JP2005350710A - Heat-resistant alloy for metallic powder to be injection-molded - Google Patents

Heat-resistant alloy for metallic powder to be injection-molded Download PDF

Info

Publication number
JP2005350710A
JP2005350710A JP2004171078A JP2004171078A JP2005350710A JP 2005350710 A JP2005350710 A JP 2005350710A JP 2004171078 A JP2004171078 A JP 2004171078A JP 2004171078 A JP2004171078 A JP 2004171078A JP 2005350710 A JP2005350710 A JP 2005350710A
Authority
JP
Japan
Prior art keywords
mass
concentration
fine powder
heat
inconel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2004171078A
Other languages
Japanese (ja)
Inventor
Tetsuya Kondo
鉄也 近藤
Makoto Kawamura
誠 川村
Takeshi Hasegawa
健 長谷川
Norihiro Ogawa
典弘 小川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daido Steel Co Ltd
Original Assignee
Daido Steel Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daido Steel Co Ltd filed Critical Daido Steel Co Ltd
Priority to JP2004171078A priority Critical patent/JP2005350710A/en
Priority to EP05012365A priority patent/EP1634972A2/en
Publication of JP2005350710A publication Critical patent/JP2005350710A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-resistant alloy which has a similar composition to Inconel (R)713C, and can be formed into fine powder to be metal-injection-molded with a spray method. <P>SOLUTION: This heat-resistant alloy comprises, by mass%, 0.08-0.20% C, 0-0.25% Mn, 0-0.015% S, 0.2-1.0% Si, 12.0-14.0% Cr, 3.80-5.20% Mo, 0-0.1% Ti, 5.50-6.50% Al, 2.58-4.74% Nb, 0-2.5% Fe, 0.05-0.15% Zr, 0-0.015% B, 0-1.00% Co, and the balance Ni with unavoidable impurities. Because the alloy has the composition which substitutes Nb for Ti in Inconel 713C and does not include Ti, it does not cause clogging during teeming in process of producing the fine powder with the spray method. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、金属粉末射出成形用耐熱合金に関し、特に、インコネル（登録商標）７１３Ｃと同等の組成を有する金属粉末射出成形用耐熱合金に関する。   The present invention relates to a heat resistant alloy for metal powder injection molding, and more particularly to a heat resistant alloy for metal powder injection molding having a composition equivalent to Inconel (registered trademark) 713C.

耐熱部品は、精密鋳造または鍛造により製造されることが多いが、金属粉末射出成形（Metal injection moulding、以下、ＭＩＭという）が、近年、適用範囲を広げている。   Although heat-resistant parts are often manufactured by precision casting or forging, metal powder injection (hereinafter referred to as “MIM”) has recently expanded its application range.

このＭＩＭは、金属微粉末をバインダ樹脂と混ぜた混合物を、金型内に射出して成形する方法であり、金属が微粉末とされていることから、充填率が高く、成型品の表面を滑らかにすることができ、また、三次元の複雑な形状をニアネットシェイプで製造できるという特徴を有する。そのため、例えばターボチャージャーベーンがＭＩＭにより製造される。   This MIM is a method in which a mixture obtained by mixing a metal fine powder with a binder resin is injected into a mold and molded, and since the metal is a fine powder, the filling rate is high and the surface of the molded product is It has a feature that it can be made smooth and a three-dimensional complicated shape can be manufactured with a near net shape. Therefore, for example, turbocharger vanes are manufactured by MIM.

また、上記金属微粉末は、溶融合金をノズルから噴霧して微粉末とする、噴霧法を用いて製造されている。   Moreover, the said metal fine powder is manufactured using the spraying method which sprays a molten alloy from a nozzle to make a fine powder.

現在、ＭＩＭに用いることができる耐熱合金粉末としては、ＳＵＳ系（３１０等）、ハステロイ（登録商標）系、ナイモニック（登録商標）系が知られているが、いずれも強度が不十分であった。   Currently, SUS (310 grade), Hastelloy (registered trademark), and Nimonic (registered trademark) are known as heat-resistant alloy powders that can be used for MIM, but all have insufficient strength. .

そこで、ＭＩＭ用の耐熱合金粉末として、鋳造用原料としてはナイモニック９０よりも高強度であることが知られているインコネル７１３Ｃを用いることが考えられる。なお、インコネル７１３Ｃは、以下の組成を有する合金である（単位は質量％）。
Ｃ：０．０８〜０．２０、Ｍｎ：０．２５ｍａｘ、Ｓ：０．０１５ｍａｘ、Ｓｉ：０．５０ｍａｘ、Ｃｒ：１２．０〜１４．０、Ｍｏ：３．８０〜５．２０、Ｔｉ：０．５０〜１．００、Ａｌ：５．５０〜６．５０、Ｆｅ：２．５ｍａｘ、Ｎｂ：１．８０〜２．８０、Ｚｒ：０．０５〜０．１５、Ｂ：０．００５〜０．０１５、Ｃｏ：１．００ｍａｘ、Ｎｉ：残部 Therefore, it is conceivable to use Inconel 713C, which is known to have higher strength than Nimonic 90, as the casting raw material as the heat-resistant alloy powder for MIM. Inconel 713C is an alloy having the following composition (unit: mass%).
C: 0.08 to 0.20, Mn: 0.25max, S: 0.015max, Si: 0.50max, Cr: 12.0 to 14.0, Mo: 3.80 to 5.20, Ti: 0.50 to 1.00, Al: 5.50 to 6.50, Fe: 2.5max, Nb: 1.80 to 2.80, Zr: 0.05 to 0.15, B: 0.005 0.015, Co: 1.00 max, Ni: balance

しかし、インコネル７１３Ｃは、噴霧法による微粉末製造過程でノズルが閉塞してしまう、すなわち、注湯閉塞を生じてしまうので、ＭＩＭ用の微粉末を製造することができなかった。   However, with Inconel 713C, the nozzle is clogged in the process of producing the fine powder by the spraying method, that is, the molten metal is clogged, so that the MIM fine powder could not be produced.

