃）としたとき、２ＭＰｍｉｎ／３以上の温度で、かつ５ＭＰａ以上の圧力で焼結する加圧焼結工程と、を備え、前記溶解原料は、直接溶解ガスアトマイズ法またはプラズマアーク加熱法に用いるものであり、前記原料粉末は、融点が１６００℃以上の高融点金属元素を少なくとも二種類含み、前記高融点金属元素は、タングステン、レニウム、オスミウム、タンタル、モリブデン、ニオブ、ハフニウム、テクチニウム、バナジウム、クロム、ジルコニウム、トリウムおよびチタンから少なくとも１種以上含むことを特徴とする溶解原料の製造方法である。また本発明は、溶解・噴霧させて合金粉末を得るための溶解原料であって、複数種の原料粉末からなる混合粉末を、前記原料粉末を構成する元素の中で最も融点が低い元素の融点をＭＰｍｉｎ（℃）としたとき、２ＭＰｍｉｎ／３以上の温度で、かつ５ＭＰａ以上の圧力で焼結する加圧焼結工程と、を備え前記溶解原料は、直接溶解ガスアトマイズ法またはプラズマアーク加熱法に用いるものであり、前記原料粉末は、融点が１６００℃以上の高融点金属元素を少なくとも二種類含み、前記合金粉末がハイエントロピー合金であることを特徴とする溶解原料の製造方法である。前記原料粉末において、原子％で、チタンは３３．３３％以下である。 The present invention relates to a method for producing a molten raw material for obtaining an alloy powder by melting and atomizing the raw material, the method comprising: a pressure sintering step of sintering a mixed powder consisting of a plurality of raw material powders at a temperature of 2 MPmin /3 or more and a pressure of 5 MPa or more, where MPmin (°C) is the melting point of the element having the lowest melting point among the elements constituting the raw material powder; the molten raw material is used in a direct melting gas atomization method or a plasma arc heating method; the raw material powder contains at least two high-melting point metal elements having a melting point of 1600°C or more, and the high-melting point metal elements contain at least one of tungsten, rhenium, osmium, tantalum, molybdenum, niobium, hafnium, tectinium, vanadium, chromium, zirconium, thorium, and titanium. The present invention also relates to a method for producing a molten raw material for obtaining an alloy powder by melting and atomizing, the method comprising a pressure sintering step of sintering a mixed powder consisting of a plurality of kinds of raw material powders at a temperature of 2 MPmin /3 or more and a pressure of 5 MPa or more, where MPmin (°C) is the melting point of the element with the lowest melting point among the elements constituting the raw material powder, the molten raw material is used for a direct melting gas atomization method or a plasma arc heating method, the raw material powder contains at least two kinds of high melting point metal elements with melting points of 1600°C or more, and the alloy powder is a high entropy alloy. In the raw material powder, titanium is 33.33% or less in atomic %.
また、前記複数種の原料粉末のうち、少なくとも一つの原料粉末が２種類以上の高融点金属元素を含んでいることが好ましい。 It is also preferable that at least one of the multiple raw material powders contains two or more types of high-melting point metal elements.
また、前記加圧焼結工程において、熱間等方加圧焼結法を用いることが好ましい。 In addition, it is preferable to use hot isostatic sintering in the pressure sintering process.
また本発明は、溶解・噴霧させて合金粉末を得るために用いる溶解原料であって、融点が１６００℃以上の高融点金属元素を少なくとも二種類含み、前記溶解原料は、直接溶解ガスアトマイズ法またはプラズマアーク加熱法に用いるものであり、前記高融点金属元素は、タングステン、レニウム、オスミウム、タンタル、モリブデン、ニオブ、ハフニウム、テクチニウム、バナジウム、クロム、ジルコニウム、トリウムおよびチタンであり、空隙率が５％未満の焼結体であることを特徴とする溶解原料である。また本発明は、溶解・噴霧させて合金粉末を得るために用いる溶解原料であって、融点が１６００℃以上の高融点金属元素を少なくとも二種類含み、前記溶解原料は、直接溶解ガスアトマイズ法またはプラズマアーク加熱法に用いるものであり、前記合金粉末がハイエントロピー合金であり、原子％で、前記チタンが３３．３３％以下であり、空隙率が５％未満の焼結体であることを特徴とする溶解原料である。 The present invention also provides a melting raw material used to obtain an alloy powder by melting and atomizing, the melting raw material containing at least two kinds of high-melting-point metal elements having a melting point of 1600°C or higher, the melting raw material being used in a direct melting gas atomizing method or a plasma arc heating method, the high-melting-point metal elements being tungsten, rhenium, osmium, tantalum, molybdenum, niobium, hafnium, tectinium, vanadium, chromium, zirconium, thorium, and titanium, and the melting raw material being a sintered body having a porosity of less than 5%. The present invention also provides a melting raw material used to obtain an alloy powder by melting and atomizing, the melting raw material containing at least two kinds of high-melting-point metal elements having a melting point of 1600°C or higher, the melting raw material being used in a direct melting gas atomizing method or a plasma arc heating method, the alloy powder being a high-entropy alloy, the titanium being 33.33% or less in atomic %, and the melting raw material being a sintered body having a porosity of less than 5%.
本発明によれば、高融点元素を含む合金粉末について、例えば、金属積層造形、圧粉成型、粉末冶金、金属射出成型等に用いる合金粉末を安定的に製造できる溶解原料の製造方法、および溶解原料を提供することができる。 The present invention provides a method for producing a melting raw material that can stably produce alloy powder containing a high melting point element for use in, for example, metal additive manufacturing, powder compaction, powder metallurgy, metal injection molding, etc., and the melting raw material.
まず、本発明者等は、既存の溶融（溶解）設備では均一に溶解することが難しい高融点の元素を多量に含む金属粉末の製法について鋭意研究を重ねた。その結果、融点が１６００℃以上の金属元素を含む複数の原料粉末を目的とする組成となるように均一に混合して、これを所定の温度と圧力で焼結する事で製造したい金属粉末と略同一の組成を有する焼結体（原料棒材と言う場合もある）を製作する。そしてこの焼結体を局所的に溶解して得られる融液を粉末化することで所望の組成を有する合金粉末（プレアロイ粉）を安定して得られることを見出した。 First, the inventors conducted extensive research into a method for producing metal powders that contain large amounts of high-melting-point elements that are difficult to melt uniformly using existing melting (dissolving) equipment. As a result, they discovered that by uniformly mixing multiple raw material powders containing metal elements with melting points of 1600°C or higher to achieve the desired composition and sintering this at a specified temperature and pressure, a sintered body (sometimes called a raw material bar) with approximately the same composition as the metal powder to be produced can be produced. They then discovered that by locally melting this sintered body and powdering the resulting molten liquid, alloy powder (pre-alloy powder) with the desired composition can be stably obtained.
