JP3092887B2 - Surface-finished sintered alloy and method for producing the same - Google Patents
Surface-finished sintered alloy and method for producing the sameInfo
- Publication number
- JP3092887B2 JP3092887B2 JP04337974A JP33797492A JP3092887B2 JP 3092887 B2 JP3092887 B2 JP 3092887B2 JP 04337974 A JP04337974 A JP 04337974A JP 33797492 A JP33797492 A JP 33797492A JP 3092887 B2 JP3092887 B2 JP 3092887B2
- Authority
- JP
- Japan
- Prior art keywords
- sintered alloy
- oxide
- surface layer
- silicon
- powder
- 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.)
- Expired - Fee Related
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Description
【０００１】[0001]
【産業上の利用分野】本発明は酸化アルミニウムを主成
分とする硬質相と高融点金属を含む結合相とからなる焼
結合金の表面部における組成成分を改質してなる表面調
質焼結合金及びその製造方法に関し、具体的には、例え
ば旋削工具，フライス工具，ドリル，エンドミル等の切
削工具、ダイス，パンチ，スリッター等の耐摩耗工具、
高温炉治具，パイプ，ノズル，ボルト等の高温装置用部
品等の耐熱耐酸化性部品に代表される工具や部品として
最適な表面調質焼結合金及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-hardened joint obtained by modifying the composition of the surface of a sintered alloy comprising a hard phase mainly composed of aluminum oxide and a binder phase containing a high melting point metal. Regarding gold and its manufacturing method, specifically, for example, cutting tools such as turning tools, milling tools, drills, end mills, wear-resistant tools such as dies, punches, and slitters;
The present invention relates to a surface-finished sintered alloy which is most suitable as a tool or a component typified by a heat-resistant and oxidation-resistant component such as a component for a high-temperature device such as a high-temperature furnace jig, a pipe, a nozzle, and a bolt, and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化アルミニウムを主成分とする硬質相
と高融点金属を含む結合相とからなる焼結合金として
は、Ａｌ2Ｏ3−Ｃｒ焼結合金，Ａｌ2Ｏ3−Ｍｏ−Ｃｒ焼
結合金，又はＡｌ2Ｏ3−Ｗ−Ｃｒ焼結合金が高温部品と
して一部実用されている。 2. Description of the Related Art Sintered alloys composed of a hard phase containing aluminum oxide as a main component and a binder phase containing a high melting point metal include Al 2 O 3 —Cr sintered alloy and Al 2 O 3 —Mo—Cr sintered alloy. binding alloy, or Al 2 O 3 -W-Cr sintered alloy is partially practically as a high-temperature parts.
【０００３】しかしながら、これらの高温部品は、強度
及び靭性が低く、用途が非常に制限されるという問題が
ある。[0003] However, these high-temperature components have a problem that their strength and toughness are low, and their use is very limited.
【０００４】この問題を解決しようとして提案されてい
る代表的なものに、特開昭５４−４９１５号公報及び特
開昭５５−８５６５３号公報がある。[0004] Representative examples proposed to solve this problem include JP-A-54-4915 and JP-A-55-85653.
【０００５】[0005]
【発明が解決しようとする課題】酸化アルミニウムと高
融点金属とを含む焼結合金の先行技術としての特開昭５
４−４９１５号公報には、酸化アルミニウム，酸化ジル
コニウム又はこれらの混合物からなる酸化物相１０〜９
５重量％、及び３０重量％ジルコニウム含有ニッケル合
金からなる金属相５〜９０重量％とでなる工具用酸化ア
ルミニウム含有金属組成物について記載されている。A sintered alloy containing aluminum oxide and a high melting point metal is disclosed in Japanese Patent Application Laid-Open
JP-A-4-4915 discloses oxide phases 10 to 9 comprising aluminum oxide, zirconium oxide or a mixture thereof.
An aluminum oxide-containing metal composition for tools comprising 5% by weight and 5% to 90% by weight of a metal phase comprising a 30% by weight zirconium-containing nickel alloy is described.