本発明は、以上の事情を背景として為されたものであり、その目的とするところは、インコネル７１３Ｃと同等の組成を有し、ＭＩＭ用に噴霧法にて微粉末とすることができる組成を有する耐熱合金を提供することにある。   The present invention has been made against the background of the above circumstances, and its object is to have a composition that is equivalent to Inconel 713C and can be made into a fine powder by spraying for MIM. The object is to provide a heat-resistant alloy.

前記インコネル７１３Ｃが噴霧法による微粉末製造工程において注湯閉塞を起こすのは、それに含まれるＴｉ含量の範囲に問題があることを突き止めた。すなわち、Ｔｉ濃度が０．１質量％よりも大きく、１質量％以下の範囲である場合に、注湯閉塞を起こしてしまうことを突き止めた。   It has been found that the inconel 713C has a problem in the range of the Ti content contained in the molten metal in the fine powder manufacturing process by the spray method. That is, when the Ti concentration is larger than 0.1% by mass and in the range of 1% by mass or less, it has been found that pouring clogging occurs.

そこで、本発明は、Ｔｉ含量を上記範囲外としつつ、Ｔｉ原子と、Ｔｉ原子と同様に固溶強化の目的で添加されるＮｂ原子の合計原子数がインコネル７１３Ｃと同程度となるように、Ｎｂの濃度を調整したものである。   Therefore, in the present invention, the Ti content is out of the above range, and the total number of Ti atoms and Nb atoms added for the purpose of solid solution strengthening is the same as that of Inconel 713C. The Nb concentration is adjusted.

すなわち、前記目的を達成するための第１発明は、Ｃ：０．０８〜０．２０質量％、Ｍｎ：０〜０．２５質量％、Ｓ：０〜０．０１５質量％、Ｓｉ：０．２〜１．０質量％、Ｃｒ：１２．０〜１４．０質量％、Ｍｏ：３．８０〜５．２０質量％、Ｔｉ：０〜０．１質量％、Ａｌ：５．５０〜６．５０質量％、Ｎｂ：２．５８〜４．７４質量％、Ｆｅ：０〜２．５質量％、Ｂ：０〜０．０１５質量％、Ｃｏ：０〜１．００質量％を含み、残部がＮｉおよび不可避不純物であることを特徴とする金属粉末射出成形用耐熱合金である。   That is, the first invention for achieving the above object is as follows: C: 0.08 to 0.20 mass%, Mn: 0 to 0.25 mass%, S: 0 to 0.015 mass%, Si: 0.00. 2-1.0 mass%, Cr: 12.0-14.0 mass%, Mo: 3.80-5.20 mass%, Ti: 0-0.1 mass%, Al: 5.50-6. 50% by mass, Nb: 2.58 to 4.74% by mass, Fe: 0 to 2.5% by mass, B: 0 to 0.015% by mass, Co: 0 to 1.00% by mass, the balance being A heat-resistant alloy for metal powder injection molding characterized by Ni and inevitable impurities.

また、前記目的を達成するための第２発明は、Ｃ：０．０８〜０．２０質量％、Ｍｎ：０〜０．２５質量％、Ｓ：０〜０．０１５質量％、Ｓｉ：０．２〜１．０質量％、Ｃｒ：１２．０〜１４．０質量％、Ｍｏ：３．８０〜５．２０質量％、Ｔｉ：１．００〜２．４４質量％、Ａｌ：５．５０〜６．５０質量％、Ｆｅ：０〜２．５質量％、Ｂ：０〜０．０１５質量％、Ｃｏ：０〜１．００質量％を含み、前記Ｔｉ濃度をαとしたとき、Ｎｂの濃度（質量％）が、（１．４３−α）×９２．９１／４７．８８〜（２．４４−α）×９２．９１／４７．８８であり、残部がＮｉおよび不可避不純物であることを特徴とする金属粉末射出成形用耐熱合金である。   Moreover, 2nd invention for achieving the said objective is C: 0.08-0.20 mass%, Mn: 0-0.25 mass%, S: 0-0.015 mass%, Si: 0.00. 2 to 1.0% by mass, Cr: 12.0 to 14.0% by mass, Mo: 3.80 to 5.20% by mass, Ti: 1.00 to 2.44% by mass, Al: 5.50 to 6.50% by mass, Fe: 0 to 2.5% by mass, B: 0 to 0.015% by mass, Co: 0 to 1.00% by mass, where the Ti concentration is α, the concentration of Nb (% By mass) is (1.43-α) × 92.91 / 47.88 to (2.44−α) × 92.91 / 47.88, and the balance is Ni and inevitable impurities. A heat-resistant alloy for metal powder injection molding.

第１発明よれば、Ｔｉ濃度が０〜０．１質量％あるので、注湯閉塞を生じることなく噴霧法にてＭＩＭ用粉末が製造できる。   According to the first invention, since the Ti concentration is 0 to 0.1% by mass, the MIM powder can be produced by the spray method without causing pouring clogging.

