JP2002302726A - HIGH HARDNESS- AND HIGH CORROSION-RESISTANT Ni ALLOY - Google Patents
HIGH HARDNESS- AND HIGH CORROSION-RESISTANT Ni ALLOYInfo
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気めっき用通電
ロール、プラスチック射出成形機用シャフト、ディーゼ
ルエンジンの燃料噴射ノズル等、高い硬さと耐食性とを
要する用途に適したＮｉ基合金とその製造方法に関す
る。The present invention relates to a Ni-based alloy suitable for applications requiring high hardness and corrosion resistance, such as a conductive roll for electroplating, a shaft for a plastic injection molding machine, and a fuel injection nozzle for a diesel engine, and a method for producing the same. About.
【０００２】[0002]
【従来の技術】電気めっき用通電ロール、プラスチック
射出成形機用シャフト、ディーゼルエンジンの燃料噴射
ノズル等の機械部品は、腐食性の強い環境において他の
部品と高い面圧で摩擦する状態で使用される。すなわ
ち、電気めっき用通電ロールは、金属めっき溶液、例え
ば、亜鉛めっき溶液槽に浸漬して使用され、通電中に腐
食が発生する。同時に、被めっき材との回転接触により
摩耗が生じる。プラスチック射出成形機用シャフトで
は、フッ素系樹脂などの腐食性が強い樹脂の成形時に
は、シャフトが腐食される場合があり、また、樹脂中に
ガラス繊維等を混入した繊維強化樹脂を成形することも
あってシャフトの摩耗が問題となる。ディーゼルエンジ
ンの燃料噴射ノズルでは、燃料に含有される硫黄分など
による腐食と同時に、ニードル弁と高い面圧で接触し、
それらの摺動による摩耗が発生する。そのため、これら
の用途に用いられる材料には、高い面圧に耐え、耐摩耗
性をもたらす高い硬さと耐食性とが要求される。2. Description of the Related Art Mechanical parts such as a current-carrying roll for electroplating, a shaft for a plastic injection molding machine, and a fuel injection nozzle for a diesel engine are used in a highly corrosive environment in a state of friction with other parts at a high surface pressure. You. That is, the current-carrying roll for electroplating is used by being immersed in a metal plating solution, for example, a galvanizing solution bath, and corrosion occurs during power-on. At the same time, abrasion occurs due to rotational contact with the material to be plated. Shafts for plastic injection molding machines can be corroded when molding highly corrosive resins such as fluorocarbon resins.Fiber-reinforced resins with glass fibers mixed into the resin can also be molded. Therefore, wear of the shaft becomes a problem. In diesel engine fuel injection nozzles, at the same time as corrosion due to sulfur content in the fuel, it comes in contact with the needle valve with high surface pressure,
Wear due to their sliding occurs. For this reason, materials used for these applications are required to have high hardness and corrosion resistance, which withstand high surface pressure and provide wear resistance.
【０００３】従来、上述のような用途には、インコネル
６２５（Ｎｉ−２１Ｃｒ−９Ｍｏ−４Ｎｂ合金）やハス
テロイＣ（Ｎｉ−１７Ｃｒ−１９Ｍｏ−５Ｗ合金）等の
Ｎｉ基超合金が用いられている。しかし、硬さが十分で
ないという問題があった。前記Ｎｉ基耐食合金を改良し
て、特性を向上した合金として、ガンマプライム（Ｎｉ
3（Ａｌ、Ｔｉ））の析出硬化を利用したＮｉ基合金
（特開平２−２７０９３９号公報）や、固溶強化を利用
したＮｉ基合金（特開平１０−２０４５６１号公報）が
開示されている。しかし、前者は、耐食性が未だ十分で
はなく、また後者では、結晶粒界に斜方晶のδ相（Ｎｉ
3（Ｎｂ、Ｔａ））が析出するため結晶粒界の耐食性を
損なうことがあり、さらに、硬さも３００ＨＶ以下で不
十分であった。一方、σ相の析出硬化を利用したＮｉ基
合金（例えば、特開平５−１９５１３７号公報）は、３
８０ＨＶ以上の高い硬さは得られるがσ相と母相との耐
食性の差異に起因する微細腐食によって、合金表面が白
濁状の概観を呈するといった不都合を生じることがあっ
た。Conventionally, Ni-based superalloys such as Inconel 625 (Ni-21Cr-9Mo-4Nb alloy) and Hastelloy C (Ni-17Cr-19Mo-5W alloy) have been used for the above-mentioned applications. However, there is a problem that the hardness is not sufficient. As an alloy having improved characteristics by improving the Ni-based corrosion resistant alloy, gamma prime (Ni
3 (Al, Ti)) and a Ni-based alloy utilizing precipitation hardening (Japanese Patent Application Laid-Open No. 2-270939) and a Ni-based alloy using solid solution strengthening (Japanese Patent Application Laid-Open No. 10-204561) are disclosed. . However, in the former, the corrosion resistance is not yet sufficient, and in the latter, the orthorhombic δ phase (Ni
Since 3 (Nb, Ta)) precipitates, the corrosion resistance of the crystal grain boundaries may be impaired, and the hardness is insufficient at 300 HV or less. On the other hand, Ni-based alloys utilizing precipitation hardening of the σ phase (for example, Japanese Patent Application Laid-Open No. 5-195137)
Although a high hardness of 80 HV or more can be obtained, there is a case where a problem such as a cloudy appearance on the alloy surface may occur due to fine corrosion caused by a difference in corrosion resistance between the σ phase and the mother phase.