【０００６】また、特開昭５５−８５６５３号公報に
は、Ａｌ2Ｏ3とＴｉＮとを主成分としてなるマトリック
スを金属Ｔｉで分散強化した切削工具用セラミックス焼
結体について記載されている。Japanese Patent Application Laid-Open No. 55-85653 describes a ceramic sintered body for a cutting tool in which a matrix mainly composed of Al 2 O 3 and TiN is dispersed and strengthened with metallic Ti.
【０００７】これら両公報に記載されている酸化アルミ
ニウムと高融点金属とを含む焼結合金は、強度及び靭性
の向上を目的とし、切削時における耐欠損性が向上して
いるが、まだ満足できるものでなく、満足できるに至る
ような耐欠損性にすると、逆に耐摩耗性の低下が顕著に
なるという問題がある。The sintered alloys described in these publications containing aluminum oxide and a high melting point metal have improved fracture resistance during cutting for the purpose of improving strength and toughness, but are still satisfactory. However, if the chipping resistance is not satisfactory and the chipping resistance is satisfactory, there is a problem that the wear resistance is significantly reduced.
【０００８】本発明は、上述のような問題点を解決した
もので、具体的には、焼結合金の内部の強度及び靭性を
高め、被加工物と直接接触する焼結合金の表面部の組成
成分を漸次最適に改質させて、耐摩耗性，強度及び靭性
をバランスよく保持させた表面調質焼結合金及びその製
造方法の提供を目的とする。The present invention has solved the above-mentioned problems. Specifically, the present invention has improved the internal strength and toughness of the sintered alloy, and has improved the surface of the sintered alloy in direct contact with the workpiece. It is an object of the present invention to provide a surface-finished sintered alloy in which the composition components are gradually and optimally modified to maintain a good balance between wear resistance, strength and toughness, and a method for producing the same.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、従来の酸
化アルミニウムを主成分として含む焼結合金のように金
属の結合相成分の調整でもって、強度及び靭性を向上さ
せても、逆に耐摩耗性，耐熱性，耐酸化性，耐腐食性が
低下することから、その検討を行っていた所、焼結合金
の内部においては強度及び靭性に寄与する結合相とし、
焼結合金の表面部においては、焼結合金の内部の結合相
とは異なった改質された結合相とし、かつ表面部の結合
相を構成する元素の濃度を変化させることにより、焼結
合金の特性がバランスよく向上するという知見を得て、
本発明を完成するに至ったものである。Means for Solving the Problems The inventors of the present invention can improve the strength and toughness by adjusting the binder phase component of a metal as in a conventional sintered alloy containing aluminum oxide as a main component, and can improve the strength. In addition, the wear resistance, heat resistance, oxidation resistance, and corrosion resistance deteriorated.
At the surface of the sintered alloy, a modified binder phase different from the internal binder phase of the sintered alloy is used, and by changing the concentration of the elements constituting the surface phase, the sintered alloy is Gained the knowledge that the characteristics of
The present invention has been completed.
【００１０】すなわち、本発明の焼結合金は、周期律表
の４ａ，５ａ，６ａ族の金属、Ｎｉ，Ｃｏ，Ｆｅ，Ａｌ
及びこれらの相互合金の中の少なくとも１種の結合相２
〜５０体積％と、残部が酸化アルミニウムの硬質相、又
は酸化アルミニウム５０体積％以上と残り酸化ジルコニ
ウム，部分安定化酸化ジルコニウム，酸化ハフニウム，
酸化クロム，酸化ケイ素，炭化ケイ素，窒化ケイ素，周
期律表の４ａ，５ａ，６ａ族の金属の炭化物，窒化物及
びこれらの相互固溶体の中の少なくとも１種とでなる硬
質相と不可避不純物とからなる焼結合金の１部の面もし
くは全面に表面から少なくとも０．０１ｍｍ内部までの
厚さでなる表面層が形成されており、該表面層が酸化ア
ルミニウムと周期律表の４ａ，５ａ，６ａ族の金属の炭
化物，窒化物，酸化物，ホウ化物，ケイ化物及びこれら
の相互固溶体の中の少なくとも１種の高融点金属化合物
とでなり、あるいは、酸化アルミニウムと該高融点金属
化合物と該結合相とでなる表面層を有する焼結合金であ
って、該表面層中の該結合相の平均量が該焼結合金の内
部の該結合相の平均量よりも少なく、かつ該表面層中に
存在している炭素，窒素，酸素，ホウ素，ケイ素の中の
少なくとも１種の拡散元素が該表面層の表面から該焼結
合金の内部に向って漸減していることを特徴とする。[0010] That is, the sintered alloy of the present invention is composed of metals belonging to groups 4a, 5a and 6a of the periodic table, Ni, Co, Fe and Al.
