JP2016216762A - Alloy powder - Google Patents
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本発明は、耐摩耗性を有する合金粉末に関するものである。 The present invention relates to an alloy powder having wear resistance.
従来、耐摩耗性を有する合金は、石油・ガスプラント、エンジン用盛り金、発電設備等、幅広い分野で使用されている。その使用される形態としては粉末冶金法を用いた構造材料や、溶射材料、肉盛り材料等の形態で用いられる。例えば特開平１１−３１０８５４号公報（特許文献１）に開示されているように、重量％で、Ｍｏ：２０〜７０％、Ｃ：０．５〜３％、Ｎｉ：５〜４０％、および残部：Ｆｅおよび不可避不純物からなる肉盛合金を肉盛りによって耐摩耗性合金粉末を肉盛りし、耐摩耗合金として使用し、良好な耐摩耗性を有したエンジン用肉盛合金が提案されている。 Conventionally, alloys having wear resistance have been used in a wide variety of fields such as oil and gas plants, engine deposits, and power generation facilities. As the form to be used, it is used in the form of a structural material using a powder metallurgy method, a thermal spray material, a build-up material or the like. For example, as disclosed in JP-A-11-310854 (Patent Document 1), by weight, Mo: 20 to 70%, C: 0.5 to 3%, Ni: 5 to 40%, and the balance : A build-up alloy for engines having good wear resistance has been proposed in which a build-up alloy composed of Fe and inevitable impurities is built up to build up wear-resistant alloy powder and used as a wear-resistant alloy.
一方、特開２００２−３５６７０４号公報（特許文献２）に開示されている、質量％で、Ｓｉ：１．０〜１２％、Ｍｏ：２０〜５０％、Ｍｎ：０．５〜５．０％、および残部がＦｅ、Ｎｉ、Ｃｏのうち少なくとも１種以上と不可避不純物からなる耐摩耗性合金粉末を他の粉末の混ぜ合わせ焼結することで良好な耐摩耗性を有した焼結材が提案されている。 On the other hand, as disclosed in JP-A-2002-356704 (Patent Document 2), by mass%, Si: 1.0 to 12%, Mo: 20 to 50%, Mn: 0.5 to 5.0% Proposed a sintered material with good wear resistance by mixing and sintering other wear-resistant alloy powder consisting of at least one of Fe, Ni, and Co and inevitable impurities. Has been.
上述した特許文献１のような肉盛合金や特許文献２のような焼結合金による従来の耐摩耗材料よりさらなる耐摩耗性が求められていた。上記の要請に応えるべくより優れた耐摩耗性を図ることを可能とした発明を提供するものである。 There has been a demand for further wear resistance than conventional wear-resistant materials such as the above-described overlay alloys such as Patent Document 1 and sintered alloys such as Patent Document 2. The present invention provides an invention capable of achieving higher wear resistance in order to meet the above demand.
上述のような要求を十分達成するために、発明者らは鋭意開発を進めた結果、ＭｏとＮｂ，Ｖ，Ｔａ，Ｗから選択される１種類以上を組み合わせること、さらには合金粉末中の水素含有量を低減させることで、耐摩耗性を向上させることを可能としたものである。その発明の要旨とするところは、
（１）質量％で、Ｍｏ：５〜４９％、Ｃｒ：５〜２５％、Ｓｉ：１〜５％、Ｎｂ，Ｖ，Ｔａ，Ｗから選択される１種類以上：０〜４９％、かつＭｏ＋Ｎｂ＋Ｖ＋Ｔａ＋Ｗが５４％以下、残部がＣｏ、Ｎｉ、Ｆｅのうち少なくとも１種類以上と不可避不純物からなる合金粉末。
In order to sufficiently achieve the above-described requirements, the inventors have intensively developed, and as a result, combined Mo and one or more selected from Nb, V, Ta, and W, and further, hydrogen in the alloy powder. The wear resistance can be improved by reducing the content. The gist of the invention is that
(1) By mass%, Mo: 5 to 49%, Cr: 5 to 25%, Si: 1 to 5%, one or more selected from Nb, V, Ta, W: 0 to 49%, and Mo + Nb + V + Ta + W Is an alloy powder consisting of at least one of Co, Ni, and Fe and unavoidable impurities.