第２発明によれば、Ｔｉ濃度が１．００質量％よりも多いので、注湯閉塞を生じることなく噴霧法にてＭＩＭ用粉末が製造できる。   According to the second invention, since the Ti concentration is higher than 1.00% by mass, the MIM powder can be produced by the spraying method without causing pouring clogging.

本発明の合金の組成は、前述のインコネル７１３Ｃを基本としており、Ｓｉ、Ｔｉ、Ｎｂ、Ｂ、およびＺｒの割合がインコネル７１３Ｃと異なっている。その異なっているものについて、以下に詳述する。   The composition of the alloy of the present invention is based on the aforementioned Inconel 713C, and the ratio of Si, Ti, Nb, B, and Zr is different from that of Inconel 713C. The differences will be described in detail below.

Ｓｉは、溶融合金の酸化防止のために添加するものであり、０．２ｗｔ％より少ないと、酸化防止効果が不十分となって、前述の注湯閉塞が生じてしまう。一方、添加量が多くなりすぎると、硬さが増加するため割れが発生しやすくなる。また、融点が低下するため、耐熱温度も低下するので、１．０ｗｔ％よりも少なくする必要がある。   Si is added to prevent oxidation of the molten alloy. If it is less than 0.2 wt%, the anti-oxidation effect becomes insufficient and the above-mentioned pouring of the molten metal is caused. On the other hand, if the amount added is too large, the hardness increases and cracks are likely to occur. Further, since the melting point is lowered, the heat-resistant temperature is also lowered, so it is necessary to make it less than 1.0 wt%.

Ｂは、インコネル７１３Ｃでは、鋳造工程において結晶粒が大きくならないように添加されているが、ＭＩＭでは、合金が微粉末とされているため、必ずしも添加する必要はない。ただし、Ｂの添加には粒界強化という目的もあるため、インコネル７１３Ｃと同量添加されてもよい。すなわち、本発明におけるＢの濃度範囲は、０〜０．０１５ｗｔ％である。   In Inconel 713C, B is added so that the crystal grains do not become large in the casting process. However, in MIM, the alloy is made into a fine powder, so it is not always necessary to add B. However, since the addition of B also has the purpose of strengthening the grain boundary, it may be added in the same amount as Inconel 713C. That is, the concentration range of B in the present invention is 0 to 0.015 wt%.

Ｚｒは、噴霧法によって噴霧冷却される際に酸化物を生成して、その酸化物がノズルに詰まり易いので、本発明では、添加していない。   Zr is not added in the present invention because Zr generates an oxide when spray-cooled by a spraying method and the oxide easily clogs the nozzle.

次に、ＴｉおよびＮｂの割合について説明する。前述のように、インコネル７１３Ｃには、Ｔｉが０．５０〜１．００ｗｔ％添加され、Ｎｂが１．８０〜２．８０ｗｔ％添加されている。ここで、Ｎｂ原子（原子量９２．９１）を全てＴｉ原子（原子量４７．８８）に置き換えた場合を考えると、式１、２から、Ｎｂ＝１．８０ｗｔ％はＴｉ＝０．９３ｗｔ％に相当し、Ｎｂ＝２．８０ｗｔ％はＴｉ＝１．４４ｗｔ％に相当する。
（式１） １．８０×（４７．８８／９２．９１）＝０．９３
（式２） ２．８０×（４７．８８／９２．９１）＝１．４４ Next, the ratio of Ti and Nb will be described. As described above, 0.50 to 1.00 wt% of Ti and 1.80 to 2.80 wt% of Nb are added to Inconel 713C. Here, considering the case where all of the Nb atoms (atomic weight 92.91) are replaced with Ti atoms (atomic weight 47.88), Nb = 1.80 wt% is equivalent to Ti = 0.93 wt% from Formulas 1 and 2. Nb = 2.80 wt% corresponds to Ti = 1.44 wt%.
(Formula 1) 1.80 × (47.88 / 92.91) = 0.93
(Formula 2) 2.80 × (47.88 / 92.91) = 1.44

従って、Ｎｂ原子を全てＴｉ原子に置き換えた場合、Ｔｉ濃度範囲の下限は、０．５０＋０．９３＝１．４３ｗｔ％となり、Ｔｉ濃度範囲の上限は、１．０＋１．４４＝２．４４ｗｔ％となる。また、このときのＮｂ濃度は、Ｔｉ添加量によって定まる。すなわち、添加されているＮｂ原子を全てＴｉ原子に置き換えた場合、Ｔｉ濃度範囲は１．４３〜２．４４ｗｔ％となる必要があるから、Ｔｉ添加量をα（ｗｔ％）とすると、Ｔｉ：１．４３−α〜２．４４−α（ｗｔ％）に相当するＮｂ原子が添加される必要がある。従って、Ｎｂ濃度範囲の下限および上限は、それぞれ、式３、４で示される。
（式３） （１．４３−α）×９２．９１／４７．８８
（式４） （２．４４−α）×９２．９１／４７．８８ Therefore, when all Nb atoms are replaced with Ti atoms, the lower limit of the Ti concentration range is 0.50 + 0.93 = 1.43 wt%, and the upper limit of the Ti concentration range is 1.0 + 1.44 = 2.44 wt%. Become. Further, the Nb concentration at this time is determined by the amount of Ti added. That is, when all of the added Nb atoms are replaced with Ti atoms, the Ti concentration range needs to be 1.43 to 2.44 wt%. Therefore, when the Ti addition amount is α (wt%), Ti: It is necessary to add Nb atoms corresponding to 1.43-α to 2.44-α (wt%). Therefore, the lower limit and upper limit of the Nb concentration range are expressed by equations 3 and 4, respectively.
(Formula 3) (1.43-α) × 92.91 / 47.88
(Formula 4) (2.44−α) × 92.91 / 47.88

そして、Ｔｉ濃度を減少させて０〜０．１ｗｔ％とする場合、Ｎｂ濃度を求めるには、上記式３、４に、それぞれα＝０．１、α＝０を代入すればよいことから、Ｎｂ濃度は、２．５８〜４．７４（ｗｔ％）となる。   When the Ti concentration is decreased to 0 to 0.1 wt%, the Nb concentration can be obtained by substituting α = 0.1 and α = 0 into the above equations 3 and 4, respectively. The Nb concentration is 2.58 to 4.74 (wt%).

