JPH05214479A - High corrosion resistant and high strength hard sintered alloy - Google Patents
High corrosion resistant and high strength hard sintered alloyInfo
- Publication number
- JPH05214479A JPH05214479A JP3834592A JP3834592A JPH05214479A JP H05214479 A JPH05214479 A JP H05214479A JP 3834592 A JP3834592 A JP 3834592A JP 3834592 A JP3834592 A JP 3834592A JP H05214479 A JPH05214479 A JP H05214479A
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- JP
- Japan
- Prior art keywords
- content
- boride
- hard
- phase
- strength
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、正方晶系のＭ3Ｂ2型複
硼化物相を主とする硬質相と、該硬質相を結合するＮｉ
基の結合相からなり、耐摩耗性および耐食性に優れるば
かりでなく、常温および高温において十分な強度と耐酸
化性を有した高耐食性高強度硬質焼結合金に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard phase mainly composed of a tetragonal M 3 B 2 type double boride phase and a Ni phase which bonds the hard phase.
The present invention relates to a high-corrosion-resistant high-strength hard sintered alloy which is composed of a basic binder phase and has not only excellent wear resistance and corrosion resistance but also sufficient strength and oxidation resistance at room temperature and high temperature.
【０００２】[0002]
【従来の技術】耐摩耗性を有する硬質焼結材料に対する
要求は年々厳しくなり、単なる耐摩耗性ばかりでなく、
耐食性、耐酸化性、常温および高温における高強度を合
わせ持った材料が求められている。硬質焼結材料として
は、従来よりＷＣ基超硬合金やＴｉＣＮ系サーメットに
代表される炭化物、窒化物及び炭窒化物を利用した材料
がよく知られているものの、腐食環境下での使用には問
題がある。近年これらに代わる材料として、硼化物の持
つ高硬度、高融点、電気伝導性などの優れた特性に着目
し、ＷＢ，ＴｉＢ2などの金属硼化物、並びにＭｏ2Ｆｅ
Ｂ2およびＭｏ2ＮｉＢ2などの金属複硼化物を利用し
た、硬質合金及びセラミックスが提案されている。2. Description of the Related Art The demand for hard sintered materials having wear resistance is becoming stricter year by year.
There is a demand for a material that has both corrosion resistance, oxidation resistance, and high strength at room temperature and high temperature. As hard sintered materials, conventionally, materials using carbides, nitrides and carbonitrides typified by WC-based cemented carbide and TiCN cermet are well known, but are not suitable for use in corrosive environments. There's a problem. In recent years, as alternative materials, attention has been paid to the excellent properties of boride such as high hardness, high melting point, and electrical conductivity, and metal borides such as WB and TiB 2 and Mo 2 Fe.
Hard alloys and ceramics utilizing metal double borides such as B 2 and Mo 2 NiB 2 have been proposed.
【０００３】これらのうちＷＢをＮｉ基合金で結合した
硬質合金（特公昭５６−４５９８５〜７）は、常磁性の
耐摩耗材料、特に時計側、装飾品を目的とした合金であ
り、耐食性は優れるものの、強度が十分ではない。Ｔｉ
Ｂ2などの金属硼化物を利用したセラミクッス（例えば
特公昭６１−５０９０９、特公昭６３−５３５３）は、
高硬度で耐熱性に優れるものの、金属結合相がないた
め、耐衝撃性に劣る。Among these, a hard alloy in which WB is bonded by a Ni-based alloy (Japanese Patent Publication No. 56-45985-7) is a paramagnetic wear-resistant material, especially for watches and ornaments, and has corrosion resistance. Excellent, but not strong enough. Ti
Ceramic ceramics using a metal boride such as B 2 (for example, JP-B-61-50909 and JP-B-63-5353) are
Although it has high hardness and excellent heat resistance, it is inferior in impact resistance because it has no metallic binder phase.
【０００４】また一般的に金属硼化物に金属元素を添加
した硬質材料は、脆い第３相を形成し易く高強度が得に
くいという欠点がある。この欠点を改良したのが、焼結
中の反応により形成されるＭｏ2ＦｅＢ2やＭｏ2ＮｉＢ2
などの金属複硼化物を利用した硬質合金である。このう
ちＦｅ基結合相を有したＭｏ2ＦｅＢ2系硬質合金（特公
昭６０−５７４９９）は、常温における強度および耐摩
耗性には優れるものの、Ｆｅ基結合相を有するため耐食
性は十分でない。また、Ｎｉ基結合相を有したＭｏ2Ｎ
ｉＢ2系硬質合金（例えば特開昭６２−１９６３５３、
特開昭６３−１４３２３６、特開平１−１３１０７０、
特開平１−１３１０７１、特開平２−１５１４０、特開
平２−１９４４１）は、Ｍｏ2ＦｅＢ2系硬質合金の耐食
性改善を目的として発明されたものであり、耐食性には
優れるが、常温における強度が十分でない。また、これ
らのＮｉ基の結合相を有する硬質合金の場合に、硬質相
であるＭｏ2ＮｉＢ2、およびこれにＷ，Ｃｒ，Ｃｏ等の
元素が固溶したＭ3Ｂ2型複硼化物の結晶構造としてはこ
れまでに斜方晶系のものしか報告されておらず、Ｍ3Ｂ2
型複硼化物と同定されているこれらの特許に記載された
硬質合金のＭ3Ｂ2型複硼化物の結晶構造は、正方晶系で
はなく、斜方晶系である。さらに、特開昭６３−４５３
４４、特開昭６３−２９３１３４に開示されているＮｉ
基結合相を有する硬質合金の硬質相であるＭ3Ｂ2型複硼
化物は、（Ｍｏ，Ｃｒ，Ｎｉ）3Ｂ2で表されるが、該特
許に記載されているＸ線回折図をみると、斜方晶系でも
正方晶系でもないことが明らかである。このように、同
じＮｉ基の結合相を有する硬質合金の硬質相であるＭ3
Ｂ2型複硼化物にも、その合金組成や製造方法によって
種々の結晶系のものがあり、そのために異なった特性を
持ち、これまでに耐摩耗性、耐食性、耐酸化性および高
強度の全ての特性を兼ね備えた材料は得られなかった。Further, generally, a hard material obtained by adding a metal element to a metal boride has a drawback that it tends to form a brittle third phase and it is difficult to obtain high strength. This defect was improved by Mo 2 FeB 2 and Mo 2 NiB 2 formed by the reaction during sintering.
It is a hard alloy that utilizes metal double borides such as. Of these, the Mo 2 FeB 2 -based hard alloy having a Fe-based bonded phase (Japanese Patent Publication No. 60-57499) is excellent in strength and wear resistance at room temperature, but has a Fe-based bonded phase and thus is not sufficient in corrosion resistance. Further, Mo 2 N having a Ni-based binder phase
iB 2 type hard alloy (for example, JP-A-62-196353,
JP-A-63-143236, JP-A-1-131070,
JP-A-1-131071, JP-A-2-15140, and JP-A-2-19441) were invented for the purpose of improving the corrosion resistance of Mo 2 FeB 2 -based hard alloys, and are excellent in corrosion resistance, but have high strength at room temperature. not enough. Further, in the case of a hard alloy having these Ni-based binder phases, the hard phase of Mo 2 NiB 2 and M 3 B 2 type double boride in which elements such as W, Cr and Co are solid-dissolved As for the crystal structure, only an orthorhombic one has been reported so far, and M 3 B 2
The hard alloy M 3 B 2 type double boride described in these patents identified as type double boride is orthorhombic rather than tetragonal. Further, JP-A-63-453
44, Ni disclosed in JP-A-63-293134
The M 3 B 2 type complex boride, which is a hard phase of a hard alloy having a base bonding phase, is represented by (Mo, Cr, Ni) 3 B 2 , and the X-ray diffraction diagram described in the patent is used. It is clear that it is neither orthorhombic nor tetragonal. Thus, M 3 which is a hard phase of a hard alloy having the same Ni-based binder phase
B 2 -type compound borides also have various crystal systems depending on their alloy composition and manufacturing method, and therefore have different characteristics, so far, all of wear resistance, corrosion resistance, oxidation resistance and high strength have been achieved. It was not possible to obtain a material having the above characteristics.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記Ｎｉ基
結合相を有するＭｏ2ＮｉＢ2系硬質合金の特性改善を目
的としたものであり、耐摩耗性、耐食性、耐酸化性に加
えて、常温および高温における十分な強度を合わせ持っ
た、高耐食性高強度硬質焼結合金を提供することを目的
としている。SUMMARY OF THE INVENTION The present invention is intended to improve the properties of Mo 2 NiB 2 type hard alloys having the above Ni-based bonding phase, and in addition to wear resistance, corrosion resistance and oxidation resistance, An object of the present invention is to provide a high-corrosion, high-strength hard sintered alloy having sufficient strength at room temperature and high temperature.
【０００６】[0006]
【課題を解決するための手段】本発明は、硼化物より成
る硬質相３５〜９５％と、該硬質相を結合するＮｉ基の
結合相からなり、かつ全硬質相量のうち、正方晶系のＭ
3Ｂ2型複硼化物を６０％以上含み、残部が斜方晶系のＭ
3Ｂ2型複硼化物あるいは他の硼化物よりなる高耐食性高
強度硬質焼結合金において、Ｂ含有量が３〜７．５％、
Ｍｏ含有量がＭｏ／Ｂ原子比で０．８〜（１．６−０．
０５Ｘ）（Ｘ：含有するＢの重量％）、ＣｒおよびＶ含
有量がいずれか一方または両者の合計で（９−Ｘ）〜
（５５−５Ｘ）％、残部が１０％以上のＮｉ、および不
可避的不純物よりなる組成の合金、およびＢ含有量が３
〜７．５％、Ｗ含有量が０．１〜３０％、Ｍｏ含有量が
ＭｏおよびＷ含有量の合計で、（Ｍｏ＋Ｗ）／Ｂ原子比
で０．８〜（１．６−０．０５Ｘ）、ＣｒおよびＶ含有
量がいずれか一方または両者の合計で（９−Ｘ）〜（５
５−５Ｘ）％、残部が１０％以上のＮｉ、および不可避
的不純物よりなる組成の高耐食性高強度硬質焼結合金を
提供するものである。さらに、耐食性向上にＣｕ添加、
高温特性向上にＣｏ添加、そして機械的特性向上にＮｂ
添加が有効である。ゆえに、上記組成に加えて、Ｍｏ，
Ｗ，Ｃｒ，ＶおよびＮｉのいずれか一種または二種以上
の一部と置換する形で、Ｃｕ含有量が０．１〜５％、Ｃ
ｏ含有量が０．２〜５％およびＮｂ含有量が０．２〜１
０％のいずれか一種または２種以上を含み、必要に応じ
てＮｂの一部または全部を、Ｚｒ，Ｔｉ，Ｔａの中から
選ばれた一種または二種以上で置換することを特徴とす
る高耐食性高強度硬質焼結合金を提供するものである。DISCLOSURE OF THE INVENTION The present invention comprises a hard phase of 35 to 95% made of boride and a Ni-based binder phase for bonding the hard phase, and the tetragonal system is contained in the total hard phase content. M
3 B 2 type compound containing more than 60% of boride and the rest is orthorhombic M
In a high corrosion resistance and high strength hard sintered alloy composed of 3 B 2 type complex boride or other boride, the B content is 3 to 7.5%,
Mo content is 0.8 to (1.6-0.