【０００４】[0004]
【発明が解決しようとする課題】上記の現状に鑑み、本
発明は、優れた耐食性を備え、かつ、４００ＨＶ以上の
高硬度を有する合金と該合金の製造方法を提供すること
を目的とする。SUMMARY OF THE INVENTION In view of the above situation, an object of the present invention is to provide an alloy having excellent corrosion resistance and a high hardness of 400 HV or more, and a method for producing the alloy.
【０００５】[0005]
【課題を解決するための手段】上記の問題を解決するた
めに種々検討した結果、発明者らは、Ｎｉ−２１Ｃｒ−
９Ｍｏ−４Ｎｂ合金をベースとして、合金組成に工夫を
加え、さらに、適切な熱処理を加え、合金生地中に体心
正方晶のガンマダブルプライム（Ｎｉ3（Ｎｂ、Ｔ
ａ））を時効析出させることにより、合金の耐食性を損
なうことなく高い硬さが得られることを見出した。As a result of various studies to solve the above problems, the inventors have found that Ni-21Cr-
Based on the 9Mo-4Nb alloy, the composition of the alloy is devised, and further, an appropriate heat treatment is applied thereto, and a body-centered tetragonal gamma double prime (Ni 3 (Nb, T
It has been found that by aging precipitation of a)), a high hardness can be obtained without impairing the corrosion resistance of the alloy.
【０００６】すなわち、本発明の高硬度高耐食性Ｎｉ基
合金は、 （１）質量％で、Ｃ：０．１０％以下、Ｓｉ：１％以
下、Ｍｎ：１％以下、Ｃｒ：１６〜２５％、Ｍｏ：８〜
２０％、Ｎｂ＋Ｔａ：５〜１０％、Ａｌ：０．０１〜１
％、Ｔｉ：０．０１〜１％、Ｆｅ：３％以下、Ｎ：０．
０２％以下、Ｏ：０．０２％以下を含み、残部実質的に
Ｎｉおよび不可避的不純物からなり、１０００〜１２０
０℃の温度で固溶化処理後、６００〜７５０℃の温度で
８〜３２時間時効処理することを特徴とする。 （２）質量％で、Ｃ：０．１０％以下、Ｓｉ：１％以
下、Ｍｎ：１％以下、Ｃｕ：０．１〜５％、Ｃｒ：１６
〜２５％、Ｍｏ：８〜２０％、Ｎｂ＋Ｔａ：５〜１０
％、Ａｌ：０．０１〜１％、Ｔｉ：０．０１〜１％、Ｆ
ｅ：３％以下、Ｎ：０．０２％以下、Ｏ：０．０２％以
下を含み、残部実質的にＮｉおよび不可避的不純物から
なり、１０００〜１２００℃の温度で固溶化処理後、６
００〜７５０℃の温度で８〜３２時間時効処理すること
を特徴とする。That is, the high hardness and high corrosion resistance Ni-based alloy of the present invention is as follows: (1) In mass%, C: 0.10% or less, Si: 1% or less, Mn: 1% or less, Cr: 16 to 25% , Mo: 8 ~
20%, Nb + Ta: 5 to 10%, Al: 0.01 to 1
%, Ti: 0.01-1%, Fe: 3% or less, N: 0.
O: 0.02% or less, and the balance substantially consists of Ni and unavoidable impurities.
After solution treatment at a temperature of 0 ° C, aging treatment is performed at a temperature of 600 to 750 ° C for 8 to 32 hours. (2) In mass%, C: 0.10% or less, Si: 1% or less, Mn: 1% or less, Cu: 0.1 to 5%, Cr: 16
-25%, Mo: 8-20%, Nb + Ta: 5-10
%, Al: 0.01 to 1%, Ti: 0.01 to 1%, F
e: 3% or less, N: 0.02% or less, O: 0.02% or less, the balance substantially consisting of Ni and unavoidable impurities, and after solid solution treatment at a temperature of 1000 to 1200 ° C, 6
The aging treatment is performed at a temperature of 00 to 750 ° C. for 8 to 32 hours.
【０００７】また、本発明の高硬度高耐食性Ｎｉ基合金
の製造方法は、 （３）質量％で、Ｃ：０．１０％以下、Ｓｉ：１％以
下、Ｍｎ：１％以下、Ｃｒ：１６〜２５％、Ｍｏ：８〜
２０％、Ｎｂ＋Ｔａ：５〜１０％、Ａｌ：０．０１〜１
％、Ｔｉ：０．０１〜１％、Ｆｅ：３％以下、Ｎ：０．
０２％以下、Ｏ：０．０２％以下を含み、残部実質的に
Ｎｉおよび不可避的不純物からなる合金粉末を、成形
し、焼結し、１０００〜１２００℃の温度で固溶化処理
した後、６００〜７５０℃の温度で８〜３２時間時効処
理することを特徴とする。The method for producing a high hardness and high corrosion resistance Ni-based alloy of the present invention is as follows: (3) In mass%, C: 0.10% or less, Si: 1% or less, Mn: 1% or less, Cr: 16 ~ 25%, Mo: 8 ~
20%, Nb + Ta: 5 to 10%, Al: 0.01 to 1
%, Ti: 0.01-1%, Fe: 3% or less, N: 0.