次に、Ｔｉ濃度を増加させて１．０ｗｔ％より大きくする場合を考える。この場合のＴｉ濃度範囲の上限は、Ｎｂ原子を全てＴｉ原子に置き換えた場合であるので、前述のように、２．４４ｗｔ％となる。そして、Ｔｉ濃度を増加させて１．０ｗｔ％より大きくしたときのＮｂ濃度範囲は、前述の式３、４により示される（ただし、この場合のαは１より大きく、また、αが１．４３以上であり、式３の値がマイナスとなる場合には、Ｎｂ濃度は０である）。   Next, consider a case where the Ti concentration is increased to be greater than 1.0 wt%. In this case, the upper limit of the Ti concentration range is the case where all Nb atoms are replaced with Ti atoms, so that it becomes 2.44 wt% as described above. The Nb concentration range when the Ti concentration is increased to be greater than 1.0 wt% is expressed by the above-described equations 3 and 4 (where α is greater than 1 and α is 1.43). (If the value of Equation 3 is negative, the Nb concentration is 0).

次に、本発明の実施例を比較例とともに示す。まず、本発明の組成範囲であれば、噴霧法による微粉末の製造が可能であることを示す実験について説明する。   Next, the Example of this invention is shown with a comparative example. First, an experiment showing that a fine powder can be produced by a spraying method within the composition range of the present invention will be described.

表１は、実施例、比較例の噴霧法による金属微粉末製造試験の結果を示している。噴霧法の条件を以下に示す。
＜噴霧法の条件＞
・噴霧圧力：７５０ｋｇｆ／ｃｍ２（７３５０Ｎ／ｃｍ２）
・噴霧水量：５４０Ｌ／ｍｉｎ
・注湯ノズル径：φ５ｍｍ
・出湯温度：１７３０℃ Table 1 shows the results of the metal fine powder production test by the spraying method of Examples and Comparative Examples. The conditions of the spray method are shown below.
<Conditions for spraying method>
Spray pressure: 750 kgf / cm 2 (7350 N / cm 2 )
・ Amount of spray water: 540 L / min
-Pouring nozzle diameter: φ5mm
・ Tapping temperature: 1730 ° C

Figure 2005350710
Figure 2005350710

実施例１は、Ｔｉ濃度を０それよりも少し大きい値とし、Ｎｂ濃度は、そのＴｉ濃度を前記式３に代入することによって求められる最低値としたものであり、この組成では、噴霧法による微粉末の製造が可能であった。実施例２は、Ｔｉ濃度は実施例１と同じであるが、Ｎｂ濃度は、そのＴｉ濃度を前記式４に代入することによって求められる最大値としたものである。この組成でも、噴霧法による微粉末の製造が可能であった。また、実施例８は、Ｎｂ濃度が実施例１と２の中間的な値であり、他の組成は実施例１、２と同じである。この組成でも、噴霧法による微粉末の製造が可能であった。従って、実施例１、２、８から、Ｔｉ濃度が極めて低い場合には、Ｎｂ濃度が前記式３および式４によって定まる範囲の全てにおいて、噴霧法による微粉末製造が可能であることが分かる。   In Example 1, the Ti concentration is set to a value slightly larger than 0, and the Nb concentration is set to the lowest value obtained by substituting the Ti concentration into the above-described Equation 3. In this composition, the spray method is used. A fine powder could be produced. In Example 2, the Ti concentration is the same as that in Example 1, but the Nb concentration is set to the maximum value obtained by substituting the Ti concentration into Equation 4. Even with this composition, it was possible to produce a fine powder by a spraying method. In Example 8, the Nb concentration is an intermediate value between Examples 1 and 2, and the other compositions are the same as those in Examples 1 and 2. Even with this composition, it was possible to produce a fine powder by a spraying method. Therefore, it can be seen from Examples 1, 2, and 8 that when the Ti concentration is extremely low, the fine powder can be produced by the spraying method in the entire range in which the Nb concentration is determined by the above formulas 3 and 4.