（２）質量％で、Ｍｏ：１０〜４９％、Ｃｒ：５〜２０％、Ｓｉ：１〜５％、Ｎｂ，Ｖ，Ｔａ，Ｗから選択される１種類以上：５〜４９％、かつＭｏ＋Ｎｂ＋Ｖ＋Ｔａ＋Ｗが５４％以下、残部がＣｏ、Ｎｉ、Ｆｅのうち少なくとも１種類以上と不可避不純物からなる合金粉末。
（３）前記（１）、（２）に記載の組成にＴｉ，Ｚｒ，Ｈｆ，Ａｌ，Ｍｎ，Ｐ，Ｃから選択される１種類以上を１０％以下添加してなる合金粉末。
（４）前記（１）〜（３）のいずれか１に記載の合金粉末でＨが８０ｐｐｍ以下であることを特徴とした合金粉末にある。
(2) By mass%, Mo: 10 to 49%, Cr: 5 to 20%, Si: 1 to 5%, one or more selected from Nb, V, Ta, W: 5 to 49%, and Mo + Nb + V + Ta + W Is an alloy powder consisting of at least one of Co, Ni, and Fe and unavoidable impurities.
(3) Alloy powder obtained by adding 10% or less of one or more selected from Ti, Zr, Hf, Al, Mn, P, and C to the composition described in (1) and (2).
(4) The alloy powder according to any one of (1) to (3), wherein H is 80 ppm or less.
以上、述べたとおり本発明は、ＭｏとＮｂ，Ｖ，Ｔａ，Ｗから選択される１種類以上を組み合わせること、さらには合金粉末中の水素含有量を低減させることで、より耐摩耗性に優れた合金粉末を提供することにある。 As described above, the present invention is more excellent in wear resistance by combining Mo and one or more selected from Nb, V, Ta, W and further reducing the hydrogen content in the alloy powder. It is to provide an alloy powder.
以下、本発明に係わる成分組成の限定理由を説明する
本発明は耐摩耗性を有する合金粉末に関するもので、より十分な耐摩耗性が必要である。Ｍｏが質量％で５〜４９％
Ｍｏは、耐摩耗性を向上させる元素である。しかし、５％未満ではその効果は薄く、また、４９％を超えると耐摩耗性以前に靱性を失い耐摩耗性合金として使用できなくなる。したがって、その範囲を５〜４９％とした。望ましくは１０〜４９％、さらに望ましくは１５〜４５％とする。
Hereinafter, the present invention for explaining the reason for limiting the component composition according to the present invention relates to an alloy powder having wear resistance, and more sufficient wear resistance is required. Mo is 5 to 49% by mass
Mo is an element that improves wear resistance. However, if it is less than 5%, the effect is thin, and if it exceeds 49%, it loses toughness before wear resistance and cannot be used as a wear resistant alloy. Therefore, the range was made 5 to 49%. Desirably, it is 10 to 49%, and more desirably 15 to 45%.
Ｃｒが質量％で５〜２５％
Ｃｒは、硬さを向上させ、耐摩耗性を向上させる。しかし、５％未満ではその効果は薄く、また、２５％を超えると同様に効果が薄くなる。したがって、その範囲を５〜２５％とした。望ましくは８〜２３％、より望ましくは８〜２０％とする。
Cr is 5-25% by mass
Cr improves hardness and improves wear resistance. However, if it is less than 5%, the effect is thin, and if it exceeds 25%, the effect is similarly reduced. Therefore, the range was made 5 to 25%. Desirably, it is 8 to 23%, more desirably 8 to 20%.