An alloy powder containing 02% or less, O: 0.02% or less, the balance substantially consisting of Ni and unavoidable impurities is molded, sintered, and subjected to a solution treatment at a temperature of 1000 to 1200 ° C. The aging treatment is carried out at a temperature of up to 750 ° C. for 8 to 32 hours.
【０００８】さらに、 （４）質量％で、Ｃ：０．１０％以下、Ｓｉ：１％以
下、Ｍｎ：１％以下、Ｃｕ：０．１〜５％、Ｃｒ：１６
〜２５％、Ｍｏ：８〜２０％、Ｎｂ＋Ｔａ：５〜１０
％、Ａｌ：０．０１〜１％、Ｔｉ：０．０１〜１％、Ｆ
ｅ：３％以下、Ｎ：０．０２％以下、Ｏ：０．０２％以
下を含み、残部実質的にＮｉおよび不可避的不純物から
なる合金粉末を、成形し、焼結し、１０００〜１２００
℃の温度で固溶化処理した後、６００〜７５０℃の温度
で８〜３２時間時効処理することを特徴とする。(4) In mass%, C: 0.10% or less, Si: 1% or less, Mn: 1% or less, Cu: 0.1 to 5%, Cr: 16
-25%, Mo: 8-20%, Nb + Ta: 5-10
%, Al: 0.01 to 1%, Ti: 0.01 to 1%, F
e: An alloy powder containing 3% or less, N: 0.02% or less, O: 0.02% or less, and substantially consisting of Ni and unavoidable impurities, is molded and sintered, and is subjected to 1000 to 1200.
After the solution treatment at a temperature of 600C, aging treatment is performed at a temperature of 600 to 750C for 8 to 32 hours.
【０００９】[0009]
【発明の実施の形態】以下、本発明の高硬度高耐食性Ｎ
ｉ基合金において、化学成分の含有率を限定する理由に
ついて説明する。 Ｃ：０．１０％以下 Ｃは、Ｎｂ、Ｔｉ、Ｃｒと結合して炭化物を形成する
が、過剰に含有すると、母相中のＮｂ、Ｔｉ、Ｃｒの濃
度低下をきたして合金の硬さ低下、耐食性の低下を招
く。上記の弊害の許し得る限界として、Ｃ含有率の上限
を０．１０％とする。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the high hardness and high corrosion resistance N of the present invention will be described.
The reason for limiting the content of the chemical component in the i-base alloy will be described. C: 0.10% or less C combines with Nb, Ti, and Cr to form a carbide, but when contained excessively, the concentration of Nb, Ti, and Cr in the matrix decreases, and the hardness of the alloy decreases. , Causing a decrease in corrosion resistance. The upper limit of the C content is set to 0.10% as a limit at which the above adverse effects can be tolerated.
【００１０】Ｓｉ：１％以下 Ｓｉは、合金の溶製時に脱酸元素として作用し、合金の
清浄化に寄与する。しかし、過剰に含有すると合金の靭
性を低下せしめるので、許し得る限界として、Ｓｉ含有
率の上限を１％とする。Si: 1% or less Si acts as a deoxidizing element during melting of an alloy, and contributes to cleaning of the alloy. However, an excessive content lowers the toughness of the alloy. Therefore, as an allowable limit, the upper limit of the Si content is set to 1%.
【００１１】Ｍｎ：１％以下 Ｍｎは、合金の溶解時に脱酸・脱硫元素として有効な元
素であるが、過剰に含有すると合金の耐食性を低下させ
るので、許し得る限界として、Ｍｎ含有率の上限を１％
とする。Mn: 1% or less Mn is an element effective as a deoxidizing / desulfurizing element when dissolving an alloy. However, if contained excessively, the corrosion resistance of the alloy is reduced. 1%
And
【００１２】Ｃｒ：１６〜２５％ Ｃｒは、合金の耐食性を向上するために重要な元素であ
る。前記効果を発揮するためには、Ｃｒを１６％以上含
有する必要がある。しかし、過剰に含有するとσ相を析
出して耐食性が低下するばかりでなく、合金の靭性が低
下する。それゆえ、Ｃｒ含有率の上限を２５％とする。Cr: 16 to 25% Cr is an important element for improving the corrosion resistance of the alloy. In order to exhibit the above effects, it is necessary to contain Cr in an amount of 16% or more. However, if it is contained excessively, not only the σ phase is precipitated and the corrosion resistance is lowered, but also the toughness of the alloy is lowered. Therefore, the upper limit of the Cr content is set to 25%.
【００１３】Ｍｏ：８〜２０％ Ｍｏは、合金の耐食性を向上するために添加する。前記
効果を発揮するためには、Ｍｏの含有率を８％以上とす
る必要がある。しかし、過剰にＭｏを含有すると合金の
靭性を低下させるのでＭｏ含有率の上限を２０％とす
る。Mo: 8 to 20% Mo is added to improve the corrosion resistance of the alloy. In order to exhibit the above effects, the content of Mo needs to be 8% or more. However, an excessive Mo content lowers the toughness of the alloy, so the upper limit of the Mo content is set to 20%.