＜溶解原料の製造方法＞
以下、図１を用いて、本発明の製造方法の実施形態を説明していく。図１は本発明の実施形態に係る溶解原料の製造方法と、溶解原料を用いて合金粉末を得る際の好適な製造方法を示す工程図である。
<Method of producing melting raw materials>
Hereinafter, an embodiment of the manufacturing method of the present invention will be described with reference to Fig. 1. Fig. 1 is a process diagram showing a manufacturing method of a raw material for melting according to an embodiment of the present invention and a suitable manufacturing method for obtaining an alloy powder using the raw material for melting.
［加圧焼結工程（Ｓ１０１）］
まず、原料粉末について説明する。所望の合金粉末の組成に合わせて高融点金属を含む原料粉末を混合して混合粉末を得る。このとき１つの原料粉末には、１６００℃以上の融点を有する金属元素（高融点金属元素）を含むものであり、このような原料粉末を２つ以上混合することで少なくとも二種類以上の高融点金属元素を含む混合粉末を得る。高融点金属元素としては、例えば、タングステン（Ｗ）、レニウム（Ｒｅ）、オスミウム（Ｏｓ）、タンタル（Ｔａ）、モリブデン（Ｍｏ）、ニオブ（Ｎｂ）、イリジウム（Ｉｒ）、ルテニウム（Ｒｕ）、ハフニウム（Ｈｆ）、テクチニウム（Ｔｃ）、ロジウム（Ｒｈ）、バナジウム（Ｖ）、クロム（Ｃｒ）、ジルコニウム（Ｚｒ）、トリウム（Ｔｈ）、チタン（Ｔｉ）などがある。混合方法は特に限定しないが、例えば、ボールミル等の各種粉末混合機を用いることができる。原料粉末の製法としては、原料に応じて、化学還元法、粉砕法などが選択される。また、原料粉末にはアトマイズ法によって製造した粉末を含めても良い。
[Pressure sintering step (S101)]
First, the raw material powder will be described. A mixed powder is obtained by mixing raw material powders containing high melting point metals according to the composition of the desired alloy powder. At this time, one raw material powder contains a metal element (high melting point metal element) having a melting point of 1600 ° C or more, and by mixing two or more such raw material powders, a mixed powder containing at least two or more high melting point metal elements is obtained. Examples of high melting point metal elements include tungsten (W), rhenium (Re), osmium (Os), tantalum (Ta), molybdenum (Mo), niobium (Nb), iridium (Ir), ruthenium (Ru), hafnium (Hf), tectinium (Tc), rhodium (Rh), vanadium (V), chromium (Cr), zirconium (Zr), thorium (Th), and titanium (Ti). The mixing method is not particularly limited, and various powder mixers such as a ball mill can be used. As a manufacturing method of the raw material powder, a chemical reduction method, a pulverization method, or the like is selected depending on the raw material. In addition, the raw material powder may include a powder manufactured by an atomization method.
また、原料粉末には、高融点の金属元素を含む粉末同士を予め混合し、二種類以上の高融点金属元素を予め含む原料粉末を用いても良く、混合方法としても上記同様、例えば、ボールミル等の各種粉末混合機を用いることで均一に混合しておくことが好ましい。 In addition, powders containing high melting point metal elements may be mixed together in advance to use raw material powders containing two or more high melting point metal elements in advance. As for the mixing method, it is preferable to mix uniformly in the same manner as above, for example, by using various powder mixers such as a ball mill.
原料粉末の平均粒径としては、１μｍ以上１ｍｍ以下に設定することが好ましい。平均粒径が１μｍ以上であると粉末の流動性を確保でき、粉末が舞い上がることも抑制できる。そして、平均粒径を１ｍｍ以下とすることで、後述する加圧焼結工程において、粉末間の空隙が残存することを抑制できる。 It is preferable to set the average particle size of the raw material powder to 1 μm or more and 1 mm or less. If the average particle size is 1 μm or more, the fluidity of the powder can be ensured and the powder can be prevented from flying up. Furthermore, by setting the average particle size to 1 mm or less, it is possible to prevent voids from remaining between the powder in the pressure sintering process described below.
次に、混合粉末を、加圧焼結して溶解原料を作製する方法を説明する。
本明細書でいう溶解原料は、溶解・噴霧させて合金粉末を得るためのものであり、原料粉末を混合することで少なくとも二種類以上の高融点金属元素を含む混合粉末を加圧焼結したものである。よって、焼結体になったものを指すが、溶解原料、原料棒材、消耗電極と換言することもできる。また、焼結体の形状は特に限定しないが、棒状にすると、溶解・噴霧工程において取扱い易いので好ましい。以下、加圧焼結工程（Ｓ１０１）から溶解・噴霧工程（Ｓ１０３）について、焼結体の形状を棒材とし、原料棒材と称して説明する。
Next, a method for producing a molten raw material by pressure sintering the mixed powder will be described.
The molten raw material in this specification is used to obtain alloy powder by melting and spraying, and is a mixed powder containing at least two or more high melting point metal elements by mixing raw material powders and then pressure sintering the mixed powder. Therefore, it refers to a sintered body, but it can also be called a molten raw material, a raw material bar, or a consumable electrode. The shape of the sintered body is not particularly limited, but a rod-shaped body is preferable because it is easy to handle in the melting and spraying process. Hereinafter, the pressure sintering process (S101) to the melting and spraying process (S103) will be described assuming that the shape of the sintered body is a bar, which is referred to as a raw material bar.