Ｓｉが質量％で１〜５％
Ｓｉは、アトマイズ性を改善する元素である。しかし、１％未満ではその効果は薄く、また、５％を超えると珪化物を多量に形成し、靱性を失う。したがって、その範囲を１〜５％とした。望ましくは１〜４％とする。
Si is 1 to 5% by mass
Si is an element that improves atomization. However, if it is less than 1%, the effect is thin, and if it exceeds 5%, a large amount of silicide is formed and the toughness is lost. Therefore, the range was made 1 to 5%. Desirably, it is 1 to 4%.
Ｎｂ、Ｖ、Ｔａ、Ｗから選択される１種以上が０〜４９％、かつＭｏ＋Ｎｂ＋Ｖ＋Ｔａ＋Ｗが５４％以下
Ｎｂ、Ｖ、Ｔａ、ＷはＭｏと組み合わせることで耐摩耗性を改善させる。５％以上でその効果がより表れる傾向にある。また、Ｎｂ、Ｖ、Ｔａ、Ｗから選択される１種以上が４９％を超えると靱性が失われ、脆くなる。望ましくは５〜４４％とした。さらに望ましくはＮｂ、Ｖ、Ｔａ、Ｗから選択される１種以上が８〜４４％とする。またＭｏ＋Ｎｂ＋Ｖ＋Ｔａ＋Ｗが５４％以下をする。
One or more selected from Nb, V, Ta, and W is 0 to 49%, and Mo + Nb + V + Ta + W is 54% or less. Nb, V, Ta, and W are combined with Mo to improve wear resistance. The effect tends to be more apparent at 5% or more. Moreover, when 1 or more types selected from Nb, V, Ta, and W exceed 49%, toughness will be lost and it will become weak. Desirably, it was 5 to 44%. More desirably, at least one selected from Nb, V, Ta, and W is 8 to 44%. Further, Mo + Nb + V + Ta + W is 54% or less.
残部がＣｏ、Ｎｉ、Ｆｅのうち少なくとも１種類以上
ＦｅとＮｉはＣｏと同じ８族元素で耐摩耗性を維持できる。望ましくはＣｏを基本とし、Ｃｏの質量％量に対し、０〜１／２までの量をＦｅまたはＮｉから選択される１種以上に置換する。さらに望ましくは０〜１／３までの置換とする。
The balance is at least one of Co, Ni, and Fe. Fe and Ni are the same group 8 elements as Co and can maintain wear resistance. Desirably, based on Co, the amount of 0 to 1/2 is substituted with one or more selected from Fe or Ni with respect to the mass% amount of Co. More preferably, the substitution is 0 to 1/3.
Ｔｉ、Ｚｒ、Ｈｆ、Ａｌ、Ｍｎ、Ｐ、Ｃから選択される１種類以上を１０％以下
Ｔｉ、Ｚｒ、Ｈｆ、Ａｌ、Ｍｎ、Ｐ、Ｃは耐摩耗性に悪影響を及ぼさないかあるいは改善する。少量の添加はしてもよいが、Ｔｉ、Ｚｒ、Ｈｆ、Ａｌ、Ｍｎ、Ｐ、Ｃは、１０％を超えて添加すると耐摩耗性を悪化させる。したがって、１０％以下とする。望ましくは８％以下とする。
10% or less of one or more selected from Ti, Zr, Hf, Al, Mn, P, and C. Ti, Zr, Hf, Al, Mn, P, and C do not adversely affect or improve wear resistance. . A small amount may be added, but when Ti, Zr, Hf, Al, Mn, P, and C are added over 10%, the wear resistance is deteriorated. Therefore, it is 10% or less. Desirably, it is 8% or less.
Ｈが８０ｐｐｍ以下
Ｈは、８０ｐｐｍを超えて添加されると脆化を起こし、耐摩耗性を悪化させる。したがって、８０ｐｐｍ以下とする。望ましくは４０ｐｐｍ以下、さらに望ましくは２０ｐｐｍ以下とする。
If H is added in an amount of 80 ppm or less, if H exceeds 80 ppm, it causes embrittlement and deteriorates the wear resistance. Therefore, it is 80 ppm or less. Desirably, it is 40 ppm or less, More desirably, it is 20 ppm or less.