【００１４】Ｎｂ＋Ｔａ：５〜１０％ ＮｂおよびＴａは、いずれも合金生地中にガンマダブル
プライム相（Ｎｉ3（Ｎｂ、Ｔａ））を析出し合金の硬
さを向上させるために添加する。前記効果を十分に発揮
するためには、少なくとも５％以上の（Ｎｂ＋Ｔａ）を
含有する必要がある。しかし、過剰に（Ｎｂ＋Ｔａ）を
含有すると、硬さの上昇の効果が飽和していたずらにコ
ストを上昇するばかりでなく、固溶化処理および時効処
理において、結晶粒界にδ相が析出して合金の靭性が低
下するとともに耐食性も低下するので（Ｎｂ＋Ｔａ）含
有率の上限を１０％とする。Nb + Ta: 5 to 10% Nb and Ta are both added to precipitate a gamma double prime phase (Ni 3 (Nb, Ta)) in the alloy material and improve the hardness of the alloy. In order to exert the above effect sufficiently, it is necessary to contain at least 5% or more of (Nb + Ta). However, when (Nb + Ta) is excessively contained, not only does the effect of increasing the hardness become saturated but the cost rises unnecessarily, but also in the solution treatment and the aging treatment, a δ phase precipitates at the crystal grain boundaries to cause an alloy. The lower limit of the (Nb + Ta) content is set to 10% because the toughness of the steel decreases and the corrosion resistance also decreases.
【００１５】Ａｌ：０．０１〜１％、Ｔｉ：０．０１〜
１％ ＡｌおよびＴｉは、いずれもガンマダブルプライム相
（Ｎｉ3（Ｎｂ、Ｔａ））を安定化しσ相の析出を抑制
するために添加する。前記効果を発揮するためにはＡｌ
は０．０１％以上、Ｔｉは０．０１％以上を含有する必
要がある。しかし、過剰に含有すると、むしろガンマダ
ブルプライム相を不安定にしてしまう。また、アトマイ
ズ法によって合金粉末を製造する際に、噴霧ノズルを閉
塞せしめるなどの不都合を生じるので、ＡｌおよびＴｉ
の含有率の上限を、それぞれ、１％とする。Al: 0.01-1%, Ti: 0.01-
1% Al and Ti are both added to stabilize the gamma double prime phase (Ni 3 (Nb, Ta)) and suppress the precipitation of the σ phase. In order to exhibit the above-mentioned effect, Al
Must contain 0.01% or more, and Ti must contain 0.01% or more. However, an excessive content rather makes the gamma double prime phase unstable. In addition, when producing alloy powder by the atomizing method, disadvantages such as closing a spray nozzle are caused.
Is set to 1%.
【００１６】Ｆｅ：３％以下 Ｆｅは、合金の製造過程で不純物として介入し、合金の
耐食性を損なうのでＦｅの含有量は少ないほど好まし
い。しかし、極度にＦｅ含有率を低めることはコスト上
昇を招くので、耐食性低下の許し得る限界としてＦｅ含
有率の上限を３％とする。Fe: 3% or less Fe intervenes as an impurity in the production process of the alloy and impairs the corrosion resistance of the alloy. Therefore, the smaller the Fe content, the better. However, extremely lowering the Fe content leads to an increase in cost. Therefore, the upper limit of the Fe content is set to 3% as a permissible limit of the decrease in corrosion resistance.
【００１７】Ｎ：０．０２％以下 Ｎは、Ａｌ、Ｔｉと結合して窒化物を形成し、Ａｌ、Ｔ
ｉの効果を低減するので、Ｎの含有率は低いほど好まし
いが、経済性を考慮して、Ｎ含有率の上限を０．０２％
とする。N: 0.02% or less N combines with Al and Ti to form a nitride, and Al, T
Since the effect of i is reduced, the lower the content of N, the better. However, in consideration of economy, the upper limit of the N content is set to 0.02%.
And
【００１８】Ｏ：０．０２％以下 Ｏは、Ａｌと結合して酸化物を形成し、Ａｌの添加効果
を損なう。また、合金粉末製造時に合金粉末表面に形成
される酸化膜は、焼結固化後の合金の耐食性を劣化する
原因となる。合金に対する前記弊害の許し得る限界とし
て、Ｏ含有率の上限を０．０２％とする。O: 0.02% or less O combines with Al to form an oxide and impairs the effect of adding Al. Further, the oxide film formed on the surface of the alloy powder during the production of the alloy powder causes deterioration of the corrosion resistance of the alloy after sintering and solidification. The upper limit of the O content is set to 0.02% as a limit at which the above harmful effects on the alloy can be tolerated.
【００１９】Ｃｕ：０．１〜５％ Ｃｕは、合金の耐食性を向上する効果を有するので添加
することができる。その効果を発揮するためには０．１
％以上添加することが必要である。しかし、過剰に含有
すると合金の硬さを低下させるので、Ｃｕ含有率の上限
を５％とする。Cu: 0.1 to 5% Cu can be added because it has an effect of improving the corrosion resistance of the alloy. 0.1%
% Or more must be added. However, an excessive content lowers the hardness of the alloy, so the upper limit of the Cu content is set to 5%.
【００２０】本発明の高硬度高耐食性Ｎｉ基合金は、前
記のように調整された化学組成を有するとともに、１０
００〜１２００℃の温度で固溶化処理後、６００〜７５
０℃の温度で８〜３２時間時効処理されることによって
所要の高硬度と高耐食性とを発揮するものである。The high hardness and high corrosion resistance Ni-based alloy of the present invention has a chemical composition adjusted as described above,
After a solution treatment at a temperature of 00 to 1200 ° C.,
By aging at a temperature of 0 ° C. for 8 to 32 hours, required high hardness and high corrosion resistance are exhibited.