05X) (X: wt% of B contained), Cr and / or V content is either (9-X)-
An alloy having a composition of (55-5X)%, the balance of Ni being 10% or more, and inevitable impurities, and a B content of 3
˜7.5%, W content 0.1 to 30%, Mo content is the sum of Mo and W contents, and (Mo + W) / B atomic ratio is 0.8 to (1.6-0.05X ), Cr and V contents are either (9-X) to (5) in total.
The present invention provides a high corrosion resistance and high strength hard sintered alloy having a composition of 5-5X)%, the balance of 10% or more of Ni, and unavoidable impurities. Furthermore, Cu is added to improve corrosion resistance,
Add Co to improve high temperature characteristics, and Nb to improve mechanical characteristics
Addition is effective. Therefore, in addition to the above composition, Mo,
The content of Cu is 0.1 to 5%, and C is substituted with a part of one or more of W, Cr, V and Ni.
o content 0.2-5% and Nb content 0.2-1
0% of any one kind or two kinds or more, and if necessary, a part or all of Nb is replaced with one kind or two kinds or more selected from Zr, Ti and Ta. Provided is a corrosion resistant high strength hard sintered alloy.
【０００７】以下本発明の限定理由について詳細に説明
する。高強度の耐食性に優れたＭｏ2ＮｉＢ2系の耐摩耗
材料を種々検討したところ、合金の組成だけでなく、そ
の合金を構成している相の構造、すなわち結晶系が機械
的特性を始めとした諸特性に大きく影響していた。そし
て、斜方晶系に代わり、正方晶系のＭ3Ｂ2型複硼化物か
らなる硬質相と、Ｎｉ基の結合相を組み合わせることに
より、高強度の耐摩、耐食材料を得た。Ｘ線回折測定に
よる調査の結果、Ｍｏ2ＮｉＢ2、Ｗ2ＮｉＢ2および（Ｍ
ｏ，Ｗ）2ＮｉＢ2、あるいはこれらにＣｒ、Ｃｏ等の金
属元素が固溶した斜方晶系のＭ3Ｂ2型複硼化物とＮｉ基
の結合相の組み合わせでは高い強度は得られないもの
の、合金組成を厳密に管理するとともに、焼結中の反応
により斜方晶系ではなく、正方晶系のＭ3Ｂ2型複硼化物
を積極的に形成させ、正方晶系のＭ3Ｂ2型複硼化物とＮ
ｉ基の結合相からなる新規な焼結合金を開発することに
より、耐摩耗性および耐食性を減じることなく、強度の
倍増を可能にした。これは、斜方晶系よりも正方晶系の
Ｍ3Ｂ2型複硼化物の方が、面心立方晶系のＮｉ基結合相
との整合性が良いためと推察される。すなわち、耐食性
に優れたＮｉ基の硬質合金において高い強度を得るに
は、Ｍｏ／Ｂ原子比あるいは（Ｍｏ＋Ｗ）／Ｂ原子比に
くわえて、ＣｒおよびＶのどちらか一方または両者の含
有量を適正な範囲内に管理することにより、斜方晶系の
Ｍ3Ｂ2型複硼化物の形成を抑え、正方晶系のＭ3Ｂ2型複
硼化物を６０％以上焼結中の反応により形成させること
が必要不可欠である。この場合、正方晶系のＭ3Ｂ2型複
硼化物は、Ｍｏ2（Ｃｒ，Ｎｉ）Ｂ2、Ｍｏ2（Ｖ，Ｎ
ｉ）Ｂ2、Ｍｏ2（Ｃｒ，Ｖ，Ｎｉ）Ｂ2、（Ｍｏ，Ｗ）2
（Ｃｒ，Ｎｉ）Ｂ2、（Ｍｏ，Ｗ）2（Ｖ，Ｎｉ）Ｂ2お
よび（Ｍｏ，Ｗ）2（Ｃｒ，Ｖ，Ｎｉ）Ｂ2に近い組成で
表される。The reasons for limitation of the present invention will be described in detail below. When various studies were carried out on Mo 2 NiB 2 wear resistant materials having high strength and excellent corrosion resistance, it was found that not only the composition of the alloy but also the structure of the phases constituting the alloy, that is, the crystal system, including mechanical properties It had a great influence on the characteristics. Then, in place of the orthorhombic system, a hard phase made of tetragonal M 3 B 2 type complex boride and a Ni-based binder phase were combined to obtain a high-strength wear-resistant and corrosion-resistant material. As a result of investigation by X-ray diffraction measurement, Mo 2 NiB 2 , W 2 NiB 2 and (M
o, W) 2 NiB 2 or a combination of an orthorhombic M 3 B 2 type double boride in which a metal element such as Cr or Co forms a solid solution with Ni and a binder phase of Ni group cannot provide high strength. However, while strictly controlling the alloy composition, the reaction during sintering positively forms a tetragonal M 3 B 2 type double boride rather than an orthorhombic system, and a tetragonal system M 3 B Type 2 compound boride and N
By developing a new sintered alloy consisting of an i-based binder phase, it has become possible to double the strength without reducing wear resistance and corrosion resistance. It is speculated that this is because the tetragonal M 3 B 2 type complex boride has better compatibility with the face-centered cubic Ni-based bonded phase than the orthorhombic system. That is, in order to obtain high strength in a Ni-based hard alloy having excellent corrosion resistance, in addition to the Mo / B atomic ratio or (Mo + W) / B atomic ratio, the content of either one or both of Cr and V is appropriate. By controlling the content within the above range, formation of orthorhombic M 3 B 2 type complex boride is suppressed and tetragonal M 3 B 2 type complex boride is formed by reaction during sintering of 60% or more. It is essential to let them do it. In this case, the tetragonal M 3 B 2 type double boride is Mo 2 (Cr, Ni) B 2 or Mo 2 (V, N
i) B 2 , Mo 2 (Cr, V, Ni) B 2 , (Mo, W) 2
(Cr, Ni) B 2 , (Mo, W) 2 (V, Ni) B 2 and (Mo, W) 2 (Cr, V, Ni) B 2 are represented by compositions close to each other.
【０００８】本硬質焼結合金の耐摩耗性は、主として硬
度、つまり硼化物よりなる硬質相の量に依存する。硬質
相の量が３５％未満になると、本硬質合金の硬度は、ロ
ックウエルＡスケールで７５以下となり、耐摩耗性が低
下する。一方、硬質相の量が９５％を越えると硬度は高
くなるものの、強度の低下が著しい。よって本硬質合金
中の硬質相の割合は、３５〜９５％とする。The wear resistance of the present hard sintered alloy depends mainly on the hardness, that is, the amount of the hard phase composed of boride. When the amount of the hard phase is less than 35%, the hardness of the present hard alloy becomes 75 or less on the Rockwell A scale, and the wear resistance decreases. On the other hand, when the amount of the hard phase exceeds 95%, the hardness becomes high, but the strength is remarkably reduced. Therefore, the proportion of the hard phase in the present hard alloy is 35 to 95%.
【０００９】本硬質焼結合金の強度は、主として全硬質
相中に占める、正方晶系のＭ3Ｂ2型複硼化物の量に依存
する。全硬質相中に占める正方晶系のＭ3Ｂ2型複硼化物
の量が６０％未満になり、残部の斜方晶系のＭ3Ｂ2型複
硼化物および他の硼化物のいずれか一方または両者の合
計量が４０％を越えると、硬質焼結合金の強度の低下を
もたらす。よって、全硬質相中に占める正方晶系のＭ3
Ｂ2型複硼化物の量を６０％以上とする。つまり、硬質
焼結合金全体に占める正方晶系のＭ3Ｂ2型複硼化物の量
は、下限が３５×０．６＝２１％であり、２１〜９５％
となる。The strength of the present hard sintered alloy mainly depends on the amount of tetragonal M 3 B 2 type double boride in the total hard phase. The amount of tetragonal M 3 B 2 type complex boride in the total hard phase is less than 60%, and the balance is either orthorhombic M 3 B 2 type complex boride or other boride. If the total amount of one or both exceeds 40%, the strength of the hard sintered alloy decreases. Therefore, tetragonal M 3 occupies in the total hard phase
The amount of B 2 type complex boride is set to 60% or more. That is, the lower limit of the amount of the tetragonal M 3 B 2 type complex boride in the entire hard sintered alloy is 35 × 0.6 = 21%, which is 21 to 95%.
Becomes
【００１０】Ｂは、本硬質焼結合金中の硬質相となる硼
化物を形成するために必要不可欠な元素であり、Ｂ含有
量が３％未満になると、硼化物よりなる硬質相の割合が
３５％をきることになる。一方７．５％を越えると、硬
質相の量は９５％を越え、強度の低下をもたらす。よっ
て、本硬質焼結合金中のＢ含有量は、３〜７．５％とす
る。B is an essential element for forming a boride which becomes a hard phase in the hard sintered alloy of the present invention. When the B content is less than 3%, the proportion of the hard phase composed of boride is reduced. It will be below 35%. On the other hand, if it exceeds 7.5%, the amount of the hard phase exceeds 95%, resulting in a decrease in strength. Therefore, the B content in the present hard sintered alloy is set to 3 to 7.5%.