加圧焼結工程は、原料粉末を構成する元素の中で最も融点が低い元素の融点をＭＰｍｉｎ（℃）としたとき、２ＭＰｍｉｎ／３以上の温度で、且つ５ＭＰａ以上の圧力により混合粉末を加圧焼結することで原料棒材を得る工程である。原料粉末を構成する元素の中で最も融点が低い元素の融点ＭＰｍｉｎの２／３以上の温度と、５ＭＰａ以上の圧力という条件とすることで、焼結体の空隙率を５％未満とすることができる。これにより焼結体を溶解して粉末化する溶解・噴霧工程における焼結体の破損や空気の混入を防ぐことができるため好適である。より好ましい温度は、ＭＰｍｉｎの５／７以上であり、さらに好ましくは３／４以上の温度である。また、より好ましい圧力は２０ＭＰａ以上であり、さらに好ましい圧力は４０ＭＰａ以上である。また、温度の上限は特に限定しないが、温度をＭＰｍｉｎ未満とすることで、原料粉末間で液相の反応が生じにくくでき、組成の均一性を確保しやすくなるため好適である。また、圧力の上限は炉体の強度に依存し、３００ＭＰａ程度である。 The pressure sintering process is a process of obtaining a raw material bar by pressure sintering the mixed powder at a temperature of 2MP min /3 or more and a pressure of 5 MPa or more, where MP min (°C) is the melting point of the element with the lowest melting point among the elements constituting the raw material powder. By setting the conditions of a temperature of 2/3 or more of the melting point MP min of the element with the lowest melting point among the elements constituting the raw material powder and a pressure of 5 MPa or more, the porosity of the sintered body can be made less than 5%. This is preferable because it can prevent damage to the sintered body and the inclusion of air in the dissolving and spraying process in which the sintered body is dissolved and powdered. A more preferable temperature is 5/7 or more of MP min , and even more preferable is a temperature of 3/4 or more. Moreover, a more preferable pressure is 20 MPa or more, and even more preferable is a pressure of 40 MPa or more. In addition, the upper limit of the temperature is not particularly limited, but by setting the temperature below MP min , it is preferable because it is difficult for a liquid phase reaction to occur between the raw material powders and it is easy to ensure the uniformity of the composition. In addition, the upper limit of the pressure depends on the strength of the furnace body and is about 300 MPa.
このような原料棒材を加圧焼結して製造する方法としては、圧粉焼結法、一軸加圧焼結法（ホットプレスや放電プラズマ焼結（ＳＰＳ：Ｓｐａｒｋ Ｐｌａｓｍａ Ｓｉｎｔｅｒｉｎｇ）、熱間等方加圧焼結法（ＨＩＰ：Ｈｏｔ Ｉｓｏｓｔａｔｉｃ Ｐｒｅｓｓ）を用いることができるが、焼結密度などの点から、均等に圧縮することができる一軸加圧焼結法、もしくは熱間等方加圧焼結法を用いることが好ましい。 Methods for producing such raw material bars by pressure sintering include powder compaction sintering, uniaxial pressure sintering (hot pressing or spark plasma sintering (SPS)), and hot isostatic pressure sintering (HIP). From the standpoint of sintered density, however, it is preferable to use uniaxial pressure sintering or hot isostatic pressure sintering, which can be compressed evenly.
加圧焼結方法の中でも、均等に圧縮することができる一軸加圧焼結法（ホットプレス、ＳＰＳ法）または熱間等方加圧焼結法（ＨＩＰ法）を用いることが特に好ましい。これら加圧焼結方法であれば、原料粉末間の空隙をより効果的に低減し、空隙率が２％未満の原料棒材を得ることができるのでより好ましい。また、等方的に加圧できる熱間等方加圧焼結法は、材料を均一に収縮させて固化することができるので、さらに好ましい。このような加圧焼結工程を経て作製された焼結体であれば、溶解・噴霧工程（Ｓ１０３）における不良の発生をより一層抑制することができる。
なお、本明細書でいう空隙率とは、観察した領域（視野面積）に対して空隙が占める面積の比である。例えば、得られた溶解原料（試料）の任意箇所を切断し、切断面を研磨する。研磨された試料表面を２００～１０００倍の倍率で光学顕微鏡等を用いて観察し、観察した領域を写真などの画像データとして取得する。空隙箇所は画像上で黒く示されるので、画像を２値化するなどして、黒い箇所が占める面積、すなわち空隙が占める面積を算出すればよい。
Among the pressure sintering methods, it is particularly preferable to use the uniaxial pressure sintering method (hot press, SPS method) or the hot isostatic pressure sintering method (HIP method) which can compress uniformly. These pressure sintering methods are more preferable because they can more effectively reduce the voids between the raw material powder and obtain a raw material bar with a void ratio of less than 2%. In addition, the hot isostatic pressure sintering method, which can apply pressure isotropically, is even more preferable because it can shrink and solidify the material uniformly. If the sintered body is produced through such a pressure sintering process, the occurrence of defects in the melting and spraying process (S103) can be further suppressed.
In this specification, the porosity is the ratio of the area occupied by voids to the observed area (field of view area). For example, the obtained molten raw material (sample) is cut at an arbitrary location and the cut surface is polished. The polished sample surface is observed at a magnification of 200 to 1000 times using an optical microscope or the like, and the observed area is obtained as image data such as a photograph. Since the voids are shown in black on the image, the area occupied by the black areas, i.e., the area occupied by the voids, can be calculated by binarizing the image, for example.
加圧焼結工程にＨＩＰ法を用いた場合について、より具体的に説明する。
まず、原料棒材の大きさに合わせたカプセル（容器）に原料粉末を封入し、脱気して密封する。カプセルの大きさはＨＩＰ処理後の形状収縮を考慮して適切に設定する。その後にＨＩＰ装置に装填し、前記の設定温度と設定圧力、即ち、最も融点が低い元素の融点をＭＰｍｉｎ（℃）としたとき、２ＭＰｍｉｎ／３以上の温度と５ＭＰａ以上の圧力によってＨＩＰ処理を行う。処理後にカプセルを除去することで原料棒材を得る。なお、カプセルの代わりに他の手法にて仮成形した原料棒材の素材を準備し、ＨＩＰ処理を行うカプセルフリー法（オープンＨＩＰ法）によっても原料棒材を作製する事は可能である。
The case where the HIP method is used in the pressure sintering step will be described more specifically.
First, the raw material powder is enclosed in a capsule (container) that matches the size of the raw material bar, and is degassed and sealed. The size of the capsule is appropriately set taking into consideration the shape shrinkage after HIP treatment. Then, it is loaded into the HIP device and HIP treatment is performed at the above-mentioned set temperature and set pressure, that is, a temperature of 2MP min /3 or more and a pressure of 5 MPa or more when the melting point of the element with the lowest melting point is MP min (°C). After the treatment, the capsule is removed to obtain the raw material bar. It is also possible to prepare the raw material bar by a capsule-free method (open HIP method) in which a raw material bar that has been provisionally formed by another method is prepared instead of the capsule and HIP treatment is performed.