【００２１】すなわち、固溶化処理によって、合金の凝
固時または合金粉末の焼結時に該合金の結晶粒界に析出
したδ相を生地に固溶させる。固溶化処理温度が１００
０℃未満であると前記δ相の固溶が十分でなく、後述の
時効処理で高い硬さが得られないので固溶化処理温度の
下限を１０００℃とする。また、固溶化処理温度が１２
００℃を超えると結晶粒の粗大化が顕著となり、合金の
耐食性が低下するので固溶化処理温度の上限を１２００
℃とする。That is, by the solution treatment, the δ phase precipitated at the crystal grain boundaries of the alloy during solidification of the alloy or sintering of the alloy powder is dissolved in the material. Solution treatment temperature of 100
When the temperature is lower than 0 ° C., the solid solution of the δ phase is not sufficient, and a high hardness cannot be obtained by the aging treatment described later. Further, when the solution treatment temperature is 12
When the temperature exceeds 00 ° C., the crystal grains become remarkably coarse, and the corrosion resistance of the alloy is reduced.
° C.
【００２２】時効処理は、前記固溶化処理を施した合金
中にガンマダブルプライム相（Ｎｉ 3（Ｎｂ、Ｔａ））
を析出させ、合金を４００ＨＶ以上の高硬度にするため
に行う。時効処理温度が６００℃未満ではガンマダブル
プライム相の析出が十分に行われないので前記高硬度が
得られず、時効処理温度が７５０℃を超えるとδ相の析
出により硬さが低下する。また、時効処理時間が８時間
未満ではガンマダブルプライム相の析出が十分に行われ
ず、時効処理時間が３２時間を超えると過時効となって
いずれも高い硬さが得られない。合金を４００ＨＶ以上
の高硬度にするためには、時効処理温度の下限を６００
℃、上限を７５０℃とし、時効処理時間の下限を８時
間、上限を３２時間とする必要がある。The aging treatment is performed on the alloy subjected to the solution treatment.
Gamma double prime phase (Ni Three(Nb, Ta))
To make the alloy harder than 400HV
To do. Gamma double when aging temperature is below 600 ℃
Since the precipitation of the prime phase is not performed sufficiently, the high hardness
When the aging temperature exceeds 750 ° C., the δ phase precipitates.
The hardness decreases due to protrusion. In addition, aging processing time is 8 hours
If it is less than, the gamma double prime phase is sufficiently precipitated.
If the aging time exceeds 32 hours, it will be overaged
In any case, high hardness cannot be obtained. 400 HV or more alloy
In order to obtain high hardness, the lower limit of the aging treatment temperature is 600
℃, the upper limit is 750 ° C, and the lower limit of the aging treatment time is 8:00
The upper limit must be 32 hours.
【００２３】次に、本発明の高硬度高耐食性Ｎｉ基合金
の製造方法について説明する。本発明の高硬度高耐食性
Ｎｉ基合金は、所要の化学組成を有する合金粉末を成形
し、焼結し、１０００〜１２００℃の温度で固溶化処理
後、６００〜７５０℃の温度で８〜３２時間時効処理し
て製造する。Next, a method for producing the high hardness and high corrosion resistance Ni-based alloy of the present invention will be described. The high hardness and high corrosion resistance Ni-based alloy of the present invention is obtained by molding and sintering an alloy powder having a required chemical composition, performing a solution treatment at a temperature of 1000 to 1200 ° C., and then forming a solution at a temperature of 600 to 750 ° C. to 8 to 32. Manufactured by time aging.
【００２４】前記合金粉末は、公知の合金粉末製造方法
によって製造することができる。該合金粉末の粉末粒度
は１０００μｍ以下で、見掛け密度４．５ｇ／ｃｍ3、
タップ充填密度５．５ｇ／ｃｍ3以上とすることが好ま
しい。成形および焼結は、公知の粉末冶金法によって行
う。好ましくは、ＨＩＰ処理によって成形、焼結して高
密度化する。次いで、固溶化処理、時効処理を施して高
硬度高耐食性Ｎｉ基合金とする。The alloy powder can be produced by a known alloy powder production method. The powder size of the alloy powder is 1000 μm or less, the apparent density is 4.5 g / cm 3 ,
The tap packing density is preferably 5.5 g / cm 3 or more. The molding and sintering are performed by a known powder metallurgy method. Preferably, it is formed and sintered by HIP processing to increase the density. Next, a solution treatment and an aging treatment are performed to obtain a high hardness and high corrosion resistance Ni-based alloy.
【００２５】[0025]
【実施例】アルゴンを用いたガスアトマイズ法によっ
て、表１に示す化学組成を有する合金粉末を製造し、分
級して粉末粒度５００μｍ以下の球状の合金粉末を得
た。ここに、合金ＩはＩｎｃｏｎｅｌ６２５相当合金で
ある。EXAMPLE An alloy powder having a chemical composition shown in Table 1 was produced by a gas atomization method using argon, and classified to obtain a spherical alloy powder having a powder particle size of 500 μm or less. Here, the alloy I is an Inconel 625 equivalent alloy.
【００２６】[0026]
【表１】 [Table 1]
【００２７】軟鋼製のカプセルに前記合金粉末を封入
し、１２００℃で１０００ｋｇｆ／ｃｍ2の条件でＨＩ
Ｐ処理を行って外径４０ｍｍの丸棒とした。該丸棒から
下記の各試験用素材を切出し、それぞれ所定の熱処理を
施してから各試験片に仕上げた。The above alloy powder is encapsulated in a mild steel capsule, and HI is applied at 1200 ° C. under a condition of 1000 kgf / cm 2.