【００１１】ＭｏはＢ同様硬質相となる硼化物を形成す
るために必要不可欠な元素である。本硬質焼結合金中の
硬質相である正方晶系のＭ3Ｂ2型複硼化物は、Ｍｏ
2（Ｃｒ，Ｎｉ）Ｂ2、Ｍｏ2（Ｖ，Ｎｉ）Ｂ2、Ｍｏ
2（Ｃｒ，Ｖ，Ｎｉ）Ｂ2に近い組成と推察され、Ｍｏと
Ｂの化学量論比は１：１であるが、実際は完全な化学量
論的な化合物ではなく、数％の組成範囲を有するため、
Ｍｏ／Ｂの原子比（以下Ｍｏ／Ｂ比と略す）は１である
必要はないが、１の前後のある特定の範囲にすることが
重要である。種々実験の結果、Ｍｏ／Ｂ比が１を大幅に
外れ、１より小さい場合には正方晶系のＭ3Ｂ2型複硼化
物とは異なる、正方晶系のＣｒ5Ｂ3などのＭ'5Ｂ3型
（Ｍ'：Ｃｒを主体とし、Ｍｏ、Ｎｉ等を含む）硼化物
や斜方晶系のＮｉ3ＢなどのＭ"3Ｂ型（Ｍ"：Ｎｉを主体
とし、Ｃｒ、Ｍｏ等を含む）硼化物などの他の硼化物が
第３相として形成され、０．８より小さくなると強度の
低下が著しい。一方、１より大きい場合にはＢに対して
過剰なＭｏの一部は、Ｎｉ基合金マトリックス中に固溶
し、結合相を固溶強化し、本硬質焼結合金の機械的特性
の向上をもたらす。しかしながら適正な量を越えたＭｏ
は、Ｍｏ−Ｎｉ系の金属間化合物を第３相として形成
し、強度の低下を招く。したがって、Ｎｉ基合金マトリ
ックス中のＭｏ量を厳密に管理することが必要不可欠で
ある。すなわちＢ含有量が増加するとともに、正方晶系
のＭ3Ｂ2型複硼化物量が増加し、それに伴いＮｉ基合金
マトリックスは減少するため、合金の強度を維持するに
は、それと共にマトリックス中に含まれる過剰なＭｏ量
も減少させる必要があることから、Ｍｏ含有量の上限
は、Ｂ含有量が下限の３％の場合、Ｍｏ／Ｂ比で１．４
５、上限の７．５％の場合１．２２５にする必要があ
る。これを式で表すと、Ｂ含有量をＸ％とした時１．６
−０．０５Ｘとなる。したがって、Ｍｏ／Ｂ比が、０．
８〜（１．６−０．０５Ｘ）の範囲内に有れば、正方晶
系のＭ3Ｂ2型複硼化物およびＮｉ基合金マトリックス以
外に、これらの第３相が形成されたとしても、その影響
は少なく、強度の低下は許容範囲内にある。よって、Ｍ
ｏ含有量は、Ｍｏ／Ｂ原子比で０．８〜（１．６−０．
０５Ｘ)を満足する範囲とする。Like B, Mo is an essential element for forming a boride which becomes a hard phase. The tetragonal M 3 B 2 type complex boride which is the hard phase in the hard sintered alloy is Mo.
2 (Cr, Ni) B 2 , Mo 2 (V, Ni) B 2 , Mo
It is assumed that the composition is close to 2 (Cr, V, Ni) B 2 , and the stoichiometric ratio of Mo and B is 1: 1. However, it is not a completely stoichiometric compound, and the composition range is several%. To have
The atomic ratio of Mo / B (hereinafter abbreviated as Mo / B ratio) does not have to be 1, but it is important to set it within a certain range around 1. As a result of various experiments, when the Mo / B ratio greatly deviates from 1 and is smaller than 1, it is different from the tetragonal M 3 B 2 type complex boride, and M ′ such as tetragonal Cr 5 B 3 is different. 5 B 3 type (M ': Cr mainly, including Mo, Ni, etc.) Borides and orthorhombic Ni 3 B M " 3 B type (M": Ni mainly, Cr, Mo Other borides such as borides are formed as the third phase, and if it is less than 0.8, the strength is significantly reduced. On the other hand, when it is larger than 1, a part of excess Mo with respect to B dissolves in the Ni-based alloy matrix and strengthens the binder phase to improve the mechanical properties of the hard sintered alloy. Bring However, Mo exceeding the proper amount
Forms an intermetallic compound of the Mo-Ni system as the third phase, leading to a decrease in strength. Therefore, it is essential to strictly control the amount of Mo in the Ni-based alloy matrix. That is, as the B content increases, the tetragonal M 3 B 2 type double boride content increases, and the Ni-based alloy matrix decreases accordingly. Since it is also necessary to reduce the excess Mo content contained in, the upper limit of the Mo content is 1.4 at the Mo / B ratio when the B content is 3%, which is the lower limit.
5, if the upper limit is 7.5%, it must be set to 1.225. When this is expressed by a formula, it is 1.6 when the B content is X%.
It becomes −0.05X. Therefore, the Mo / B ratio is 0.
Within the range of 8 to (1.6-0.05X), even if these third phases are formed in addition to the tetragonal M 3 B 2 type complex boride and the Ni-based alloy matrix. , Its effect is small, and the decrease in strength is within the allowable range. Therefore, M
The o content is 0.8 to (1.6-0.
05X).
【００１２】ＷはＭｏと置換可能な元素であるととも
に、適正な量の添加により形崩れが少ない良好な形状の
焼結体が得られ、ニヤネット化が図れる。さらに合金の
耐摩耗性を向上させる効果もあるが、０．１％未満では
効果が表れない。一方、３０％を越えて添加しても、添
加量ほどの特性の向上は認められないだけでなく、正方
晶系のＣｒ5Ｂ3などのＭ'5Ｂ3型（Ｍ'：Ｃｒを主体と
し、Ｗ、Ｍｏ、Ｎｉ等を含む）硼化物などの他の硼化物
が多く形成され、全硬質相中に占める正方晶系Ｍ3Ｂ2型
複硼化物量が６０％より少なくなり、抗折力が低下す
る。また、比重が高くなり、製品重量が増す。したがっ
て、Ｗ含有量は０．１〜３０％とする。Ｗを含有した本
硬質焼結合金中の硬質相である正方晶系のＭ3Ｂ2型複硼
化物は、（Ｍｏ，Ｗ）2（Ｃｒ，Ｎｉ）Ｂ2、（Ｍｏ，
Ｗ）2（Ｖ，Ｎｉ）Ｂ2および（Ｍｏ，Ｗ）2（Ｃｒ，
Ｖ，Ｎｉ）Ｂ2に近い組成と推察され、ＭｏとＷの合計
とＢの化学量論比は１：１であるが、実際は完全な化学
量論的な化合物ではなく、数％の組成範囲を有するた
め、（Ｍｏ＋Ｗ）／Ｂの原子比（以下（Ｍｏ＋Ｗ）／Ｂ
比と略す）は１である必要はないが、１の前後のある特
定の範囲にすることが重要である。種々実験の結果、
（Ｍｏ＋Ｗ）／Ｂ比が１を大幅に外れ、１より小さい場
合には正方晶系のＭ3Ｂ2型複硼化物とは異なる、正方晶
系のＣｒ5Ｂ3などのＭ'5Ｂ3型硼化物や斜方晶系のＮｉ3
ＢなどのＭ"3Ｂ型（Ｍ"：Ｎｉを主体とし、Ｃｒ、Ｗ、
Ｍｏ等を含む）硼化物などの他の硼化物が第３相として
形成され、０．８より小さくなると強度の低下が著し
い。一方、１より大きい場合にはＢに対して過剰なＭｏ
およびＷの一部は、Ｎｉ基合金マトリックス中に固溶
し、結合相を固溶強化し、本硬質焼結合金の機械的特性
の向上をもたらす。しかしながら適正な量を越えたＭｏ
およびＷは、Ｍｏ−Ｗ−Ｎｉ系の金属間化合物を第３相
として形成し、強度の低下を招く。したがって、Ｎｉ基
合金マトリックス中のＭｏおよびＷ量を厳密に管理する
ことが必要不可欠である。すなわちＢ含有量が増加する
とともに、正方晶系のＭ3Ｂ2型複硼化物量が増加し、そ
れに伴いＮｉ基合金マトリックスは減少するため、合金
の強度を維持するには、それと共にマトリックス中に含
まれる過剰なＭｏおよびＷ量も減少させる必要があるこ
とから、ＭｏおよびＷ含有量の上限は、Ｂ含有量が下限
の３％の場合、（Ｍｏ＋Ｗ）／Ｂ比で１．４５、上限の
７．５％の場合１．２２５にする必要がある。これを式
で表すと、Ｂ含有量をＸ％とした時１．６−０．０５Ｘ
となる。したがって、（Ｍｏ＋Ｗ）／Ｂ比が０．８〜
（１．６−０．０５Ｘ）の範囲内に有れば、正方晶系の
Ｍ3Ｂ2型複硼化物およびＮｉ基合金マトリックス以外
に、これらの第３相が形成されたとしても、その影響は
少なく、強度の低下は許容範囲内にある。よってＷを
０．１〜３０％含有した場合の（Ｍｏ＋Ｗ）／Ｂ原子比
は、０．８〜（１．６−０．０５Ｘ)を満足する範囲と
する。W is an element capable of substituting for Mo, and when added in an appropriate amount, a sintered body having a good shape with less deformation can be obtained, and a near net can be achieved. Further, it has an effect of improving the wear resistance of the alloy, but if it is less than 0.1%, the effect is not exhibited. On the other hand, even when added in excess of 30%, not only observed improvement in the properties of the higher amount, M '5 B 3 type (M', such as Cr 5 B 3 tetragonal: mainly Cr Other boride such as boride (including W, Mo, Ni, etc.) is formed in large amounts, and the amount of tetragonal M 3 B 2 type complex boride in the total hard phase is less than 60%. Folding strength decreases. In addition, the specific gravity is increased and the product weight is increased. Therefore, the W content is 0.1 to 30%. The tetragonal M 3 B 2 type complex boride which is the hard phase in the present hard sintered alloy containing W is (Mo, W) 2 (Cr, Ni) B 2 , (Mo,
W) 2 (V, Ni) B 2 and (Mo, W) 2 (Cr,
V, Ni) It is inferred that the composition is close to B 2 , and the stoichiometric ratio of Mo and W to B is 1: 1. However, it is not a completely stoichiometric compound, but a composition range of several%. Has an atomic ratio of (Mo + W) / B (hereinafter (Mo + W) / B
The ratio (abbreviated as ratio) does not have to be 1, but it is important to set it within a certain range around 1. The results of various experiments,
When the (Mo + W) / B ratio largely deviates from 1 and is smaller than 1, it is different from the tetragonal M 3 B 2 type double boride, and M ′ 5 B 3 such as tetragonal Cr 5 B 3 is different. -Type borides and orthorhombic Ni 3
B such as M " 3 B type (M": Ni as the main component, Cr, W,
Other borides such as borides (including Mo, etc.) are formed as the third phase, and if it is smaller than 0.8, the strength is significantly reduced. On the other hand, when it is larger than 1, excessive Mo is added to B.