比較例２は、Ｔｉ濃度を実施例１のものよりも少し高くし、Ｎｂ濃度は、実施例１と同様に、そのＴｉ濃度を前記式３に代入することによって求められる最低値とした実験であるが、比較例２の場合には、注湯閉塞が生じてしまい噴霧法によって微粉末を製造することができなかった。また、比較例３は、Ｔｉ濃度を実施例２のものよりも少し高くし、Ｎｂ濃度は、実施例２と同様に、そのＴｉ濃度を前記式４に代入することによって求められる最大値とした実験であるが、比較例３の場合にも、注湯閉塞が生じてしまい噴霧法によって微粉末を製造することができなかった。従って、比較例２と実施例１との比較、および比較例３と実施例２との比較から、Ｔｉ＋Ｎｂの原子数が等しくても、Ｔｉ濃度が０．１ｗｔ％よりも高い場合には、噴霧法による微粉末製造ができないことが分かる。   Comparative Example 2 is an experiment in which the Ti concentration is slightly higher than that of Example 1, and the Nb concentration is the lowest value obtained by substituting the Ti concentration into Equation 3 as in Example 1. However, in the case of Comparative Example 2, the molten metal was clogged, and it was not possible to produce a fine powder by the spray method. Further, in Comparative Example 3, the Ti concentration was slightly higher than that in Example 2, and the Nb concentration was set to the maximum value obtained by substituting the Ti concentration into Equation 4 as in Example 2. Although it was an experiment, in the case of Comparative Example 3 as well, the molten metal was clogged, and the fine powder could not be produced by the spray method. Therefore, from the comparison between Comparative Example 2 and Example 1 and the comparison between Comparative Example 3 and Example 2, even when the number of Ti + Nb atoms is equal, the Ti concentration is higher than 0.1 wt%. It can be seen that fine powder cannot be produced by the method.

比較例４は、Ｔｉ濃度が、第１発明の上限値と第２発明の下限値との間の中間的な値であり、この組成では、注湯閉塞が生じてしまい、微粉末の製造ができなかった。   In Comparative Example 4, the Ti concentration is an intermediate value between the upper limit value of the first invention and the lower limit value of the second invention. With this composition, pouring clogging occurs, and the production of fine powder is difficult. could not.

実施例３は、Ｔｉ濃度を１よりも少し大きい値とし、Ｎｂ濃度は、そのＴｉ濃度を前記式３に代入することによって求められる最低値としたものであり、この組成でも、噴霧法による微粉末の製造が可能であった。また、実施例４は、Ｔｉ濃度は実施例３と同じであるが、Ｎｂ濃度を、そのＴｉ濃度を前記式４に代入することによって求められる最大値としたものである。この組成でも、噴霧法による微粉末の製造が可能であった。これらのことから、Ｔｉ濃度が１ｗｔ％よりも大きければ、Ｎｂ濃度が前記式３および式４によって定まる範囲の全てにおいて、噴霧法による微粉末製造が可能であることが分かる。   In Example 3, the Ti concentration is set to a value slightly larger than 1, and the Nb concentration is set to the lowest value obtained by substituting the Ti concentration into the above-described formula 3. It was possible to produce a powder. In Example 4, the Ti concentration is the same as that in Example 3, but the Nb concentration is set to the maximum value obtained by substituting the Ti concentration into the above-described equation 4. Even with this composition, it was possible to produce a fine powder by a spraying method. From these facts, it can be seen that if the Ti concentration is higher than 1 wt%, the fine powder can be produced by the spraying method in the whole range where the Nb concentration is determined by the above formulas 3 and 4.

比較例５、６は、それぞれ、実施例３、４とＴｉ濃度が僅かに異なり、それに伴って、Ｎｂ濃度も僅かに異なっていること以外は、実施例３、４と同じ組成である。すなわち、比較例５は、Ｔｉ濃度を１よりも少し小さい値とし、Ｎｂ濃度は、実施例３と同様に、前記式３から求められる最低値としたものであり、比較例６は、Ｔｉ濃度は比較例５と同じであるが、Ｎｂ濃度を、実施例４と同様に、前記式４から求められる最大値としたものである。しかしながら、これら比較例５および６は、いずれも、噴霧法によって微粉末を製造することができなかった。このことから、Ｔｉ濃度が１ｗｔ％以下の場合には、Ｎｂ濃度が前記式３および式４によって定まる範囲内においてどのような濃度としても、噴霧法による微粉末製造ができないことが分かる（ただし、Ｔｉ濃度が０．１ｗｔ％以下の極微量である場合は噴霧法が可能であることは前述の通りである）。   Comparative Examples 5 and 6 have the same composition as Examples 3 and 4 except that Ti concentrations are slightly different from Examples 3 and 4, respectively, and accordingly Nb concentrations are also slightly different. That is, in Comparative Example 5, the Ti concentration was set to a value slightly smaller than 1, and the Nb concentration was set to the lowest value obtained from Equation 3 in the same manner as in Example 3. Is the same as in Comparative Example 5, but the Nb concentration is set to the maximum value obtained from Equation 4 as in Example 4. However, neither of these Comparative Examples 5 and 6 was able to produce fine powders by the spray method. From this, it can be seen that when the Ti concentration is 1 wt% or less, it is not possible to produce fine powder by the spray method regardless of the Nb concentration within the range determined by the above formulas 3 and 4. As described above, when the Ti concentration is a very small amount of 0.1 wt% or less, the spray method is possible).

比較例１は、実施例１とＳｉの添加量が異なるのみであるが、噴霧法による微粉末の製造はできなかった。また、実施例９は、実施例１と同様に、Ｔｉは極微量であり、Ｓｉ濃度が実施例１よりもさらに低下させられた組成である。この実施例９は、噴霧法が可能であった。これらのことから、Ｓｉは、０．２ｗｔ％は必要であることが分かる。   Comparative Example 1 was different from Example 1 only in the amount of Si added, but fine powder could not be produced by the spray method. In addition, Example 9 has a composition in which Ti is extremely small and Si concentration is further reduced as compared with Example 1, as in Example 1. In Example 9, a spraying method was possible. From these, it can be seen that 0.2 wt% of Si is necessary.