P treatment was performed to obtain a round bar having an outer diameter of 40 mm. The following test materials were cut out from the round bar, and each test piece was finished after being subjected to a predetermined heat treatment.
【００２８】硬さ測定：ビッカース硬さ計を用い、荷重
５ｋｇｆで室温における硬さを測定した。５点の硬さ測
定値の平均をもって試験片の硬さの代表値とした。 パルス通電腐食試験：電解液中で通電している時に生じ
る腐食に対する耐食性を調べるため、直径１０ｍｍ×２
０ｍｍの円筒表面を試験面とする試験片について、液温
５０℃の鉄イオンを含む硫酸水溶液中で、１サイクル
０．７秒のうち電流密度２６０ｍＡ／ｄｍ2で０．２秒
間通電、０．５秒間通電なしの通電サイクルを８時間繰
返した後の腐食減量を測定し、試験片の単位表面積当り
の腐食減量を算出してパルス通電腐食量とした。Hardness measurement: The hardness at room temperature was measured under a load of 5 kgf using a Vickers hardness meter. The average of the five measured hardness values was used as a representative value of the hardness of the test piece. Pulse electric current corrosion test: 10 mm in diameter x 2 to examine the corrosion resistance to corrosion that occurs when electricity is applied in an electrolytic solution.
A test piece having a cylindrical surface of 0 mm as a test surface was subjected to a current density of 260 mA / dm 2 for 0.2 second in 0.7 second per cycle in an aqueous sulfuric acid solution containing iron ions at a liquid temperature of 50 ° C. for 0.2 second. The corrosion loss after repeating the power-supply cycle without power-on for 5 seconds for 8 hours was measured, and the corrosion loss per unit surface area of the test piece was calculated to be the pulse current corrosion amount.
【００２９】アノード分極特性測定：液温５０℃の２０
％硫酸水溶液中でアノード分極曲線を測定し、ｉ
crit（不動態化のために表れる最大電流密度）および
（飽和甘こう電極基準＋０．４Ｖにおける電流密度）に
よって耐食性を評価した。上記の各測定・試験の結果を
表２に示す。Measurement of anodic polarization characteristics: 20 at a liquid temperature of 50 ° C.
The anodic polarization curve was measured in
Corrosion resistance was evaluated by crit (maximum current density appearing for passivation) and (current density at +0.4 V with respect to saturated gizzard electrode). Table 2 shows the results of the above measurements and tests.
【００３０】[0030]
【表２】 [Table 2]
【００３１】表２によれば実施例１〜７は、いずれも４
００ＨＶ以上の硬さを示し、（Ｎｂ＋Ｔａ）含有率が低
い比較例１（Ｉｎｃｏｎｅｌ６２５相当合金）に比べて
硬さは高く、また、パルス通電腐食量は比較例１と同等
であるが、ｉcritおよびｉ0. 4は比較例１よりも小さ
く、耐食性は、比較例１よりも優れていることが判る。According to Table 2, Examples 1 to 7 were all 4
Shows the above hardness 00HV, (Nb + Ta) hardness as compared with the comparative low content Example 1 (Inconel 625 corresponding alloy) is high, also, the pulse current corrosion amount is equivalent to Comparative Example 1, i crit and i 0. 4 is smaller than Comparative example 1, corrosion resistance is seen to be superior to Comparative example 1.
【００３２】Ｍｏ含有率が低い比較例２は、パルス通電
腐食量、ｉcritおよびｉ0.4が高く、耐食性が劣る。Ｃ
ｒ含有率が高い比較例３は、σ相の析出によって硬さは
高いが耐食性が劣る。In Comparative Example 2 having a low Mo content, the pulse current corrosion amount, i crit and i 0.4 were high, and the corrosion resistance was poor. C
Comparative Example 3 having a high r content had a high hardness due to the precipitation of the σ phase, but was inferior in corrosion resistance.
【００３３】固溶化処理および時効処理のいずれも行わ
ず、ＨＩＰ処理のままの比較例４は、硬さが低く、ま
た、結晶粒界にδ相が残留しており、耐食性が劣る。１
２００℃を超える高い固溶化処理温度で処理された比較
例５は、硬さは高いが、結晶粒の粗大化のために耐食性
が劣化している。固溶化処理温度が１０００℃未満の温
度である比較例６は、δ相の固溶が十分でないために時
効硬化が十分に起こらず、硬さが低く、また、耐食性も
劣る。In Comparative Example 4 in which neither the solution treatment nor the aging treatment was performed and the HIP treatment was performed, the hardness was low, the δ phase remained at the crystal grain boundaries, and the corrosion resistance was poor. 1
Comparative Example 5, which was treated at a high solution treatment temperature exceeding 200 ° C., had high hardness, but deteriorated corrosion resistance due to coarsening of crystal grains. In Comparative Example 6 in which the solution treatment temperature was lower than 1000 ° C., age hardening did not sufficiently occur due to insufficient solid solution of the δ phase, the hardness was low, and the corrosion resistance was poor.