And a part of W are solid-solved in the Ni-based alloy matrix to solid-solution strengthen the binder phase, and improve the mechanical properties of the present hard sintered alloy. However, Mo exceeding the proper amount
And W form a Mo-W-Ni-based intermetallic compound as the third phase, which causes a decrease in strength. Therefore, it is essential to strictly control the amounts of Mo and W in the Ni-based alloy matrix. That is, as the B content increases, the tetragonal M 3 B 2 type double boride content increases, and the Ni-based alloy matrix decreases accordingly. Since it is necessary to reduce the excess amounts of Mo and W contained in, the upper limit of the Mo and W contents is 1.45 when the B content is 3%, which is the lower limit, and the upper limit is 1.45. In case of 7.5%, it is necessary to set to 1.225. When this is expressed by a formula, when the B content is X%, 1.6-0.05X
Becomes Therefore, the (Mo + W) / B ratio is 0.8 to
Within the range of (1.6-0.05X), even if these third phases are formed in addition to the tetragonal M 3 B 2 type double boride and the Ni-based alloy matrix, The influence is small and the decrease in strength is within the allowable range. Therefore, the (Mo + W) / B atomic ratio when W is contained in an amount of 0.1 to 30% is in a range satisfying 0.8 to (1.6-0.05X).
【００１３】ＣｒおよびＶは、正方晶系のＭ3Ｂ2型複硼
化物を形成するために必要不可欠な元素であり、Ｂ量に
対して一定量添加する必要がある。また、添加したＣｒ
およびＶは硬質相だけでなくＮｉ基の結合相中にも固溶
する元素であり、硬質合金の耐食性向上にも効果が大き
い。ＣｒおよびＶのどちらか一方または両者の合計含有
量の下限は、種々実験の結果、６０％以上正方晶系のＭ
3Ｂ2型複硼化物を形成させるためには、Ｂ含有量が下限
の３％の場合が６％であり、上限の７．５％の場合は理
由は不明であるが、ＣｒおよびＶの含有量は少なくて
１．５％である。これを式で表すと、Ｂ含有量をＸ％と
した時（９−Ｘ）％となる。この含有量未満では、硼化
物より成る硬質相全体に占める正方晶系のＭ3Ｂ2型複硼
化物の量が６０％未満になり、残部の斜方晶系のＭ3Ｂ2
型複硼化物および他の硼化物のいずれか一方または両者
の合計量が４０％を越え、硬質焼結合金の強度の低下を
もたらす。一方、ＣｒおよびＶのどちらか一方または両
者の合計含有量の上限は、種々実験の結果、６０％以上
正方晶系のＭ3Ｂ2型複硼化物を形成させるためには、Ｂ
含有量が下限の３％の場合が４０％であり、上限の７．
５％の場合は理由は不明であるが、１７．５％である。
これを式で表すと、Ｂ含有量をＸ％とした時（５５−５
Ｘ）％となる。この含有量を越えると、Ｎｉとの金属間
化合物や正方晶系のＣｒ5Ｂ3などのＭ'5Ｂ3型硼化物な
どの他の硼化物が第３相として形成され、硼化物より成
る硬質相全体に占める正方晶系のＭ3Ｂ2型複硼化物の量
が６０％未満になり、強度の低下を招く。したがって、
ＣｒおよびＶ含有量はいずれか一方または両者の合計
で、Ｂ含有量をＸ％とした時（９−Ｘ）〜（５５−５
Ｘ）の範囲とする。Cr and V are indispensable elements for forming a tetragonal M 3 B 2 type double boride, and must be added in a certain amount with respect to the amount of B. Also, the added Cr
And V are elements that form a solid solution not only in the hard phase but also in the Ni-based binder phase, and have a great effect on improving the corrosion resistance of the hard alloy. As a result of various experiments, the lower limit of the total content of either or both of Cr and V is 60% or more.
In order to form a 3 B 2 type double boride, the lower limit of 3% is 6% and the upper limit of 7.5% is 6%. The content is at least 1.5%. When this is expressed by a formula, it becomes (9-X)% when the B content is X%. If the content is less than this, the amount of tetragonal M 3 B 2 type complex boride in the entire hard phase composed of borides is less than 60%, and the balance is orthorhombic M 3 B 2
Either or both of the type compound boride and the other boride exceeds 40%, resulting in a decrease in strength of the hard sintered alloy. On the other hand, the upper limit of the total content of either or both of Cr and V is 60% or more as a result of various experiments, and in order to form a tetragonal M 3 B 2 type complex boride,
When the content is 3% which is the lower limit, it is 40%, and when the content is 7.
In the case of 5%, the reason is unknown, but it is 17.5%.
When this is expressed by an equation, when the B content is X% (55-5
X)%. Beyond this amount, other borides, such as M '5 B 3 type borides such as Cr 5 B 3 intermetallic compounds and tetragonal and Ni is formed as the third phase, consisting of borides The amount of tetragonal M 3 B 2 type double boride in the entire hard phase is less than 60%, resulting in a decrease in strength. Therefore,
The Cr and V contents are either one or both in total, and when the B content is X%, (9-X) to (55-5).
X) range.
【００１４】Ｎｉは、正方晶系のＭ3Ｂ2型複硼化物形成
に必要不可欠な元素である。また、結合相を構成する主
な元素であり、本高耐食性高強度硬質合金の優れた耐食
性に寄与する。Ｎｉ含有量が１０％未満になると、種々
実験の結果、硼化物より成る硬質相全体に占める正方晶
系のＭ3Ｂ2型複硼化物の量が６０％未満になり、強度の
低下を招く。したがって、残部は１０％以上のＮｉとす
る。なお、Ｂ，Ｍｏ，Ｗ，Ｃｒ，Ｖ，Ｃｕ，Ｃｏ，Ｎ
ｂ，Ｚｒ，Ｔｉ，Ｔａの合計量が１００％を越え、Ｎｉ
を１０％含有できない場合には、いうまでもなく、各元
素の許容される重量％の範囲内において、その量を減じ
て、残部に１０％以上のＮｉを確保する。Ni is an essential element for forming a tetragonal M 3 B 2 type double boride. Further, it is a main element constituting the binder phase and contributes to the excellent corrosion resistance of the present high corrosion resistance and high strength hard alloy. When the Ni content is less than 10%, as a result of various experiments, the amount of tetragonal M 3 B 2 type complex boride occupying the whole hard phase composed of borides is less than 60%, resulting in a decrease in strength. .. Therefore, the balance is 10% or more of Ni. In addition, B, Mo, W, Cr, V, Cu, Co, N
b, Zr, Ti, Ta total amount exceeds 100%, Ni
When 10% cannot be contained, it goes without saying that the amount is reduced within the allowable weight% range of each element to secure 10% or more of Ni in the balance.
【００１５】Ｃｕは、主としてＮｉ基合金結合相中に固
溶し、本高耐食性高強度硬質焼結合金の耐食性の改善に
効果を示す。添加量が０．１％未満ではこれらの効果は
認められず、５％を越えると機械的特性が低下する。よ
って本高耐食性高強度硬質焼結合金にＣｕを添加した場
合の含有量は、０．１〜５％とする。Cu mainly forms a solid solution in the Ni-based alloy binder phase and exhibits an effect of improving the corrosion resistance of the present high corrosion resistance and high strength hard sintered alloy. If the amount added is less than 0.1%, these effects are not observed, and if it exceeds 5%, the mechanical properties deteriorate. Therefore, when Cu is added to the present high corrosion resistance and high strength hard sintered alloy, the content is set to 0.1 to 5%.
【００１６】Ｃｏは、主としてＮｉ基合金結合相中に固
溶し、本高耐食性高強度硬質焼結合金の高温強度、耐酸
化性の改善に効果を示す。添加量が０．２％未満ではこ
れらの効果は認められず、５％を越えると機械的特性が
低下する。よって本高耐食性高強度硬質焼結合金にＣｏ
を添加した場合の含有量は、０．２〜５％とする。Co is mainly solid-dissolved in the Ni-base alloy binder phase and has an effect of improving the high temperature strength and oxidation resistance of the present high corrosion resistance and high strength hard sintered alloy. If the added amount is less than 0.2%, these effects are not observed, and if it exceeds 5%, the mechanical properties deteriorate. Therefore, this high corrosion resistance and high strength hard sintered alloy can be
The content in the case of adding is 0.2 to 5%.