And at least one binder phase 2 in these mutual alloys
To 50% by volume, the balance being a hard phase of aluminum oxide, or 50% by volume or more of aluminum oxide and remaining zirconium oxide, partially stabilized zirconium oxide, hafnium oxide,
A hard phase composed of chromium oxide, silicon oxide, silicon carbide, silicon nitride, carbides and nitrides of metals belonging to groups 4a, 5a and 6a of the periodic table, and their mutual solid solutions, and unavoidable impurities A surface layer having a thickness of at least 0.01 mm from the surface is formed on a part or the whole surface of the sintered alloy, and the surface layer is made of aluminum oxide and 4a, 5a, 6a group of the periodic table. At least one refractory metal compound among the carbides, nitrides, oxides, borides, silicides and mutual solid solutions thereof, or aluminum oxide, the refractory metal compound and the binder phase A sintered alloy having a surface layer consisting of the following: wherein the average amount of the binder phase in the surface layer is smaller than the average amount of the binder phase inside the sintered alloy, and is present in the surface layer. Carbon Nitrogen, oxygen, boron, and wherein at least one diffusing element in the silicon is gradually decreased toward the surface of the surface layer to the interior of said sintered alloy.
【００１１】本発明の焼結合金における結合相は、具体
的には、例えばＴｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，Ｃ
ｒ，Ｍｏ，Ｗ，Ｎｉ，Ｃｏ，Ｆｅ，Ａｌ，ＺｒＭｏ2，
ＴａＣｒ2，ＺｒＷ2，ＴｉＡｌ，ＴｉＡｌ3，Ｎｂ3Ａ
ｌ，Ｎｉ3Ａｌ，Ｖ3Ａｌ，Ｍｏ3Ａｌ，Ｗ3Ａｌ，ＮｉＡ
ｌ，Ｆｅ3Ａｌ，Ｃｏ2Ａｌ9，Ｚｒ3Ａｌ，Ｃｏ3Ａｌ，
Ｎｉ3（Ａｌ，Ｔｉ）又はこれらに固溶限度内の炭素，
窒素及び／又は酸素（例えば０．０１原子％以下）の含
有した場合を挙げることができる。これらの結合相の
内、特に、周期律表の４ａ，５ａ，６ａ族の金属の中の
１種以上を含んだ高融点金属の結合相であると表面層の
形成の容易性及び耐熱性，耐酸化性，耐腐食性等の合金
特性上からも好ましい。この結合相の量が焼結合金全体
に対して２体積％未満になると、強度及び靭性の低下が
著しく、逆に５０体積％を超えて多くなると、耐熱性，
耐酸化性，耐摩耗性の低下が著しくなるために、２〜５
０体積％と定めたものである。The binder phase in the sintered alloy of the present invention is, for example, Ti, Zr, Hf, V, Nb, Ta, C
r, Mo, W, Ni, Co, Fe, Al, ZrMo 2 ,
TaCr 2 , ZrW 2 , TiAl, TiAl 3 , Nb 3 A
1, Ni 3 Al, V 3 Al, Mo 3 Al, W 3 Al, NiA
1, Fe 3 Al, Co 2 Al 9 , Zr 3 Al, Co 3 Al,
Ni 3 (Al, Ti) or carbon within the solid solution limit thereof,
Examples include the case where nitrogen and / or oxygen (for example, 0.01 atomic% or less) is contained. Among these binder phases, in particular, a binder phase of a high melting point metal containing at least one of metals belonging to groups 4a, 5a and 6a of the periodic table makes it easy to form a surface layer and has high heat resistance. It is preferable from the viewpoint of alloy characteristics such as oxidation resistance and corrosion resistance. When the amount of the binder phase is less than 2% by volume with respect to the entire sintered alloy, the strength and toughness are significantly reduced, and when the amount exceeds 50% by volume, heat resistance and
Oxidation resistance and abrasion resistance are significantly reduced.