加圧焼結条件は上述の通りであるが、例えば、原料粉末である高融点材料を封入したカプセルを０．０１ＭＰａ以下に脱気をして密封する。そして、カプセルをＨＩＰ設備に配して、１００℃～２０００℃の温度と、１０ＭＰａ～２００ＭＰａの圧力で、１時間～１０時間程度加圧保持し、カプセル中の原料粉末を固化させて、原料棒材を作製する。 The pressure sintering conditions are as described above, but for example, a capsule containing the raw material powder (high melting point material) is degassed to 0.01 MPa or less and sealed. The capsule is then placed in a HIP machine and kept pressurized at a temperature of 100°C to 2000°C and a pressure of 10 MPa to 200 MPa for about 1 to 10 hours, solidifying the raw material powder in the capsule and producing the raw material bar.
原料棒材は、例えば、溶解・噴霧工程で用いられる設備に応じて直径１０ｍｍ以上５００ｍｍ以下、長さ１０ｍｍ以上３０００ｍｍ以下に設定される。得られた原料棒材の断面観察による空隙面積の評価によって規定される原料粉末間の空隙は５％未満、より好ましくは２％未満とすることができる。かかる原料棒材は、原料棒材の溶解・噴霧工程における棒材の破損や空気の混入を防ぐことができ好適である。このように本工程で得られる原料棒材は機械強度に優れている。 The raw material bar is set, for example, to a diameter of 10 mm to 500 mm and a length of 10 mm to 3000 mm depending on the equipment used in the melting and spraying process. The gap between the raw material powders, as determined by evaluating the gap area through cross-sectional observation of the obtained raw material bar, can be less than 5%, and more preferably less than 2%. Such raw material bar is preferable because it can prevent breakage of the bar and the inclusion of air during the melting and spraying process of the raw material bar. Thus, the raw material bar obtained in this process has excellent mechanical strength.
［溶解・噴霧工程（Ｓ１０３）］
次に、原料棒材を用いて合金粉末を得る際の好適な溶解・噴霧工程について、図２および図３を用いて説明する。
図２は合金粉末の製造方法の溶解・噴霧工程の好適な一形態を示す図であり、直接溶解ガスアトマイズ法を示す。図３は、溶解・噴霧工程の別形態を示す図であり、プラズマアーク加熱法を示す。以下に述べる直接溶解ガスアトマイズ法およびプラズマアーク加熱法であれば、融液が坩堝等に触れることがなく、融液の清浄度を確保できるため好適である。
まず、図２を用いて、直接溶解ガスアトマイズ法を適用した場合の実施形態について説明する。
[Dissolving and spraying process (S103)]
Next, a preferred melting and atomizing process for obtaining alloy powder from raw material rods will be described with reference to FIGS. 2 and 3. FIG.
Fig. 2 is a diagram showing a preferred embodiment of the melting and atomizing process in the method for producing alloy powder, which shows a direct melting gas atomizing method. Fig. 3 is a diagram showing another embodiment of the melting and atomizing process, which shows a plasma arc heating method. The direct melting gas atomizing method and the plasma arc heating method described below are preferred because the melt does not come into contact with the crucible or the like, and the cleanliness of the melt can be ensured.
First, an embodiment in which the direct dissolution gas atomization method is applied will be described with reference to FIG.
まず、原料棒材１１を粉末製造装置１２の誘導加熱装置１３中に配置する。原料棒材は誘導加熱装置に対し、中心軸を合わせて固定しても良いし、原料棒材１１の均熱化を図るために中心軸周りで回転させても良い。 First, the raw material bar 11 is placed in the induction heating device 13 of the powder manufacturing device 12. The raw material bar may be fixed with its central axis aligned with the induction heating device, or may be rotated around its central axis to ensure uniform heating of the raw material bar 11.
その後、粉末製造装置１２内の雰囲気を真空のような減圧雰囲気または不活性ガス雰囲気とし、誘導加熱装置１３によって原料棒材１１の一端を溶解していく。溶解されている原料棒材１１の一端から融液１４が形成され、重力により下方へ落下させる。このとき、誘導加熱によって生じる流れ場によって融液１４は均一に攪拌されている。そして、下方へ落下した融液１４に対してガスノズル１５から噴出するアルゴン、窒素、空気などの高圧ガス１６によって融液を噴霧し、飛散中に融液１４を冷却、固化させることで噴霧粉末１７を得る。 The atmosphere inside the powder manufacturing device 12 is then set to a reduced pressure atmosphere such as a vacuum or an inert gas atmosphere, and one end of the raw material bar 11 is melted by the induction heating device 13. A molten liquid 14 is formed from one end of the molten raw material bar 11, and is allowed to fall downward by gravity. At this time, the molten liquid 14 is uniformly stirred by the flow field generated by the induction heating. The molten liquid is then sprayed onto the molten liquid 14 that has fallen downward by high-pressure gas 16 such as argon, nitrogen, or air ejected from a gas nozzle 15, and the molten liquid 14 is cooled and solidified during scattering, obtaining the atomized powder 17.
より具体的には、得られた原料棒材１１を、直接溶解ガスアトマイズ法を適用して合金粉末１７を製造することができる。原料棒材１１を直接溶解ガスアトマイズ装置に設置し、雰囲気を０．０１ＭＰａ以下の減圧雰囲気とする。そして、原料棒材１１の端部近傍に配した誘導加熱装置によって原料棒材１１の端部を溶解して融液を得て、下方へ落下する融液に２～２０ＭＰａ、１００～１５００Ｌ／分の純アルゴンガスを吹き付けて融液を噴霧し、飛散中に冷却、凝固することで噴霧粉末を得ることができる。 More specifically, the obtained raw material bar 11 can be subjected to a direct dissolution gas atomization method to produce alloy powder 17. The raw material bar 11 is placed in a direct dissolution gas atomization device, and the atmosphere is reduced to a reduced pressure of 0.01 MPa or less. The end of the raw material bar 11 is melted by an induction heating device disposed near the end of the raw material bar 11 to obtain a molten liquid, and pure argon gas at 2 to 20 MPa and 100 to 1,500 L/min is sprayed onto the molten liquid that falls downward, and the molten liquid is cooled and solidified during scattering, thereby obtaining an atomized powder.