【００１７】Ｎｂは硼化物形成元素であり、本高耐食性
高強度硬質焼結合金に添加した場合、硬質相中に固溶す
るとともに、一部は硼化物を形成し、硬度の上昇をもた
らすばかりでなく、結合相中にも固溶し液相焼結時の結
晶粒の粗大化を抑制する働きを持つ。Ｎｂは少量の添加
で効果を示すが、０．２％未満では効果が表れない。一
方、１０％を越えて添加しても、添加量ほどの特性の向
上は認められない。よって、Ｎｂの添加量は、０．２〜
１０％とする。さらに、Ｚｒ，Ｔｉ，ＴａはＮｂと同様
に硼化物形成元素であり、本高耐食性高強度硬質焼結合
金に添加した場合、硬質相中に固溶するとともに、一部
は硼化物を形成し、硬度の上昇をもたらすばかりでな
く、結合相中にも固溶し液相焼結時の結晶粒の粗大化を
抑制する働きを持つ。これらの元素は少量の添加で効果
を示すが、０．２％未満では効果が表れない。一方、１
０％を越えて添加しても、添加量ほどの特性の向上は認
められないだけでなく、全般にこれらの元素は高価であ
るため、コストの上昇を招く。これらの元素は、各々単
独で添加できるだけでなく、２種以上の元素の複合添加
をすることも可能である。よって、これらの元素の添加
量はＮｂ，Ｚｒ，Ｔｉ，Ｔａの１種または２種以上の合
計で、０．２〜１０％とする。Nb is a boride-forming element, and when added to the present high corrosion resistance and high-strength hard sintered alloy, it forms a solid solution in the hard phase and partly forms boride, which not only increases the hardness. Not only that, it also forms a solid solution in the binder phase and has the function of suppressing the coarsening of crystal grains during liquid phase sintering. Nb shows an effect even if added in a small amount, but no effect appears if it is less than 0.2%. On the other hand, even if it is added in excess of 10%, the improvement in characteristics as much as the addition amount is not recognized. Therefore, the amount of Nb added is 0.2 to
10%. Further, Zr, Ti, and Ta are boride-forming elements like Nb, and when added to this high corrosion-resistant high-strength hard sintered alloy, they form a solid solution in the hard phase and partly form boride. Not only does it increase hardness, but also acts as a solid solution in the binder phase to suppress coarsening of crystal grains during liquid phase sintering. These elements are effective when added in a small amount, but the effect is not exhibited when less than 0.2%. On the other hand, 1
Even if added in excess of 0%, not only the improvement in characteristics as much as the added amount is not recognized, but also since these elements are generally expensive, the cost is increased. These elements can be added not only individually but also as a composite addition of two or more kinds of elements. Therefore, the addition amount of these elements is 0.2 to 10% in total of one kind or two kinds or more of Nb, Zr, Ti, and Ta.
【００１８】本高耐食性高強度硬質焼結合金中に含まれ
る不可避的不純物元素の主なものは、Ｆｅ，Ｓｉ，Ａ
ｌ，Ｍｎ，Ｍｇ，Ｐ，Ｓ，Ｎ，Ｏ，Ｃ等であり、Ｆｅを
除くＳｉ，Ａｌ，Ｍｎ，Ｍｇ，Ｐ，Ｓ，Ｎ，Ｏ，Ｃ等の
不純物元素の含有量は、正方晶系のＭ3Ｂ2型複硼化物形
成のためには極力少ない方がよく、含有量の合計が１．
５％以下であれば特性の低下は比較的少ない。なお、Ｆ
ｅは本高耐食性高強度硬質焼結合金を製造する過程で、
原料粉末および製造容器等から混入し易い不純物であ
り、合金強度におよぼす影響は少ないものの、耐食性の
低下をもたらすため、本高耐食性高強度硬質焼結合金中
の含有量は少ない方がよく、４％以下とする。よって本
高耐食性高強度硬質焼結合金中に含まれる不可避的不純
物元素の含有量は、Ｆｅが４％以下、好ましくは２％以
下、より好ましくは１％以下とする。Ｆｅを除くＳｉ，
Ａｌ，Ｍｎ，Ｍｇ，Ｐ，Ｓ，Ｎ，Ｏ，Ｃ等の含有量の合
計で１．５％以下、好ましくは１％以下とする。なお、
本高耐食性高強度硬質焼結合金を強度を余り必要としな
い耐摩耗被覆として用い、耐酸化性向上のために意識的
にＳｉ，Ａｌなどを添加する場合はこの限りではない。
また、Ｃは本高耐食性高強度硬質焼結合金中に炭化物を
形成し、強度を低下させるものの、硬度の上昇および耐
摩耗性を改善するため、特に耐摩耗性を要求される用途
に関して、意識的にＣを添加する場合もこの限りではな
い。さらに、ＦｅはＮｉと置換可能な安価な元素であ
り、本高耐食性高強度硬質焼結合金の耐食性を低下させ
るものの、特に廉価な用途に関して、意識的にＦｅを添
加する場合もこの限りではない。The main unavoidable impurity elements contained in the present high corrosion resistance and high strength hard sintered alloy are Fe, Si and A.
The content of impurity elements such as Si, Al, Mn, Mg, P, S, N, O, and C other than Fe is tetragonal. In order to form the M 3 B 2 type double boride in the system, it is preferable that the amount is as small as possible, and the total content is 1.
If it is 5% or less, the deterioration of the characteristics is relatively small. In addition, F
e is the process of manufacturing the high corrosion resistant high strength hard sintered alloy,
Although it is an impurity that is easily mixed from the raw material powder and manufacturing container, and has little effect on alloy strength, it causes a decrease in corrosion resistance. Therefore, it is better that the content in this high corrosion resistance high strength hard sintered alloy is small. % Or less. Therefore, the content of the unavoidable impurity element contained in the present high corrosion resistance and high strength hard sintered alloy is 4% or less of Fe, preferably 2% or less, and more preferably 1% or less. Si excluding Fe,
The total content of Al, Mn, Mg, P, S, N, O, C, etc. is 1.5% or less, preferably 1% or less. In addition,
This does not apply when the present high corrosion resistance and high strength hard sintered alloy is used as a wear resistant coating that does not require much strength and Si, Al, etc. are intentionally added to improve the oxidation resistance.
Further, although C forms carbide in the high corrosion resistance and high strength hard sintered alloy to reduce the strength, it improves the hardness and improves the wear resistance, so that it is necessary to consider the wear resistance in particular. This does not apply even when C is added intentionally. Further, Fe is an inexpensive element that can be replaced with Ni, and reduces the corrosion resistance of the present high corrosion resistance and high strength hard sintered alloy, but it is not limited to the case where Fe is intentionally added for particularly inexpensive applications. ..
【００１９】本高耐食性高強度硬質焼結合金は、Ｎｉ，
Ｍｏ，Ｃｒ，Ｖ，Ｗ，Ｃｕ，Ｃｏ，Ｎｂ，Ｚｒ，Ｔｉ，
Ｔａの元素の内１種または２種以上の元素とＢとの合金
粉末、もしくはＢ単体粉末と、Ｎｉ，Ｍｏ，Ｃｒ，Ｖ，
Ｗ，Ｃｕ，Ｃｏ，Ｎｂ，Ｚｒ，Ｔｉ，Ｔａの単体金属粉
末、もしくはこれらの元素の内２種以上を含む合金粉末
を、振動ボールミルなどにより有機溶媒中で湿式混合粉
砕後、乾燥・造粒・成形を行い、その後真空、還元性ガ
ス、あるいは不活性ガス中などの非酸化性雰囲気中で、
液相焼結を行うことにより製造される。なお、原料粉で
あるＮｉ，Ｍｏ，Ｃｒ，Ｖ，Ｗ，Ｃｕ，Ｃｏ，Ｎｂ，Ｚ
ｒ，Ｔｉ，Ｔａの元素の内１種または２種以上の元素と
Ｂとの合金粉末は、水またはガスアトマイズ法等により
製造してもさしつかえない。本高耐食性高強度硬質焼結
合金の硬質相となる正方晶系のＭ3Ｂ2型複硼化物は、上
記原料粉末の焼結中の反応により形成されるが、あらか
じめＭｏ，Ｗ，Ｃｒ，ＶおよびＮｉ等の硼化物、Ｂ単体
粉末などと、Ｍｏ，Ｗ，Ｃｒ，ＶおよびＮｉなどの金属
粉末を炉中で反応させることにより、Ｍｏ2（Ｃｒ，Ｎ
ｉ）Ｂ2、Ｍｏ2（Ｖ，Ｎｉ）Ｂ2、Ｍｏ2（Ｃｒ，Ｖ，Ｎ
ｉ）Ｂ2、（Ｍｏ，Ｗ）2（Ｃｒ，Ｎｉ）Ｂ2、（Ｍｏ，
Ｗ）2（Ｖ，Ｎｉ）Ｂ2および（Ｍｏ，Ｗ）2（ Ｃｒ，
Ｖ，Ｎｉ）Ｂ2などの正方晶系Ｍ3Ｂ2型複硼化物を製造
し、これらの複硼化物粉末に、Ｎｉ基合金マトリックス
となるＮｉおよびＣｒ，Ｖ，Ｍｏ，Ｗなどの金属粉末を
配合した粉末を原料粉末として用いても差しつかえな
い。本高耐食性高強度硬質焼結合金の湿式混合粉砕は、
振動ボールミルなどにより有機溶媒中で行われ、焼結中
の正方晶系Ｍ3Ｂ2型複硼化物形成反応を迅速、かつ十分
に行わせるために、振動ボールミル粉砕後の、粉末の平
均粒径は０．２〜２μｍが好ましい。なお、０．２μｍ
未満まで粉砕しても、微細化による効果向上は少ないば
かりでなく、粉砕に長時間を要する。また、２μｍを越
えると正方晶系Ｍ3Ｂ2型複硼化物形成反応が迅速に進行
せず、焼結体中の硬質相の粒径も大きくなり、機械的特
性の低下が著しい。本高耐食性高強度硬質焼結合金の液
相焼結は、合金組成により異なるが、一般的には１１５
０〜１３５０℃の温度で５〜９０分間行われる。１１５
０℃未満では正方晶系のＭ3Ｂ2型複硼化物が十分に形成
しない。一方、１３５０℃を越えると過剰の液相を生
じ、焼結体の形崩れが著しい。したがって、最終焼結温
度は１１５０〜１３５０℃とする。好ましくは１１７５
〜１３２５℃である。昇温速度は一般的には０．５〜６
０℃／分であり、０．５℃／分より遅いと所定の加熱温
度に到達するまでに長時間を要する。一方、６０℃／分
より速すぎると焼結炉の温度コントロールができない。
したがって、昇温速度は０．５〜６０℃／分、好ましく
は１〜３０℃／分である。なお１１５０〜１３５０℃で
行う液相焼結に先立ち、１０２５〜１１２５℃の液相が
存在しない固相域において１０〜２４０分間保持し、原
料粉末中に含まれているＣにより、粉末表面の酸化被膜
を十分に還元除去することが好ましい。これは酸化被膜
が存在すると、正方晶系のＭ3Ｂ2型複硼化物が十分に形
成しないからである。したがって、原料粉末の酸化の程
度が著しい場合には、意図的にＣを原料粉末として配合
しても良い。ただし、Ｃは本来不純物元素であり、特性
を低下させるため、最終焼結体中の含有量はＦｅを除く
Ｓｉ，Ａｌ，Ｍｎ，Ｍｇ，Ｐ，Ｓ，Ｎ，Ｏ，Ｃ等の含有
量の合計で、１．５％以下とすることはいうまでもな
い。This high corrosion resistance and high strength hard sintered alloy is composed of Ni,
Mo, Cr, V, W, Cu, Co, Nb, Zr, Ti,
An alloy powder of B with one or more of the elements of Ta and B, or a powder of B alone, Ni, Mo, Cr, V,
Single metal powder of W, Cu, Co, Nb, Zr, Ti, Ta, or alloy powder containing two or more of these elements is wet-mixed and ground in an organic solvent by a vibrating ball mill or the like, and then dried and granulated.・ Molding, then in a non-oxidizing atmosphere such as vacuum, reducing gas or inert gas,
It is manufactured by performing liquid phase sintering. The raw material powders of Ni, Mo, Cr, V, W, Cu, Co, Nb, Z
The alloy powder of B with one or more of the elements of r, Ti and Ta and B may be produced by a water or gas atomizing method or the like. The tetragonal M 3 B 2 type complex boride, which is the hard phase of the high corrosion-resistant high-strength hard sintered alloy, is formed by the reaction during sintering of the above raw material powders. By reacting a boride such as V and Ni, a simple B powder or the like with a metal powder such as Mo, W, Cr, V or Ni in a furnace, Mo 2 (Cr, N
i) B 2 , Mo 2 (V, Ni) B 2 , Mo 2 (Cr, V, N
i) B 2 , (Mo, W) 2 (Cr, Ni) B 2 , (Mo,
W) 2 (V, Ni) B 2 and (Mo, W) 2 (Cr,
V, Ni) B 2 and other tetragonal M 3 B 2 type complex borides are produced, and Ni and Cr, V, Mo, W and other metal powders serving as a Ni-based alloy matrix are added to these complex boride powders. There is no problem even if a powder blended with is used as the raw material powder. Wet-mix grinding of this high corrosion-resistant high-strength hard sintered alloy
The average particle size of the powder after the vibration ball mill is pulverized in order to quickly and sufficiently carry out the tetragonal M 3 B 2 type double boride formation reaction during sintering performed in an organic solvent by a vibration ball mill or the like. Is preferably 0.2 to 2 μm. 0.2 μm
Even if it is pulverized to less than a certain amount, not only is the improvement in effect due to miniaturization small, but pulverization requires a long time. On the other hand, if it exceeds 2 μm, the tetragonal M 3 B 2 type double boride forming reaction does not proceed rapidly, the grain size of the hard phase in the sintered body becomes large, and the mechanical properties are significantly deteriorated. The liquid phase sintering of the high corrosion resistant high strength hard sintered alloy varies depending on the alloy composition, but is generally 115.