【００３４】７５０℃を超える高温で時効処理された実
施例７は、固溶化処理で消失していたδ相が再び生成し
たため硬さが低い。また、６００℃よりも低い温度で時
効処理された比較例８は、耐食性は良好であるが、時効
硬化が十分に生じていないので硬さが低い。３２時間を
超える長時間の時効処理を施した比較例９は、過時効を
生じて硬さが低下している。また、時効処理時間が８時
間未満の短時間である比較例１０は、十分な時効硬化が
生じておらず硬さが低い。上記のとおり、本発明の高硬
度高耐食性Ｎｉ基合金は、本発明が限定する化学組成と
固溶化熱処理および時効処理の条件との組合せから得ら
れるものである。Example 7, which was aged at a high temperature exceeding 750 ° C., was low in hardness because the δ phase which had disappeared in the solution treatment was formed again. Comparative Example 8, which was subjected to aging treatment at a temperature lower than 600 ° C., had good corrosion resistance, but had low hardness because of insufficient age hardening. In Comparative Example 9 which had been subjected to a long-term aging treatment of more than 32 hours, overaging occurred and the hardness was reduced. In Comparative Example 10 in which the aging treatment time was as short as less than 8 hours, sufficient age hardening did not occur and the hardness was low. As described above, the high hardness and high corrosion resistance Ni-based alloy of the present invention is obtained from a combination of the chemical composition defined by the present invention and the conditions of solution heat treatment and aging treatment.
【００３５】[0035]
【発明の効果】以上に説明したように、本発明の高硬度
高耐食性Ｎｉ基合金は、化学成分の配合と固溶化熱処理
および時効処理の条件とを工夫することによって得られ
たもので、本発明によって、優れた耐食性を備え、か
つ、４００ＨＶ以上の高硬度を有する合金と該合金の製
造方法を提供することができる。As described above, the high hardness and high corrosion resistance Ni-based alloy of the present invention is obtained by devising the combination of chemical components and the conditions of solution heat treatment and aging treatment. According to the present invention, it is possible to provide an alloy having excellent corrosion resistance and high hardness of 400 HV or more and a method for producing the alloy.
【００３６】これによって、電気めっき用通電ロール、
プラスチック射出成形機用シャフト、ディーゼルエンジ
ンの燃料噴射ノズル等、高い硬さと耐食性とを要する部
品の特性が向上することが期待され、その経済効果は極
めて大きいといえる。Thus, the energizing roll for electroplating,
It is expected that the characteristics of parts requiring high hardness and corrosion resistance, such as shafts for plastic injection molding machines and fuel injection nozzles for diesel engines, are improved, and the economic effect can be said to be extremely large.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２２Ｆ 1/00 ６３０ Ｃ２２Ｆ 1/00 ６３０Ｃ ６３０Ｄ ６４０ ６４０Ａ ６９１ ６９１Ｂ ６９１Ｃ (72)発明者 岡部 道生 愛知県名古屋市南区大同町二丁目30番地 大同特殊鋼株式会社技術研究所内 Ｆターム(参考） 4K018 AA08 FA09 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C22F 1/00 630 C22F 1/00 630C 630D 640 640A 691 691B 691C (72) Inventor Michio Okabe Nagoya-shi, Aichi 2-30, Datong-cho, Minami-ku F-term in the Technical Research Laboratory of Daido Steel Co., Ltd. (Reference) 4K018 AA08 FA09
Claims (4)
１％以下、Ｍｎ：１％以下、Ｃｒ：１６〜２５％、Ｍ
ｏ：８〜２０％、Ｎｂ＋Ｔａ：５〜１０％、Ａｌ：０．
０１〜１％、Ｔｉ：０．０１〜１％、Ｆｅ：３％以下、
Ｎ：０．０２％以下、Ｏ：０．０２％以下を含み、残部
実質的にＮｉおよび不可避的不純物からなり、１０００
〜１２００℃の温度で固溶化処理後、６００〜７５０℃
の温度で８〜３２時間時効処理することを特徴とする高
硬度高耐食性Ｎｉ基合金。C. 0.10% or less by mass%, Si:
1% or less, Mn: 1% or less, Cr: 16 to 25%, M
o: 8-20%, Nb + Ta: 5-10%, Al: 0.
01-1%, Ti: 0.01-1%, Fe: 3% or less,
N: 0.02% or less, O: 0.02% or less, the balance substantially consisting of Ni and unavoidable impurities;
600-750 ° C after solution treatment at a temperature of ~ 1200 ° C
Aging treatment at a temperature of 8 to 32 hours for a high hardness and high corrosion resistance Ni-based alloy.
１％以下、Ｍｎ：１％以下、Ｃｕ：０．１〜５％、Ｃ
ｒ：１６〜２５％、Ｍｏ：８〜２０％、Ｎｂ＋Ｔａ：５
〜１０％、Ａｌ：０．０１〜１％、Ｔｉ：０．０１〜１
％、Ｆｅ：３％以下、Ｎ：０．０２％以下、Ｏ：０．０
２％以下を含み、残部実質的にＮｉおよび不可避的不純
物からなり、１０００〜１２００℃の温度で固溶化処理
後、６００〜７５０℃の温度で８〜３２時間時効処理す
ることを特徴とする高硬度高耐食性Ｎｉ基合金。2. In mass%, C: 0.10% or less, Si:
1% or less, Mn: 1% or less, Cu: 0.1 to 5%, C
r: 16 to 25%, Mo: 8 to 20%, Nb + Ta: 5
-10%, Al: 0.01-1%, Ti: 0.01-1
%, Fe: 3% or less, N: 0.02% or less, O: 0.0
2% or less, the balance substantially consisting of Ni and unavoidable impurities, and after a solution treatment at a temperature of 1000 to 1200 ° C, an aging treatment at a temperature of 600 to 750 ° C for 8 to 32 hours. Hardness and high corrosion resistance Ni-based alloy.