このとき、ガスノズルの配置並びにガス流量、流速、圧力などは、噴霧粉末１７の粒度分布を所望の値とするように適宜調整すればよい。以上、本実施形態であれば、原料棒材１１の融液１４が坩堝などに触れることなく、噴霧粉末１７を得ることができ、噴霧粉末１７の清浄度を確保できる利点がある。また、上記の高圧ガス１６は、特に限定せず、高温の融液に対する反応性を鑑みて、アルゴンガス、窒素ガスなどの不活性ガスを適宜選定すればよい。 At this time, the arrangement of the gas nozzles and the gas flow rate, flow speed, pressure, etc. may be adjusted as appropriate to obtain the desired particle size distribution of the sprayed powder 17. As described above, in this embodiment, the sprayed powder 17 can be obtained without the melt 14 of the raw material bar 11 coming into contact with a crucible or the like, and there is an advantage in that the cleanliness of the sprayed powder 17 can be ensured. In addition, the high-pressure gas 16 is not particularly limited, and an inert gas such as argon gas or nitrogen gas may be appropriately selected in consideration of its reactivity with the high-temperature melt.
溶解・噴霧工程において、原料棒材１１の一端を局所的に溶解（溶融）していく方法としては、高周波誘導加熱法やプラズマアーク加熱法を用いることが好ましい。これにより、原料棒材１１の一端を保持した状態で他端側を非接触で溶解することが可能となり、坩堝などに融液を接さずに供給することが可能となり、不純物の混入を抑制することができる。 In the melting and spraying process, it is preferable to use high-frequency induction heating or plasma arc heating as a method for locally melting (melting) one end of the raw material bar 11. This makes it possible to melt the other end of the raw material bar 11 without contact while holding one end of the raw material bar 11, and to supply the molten liquid to a crucible or the like without contacting it, thereby suppressing the inclusion of impurities.
また、溶解棒材１１は、プラズマアーク加熱法に用いてもよい。プラズマアーク加熱法は、溶解棒材をプラズマアーク熱により溶解させるが、得た融液を高圧ガスへ暴露したり、原料棒材を回転させながら溶解させる回転電極法を用いたりすることで、融液を遠心力で飛散させたり、融液に超音波を加えることもできる。具体例として、回転電極法を例に説明する。回転電極法はプラズマアーク熱によって原料棒材１１を回転させながら溶解し、得た融液を遠心力で飛散させ、飛散中に固化し噴霧粉末を得る。これらは、溶解手段と合わせて選定でき、何れも坩堝などに融液を接さずに固化できるため、不純物の混入を抑制することができる。ここで、融液に付与する遠心力や微振動は、原料棒材に回転機構や振動機構を配すればよく、それら機構を用いて、噴霧粉末の粒度や円形度などに応じて、適宜設定すればよい。 The melting rod 11 may also be used in a plasma arc heating method. In the plasma arc heating method, the melting rod is melted by plasma arc heat, but the obtained melt can be exposed to high-pressure gas or the rotating electrode method, in which the raw material rod is melted while rotating, to scatter the melt by centrifugal force or to apply ultrasonic waves to the melt. As a specific example, the rotating electrode method will be described. In the rotating electrode method, the raw material rod 11 is melted while rotating by plasma arc heat, and the obtained melt is scattered by centrifugal force, and solidified during scattering to obtain sprayed powder. These can be selected in accordance with the melting means, and since both can solidify the melt without contacting the crucible, etc., it is possible to suppress the inclusion of impurities. Here, the centrifugal force and micro-vibration applied to the melt can be applied by providing a rotating mechanism or a vibrating mechanism to the raw material rod, and these mechanisms can be used to appropriately set according to the particle size, circularity, etc. of the sprayed powder.
より具体的には、図３に示すように、原料棒材２１を軸中心に回転できるよう、粉末製造装置２２の電極回転機構２３に固定する。その後、雰囲気を真空雰囲気または不活性ガス雰囲気とし、原料棒材２１を中心軸周りで１００００ｒｐｍ以上の高速で回転させる。この回転速度は噴霧粉末２６の粒径制御に用いられる。原料棒材２１を回転した状態でプラズマ加熱装置２４によって原料棒材２１の一端を溶解し、生じた融液２５を回転によって加わる遠心力で直ちに飛散させる。そして、飛散中に融液を冷却、凝固させることで噴霧粉末２６を得る。 More specifically, as shown in FIG. 3, the raw material bar 21 is fixed to an electrode rotation mechanism 23 of a powder manufacturing device 22 so that it can rotate around its axis. The atmosphere is then set to a vacuum or inert gas atmosphere, and the raw material bar 21 is rotated around its central axis at a high speed of 10,000 rpm or more. This rotation speed is used to control the particle size of the sprayed powder 26. While the raw material bar 21 is rotating, one end of the raw material bar 21 is melted by a plasma heating device 24, and the resulting molten liquid 25 is immediately scattered by the centrifugal force applied by the rotation. The molten liquid is then cooled and solidified during scattering to obtain the sprayed powder 26.
原料棒材を電極回転機構２３に設置し、雰囲気を０．０１ＭＰａ以下の減圧雰囲気とする。そして、原料棒材２１を例えば１００００ｒｐｍの回転速度にて、棒材の長軸を中心に回転させる。原料棒材２１の端部近傍に配したプラズマ加熱装置によって回転する原料棒材２１の端部を溶解して融液を得て、原料棒材２１の回転で生じる遠心力によって側方へ飛散させる。そして、飛散中に融液を冷却、凝固することで噴霧粉末２６を得る。 The raw material bar is placed in the electrode rotation mechanism 23, and the atmosphere is reduced to a reduced pressure of 0.01 MPa or less. The raw material bar 21 is then rotated around the longitudinal axis of the bar at a rotation speed of, for example, 10,000 rpm. A plasma heating device disposed near the end of the raw material bar 21 melts the end of the rotating raw material bar 21 to obtain a molten liquid, which is then scattered to the side by the centrifugal force generated by the rotation of the raw material bar 21. The molten liquid is then cooled and solidified during scattering to obtain the atomized powder 26.
上記の溶解・噴霧工程であれば、焼結体（原料棒材）の融液から直接に噴霧粉末を得ることができ、噴霧粉末の清浄度を確保できる利点がある。また、噴霧粉末は高圧ガスとの相互作用無しに形成できるため、ガスアトマイズ法で得た合金粉末に比べて真球度の高い噴霧粉末とすることができる。 The above melting and spraying process has the advantage that the atomized powder can be obtained directly from the melt of the sintered body (raw bar material), ensuring the cleanliness of the atomized powder. In addition, the atomized powder can be formed without interacting with high-pressure gas, so the atomized powder can have higher sphericity than the alloy powder obtained by the gas atomization method.