It is carried out at a temperature of 0 to 1350 ° C. for 5 to 90 minutes. 115
If the temperature is lower than 0 ° C., tetragonal M 3 B 2 type double boride is not sufficiently formed. On the other hand, when the temperature exceeds 1350 ° C., an excessive liquid phase is generated, and the shape of the sintered body is significantly lost. Therefore, the final sintering temperature is 1150 to 1350 ° C. Preferably 1175
~ 1325 ° C. The heating rate is generally 0.5 to 6
It is 0 ° C./minute, and if it is slower than 0.5 ° C./minute, it takes a long time to reach a predetermined heating temperature. On the other hand, if it is faster than 60 ° C / min, the temperature of the sintering furnace cannot be controlled.
Therefore, the rate of temperature rise is 0.5 to 60 ° C / min, preferably 1 to 30 ° C / min. Prior to the liquid phase sintering performed at 1150 to 1350 ° C., the powder surface was kept at 1025 to 1125 ° C. for 10 to 240 minutes in the solid phase region where the liquid phase did not exist, and was oxidized by the C contained in the raw material powder. It is preferable to sufficiently reduce and remove the coating. This is because if an oxide film is present, tetragonal M 3 B 2 type complex boride is not sufficiently formed. Therefore, when the degree of oxidation of the raw material powder is remarkable, C may be intentionally mixed as the raw material powder. However, since C is an impurity element by nature and deteriorates the characteristics, the content in the final sintered body is the content of Si, Al, Mn, Mg, P, S, N, O, C, etc. excluding Fe. It goes without saying that the total is 1.5% or less.
【００２０】[0020]
【作用】本発明は、硼化物より成る硬質相３５〜９５％
と、該硬質相を結合するＮｉ基の結合相からなり、かつ
全硬質相量のうち、正方晶系のＭ3Ｂ2型複硼化物を６０
％以上含み、残部が斜方晶系のＭ3Ｂ2型複硼化物あるい
は他の硼化物よりなる高耐食性高強度硬質焼結合金を提
供するものであり、Ｂ含有量は３〜７．５％、Ｍｏ含有
量はＭｏ／Ｂ原子比で０．８〜（１．６−０．０５Ｘ）
（Ｘ：含有するＢの重量％）、ＣｒおよびＶ含有量はい
ずれか一方または両者の合計で、（９−Ｘ）〜（５５−
５Ｘ）％を満足する範囲内に限定することにより、硼化
物系硬質合金中に形成され易い、斜方晶系のＭ3Ｂ2型複
硼化物および他の硼化物等の第３相の形成を抑制し、正
方晶系のＭ3Ｂ2型複硼化物とＮｉ基合金マトリックスの
主として２相からなる高耐食性高強度硬質焼結合金が得
られる。また、０．１〜３０％の必要量のＷ添加は焼結
性改善および耐摩耗性向上に効果があり、この場合に
は、Ｍｏ含有量を（Ｍｏ＋Ｗ）／Ｂ原子比で０．８〜
（１．６−０．０５Ｘ）に限定する。さらにＣｕ添加に
より本高耐食性高強度硬質焼結合金の耐食性、Ｃｏ添加
により高温強度および耐酸化性、Ｎｂ，Ｚｒ，Ｔｉ，Ｔ
ａ添加により機械的特性が大幅に改善される。In the present invention, the hard phase composed of boride is 35 to 95%.
And a tetragonal M 3 B 2 type boride composed of a Ni-based binder phase that bonds the hard phase and out of the total hard phase content.
% Or more, with the balance being an orthorhombic M 3 B 2 type complex boride or other boride, which has high corrosion resistance and high strength, and has a B content of 3 to 7.5. %, Mo content is 0.8 to (1.6-0.05X) in Mo / B atomic ratio.
(X:% by weight of B contained), Cr and V contents are either one or a total of (9-X) to (55-
The formation of a third phase, such as an orthorhombic M 3 B 2 type complex boride and other borides, which is likely to be formed in a boride-based hard alloy, by limiting the content to a range satisfying 5X)%. And a high corrosion resistance and high strength hard sintered alloy mainly composed of two phases of a tetragonal M 3 B 2 type double boride and a Ni-based alloy matrix can be obtained. Further, the addition of a required amount of W of 0.1 to 30% is effective in improving the sinterability and the wear resistance. In this case, the Mo content is (Mo + W) / B atomic ratio of 0.8 to
Limited to (1.6-0.05X). Furthermore, by adding Cu, the corrosion resistance of this high-corrosion-resistant high-strength hard sintered alloy, by adding Co, high-temperature strength and oxidation resistance, Nb, Zr, Ti, T
Addition of a significantly improves the mechanical properties.
【００２１】[0021]
【実施例】本発明の実施例及び比較例を表１〜８により
説明する。EXAMPLES Examples and comparative examples of the present invention will be described with reference to Tables 1 to 8.
【００２２】原料粉末として、表１に示す化合物粉末お
よび表２に示す純金属粉末を用い、これらの粉末を表３
および４に示す組成になるように、表５および６に示す
配合比で配合後、振動ボールミルによりアセトン中で３
０時間、湿式混合粉砕を行った。ボールミル後の粉末は
乾燥・造粒を行い、できた微粉末を所定の形状にプレス
成形後、真空中において１１００℃の温度に９０分間保
持した後、１２２０〜１３４０℃の温度で３０分間焼結
を行った。昇温速度は１０℃／分とした。なお、比較例
１０および１１に示すステンレス鋼ＳＵＳ３０４および
ＳＵＳ４４０Ｃは市販品を使用した。As raw material powders, the compound powders shown in Table 1 and the pure metal powders shown in Table 2 were used.
And 4 to obtain the compositions shown in Tables 5 and 6, and then 3 in acetone by a vibration ball mill.
Wet mixing and grinding was performed for 0 hours. The powder after ball milling is dried and granulated, and the fine powder thus obtained is press-molded into a predetermined shape, held at a temperature of 1100 ° C for 90 minutes in vacuum, and then sintered at a temperature of 1220 to 1340 ° C for 30 minutes. I went. The heating rate was 10 ° C./min. Commercially available stainless steels SUS304 and SUS440C shown in Comparative Examples 10 and 11 were used.
【００２３】 [0023]
【００２４】 [0024]
【００２５】 [0025]
【００２６】 [0026]
【００２７】 [0027]
【００２８】 [0028]
【００２９】実施例に示す組成の本高耐食性高強度硬質
焼結合金および比較例の、焼結後の試片の常温における
硬質相および全硬質相中の正方晶系Ｍ3Ｂ2型複硼化物の
重量％、抗折力および硬度の測定結果と共に、８００℃
における高温抗折力を表７および８に示す。さらに腐食
性の強い雰囲気である４０℃、１０％弗化水素酸水溶液
中１０時間浸漬後の腐食減量を測定し、１時間当たりの
腐食減量（mg/cm2/h）に換算した結果、および９００℃
静止大気中、１時間保持後の酸化増量の測定結果を示
す。なお、全硬質相中の正方晶系Ｍ3Ｂ2型複硼化物量
は、Ｘ線回折装置を用いて定量分析した。また、高温抗
折力は常温において高い強度を示す試料のみ実施した。Tetragonal M 3 B 2 type double boron in the hard phase and the total hard phase of the sintered samples of the high corrosion resistance and high strength hard alloys of the compositions shown in the examples and the comparative examples. Along with the measurement results of the weight% of the compound, bending strength and hardness
The high temperature transverse rupture strengths of the above are shown in Tables 7 and 8. Furthermore, the corrosion weight loss after immersion in a 10% hydrofluoric acid aqueous solution at 40 ° C., which is a highly corrosive atmosphere, for 10 hours was measured and converted into the corrosion weight loss per hour (mg / cm 2 / h), and 900 ° C
The measurement result of the oxidation increase after 1 hour holding | maintenance in a stationary atmosphere is shown. The amount of tetragonal M 3 B 2 type double boride in all hard phases was quantitatively analyzed using an X-ray diffractometer. Further, the high temperature transverse rupture strength was carried out only for the samples showing high strength at room temperature.