比較例７は、Ｔｉ濃度およびＮｂ濃度は実施例３と同じであるが、Ｓｉの添加量が０．２ｗｔ％よりも少なくなっており、この組成では、噴霧法による微粉末製造はできなかった。また、実施例１０は、Ｔｉ濃度は実施例３および比較例７とほぼ同じであるが、Ｓｉの添加量が、それらの間とされている。この実施例１０は噴霧法が可能であった。これらのことから、Ｔｉ濃度が１．０ｗｔ％よりも大きい場合にも、Ｓｉが０．２ｗｔ％以上必要であることが分かる。   In Comparative Example 7, the Ti concentration and the Nb concentration were the same as in Example 3, but the amount of Si added was less than 0.2 wt%, and with this composition, fine powder could not be produced by the spray method. . In Example 10, the Ti concentration is substantially the same as in Example 3 and Comparative Example 7, but the amount of Si added is between them. In Example 10, a spraying method was possible. From these facts, it can be seen that even when the Ti concentration is higher than 1.0 wt%, Si is required to be 0.2 wt% or more.

実施例５、７は、それぞれ、実施例１、３におけるＢの濃度をインコネル７１３Ｃにおいて規定されている上限値付近の値としたものに相当する。また、実施例６は、Ｎｂ原子のほとんど全部をＴｉ原子に置き換え、且つ、Ｂの濃度をインコネル７１３Ｃにおいて規定されている上限値付近の値としたものである。実施例５〜７は、いずれも、噴霧法による微粉末の製造が可能であったことから、Ｂの添加割合は、インコネル７１３Ｃにおいて規定されている範囲であれば、本発明において規定するＴｉ、Ｎｂの濃度範囲の全てにおいて注湯閉塞に影響を及ぼさないことが分かる。   Examples 5 and 7 correspond to those in which the concentration of B in Examples 1 and 3 was set to a value near the upper limit defined in Inconel 713C, respectively. In Example 6, almost all of the Nb atoms are replaced with Ti atoms, and the B concentration is set to a value near the upper limit defined in Inconel 713C. In Examples 5 to 7, since it was possible to produce fine powders by a spraying method, the addition ratio of B is within the range defined in Inconel 713C, Ti defined in the present invention, It can be seen that the entire Nb concentration range does not affect the pouring occlusion.

次に、上記実施例において得られた微粉末を用いてＭＩＭにより製造した焼結品の特性を測定した結果を、従来からＭＩＭにより高強度の焼結品が得られることが知られているナイモニック９０（比較例８）の焼結品特性とともに表２に示す。なお、焼結品の製造方法は以下の通りである。
＜焼結品の製造方法＞
ポリプロピレン（５５ｗｔ％）、パラフィンワックス（３０ｗｔ％）、カルナバワックス（１３．５ｗｔ％）、フタル酸ジオクチル（１．５ｗｔ％）からなるバインダーの添加量を６０ｖｏｌ％とし、１６０℃にて３０分混練し、混練後、５０ｔ射出成形機により成形を行った。脱脂（バインダー樹脂の除去）は、ヘキサン気流中溶媒脱脂（６７℃×２４ｈｒ）の後、加熱脱脂（４４０℃×１ｈｒ、Ａｒ大気圧フロー）により行った。脱脂に続く焼結は、Ａｒ雰囲気中にて１２５０〜１２８０℃で行い、焼結密度がほぼ一定になるように温度を調整した。このようにして丸棒（φ１３×６０）の焼結品を製造した。 Next, as a result of measuring the characteristics of the sintered product manufactured by MIM using the fine powder obtained in the above example, it is known that a high-strength sintered product can be obtained by MIM. Table 2 shows the sintered product characteristics of 90 (Comparative Example 8). In addition, the manufacturing method of a sintered product is as follows.
<Method for producing sintered product>
Kneading is carried out for 30 minutes at 160 ° C. with an addition amount of a binder consisting of polypropylene (55 wt%), paraffin wax (30 wt%), carnauba wax (13.5 wt%) and dioctyl phthalate (1.5 wt%) being 60 vol%. After kneading, molding was performed with a 50-t injection molding machine. Degreasing (removal of the binder resin) was performed by solvent degreasing (67 ° C. × 24 hr) in a hexane stream followed by heat degreasing (440 ° C. × 1 hr, Ar atmospheric pressure flow). Sintering following degreasing was performed at 1250 to 1280 ° C. in an Ar atmosphere, and the temperature was adjusted so that the sintered density was substantially constant. In this way, a sintered product of a round bar (φ13 × 60) was produced.

Figure 2005350710
Figure 2005350710

また、表２において、引張強度は、上記丸棒からＪＩＳ Ｚ ２２０１に規定されている棒状試験片４号を切り出し、ＪＩＳ Ｚ ２２４１に規定されている方法に従って測定した。なお、試験片の形状および寸法を図１に示す。また、高温強度は、上記引張強度の測定を、高温（８５０℃、１０００℃）にて行ったものである。また、酸化増量は、上記丸棒からφ１３×１０Ｌを切り出したものを試験片とし、この試験片をアルミナ坩堝に入れて蓋をし、大気炉にて表２に示す温度および時間だけ熱処理する実験を行い、熱処理前後の重量増加を測定し、式５から求めたものである。なお、試験片表面積は、試験片の径および高さから算出した。
（式５） 酸化増量(mg/cm2)＝重量増加分(mg)／試験片表面積(cm2) In Table 2, the tensile strength was measured according to the method specified in JIS Z 2241 by cutting out bar-shaped test piece No. 4 specified in JIS Z 2201 from the round bar. In addition, the shape and dimension of a test piece are shown in FIG. The high temperature strength is obtained by measuring the tensile strength at a high temperature (850 ° C., 1000 ° C.). Further, the increase in oxidation is an experiment in which φ13 × 10 L cut out from the above round bar is used as a test piece, this test piece is put in an alumina crucible and covered, and heat treatment is performed in an atmospheric furnace for the temperature and time shown in Table 2. The weight increase before and after the heat treatment was measured, and was obtained from Equation 5. The test piece surface area was calculated from the diameter and height of the test piece.
(Formula 5) Oxidation increase (mg / cm 2 ) = weight increase (mg) / specimen surface area (cm 2 )