以上、上記のような合金粉末の製造方法の実施形態であれば、坩堝を用いることなく合金粉末を製造できるため、溶解した高融点金属を含む合金が坩堝に残置することがなく、溶け残りや坩堝との反応による組成の不均一性が生じることを抑制でき、所望組成の噴霧粉末（合金粉末と言うことがある）を得ることができる。 As described above, the embodiment of the alloy powder manufacturing method can produce alloy powder without using a crucible, so that the alloy containing the molten high-melting point metal is not left in the crucible, and the occurrence of non-uniformity in the composition due to unmelted parts or reactions with the crucible can be suppressed, and spray powder (sometimes called alloy powder) of the desired composition can be obtained.
［分級工程（Ｓ１０５）］
上記工程（Ｓ１０１～Ｓ１０３）を経てから分級工程（Ｓ１０５）を追加することが好ましい。溶解・噴霧工程（Ｓ１０３）で得られた噴霧粉末（合金粉末）は、篩別分級法、旋回気流分級法などの手法で粒度分布を調整することが好ましい。具体的な合金粉末の平均粒径としては、ハンドリング性や充填性の観点から、１０μｍ以上２００μｍ以下が好ましい。平均粒径が１０μｍ未満になると、合金粉末が舞い上がり易くなり、積層造形体の形状精度が低下する要因となる場合がある。一方、平均粒径が２００μｍ超になると、積層造形体の表面粗さが増加するのみでなく、特に高融点を有する合金粉末２０の溶融が不十分になる要因にもなる。また、この中で用いる製造方法によって好適な平均粒径は異なる。例えば金属積層造形法について例示すると、選択的レーザ溶融（Ｓｅｌｅｃｔｉｖｅ Ｌａｓｅｒ Ｍｅｌｔｉｎｇ：ＳＬＭ）法では１０μｍ以上５０μｍ以下、電子ビーム積層造形（Ｅｌｅｃｔｒｏｎ Ｂｅａｍ Ｍｅｌｔｉｎｇ：ＥＢＭ）法では４５μｍ以上１０５μｍ以下がより好ましい。
[Classification step (S105)]
It is preferable to add a classification step (S105) after the above steps (S101 to S103). It is preferable to adjust the particle size distribution of the sprayed powder (alloy powder) obtained in the dissolving and spraying step (S103) by a method such as a sieve classification method or a swirling air current classification method. The specific average particle size of the alloy powder is preferably 10 μm or more and 200 μm or less from the viewpoint of handling and filling properties. If the average particle size is less than 10 μm, the alloy powder is likely to fly up, which may cause a decrease in the shape accuracy of the layered molded body. On the other hand, if the average particle size exceeds 200 μm, not only will the surface roughness of the layered molded body increase, but it will also cause the alloy powder 20, which has a particularly high melting point, to melt insufficiently. In addition, the suitable average particle size differs depending on the manufacturing method used. For example, in the case of metal additive manufacturing, a thickness of 10 μm or more and 50 μm or less is more preferable in the selective laser melting (SLM) method, and a thickness of 45 μm or more and 105 μm or less is more preferable in the electron beam melting (EBM) method.
また、レーザビーム粉末肉盛（Ｌａｓｅｒ Ｍｅｔａｌ Ｄｅｐｏｓｉｔｉｏｎ：ＬＭＤ）法では５０μｍ以上２００μｍ以下とすると良い。 In addition, for the Laser Metal Deposition (LMD) method, it is recommended that the thickness be between 50 μm and 200 μm.
また、本実施形態の溶解原料を用いた合金粉末の製造方法であれば、高融点元素などを多種類含んだＮｂ、Ｍｏ、Ｔａ、Ｗ等から成るハイエントロピー合金（ＨＥＡ）の合金粉末を製造することも可能である。 In addition, the method for producing alloy powder using the molten raw material of this embodiment makes it possible to produce high entropy alloy (HEA) powder made of Nb, Mo, Ta, W, etc., which contain many types of high melting point elements.
以上、上記の溶解原料の製造方法の一実施形態であれば、高融点金属を含んだＨＥＡの合金粉末を製造できる。また、高融点の純金属粉を混合してＳＬＭ法で溶融する場合の課題であった、相対的に低融点のＮｂやＭｏと相対的に高融点のＴａやＷの偏析を抑制する効果も期待できるし、合金粉末を積層造形して得られた積層造形体の濃度変動をも抑制する効果も期待できる。 As described above, one embodiment of the method for producing the melting raw material makes it possible to produce alloy powder of HEA containing a high melting point metal. In addition, it is expected to have the effect of suppressing the segregation of relatively low melting point Nb and Mo and relatively high melting point Ta and W, which was an issue when mixing high melting point pure metal powders and melting them by the SLM method, and it is also expected to have the effect of suppressing concentration fluctuations in the layered product obtained by layering the alloy powder.
＜合金粉末＞
上記した好適な合金粉末の製造方法の実施形態によって、高融点な元素、具体的には融点が１６００℃以上の高融点金属元素を２種類以上含む合金粉末を得ることができる。さらに、円形度が０．５以上、好ましくは０．７以上であり、平均粒径が１０μｍ以上２００μｍ未満の合金粉末を得ることも可能である。なお合金粉末の組成は、誘導結合プラズマ発光分光分析法で評価することができる。
<Alloy powder>
The above-described preferred embodiment of the alloy powder manufacturing method can provide alloy powder containing two or more high-melting point elements, specifically high-melting point metal elements having a melting point of 1600° C. or higher. Furthermore, it is also possible to obtain alloy powder having a circularity of 0.5 or more, preferably 0.7 or more, and an average particle size of 10 μm or more and less than 200 μm. The composition of the alloy powder can be evaluated by inductively coupled plasma atomic emission spectrometry.
上記した合金粉末を用いて、図４に示すような粉末積層造形装置により、ＳＬＭ法による造形部材を積層造形することもできる。造形条件としては、例えば、レーザ出力：１００Ｗ～３００Ｗ、レーザ走査速度：５０～３００ｍｍ／秒、走査間隔：０．０１～０．１０ｍｍを適用することができるが、特に限定しない。 The alloy powder described above can be used to layer-model a modeled component by the SLM method using a powder layer-modeling device as shown in Figure 4. The modeling conditions are not particularly limited, but may be, for example, laser output: 100 W to 300 W, laser scanning speed: 50 to 300 mm/sec, and scanning interval: 0.01 to 0.10 mm.
また、例えば、得られた合金粉末に対し、図５に示すような粉末積層造形装置を用いて、ＬＭＤ法による造形部材を積層造形することもできる。造形条件として、例えば、レーザ出力：０．６～２．４ｋＷ、走査速度：１００～１５００ｍｍ／分、走査間隔：０．５～３．０ｍｍ、粉末供給量：４～１４ｇ／分を適用することができるが、特に限定しない。 For example, the obtained alloy powder can be used to layer-model a shaped component by the LMD method using a powder layer-modeling device as shown in FIG. 5. The layer-modeling conditions that can be applied are, for example, laser output: 0.6 to 2.4 kW, scanning speed: 100 to 1500 mm/min, scanning interval: 0.5 to 3.0 mm, and powder supply amount: 4 to 14 g/min, but are not particularly limited.