【００３０】 [0030]
【００３１】 [0031]
【００３２】表７、８より実施例１〜１１は、比較例に
比較して、いずれも優れた抗折力、硬度、耐食性を有す
るばかりでなく、高温においても優れた抗折力を有する
ことがわかる。また、比較例１０および１１に示すステ
ンレス鋼と比較しても、同等の優れた耐酸化性を有して
いるばかりでなく、ステンレス鋼を越える耐食性を持つ
ことが明らかである。実施例１は特許請求範囲のＢ含有
量の下限に近い組成の合金であり、Ｂ含有量が３．３
％、硼化物よりなる硬質相量は４０％である。したがっ
て硬度はやや低いものの、切削加工が可能という利点が
ある。また、正方晶系のＭ3Ｂ2型複硼化物を６０％以上
含んでいるために、抗折力は２６０ｋｇ／ｍｍ2と高い
値である。実施例２〜５は硬質相が全て正方晶系のＭ3
Ｂ2型複硼化物からなる組成の合金であり、硬度および
抗折力ともに高い値である。また、実施例４および５は
Ｗを含有した合金であり、形崩れのない良好な焼結体が
得られた。実施例６および７は、Ｂ含有量が各々６％お
よび７％であり、硬度が高く、特に実施例７は耐摩耗性
に優れる合金である。また、Ｎｉ基結合相量が少ないも
のの、正方晶系のＭ3Ｂ2型複硼化物を６０％以上含んで
おり、硬度が高いわりには抗折力も高い値を示してい
る。実施例８はＣｕを含有しており、１０％弗化水素酸
水溶液中、４０℃、１０時間浸漬後の腐食減量が少な
く、耐食性が特に優れる合金である。実施例９〜１１は
Ｎｂ、ＺｒおよびＴｉの硼化物形成元素を含有したもの
であり、硬度が高く耐摩耗性に優れる。また、結晶粒が
微細化しており、抗折力も高い値を示している。さら
に、実施例９および１１はＣｏを含有しており、９００
℃静止大気中、１時間保持後の酸化増量が少なく、耐酸
化性に優れる。それに対して比較例１は、Ｂ量が３％よ
り低い２．５％の場合であり、硬質相量が３５％より少
なく低硬度であり、耐摩耗性に問題がある。また、Ｖ含
有量がＢ含有量をＸ％とした時の（９−Ｘ）＝６．５％
より少ない５％であり、斜方晶系のＭ3Ｂ2型複硼化物が
多量に形成されており、全硬質相中に占める正方晶系の
Ｍ3Ｂ2型複硼化物量が６０％より少なく、抗折力が低
い。比較例２は、Ｂ含有量が７．５％より多い７．８％
の場合であり、硬質相量が９５％を越え、硬度は高い。
しかしながらＮｉ基結合相が少ないことにくわえて、Ｃ
ｒ含有量がＢ含有量をＸ％とした時の（５５−５Ｘ）＝
１６％を越えて１７％であり、全硬質相中に占める正方
晶系Ｍ3Ｂ2型複硼化物量が６０％より少なく、抗折力が
低い。比較例３はＭｏ／Ｂ比が０．８より小さい０．６
であり、全硬質相中に占める正方晶系Ｍ3Ｂ2型複硼化物
量が６０％より少なく、抗折力が低い。比較例４はＢ含
有量をＸ％とした時、Ｍｏ／Ｂ比が（１．６−０．０５
Ｘ）＝１．３５を越えて１．３７であり、強度低下をも
たらすＭｏ−Ｎｉ系金属間化合物が第３相として形成さ
れるとともに、ＣｒおよびＶの合計含有量が、Ｂ含有量
をＸ％とした時の（５５−５Ｘ）＝３０％を越えて３２
％であり、全硬質相中に占める正方晶系Ｍ3Ｂ2型複硼化
物量が６０％より少なく、抗折力が低い。比較例５はＣ
ｒおよびＶのどちらか一方または両者の合計含有量が０
％であり、硬質相が全て斜方晶系Ｍ3Ｂ2型複硼化物より
なり、抗折力が低い。比較例６はＣｒおよびＶの合計含
有量が、Ｂ含有量をＸ％とした時の（５５−５Ｘ）＝３
６％を越えて４５％であり、全硬質相中に占める正方晶
系Ｍ3Ｂ2型複硼化物量が６０％より少なく、抗折力が低
い。比較例７はＷ含有量が３０％より多く、全硬質相中
に占める正方晶系Ｍ3Ｂ2型複硼化物量が６０％より少な
く、抗折力が低い。また、Ｗ含有量が多いために、Ｗを
含まない組成の合金と比較すると１ポイント比重が高
く、軽量化を求められる用途に不向きである。比較例８
はＦｅを１０％含有したものであり、強度は高いもの
の、１０％弗化水素酸水溶液中、４０℃、１０時間浸漬
後の腐食減量が多く、耐食性が劣る。また、耐酸化性に
も劣る。比較例９はＮｉを全く含まない組成の合金であ
り、正方晶系Ｍ3Ｂ2型複硼化物が認められず、抗折力が
低い。From Tables 7 and 8, Examples 1 to 11 have not only excellent transverse rupture strength, hardness and corrosion resistance, but also excellent transverse rupture strength even at high temperatures, as compared with Comparative Examples. I understand. Further, even when compared with the stainless steels shown in Comparative Examples 10 and 11, it is clear that not only they have equivalent excellent oxidation resistance, but also have corrosion resistance exceeding that of stainless steel. Example 1 is an alloy having a composition close to the lower limit of the B content in the claims, and the B content is 3.3.
%, The hard phase amount consisting of boride is 40%. Therefore, although the hardness is a little low, it has an advantage that it can be cut. Further, since it contains 60% or more of tetragonal M 3 B 2 type double boride, the transverse rupture strength is as high as 260 kg / mm 2 . In Examples 2 to 5, all hard phases are tetragonal M 3
It is an alloy having a composition composed of a B 2 -type double boride, and has high hardness and bending strength. In addition, Examples 4 and 5 are alloys containing W, and good sintered bodies without deformation were obtained. In Examples 6 and 7, the B contents were 6% and 7%, respectively, and the hardness was high. In particular, Example 7 is an alloy excellent in wear resistance. Further, although the amount of Ni-based binder phase was small, it contained 60% or more of tetragonal M 3 B 2 type double boride, and although the hardness was high, the bending strength was high. Example 8 is an alloy containing Cu, which has a small corrosion weight loss after immersion in a 10% hydrofluoric acid aqueous solution at 40 ° C. for 10 hours and is particularly excellent in corrosion resistance. Examples 9 to 11 contain the boride forming elements of Nb, Zr and Ti, and have high hardness and excellent wear resistance. In addition, the crystal grains are miniaturized, and the transverse rupture strength also shows a high value. Furthermore, Examples 9 and 11 contain Co and
Excellent in oxidation resistance, with little increase in oxidation after 1 hour in static air at ℃. On the other hand, in Comparative Example 1, the amount of B is 2.5%, which is lower than 3%, the amount of hard phase is less than 35% and the hardness is low, and there is a problem in wear resistance. Further, the V content is (9−X) = 6.5% when the B content is X%.
It is less than 5%, and a large amount of orthorhombic M 3 B 2 type complex boride is formed, and the amount of tetragonal M 3 B 2 type complex boride in the total hard phase is 60%. Less and less bending strength. In Comparative Example 2, the B content is 7.8%, which is more than 7.5%.
In this case, the hard phase content exceeds 95% and the hardness is high.
However, in addition to the small amount of Ni-based bonded phase, C
r content is (55-5X) when B content is X% =
It is more than 16% and 17%, the amount of tetragonal M 3 B 2 type complex boride in the total hard phase is less than 60%, and the transverse rupture strength is low. In Comparative Example 3, the Mo / B ratio is smaller than 0.8 and is 0.6.
The tetragonal M 3 B 2 type double boride content in the total hard phase is less than 60%, and the transverse rupture strength is low. In Comparative Example 4, when the B content was X%, the Mo / B ratio was (1.6-0.05).
X) = 1.35 to 1.37, a Mo—Ni-based intermetallic compound that causes strength reduction is formed as the third phase, and the total content of Cr and V is the B content of X. % When (55-5X) = 30% over 32
%, The tetragonal M 3 B 2 type double boride content in the total hard phase is less than 60%, and the transverse rupture strength is low. Comparative Example 5 is C
The total content of either or both of r and V is 0.
%, And the hard phase is composed entirely of orthorhombic M 3 B 2 type complex boride, and the transverse rupture strength is low. In Comparative Example 6, the total content of Cr and V is (55-5X) = 3 when the B content is X%.
It is more than 6% and 45%, the amount of tetragonal M 3 B 2 type complex boride in the total hard phase is less than 60%, and the transverse rupture strength is low. Comparative Example 7 has a W content of more than 30%, a tetragonal M 3 B 2 type compound boride content of less than 60% in the total hard phase, and a low transverse rupture strength. Further, since the W content is large, it has a high one-point specific gravity as compared with an alloy having a composition not containing W, and is not suitable for applications requiring weight reduction. Comparative Example 8
Contains 10% of Fe and has high strength, but has a large corrosion weight loss after immersion in a 10% hydrofluoric acid aqueous solution at 40 ° C. for 10 hours, resulting in poor corrosion resistance. Also, it is inferior in oxidation resistance. Comparative Example 9 is an alloy having a composition containing no Ni, a tetragonal M 3 B 2 type double boride is not recognized, and the transverse rupture strength is low.