表２から、実施例１〜８の焼結品特性は、比較例８と比較して同等以上の特性を有していることが分かる。特に、実施例１〜８の焼結品は、高温における強度および耐酸化性が比較例８よりも優れている。   From Table 2, it can be seen that the sintered product characteristics of Examples 1 to 8 have characteristics equal to or higher than those of Comparative Example 8. In particular, the sintered articles of Examples 1 to 8 are superior to Comparative Example 8 in strength and oxidation resistance at high temperatures.

以上、説明したように、インコネル７１３Ｃの組成を基本とし、Ｔｉ濃度が０〜０．１質量％、または、１．００〜２．４４ｗｔ％となるようにしつつ、Ｎｂ添加量を調整することによって、Ｔｉ＋Ｎｂの原子数をインコネル７１３Ｃと同等とすれば、噴霧法による微粉末製造が可能となり、且つ、その微粉末を用いてＭＩＭにより製造した焼結品は、従来から知られているナイモニック９０を用いてＭＩＭにより製造した焼結品と比べて遜色ない特性を有している。   As described above, based on the composition of Inconel 713C, by adjusting the amount of Nb added while adjusting the Ti concentration to 0 to 0.1 mass% or 1.00 to 2.44 wt% If the number of Ti + Nb atoms is the same as that of Inconel 713C, fine powder can be produced by the spray method, and the sintered product produced by MIM using the fine powder has the conventionally known Nimonic 90. Compared to the sintered product manufactured by MIM, it has the same characteristics.

引張試験において用いた試験片の形状を示す図である。It is a figure which shows the shape of the test piece used in the tension test.

Claims (2)

Ｃ：０．０８〜０．２０質量％、Ｍｎ：０〜０．２５質量％、Ｓ：０〜０．０１５質量％、Ｓｉ：０．２〜１．０質量％、Ｃｒ：１２．０〜１４．０質量％、Ｍｏ：３．８０〜５．２０質量％、Ｔｉ：０〜０．１質量％、Ａｌ：５．５０〜６．５０質量％、Ｎｂ：２．５８〜４．７４質量％、Ｆｅ：０〜２．５質量％、Ｂ：０〜０．０１５質量％、Ｃｏ：０〜１．００質量％を含み、残部がＮｉおよび不可避不純物であることを特徴とする金属粉末射出成形用耐熱合金   C: 0.08 to 0.20 mass%, Mn: 0 to 0.25 mass%, S: 0 to 0.015 mass%, Si: 0.2 to 1.0 mass%, Cr: 12.0 to 14.0% by mass, Mo: 3.80-5.20% by mass, Ti: 0-0.1% by mass, Al: 5.50-6.50% by mass, Nb: 2.58-4.74% by mass %, Fe: 0 to 2.5 mass%, B: 0 to 0.015 mass%, Co: 0 to 1.00 mass%, the balance being Ni and inevitable impurities, Heat-resistant alloy for molding Ｃ：０．０８〜０．２０質量％、Ｍｎ：０〜０．２５質量％、Ｓ：０〜０．０１５質量％、Ｓｉ：０．２〜１．０質量％、Ｃｒ：１２．０〜１４．０質量％、Ｍｏ：３．８０〜５．２０質量％、Ｔｉ：１．００〜２．４４質量％、Ａｌ：５．５０〜６．５０質量％、Ｆｅ：０〜２．５質量％、Ｂ：０〜０．０１５質量％、Ｃｏ：０〜１．００質量％を含み、
前記Ｔｉ濃度をαとしたとき、Ｎｂの濃度（質量％）が、（１．４３−α）×９２．９１／４７．８８〜（２．４４−α）×９２．９１／４７．８８であり、
残部がＮｉおよび不可避不純物であることを特徴とする金属粉末射出成形用耐熱合金。 C: 0.08 to 0.20 mass%, Mn: 0 to 0.25 mass%, S: 0 to 0.015 mass%, Si: 0.2 to 1.0 mass%, Cr: 12.0 to 14.0% by mass, Mo: 3.80 to 5.20% by mass, Ti: 1.00 to 2.44% by mass, Al: 5.50 to 6.50% by mass, Fe: 0 to 2.5% by mass %, B: 0 to 0.015 mass%, Co: 0 to 1.00 mass%,
When the Ti concentration is α, the concentration (mass%) of Nb is (1.43-α) × 92.91 / 47.88 to (2.44−α) × 92.91 / 47.88. Yes,
A heat-resistant alloy for metal powder injection molding, wherein the balance is Ni and inevitable impurities.
JP2004171078A 2004-06-09 2004-06-09 Heat-resistant alloy for metallic powder to be injection-molded Pending JP2005350710A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2004171078A JP2005350710A (en) 2004-06-09 2004-06-09 Heat-resistant alloy for metallic powder to be injection-molded
EP05012365A EP1634972A2 (en) 2004-06-09 2005-06-08 Refractory alloy for metal injection molding