以下、本発明に係る合金粉末について実施例によって具体的に説明する。
表１〜３に示す本発明例に係る成分組成について、溶解原料を秤量し、減圧Ａｒガス雰囲気あるいは真空雰囲気にて耐火物坩堝内で誘導加熱溶解したあと、坩堝下部の直径８ｍｍのノズルより出湯し、Ｎガスによりアトマイズした。このガスアトマイズ粉末の１５０μｍ以上の粗粉を除去し、かつ水素含有量を低減するために、粉末中に占める、５μｍ以下の粉末の量が、１０％以下となるよう微粉を除去し、さらに恒温炉で７０℃〜１５０℃、１時間〜３時間保持した。水素量は低減する保持温度は１００℃が望ましく、また、保持時間は長ければ水素を低減する傾向がみられ、３時間程度が望ましい。評価方法としては、水素含有量は不活性ガス融解−非分散型赤外線吸収法によって測定した。また、耐摩耗性の評価は摩耗試験によって評価した。
Hereinafter, the alloy powder according to the present invention will be specifically described with reference to examples.
About the component composition which concerns on the example of this invention shown in Tables 1-3, after melt | dissolving a raw material and melt | dissolving by induction heating in a refractory crucible in a reduced pressure Ar gas atmosphere or a vacuum atmosphere, the hot water is discharged from a nozzle having a diameter of 8 mm at the bottom of the crucible. Atomized with N gas. In order to remove coarse powder of 150 μm or more from this gas atomized powder and reduce the hydrogen content, fine powder is removed so that the amount of powder of 5 μm or less in the powder is 10% or less, and a constant temperature furnace And kept at 70 to 150 ° C. for 1 to 3 hours. The holding temperature at which the amount of hydrogen is reduced is preferably 100 ° C., and if the holding time is long, there is a tendency to reduce hydrogen, and it is preferably about 3 hours. As an evaluation method, the hydrogen content was measured by an inert gas melting-non-dispersive infrared absorption method. The abrasion resistance was evaluated by an abrasion test.
上記ように準備した粉末を２５ｍａｓｓ％と黒鉛粉末を０．７５ｍａｓｓ％、水アトマイズ鉄粉末を残部の割合で混合し、成形圧力６４０ＭＰａでリング状に成形し、１１５０℃で焼結し、焼結体を得た。得られたリング状焼結体を加工し内径面に４５°のテーパー面をつけ、アルミ合金製台座に圧入し、リングのテーパー面と形状が合致する４５°のテーパーを有するＳＵＨ−３５製の相手材をＬＰＧで加熱しながら、繰り返し衝突させた。衝突回数は２８００回／６０秒にて６時間、リング状焼結体が２５０℃になるようにＳＵＨ−３５を加熱しながら行った。衝突前後でのリング状焼結体の形状を摩耗量として評価した。 The powder prepared as described above was mixed in 25 mass%, graphite powder in 0.75 mass%, and water atomized iron powder in the remaining proportion, molded into a ring shape at a molding pressure of 640 MPa, sintered at 1150 ° C., and sintered body. Got. The obtained ring-shaped sintered body was processed to have a 45 ° tapered surface on the inner surface, and press-fitted into an aluminum alloy pedestal. The counterpart material was repeatedly collided while being heated with LPG. The number of collisions was 2800 times / 60 seconds for 6 hours while heating the SUH-35 so that the ring-shaped sintered body became 250 ° C. The shape of the ring-shaped sintered body before and after the collision was evaluated as the amount of wear.