［用途・製造物］
上述の好適な製造方法にて製造された合金粉末は、特に高融点金属を主成分に含む合金に対して有効であり、金属積層造形、圧粉成型、粉末冶金、金属射出成型などに好適に用いることができるが、用途や製造物は特に制限されない。
[Uses/Products]
The alloy powder produced by the above-mentioned preferred production method is particularly effective for alloys containing a high melting point metal as a main component, and can be suitably used in metal additive manufacturing, powder compaction, powder metallurgy, metal injection molding, etc., but there are no particular limitations on the applications and products.
本発明の合金粉末を用いた造形物及び成形物の用途の一例としては、高温環境に用いられる金型や電極部品や加熱熱源、熱処理炉および反応炉内構造体、Ｘ線及び粒子線フィルタ、加工工具などへの適用が好適である。本明細書でいう製造物とは、これらの機械、機器、部材、金型、部品等を総称する。 Examples of applications of shaped and molded products using the alloy powder of the present invention include dies, electrode parts, heating sources, heat treatment furnaces and reactor internal structures, X-ray and particle beam filters, machining tools, etc. that are used in high-temperature environments. In this specification, the term "manufactured products" collectively refers to these machines, devices, members, dies, parts, etc.
以下、実施例および比較例により本発明をさらに具体的に説明する。なお、本発明はこれらの実施例に限定されるものではない。 The present invention will be explained in more detail below with reference to examples and comparative examples. Note that the present invention is not limited to these examples.
［実験１］（Ａ１およびＡ２の混合粉末の作製）
表１に示す質量比で複数の原料粉末を混合し、Ａ１およびＡ２の混合粉末を用意した。原料粉末は何れも化学還元法で得られた純合金粉末であり、表１に示すように何れも融点１６００℃以上の金属元素の粉末を１０原子％以上含んでいた。Ｖミキサーによって３０分以上混合することで、各々の原料粉末内での複数の比重の異なる原料粉末を均一に混合した。
[Experiment 1] (Preparation of mixed powder of A1 and A2)
A plurality of raw material powders were mixed in the mass ratios shown in Table 1 to prepare mixed powders A1 and A2. All of the raw material powders were pure alloy powders obtained by chemical reduction, and as shown in Table 1, all contained 10 atomic % or more of powder of metal elements with melting points of 1600° C. or higher. By mixing for 30 minutes or more in a V mixer, the raw material powders with different specific gravities within each raw material powder were uniformly mixed.
［実験２］
＜原料棒材Ｂ１およびＢ２の製造＞
実験１で用意した混合粉末Ａ１とＡ２とを各々１０ｋｇを、カプセル（直径１２０ｍｍ、高さ６００ｍｍ、ＳＵＳ３０４製）に封入して０．０１ＭＰａ以下に脱気をして密封した。そして、ＨＩＰ設備に配して１２５０℃で、１１０ＭＰａの加圧雰囲気下に５時間保持し、カプセル中で各々の原料粉末を固化した。これによりＡ１とＡ２に対応する、直径１００ｍｍ、長さ５００ｍｍの原料棒材Ｂ１とＢ２を得た。
[Experiment 2]
<Production of Raw Material Bars B1 and B2>
10 kg each of the mixed powders A1 and A2 prepared in Experiment 1 were enclosed in a capsule (diameter 120 mm, height 600 mm, made of SUS304), degassed to 0.01 MPa or less, and sealed. Then, the capsule was placed in a HIP facility and held at 1250°C under a pressurized atmosphere of 110 MPa for 5 hours to solidify each raw material powder in the capsule. As a result, raw material bars B1 and B2 corresponding to A1 and A2, each having a diameter of 100 mm and a length of 500 mm, were obtained.
（実施例）
得られた原料棒材の断面観察による空隙面積の評価の結果、原料棒材Ｂ１は４％の空隙率、原料棒材Ｂ２は１％の空隙率であった。いずれも高融点組成の粉末を用いているものの、高温高圧下のＨＩＰ処理により、十分に空隙率の低い棒材に固化できた。
(Example)
As a result of evaluating the void area by observing the cross section of the obtained raw material bar, the void ratio of raw material bar B1 was 4%, and the void ratio of raw material bar B2 was 1%. Although both used powders with high melting points, they were able to be solidified into rods with sufficiently low void ratios by HIP treatment under high temperature and high pressure.
（比較例１）
Ａ１を基に、冷間プレス（室温（２２℃）、１００ＭＰａ、１０分間による原料棒材の作製を試みたが、プレスした原料は粉体同士の結合が起こらず、固化しないため、棒材を得ることができなかった。
(Comparative Example 1)
Based on A1, an attempt was made to prepare a raw material bar by cold pressing (room temperature (22°C), 100 MPa, 10 minutes). However, the pressed raw material did not solidify because the powder particles did not bond with each other, and the bar could not be obtained.
（比較例２）
Ａ１を基に、該原料粉末を構成する元素の中で最も融点が低い元素であるＺｒ（１８５５℃）の融点の２／３℃に満たない３００℃にて熱間プレス（１００ＭＰａ、１０分間）による原料棒材作製を試みたが、空隙率は高く、固化しないため、緻密な棒材を得ることができなかった。この原料棒材の断面観察による空隙面積の評価の結果、空隙率は２８％であった。
(Comparative Example 2)
Using A1 as a base, an attempt was made to produce a raw material bar by hot pressing (100 MPa, 10 minutes) at 300°C, which is less than 2/3°C of the melting point of Zr (1855°C), the element with the lowest melting point among the elements constituting the raw material powder, but the porosity was high and the bar did not solidify, so a dense bar could not be obtained. As a result of evaluating the void area by observing the cross section of this raw material bar, the porosity was 28%.