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2004171078A JP2005350710A (en) 2004-06-09 2004-06-09 Heat-resistant alloy for metallic powder to be injection-molded

Publications (1)

Publication Number Publication Date
JP2005350710A true JP2005350710A (en) 2005-12-22

Family

ID=35520747

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2004171078A Pending JP2005350710A (en) 2004-06-09 2004-06-09 Heat-resistant alloy for metallic powder to be injection-molded

Country Status (2)

Country Link
EP (1) EP1634972A2 (en)
JP (1) JP2005350710A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106011541A (en) * 2016-07-26 2016-10-12 四川六合锻造股份有限公司 Ni-Cr-Mo (nickel-chromium-molybdenum) high-temperature alloy material and preparation method thereof
WO2017026519A1 (en) * 2015-08-12 2017-02-16 山陽特殊製鋼株式会社 Ni-based super alloy powder for laminate molding
WO2017175471A1 (en) 2016-04-05 2017-10-12 三菱重工航空エンジン株式会社 Sintered body, sintered body production method, combustor panel, and combustor panel production method
WO2018198440A1 (en) 2017-04-25 2018-11-01 三菱重工航空エンジン株式会社 Metal member and method for manufacturing same
CN110512119A (en) * 2019-09-29 2019-11-29 湖南英捷高科技有限责任公司 A kind of injection moulding nickel-base alloy powder, ejection forming method and nickel-based alloy articles
JP2021021140A (en) * 2020-09-07 2021-02-18 三菱重工航空エンジン株式会社 Injection-molded article of nickel-based alloy, and method for manufacturing injection-molded article of nickel-based alloy

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017026519A1 (en) * 2015-08-12 2017-02-16 山陽特殊製鋼株式会社 Ni-based super alloy powder for laminate molding
JP2017036485A (en) * 2015-08-12 2017-02-16 山陽特殊製鋼株式会社 Ni-BASED SUPERALLOY POWDER FOR LAMINATE MOLDING
WO2017175471A1 (en) 2016-04-05 2017-10-12 三菱重工航空エンジン株式会社 Sintered body, sintered body production method, combustor panel, and combustor panel production method
US11511339B2 (en) 2016-04-05 2022-11-29 Mitsubishi Heavy Industries Aero Engines, Ltd. Sintered body, method of manufacturing sintered body, combustor panel, and method of manufacturing combustor panel
US11666967B2 (en) 2016-04-05 2023-06-06 Mitsubishi Heavy Industries Aero Engines, Ltd. Sintered body, method of manufacturing sintered body, combustor panel, and method of manufacturing combustor panel
CN106011541A (en) * 2016-07-26 2016-10-12 四川六合锻造股份有限公司 Ni-Cr-Mo (nickel-chromium-molybdenum) high-temperature alloy material and preparation method thereof
WO2018198440A1 (en) 2017-04-25 2018-11-01 三菱重工航空エンジン株式会社 Metal member and method for manufacturing same
CN110512119A (en) * 2019-09-29 2019-11-29 湖南英捷高科技有限责任公司 A kind of injection moulding nickel-base alloy powder, ejection forming method and nickel-based alloy articles
JP2021021140A (en) * 2020-09-07 2021-02-18 三菱重工航空エンジン株式会社 Injection-molded article of nickel-based alloy, and method for manufacturing injection-molded article of nickel-based alloy

Also Published As

Publication number Publication date
EP1634972A2 (en) 2006-03-15

Similar Documents

Publication Publication Date Title
EP3611282B1 (en) Cobalt based alloy powder
JP7109608B2 (en) hot parts
CA3061851C (en) Cobalt based alloy additive manufactured article, cobalt based alloy product, and method for manufacturing same
KR20180040513A (en) Ni-based superalloy powder for lamination molding
KR100768700B1 (en) Fabrication method of alloy parts by metal injection molding and the alloy parts
JP4610822B2 (en) Austenitic steel with low nickel content
SE513989C2 (en) Process for manufacturing a FeCrAl material and such a mortar
KR20090053934A (en) Metal powder
JP3856294B2 (en) Stainless steel powder for sintering, granulated powder for manufacturing sintered stainless steel, and sintered stainless steel
WO2006130153A2 (en) Method and composition for making a wire
EP1634972A2 (en) Refractory alloy for metal injection molding
KR20180021861A (en) Method for manufacturing alloy steel powder for sintered member raw material
JP7153502B2 (en) Molded body made of nitride-dispersed Ni-based alloy
KR20220030182A (en) Methdo of manufacturing cobalt-based alloy structure and cobalt-based alloy structure obtained by the same
JPH0436428A (en) Manufacture of high toughness tungsten sintered alloy
JP2786303B2 (en) Method for producing sintered alloy with excellent corrosion resistance and machinability
JPH03232904A (en) Extruded green compact of alloy powder and sintered product thereof
JP3728507B2 (en) Sintered titanium alloy and manufacturing method thereof
JPH02299740A (en) Forming mold for high-temperature molten metal
JP2797048B2 (en) Melt erosion resistant material
JP2021172851A (en) Manufacturing method of Ni-based alloy member
JPH0257666A (en) Sintered alloy having excellent mirror-finishing characteristics and its manufacture
JP2001089824A (en) Manufacture of sintered compact of chromium- molybdenum steel
JPH0551662A (en) Manufacture of cu-ni alloy sintered body
JPH055105A (en) Method for extruding alloy powder and production of sintered product of alloy powder