上記実施例と同様に、表５に示す比較例Ｎｏ．１１３〜１３１に係る成分組成について、溶解原料を秤量し、大気中にて耐火物坩堝内で誘導加熱溶解したあと、坩堝下部の直径８ｍｍのノズルより出湯し、Ｎガスによりアトマイズした。このガスアトマイズ粉末の１５０μｍ以上の粗粉を除去した。その結果、比較例Ｎｏ．１１３〜１１４は水素量が多いので摩耗量が多い。すなわち、水素量が多いために摩耗性が劣る。比較例Ｎｏ．１１５はＭｏ量が少ないので摩耗量が多い。すなわち、Ｍｏの含有量が少ないために十分な効果が得られず摩耗性が劣る。 Similar to the above example, the comparative example No. About the component composition which concerns on 113-131, after melt | dissolving a raw material and melt | dissolving by induction heating in the refractory crucible in air | atmosphere, it poured out from the nozzle with a diameter of 8 mm of the crucible lower part, and atomized with N gas. Coarse powder of 150 μm or more was removed from this gas atomized powder. As a result, Comparative Example No. 113 to 114 have a large amount of hydrogen and therefore a large amount of wear. That is, since the amount of hydrogen is large, the wearability is inferior. Comparative Example No. No. 115 has a large amount of wear because of a small amount of Mo. That is, since there is little content of Mo, sufficient effect is not acquired and abrasion is inferior.
比較例Ｎｏ．１１６はＭｏ量が多いので摩耗量が多い。すなわち、Ｍｏの含有量が逆に過剰なために耐摩耗性以前に靱性を失い摩耗性が劣化する。比較例Ｎｏ．１１７はＣｒ量が少ないので摩耗量が多い。すなわち、Ｃｒの含有量が少ないために十分な効果が得らず摩耗性が劣る。比較例Ｎｏ．１１８はＣｒ量が多いので摩耗量が多い。すなわち、Ｃｒの含有量が逆に過剰なために効果が十分得られず摩耗性が劣る。比較例Ｎｏ．１１９はＳｉ量が少ないので摩耗量が多い。すなわち、Ｓｉの含有量が少ないために十分な効果が得られず摩耗性が劣る。 Comparative Example No. Since 116 has a large amount of Mo, it has a large amount of wear. That is, since the Mo content is excessive, the toughness is lost before the wear resistance and the wear resistance is deteriorated. Comparative Example No. 117 has a large amount of wear due to a small amount of Cr. That is, since there is little content of Cr, sufficient effect is not acquired but abrasion property is inferior. Comparative Example No. Since 118 has a large amount of Cr, it has a large amount of wear. That is, since the Cr content is excessive, the effect cannot be sufficiently obtained and the wearability is inferior. Comparative Example No. Since 119 has a small amount of Si, it has a large amount of wear. That is, since the content of Si is small, a sufficient effect cannot be obtained and the wearability is inferior.
比較例Ｎｏ．１２０はＳｉ量が多いので摩耗量が多い。すなわち、Ｓｉの含有量が逆に過剰なために珪化物が多量に形成し摩耗性が劣化する。比較例Ｎｏ．１２１はＭｏ＋Ｎｂ＋Ｖ＋Ｔａ＋Ｗ量の合計量が多いので摩耗量が多い。すなわち、Ｍｏ＋Ｎｂ＋Ｖ＋Ｔａ＋Ｗ量の合計含有量が過剰なために摩耗性が劣る。比較例Ｎｏ．１２２はＮｂ量が多いので摩耗量が多い。すなわち、Ｎｂの含有量が過剰なために靱性が失われ摩耗性が劣化する。比較例Ｎｏ．１２３はその他元素の合計量が多いので摩耗量が多い。すなわち、その他元素の合計量が過剰のために摩耗性が劣る。 Comparative Example No. Since 120 has a large amount of Si, the amount of wear is large. That is, since the Si content is excessive, a large amount of silicide is formed and the wear resistance is deteriorated. Comparative Example No. Since 121 has a large total amount of Mo + Nb + V + Ta + W, the amount of wear is large. That is, since the total content of Mo + Nb + V + Ta + W is excessive, the wear resistance is inferior. Comparative Example No. Since 122 has a large amount of Nb, the amount of wear is large. That is, since the Nb content is excessive, toughness is lost and wear resistance is deteriorated. Comparative Example No. Since 123 has a large total amount of other elements, the amount of wear is large. That is, the wear amount is inferior because the total amount of other elements is excessive.