１％以下、Ｍｎ：１％以下、Ｃｒ：１６〜２５％、Ｍ
ｏ：８〜２０％、Ｎｂ＋Ｔａ：５〜１０％、Ａｌ：０．
０１〜１％、Ｔｉ：０．０１〜１％、Ｆｅ：３％以下、
Ｎ：０．０２％以下、Ｏ：０．０２％以下を含み、残部
実質的にＮｉおよび不可避的不純物からなる合金粉末
を、成形し、焼結し、１０００〜１２００℃の温度で固
溶化処理した後、６００〜７５０℃の温度で８〜３２時
間時効処理することを特徴とする高硬度高耐食性Ｎｉ基
合金の製造方法。3. In mass%, C: 0.10% or less, Si:
1% or less, Mn: 1% or less, Cr: 16 to 25%, M
o: 8-20%, Nb + Ta: 5-10%, Al: 0.
01-1%, Ti: 0.01-1%, Fe: 3% or less,
An alloy powder containing N: 0.02% or less and O: 0.02% or less, substantially consisting of Ni and unavoidable impurities is formed, sintered, and subjected to a solution treatment at a temperature of 1000 to 1200 ° C. And then aging at a temperature of 600 to 750 ° C. for 8 to 32 hours.
１％以下、Ｍｎ：１％以下、Ｃｕ：０．１〜５％、Ｃ
ｒ：１６〜２５％、Ｍｏ：８〜２０％、Ｎｂ＋Ｔａ：５
〜１０％、Ａｌ：０．０１〜１％、Ｔｉ：０．０１〜１
％、Ｆｅ：３％以下、Ｎ：０．０２％以下、Ｏ：０．０
２％以下を含み、残部実質的にＮｉおよび不可避的不純
物からなる合金粉末を、成形し、焼結し、１０００〜１
２００℃の温度で固溶化処理した後、６００〜７５０℃
の温度で８〜３２時間時効処理することを特徴とする高
硬度高耐食性Ｎｉ基合金の製造方法。4. In mass%, C: 0.10% or less, Si:
1% or less, Mn: 1% or less, Cu: 0.1 to 5%, C
r: 16 to 25%, Mo: 8 to 20%, Nb + Ta: 5
-10%, Al: 0.01-1%, Ti: 0.01-1
%, Fe: 3% or less, N: 0.02% or less, O: 0.0
An alloy powder containing 2% or less and substantially consisting of Ni and unavoidable impurities is formed and sintered,
After a solution treatment at a temperature of 200 ° C., 600-750 ° C.
Aging treatment at a temperature of 8 to 32 hours for a high hardness and high corrosion resistance Ni-based alloy.
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| KR101007582B1 (en) | 2008-06-16 | 2011-01-12 | 한국기계연구원 | Method of heat treatment of Ni based superalloy for wave type grain-boundary and Ni based superalloy the same |
| JP2014070276A (en) * | 2012-10-02 | 2014-04-21 | Hitachi Ltd | Large-sized cast member made of nickel based alloy, and its manufacturing method |
| 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 |
| US10112254B2 (en) | 2014-08-21 | 2018-10-30 | Huntington Alloys Corporation | Method for making clad metal pipe |
| WO2020032235A1 (en) * | 2018-08-09 | 2020-02-13 | 山陽特殊製鋼株式会社 | NITRIDE-DISPERSED MOLDED BODY WHICH IS FORMED OF Ni-BASED ALLOY |
| CN113020624A (en) * | 2021-03-10 | 2021-06-25 | 西北工业大学 | Heat treatment method of laser stereo-forming TC4 titanium alloy |
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| JPH10121101A (en) * | 1996-10-22 | 1998-05-12 | Nippon Steel Corp | Conductive roll for electroplating |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101007582B1 (en) | 2008-06-16 | 2011-01-12 | 한국기계연구원 | Method of heat treatment of Ni based superalloy for wave type grain-boundary and Ni based superalloy the same |
| JP2014070276A (en) * | 2012-10-02 | 2014-04-21 | Hitachi Ltd | Large-sized cast member made of nickel based alloy, and its manufacturing method |
| US10112254B2 (en) | 2014-08-21 | 2018-10-30 | Huntington Alloys Corporation | Method for making clad metal pipe |
| 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 |
| CN107709586A (en) * | 2015-08-12 | 2018-02-16 | 山阳特殊制钢株式会社 | It is laminated moulding Ni base superalloy powder |
| EP3336210A4 (en) * | 2015-08-12 | 2019-03-13 | Sanyo Special Steel Co., Ltd. | Ni-based super alloy powder for laminate molding |
| WO2020032235A1 (en) * | 2018-08-09 | 2020-02-13 | 山陽特殊製鋼株式会社 | NITRIDE-DISPERSED MOLDED BODY WHICH IS FORMED OF Ni-BASED ALLOY |
| JP2020026537A (en) * | 2018-08-09 | 2020-02-20 | 山陽特殊製鋼株式会社 | NITRIDE-DISPERSED MOLDED BODY FORMED OF Ni-BASED ALLOY |
| JP7153502B2 (en) | 2018-08-09 | 2022-10-14 | 山陽特殊製鋼株式会社 | Molded body made of nitride-dispersed Ni-based alloy |
| CN113020624A (en) * | 2021-03-10 | 2021-06-25 | 西北工业大学 | Heat treatment method of laser stereo-forming TC4 titanium alloy |
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| JP4780431B2 (en) | 2011-09-28 |
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