上述した実施形態や実施例は、本発明の理解を助けるために説明したものであり、本発明は、記載した具体的な構成のみに限定されるものではない。例えば、ある実施形態の構成の一部を他の実施形態の構成に置き換えることが可能であり、また、ある実施形態の構成に他の実施形態の構成を加えることも可能である。すなわち、本発明は、本明細書の実施形態や実施例の構成の一部について、削除したり、他の構成に置換したり、また他の構成の追加をすることが可能である。このような実施形態の調整により、本発明で開示した合金粉末は、高温部品やプラント機器、金型部材などで用いられる高融点金属部品を製造することに適用することが可能となる。 The above-mentioned embodiments and examples are described to aid in understanding the present invention, and the present invention is not limited to the specific configurations described. For example, it is possible to replace part of the configuration of one embodiment with the configuration of another embodiment, and it is also possible to add the configuration of another embodiment to the configuration of one embodiment. In other words, the present invention allows for the deletion of part of the configuration of the embodiments and examples in this specification, the replacement of part with another configuration, and the addition of another configuration. By adjusting the embodiments in this way, the alloy powder disclosed in this invention can be applied to the production of high-melting point metal parts used in high-temperature parts, plant equipment, mold components, etc.
１１：原料棒材
１２：粉末製造装置
１３：誘導加熱装置
１４：融液
１５：ガスノズル
１６：高圧ガス
１７：噴霧粉末
２２：粉末製造装置
２３：電極回転機構
２４：プラズマ加熱装置
２５：融液
２６：噴霧粉末
１００：ＳＬＭ粉末積層造形装置
１０１：造形部材
１０２：ステージ
１０３：ベースプレート
１０４：パウダー供給用コンテナ
１０５：合金粉末
１０６：リコータ
１０７：粉末床（層状粉末）
１０８：レーザ発振器
１０９：レーザビーム
１１０：ガルバノメーターミラー
１１１：未溶融粉末回収用コンテナ
１１２：２Ｄスライス形状の凝固層
２００：粉末積層造形装置
２０１：レーザヘッド
２０２：造形基材
２０３：バイス（固定治具）
２０４：テーブル
２０５：レーザ発振器
２０６：粉末供給機
２１０：装置外壁
２１１：全面ドア
２１２：操作パネル
２２０：ノズル
２２１：粉末
２２２：シールドガス
２２３：造形体
11: Raw material bar 12: Powder manufacturing device 13: Induction heating device 14: Melt 15: Gas nozzle 16: High pressure gas 17: Sprayed powder 22: Powder manufacturing device 23: Electrode rotation mechanism 24: Plasma heating device 25: Melt 26: Sprayed powder 100: SLM powder additive manufacturing device 101: Modeling member 102: Stage 103: Base plate 104: Powder supply container 105: Alloy powder 106: Recoater 107: Powder bed (layered powder)
108: Laser oscillator 109: Laser beam 110: Galvanometer mirror 111: Container for collecting unmelted powder 112: Solidified layer of 2D slice shape 200: Powder additive manufacturing device 201: Laser head 202: Modeling substrate 203: Vice (fixing jig)
204: Table 205: Laser oscillator 206: Powder feeder 210: Outer wall of the device 211: Front door 212: Operation panel 220: Nozzle 221: Powder 222: Shielding gas 223: Model
Claims (3)
複数種の原料粉末からなる混合粉末を、前記原料粉末を構成する元素の中で最も融点が低い元素の融点をＭＰｍｉｎ（℃）としたとき、２ＭＰｍｉｎ／３以上の温度で、かつ５ＭＰａ以上の圧力で焼結する加圧焼結工程と、を備え
前記溶解原料は、直接溶解ガスアトマイズ法またはプラズマアーク加熱法に用いるものであり、
前記原料粉末は、融点が１６００℃以上の高融点金属元素からなり、
前記高融点金属元素は、タングステン、レニウム、オスミウム、タンタル、モリブデン、ニオブ、ハフニウム、テクチニウム、クロム、ジルコニウム、トリウムおよびチタンのうち、少なくとも二種類含み、
原子％で、前記チタンが３３．３３％以下であること
を特徴とする溶解原料の製造方法。 A melting raw material to be melted and atomized to obtain an alloy powder,
a pressure sintering step of sintering a mixed powder consisting of a plurality of kinds of raw material powders at a temperature of 2 MPmin /3 or more and a pressure of 5 MPa or more, where MPmin (°C) is the melting point of the element having the lowest melting point among the elements constituting the raw material powders;
The raw material powder is made of a high-melting point metal element having a melting point of 1600° C. or more,
The high melting point metal element includes at least two of tungsten, rhenium, osmium, tantalum, molybdenum, niobium, hafnium, tectinium, chromium, zirconium, thorium, and titanium;
A method for producing a molten raw material, characterized in that the titanium content is 33.33% or less in atomic percent.
複数種の原料粉末からなる混合粉末を、前記原料粉末を構成する元素の中で最も融点が低い元素の融点をＭＰｍｉｎ（℃）としたとき、２ＭＰｍｉｎ／３以上の温度で、かつ５ＭＰａ以上の圧力で焼結する加圧焼結工程と、を備え
前記溶解原料は、直接溶解ガスアトマイズ法またはプラズマアーク加熱法に用いるものであり、
前記原料粉末は、
融点が１６００℃以上の高融点金属元素からなり、前記高融点金属元素を少なくとも二種類含み、
前記合金粉末がハイエントロピー合金であり、
前記原料粉末において、原子％で、チタンは３３．３３％以下であること
を特徴とする溶解原料の製造方法。 A melting raw material to be melted and atomized to obtain an alloy powder,
a pressure sintering step of sintering a mixed powder consisting of a plurality of kinds of raw material powders at a temperature of 2 MPmin /3 or more and a pressure of 5 MPa or more, where MPmin (°C) is the melting point of the element having the lowest melting point among the elements constituting the raw material powders;
The raw material powder is
The alloy is made of a high-melting-point metal element having a melting point of 1600° C. or higher, and contains at least two kinds of the high-melting-point metal elements ;
The alloy powder is a high entropy alloy,
The method for producing a raw material for melting, wherein the raw material powder contains titanium in an atomic percentage of 33.33 or less.
ことを特徴とする請求項１または２に記載の溶解原料の製造方法。
3. The method for producing a raw material for melting according to claim 1, wherein the pressure sintering step uses a hot isostatic pressure sintering method.
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| JP2005298855A (en) | 2004-04-07 | 2005-10-27 | Toyota Central Res & Dev Lab Inc | Titanium alloy, titanium-alloy product and method for manufacturing them |
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| WO2020115201A1 (en) | 2018-12-07 | 2020-06-11 | The Swatch Group Research And Development Ltd | Method for manufacturing precious metal alloys and precious metal alloys thus obtained |
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| JP2002241807A (en) | 2001-02-13 | 2002-08-28 | Sumitomo Titanium Corp | Method for manufacturing titanium-aluminum alloy powder |
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