比較例Ｎｏ．１２４〜１３０はＴｉ，Ｚｒ，Ｈｆ，Ａｌ，Ｍｎ，Ｐ，Ｃのそれぞれの１種における含有量が多いので摩耗量が多い。すなわち、Ｔｉ，Ｚｒ，Ｈｆ，Ａｌ，Ｍｎ，Ｐ，Ｃのそれぞれの１種における元素の含有量が過剰のために摩耗性が劣る。比較例Ｎｏ．１３１はＨ含有量が高いために、脆化を起こし、耐摩耗性を悪化させる。これに対して、本発明例Ｎｏ．１〜１１２はいずれも本発明条件を満たしているから、いずれも摩耗量が少なく耐摩耗性に優れていることが分かる。 Comparative Example No. Since 124 to 130 have a large content in each of Ti, Zr, Hf, Al, Mn, P, and C, the amount of wear is large. That is, since the element content in each of Ti, Zr, Hf, Al, Mn, P, and C is excessive, the wear resistance is inferior. Comparative Example No. Since 131 has a high H content, it causes embrittlement and deteriorates wear resistance. On the other hand, the present invention example No. 1 to 112 all satisfy the conditions of the present invention, so that it is understood that all of them have a small amount of wear and excellent wear resistance.
以上のように、Ｍｏ：５〜４９％、Ｃｒ：５〜２５％、Ｓｉ：１〜５％からなる成分組成からなるＭｏとＮｂ，Ｖ，Ｔａ，Ｗから選択される１種類以上を組み合わせること、さらには合金粉末中の水素含有量を低減させることで、材料の靱性が向上し、より耐摩耗性に優れた効果を奏する合金粉末を提供することにある。
特許出願人 山陽特殊製鋼株式会社
代理人 弁理士 椎 名 彊
As described above, Mo having a component composition of Mo: 5 to 49%, Cr: 5 to 25%, and Si: 1 to 5% is combined with at least one selected from Nb, V, Ta, and W. Another object of the present invention is to provide an alloy powder that improves the toughness of the material by reducing the hydrogen content in the alloy powder and exhibits an effect of more excellent wear resistance.
Patent Applicant Sanyo Special Steel Co., Ltd.
Attorney: Attorney Shiina
Claims (4)
Ｍｏ：５〜４９％、
Ｃｒ：５〜２５％、
Ｓｉ：１〜５％、
Ｎｂ，Ｖ，Ｔａ，Ｗから選択される１種類以上：０〜４９％、
かつＭｏ＋Ｎｂ＋Ｖ＋Ｔａ＋Ｗが５４％以下、残部がＣｏ、Ｎｉ、Ｆｅのうち少なくとも１種類以上と不可避不純物からなる合金粉末。 % By mass
Mo: 5-49%,
Cr: 5 to 25%,
Si: 1 to 5%
One or more types selected from Nb, V, Ta, and W: 0 to 49%,
An alloy powder comprising Mo + Nb + V + Ta + W of 54% or less and the balance of at least one of Co, Ni and Fe and inevitable impurities.
Ｍｏ：１０〜４９％、
Ｃｒ：５〜２０％、
Ｓｉ：１〜５％、
Ｎｂ，Ｖ，Ｔａ，Ｗから選択される１種類以上：５〜４４％、
かつＭｏ＋Ｎｂ＋Ｖ＋Ｔａ＋Ｗが５４％以下、残部がＣｏ、Ｎｉ、Ｆｅのうち少なくとも１種類以上と不可避不純物からなる合金粉末。 % By mass
Mo: 10 to 49%,
Cr: 5 to 20%,
Si: 1 to 5%
One or more types selected from Nb, V, Ta, W: 5-44%,
An alloy powder comprising Mo + Nb + V + Ta + W of 54% or less and the balance of at least one of Co, Ni and Fe and inevitable impurities.
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