【００３３】実施例に示す組成の、本高耐食性高強度硬
質焼結合金の主要硬質相である、正方晶系Ｍ3Ｂ2型複硼
化物相の、Ｃｕ−Ｋα線によるＸ線回折図形を図１に示
す。さらに同じＭ3Ｂ2型複硼化物でありながら、その量
が多くなると合金の強度を低下させる斜方晶系Ｍ3Ｂ2型
複硼化物相の、Ｃｕ−Ｋα線によるＸ線回折図形を図２
に示す。図１および２を比較すると、同じＭ3Ｂ2型複硼
化物であっても、全く結晶系が異なる異種複硼化物であ
ることが明らかである。したがって、表７および８よ
り、図１に示されるＸ線回折図形の正方晶系のＭ3Ｂ2型
複硼化物を全硬質相のうち６０％以上含むことが、本高
耐食性高強度硬質焼結合金には必要不可欠であることが
明らかである。An X-ray diffraction pattern by Cu-Kα ray of a tetragonal M 3 B 2 type complex boride phase, which is a main hard phase of the present high corrosion resistance and high strength hard sintered alloy having the composition shown in the example, is shown. As shown in FIG. Further, an X-ray diffraction pattern by Cu-Kα ray of an orthorhombic M 3 B 2 type double boride phase, which is the same M 3 B 2 type double boride and which decreases the strength of the alloy when the amount thereof increases, Figure 2
Shown in. Comparing FIGS. 1 and 2, it is clear that even the same M 3 B 2 type double boride is a different type double boride having a completely different crystal system. Therefore, from Tables 7 and 8, it is found that the content of the tetragonal M 3 B 2 type complex boride in the X-ray diffraction pattern shown in FIG. Clearly it is essential for bond money.
【００３４】[0034]
【発明の効果】以上説明したように、本発明の正方晶系
のＭ3Ｂ2型複硼化物とＮｉ基合金マトリックスよりなる
高耐食性高強度硬質焼結合金は、優れた耐食性および機
械的特性を兼ね備えており、射出成形機用部品、熱間伸
銅ダイス、軸受け、および化学工業等の高腐食環境下に
おいて使用可能な高強度耐摩耗材料として利用できる。As described above, the high corrosion resistance and high strength hard sintered alloy comprising the tetragonal M 3 B 2 type boride and the Ni-based alloy matrix of the present invention has excellent corrosion resistance and mechanical properties. Therefore, it can be used as a high-strength wear-resistant material that can be used in highly corrosive environments such as parts for injection molding machines, hot-rolled copper dies, bearings, and the chemical industry.
【図１】正方晶系Ｍ3Ｂ2型複硼化物相のＣｕ−Ｋα線に
よるＸ線回折図である。FIG. 1 is an X-ray diffraction diagram of a tetragonal M 3 B 2 type double boride phase by Cu—Kα ray.
【図２】斜方晶系Ｍ3Ｂ2型複硼化物相のＣｕ−Ｋα線に
よるＸ線回折図である。FIG. 2 is an X-ray diffraction diagram of an orthorhombic M 3 B 2 type double boride phase by Cu—Kα ray.
Claims (7)
（以下％は重量％を表す）と、該硬質相を結合するＮｉ
基の結合相からなる硬質焼結合金において、全硬質相量
のうち正方晶系のＭ3Ｂ2型（Ｍ：Ｍｏ、Ｎｉの他はＣｒ
および／またはＶ）複硼化物を６０％以上含み、残部が
斜方晶系のＭ3Ｂ2型複硼化物あるいは他の硼化物よりな
ることを特徴とする耐食性に優れた高強度硬質焼結合
金。1. Hard phase consisting of boride 35-95% by weight
(Hereinafter,% represents weight%) and Ni that binds the hard phase
In a hard sintered alloy composed of a base binder phase, tetragonal M 3 B 2 type (M: Mo, Ni other than Cr is included in the total hard phase amount).
And / or V) A high-strength hard-fired bond excellent in corrosion resistance, characterized by containing 60% or more of a compound boride and the balance being an orthorhombic M 3 B 2 type compound boride or another boride. Money.
含有量がＭｏ／Ｂ原子比で０．８〜（１．６−０．０５
Ｘ）（Ｘ：含有するＢの重量％）、ＣｒおよびＶ含有量
がいずれか一方または両者の合計で（９−Ｘ）〜（５５
−５Ｘ）％、残部が１０％以上のＮｉ、および不可避的
不純物よりなることを特徴とする請求項１の高耐食性高
強度硬質焼結合金。2. The B content in the alloy is 3 to 7.5%, Mo
The content is 0.8 to (1.6-0.05 in Mo / B atomic ratio.
X) (X: wt% of B contained), Cr and / or V content is either (9-X) to (55) in total.
-5X)%, the balance 10% or more of Ni, and unavoidable impurities, The high corrosion-resistant high-strength hard sintered alloy according to claim 1.
含有量がＭｏ／Ｂ原子比で０．８〜（１．６−０．０５
Ｘ）、ＣｒおよびＶ含有量がいずれか一方または両者の
合計で（９−Ｘ）〜（５５−５Ｘ）％、残部が１０％以
上のＮｉ、および不可避的不純物よりなる硬質焼結合金
において、Ｃｕ含有量が０．１〜５％、Ｃｏ含有量が
０．２〜５％およびＮｂ含有量が０．２〜１０％のいず
れか一種または二種以上を含むことを特徴とする請求項
１の高耐食性高強度硬質焼結合金。3. The B content in the alloy is 3 to 7.5%, Mo
The content is 0.8 to (1.6-0.05 in Mo / B atomic ratio.
X), Cr, and V contents are either one or both in total (9-X) to (55-5X)%, the balance is 10% or more of Ni, and a hard sintered alloy consisting of inevitable impurities, The Cu content is 0.1 to 5%, the Co content is 0.2 to 5%, and the Nb content is 0.2 to 10% and any one kind or two or more kinds is contained. High corrosion resistance and high strength hard sintered alloy of.
該硬質相を結合するＮｉ基の結合相からなり、かつ全硬
質相量のうち正方晶系のＭ3Ｂ2型（Ｍ：Ｍｏ、Ｗ、Ｎｉ
の他はＣｒおよび／またはＶ）複硼化物を６０％以上含
み、残部が斜方晶系のＭ3Ｂ2型複硼化物あるいは他の硼
化物よりなることを特徴とする耐食性に優れた高強度硬
質焼結合金。4. A hard phase composed of boride, 35 to 95%,
A tetragonal M 3 B 2 type (M: Mo, W, Ni consisting of a Ni-based binder phase that bonds the hard phase, and of the total hard phase content.
Other than Cr and / or V) compound boride in an amount of 60% or more, and the balance being orthorhombic M 3 B 2 type compound boride or other boride. Strong hard sintered alloy.
有量が０．１〜３０％、Ｍｏ含有量がＭｏおよびＷ含有
量の合計で、（Ｍｏ＋Ｗ）／Ｂ原子比で０．８〜（１．
６−０．０５Ｘ）、ＣｒおよびＶ含有量がいずれか一方
または両者の合計で（９−Ｘ）〜（５５−５Ｘ）％、残
部が１０％以上のＮｉ、および不可避的不純物よりなる
ことを特徴とする請求項４の高耐食性高強度硬質焼結合
金。5. The B content in the alloy is 3 to 7.5%, the W content is 0.1 to 30%, the Mo content is the sum of Mo and W contents, and the (Mo + W) / B atomic ratio is obtained. 0.8- (1.
6-0.05X), one or both of Cr and V contents is (9-X) to (55-5X)%, the balance is 10% or more of Ni, and inevitable impurities. The high-corrosion-resistant high-strength hard sintered alloy according to claim 4.
有量が０．１〜３０％、Ｍｏ含有量がＭｏおよびＷ含有
量の合計で、（Ｍｏ＋Ｗ）／Ｂ原子比で０．８〜（１．
６−０．０５Ｘ）、ＣｒおよびＶ含有量がいずれか一方
または両者の合計で（９−Ｘ）〜（５５−５Ｘ）％、残
部が１０％以上のＮｉ、および不可避的不純物よりなる
硬質焼結合金において、Ｃｕ含有量が０．１〜５％、Ｃ
ｏ含有量が０．２〜５％およびＮｂ含有量が０．２〜１
０％のいずれか一種または２種以上を含むことを特徴と
する請求項４の高耐食性高強度硬質焼結合金。6. The alloy has a B content of 3 to 7.5%, a W content of 0.1 to 30%, a Mo content of Mo and a total of W contents of (Mo + W) / B atomic ratio. 0.8- (1.
6-0.05X), the content of Cr and / or V is (9-X) to (55-5X)% in total or both, and the balance is 10% or more of Ni, and hard baking consisting of unavoidable impurities. In the bond gold, Cu content is 0.1-5%, C
o content 0.2-5% and Nb content 0.2-1
The high-corrosion-resistant high-strength hard sintered alloy according to claim 4, which contains 0% of any one kind or two or more kinds.
Ｔａの中から選ばれた一種または二種以上で置換するこ
とを特徴とする請求項３または６の高耐食性高強度硬質
焼結合金。7. Part or all of Nb is Zr, Ti,
The high-corrosion-resistant high-strength hard sintered alloy according to claim 3 or 6, which is substituted by one or more selected from Ta.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3834592A JP2631791B2 (en) | 1992-01-30 | 1992-01-30 | High corrosion resistance, high strength hard sintered alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3834592A JP2631791B2 (en) | 1992-01-30 | 1992-01-30 | High corrosion resistance, high strength hard sintered alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05214479A true JPH05214479A (en) | 1993-08-24 |
| JP2631791B2 JP2631791B2 (en) | 1997-07-16 |
Family
ID=12522700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3834592A Expired - Lifetime JP2631791B2 (en) | 1992-01-30 | 1992-01-30 | High corrosion resistance, high strength hard sintered alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2631791B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998005802A1 (en) * | 1996-08-06 | 1998-02-12 | Toyo Kohan Co., Ltd. | Hard sintered alloy |
| WO2012133328A1 (en) * | 2011-03-30 | 2012-10-04 | 東洋鋼鈑株式会社 | Hard sintered alloy |
| CN113005319A (en) * | 2021-02-22 | 2021-06-22 | 林玉婷 | Metal ceramic wear-resistant material and preparation method thereof |
-
1992
- 1992-01-30 JP JP3834592A patent/JP2631791B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998005802A1 (en) * | 1996-08-06 | 1998-02-12 | Toyo Kohan Co., Ltd. | Hard sintered alloy |
| US6030429A (en) * | 1996-08-06 | 2000-02-29 | Toyo Kohan Co., Ltd. | Hard sintered alloy |
| CN1076053C (en) * | 1996-08-06 | 2001-12-12 | 东洋钢钣株式会社 | Hard sintered alloy |
| WO2012133328A1 (en) * | 2011-03-30 | 2012-10-04 | 東洋鋼鈑株式会社 | Hard sintered alloy |
| CN113005319A (en) * | 2021-02-22 | 2021-06-22 | 林玉婷 | Metal ceramic wear-resistant material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2631791B2 (en) | 1997-07-16 |
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