It is determined to be 0% by volume.
【００１２】本発明の焼結合金における結合相は、酸化
アルミニウムのみからなる場合、又は５０体積％以上の
酸化アルミニウム（硬質相に対し）と残り、例えば酸化
ジルコニウム，ＭｇＯ，ＣａＯ，もしくはＹ2Ｏ3を含め
た希土類元素の酸化物を安定化剤として含有する部分安
定化酸化ジルコニウム，酸化ハフニウム，酸化クロム，
酸化ケイ素，炭化ケイ素，窒化ケイ素，周期律表の４
ａ，５ａ，６ａ族の金属の炭化物，窒化物，炭窒化チタ
ン，炭窒化チタン・モリブデン，炭化ジルコニウム・タ
ングステン，サイアロン，酸化ジルコニウム・ハフニウ
ムの中の１種からなる場合である。The binder phase in the sintered alloy of the present invention consists of aluminum oxide alone or aluminum oxide (relative to the hard phase) of 50% by volume or more, for example, zirconium oxide, MgO, CaO, or Y 2 O. Partially stabilized zirconium oxide, hafnium oxide, chromium oxide, containing oxides of rare earth elements including 3 as stabilizers
Silicon oxide, silicon carbide, silicon nitride, Periodic Table 4
This is a case of one of the carbides, nitrides, titanium carbonitrides, titanium carbonitride / molybdenum, zirconium / tungsten carbide, sialon, zirconium oxide / hafnium of metals belonging to the groups a, 5a and 6a.
【００１３】表面層を除いた焼結合金、いわゆる焼結合
金の内部には、上述の結合相と硬質相が緻密に混在して
いるが、出発原料に微量に含まれている不可避不純物及
び製造工程、特に出発原料の混合粉砕時に混入する微量
の不可避不純物が合金の特性を顕著に低下させない程度
に含まれてもよい。[0013] The above-mentioned binder phase and hard phase are densely mixed in the sintered alloy except the surface layer, that is, the so-called sintered alloy. A small amount of unavoidable impurities that are mixed in the process, particularly when the starting materials are mixed and pulverized, may be contained to such an extent that the properties of the alloy are not significantly reduced.
【００１４】本発明の焼結合金における表面層は、酸化
アルミニウムと周期律表４ａ，５ａ，６ａ族金属の炭化
物，窒化物，酸化物，ホウ化物，ケイ化物及びこれらの
相互固溶体の中の少なくとも１種の高融点金属化合物の
含まれている場合、又は酸化アルミニウムと高融点金属
化合物の他に、焼結合金の内部に含有している結合相の
含まれている場合がある。この表面層を構成している高
融点金属化合物としては、具体的には、例えばＴｉＣ，
ＷＣ，Ｔｉ（Ｃ，Ｎ），（Ｔｉ，Ｗ），（Ｔｉ，Ｍｏ）
Ｃ，ＺｒＮ，ＴｉＮ，（Ｔｉ，Ｎｂ）Ｎ，（Ｃｒ，Ａ
ｌ）2Ｏ3，Ａｌ2ＴｉＯ5，ＴｉＢ2，ＷＢ，ＭｏＳｉ2を
挙げることができる。表面層中に結合相を存在させる場
合は、表面層中の結合相の平均量が焼結合金の内部に存
在する結合相の平均量よりも少なくすることが焼結合金
の諸特性の向上に重要な役割をしているものである。表
面層中の結合相の平均量は、用途や形状により異なる
が、焼結合金の内部に存在する結合相の平均量の５０％
以下が好ましく、特に耐摩耗性を重視する場合には、表
面層中の結合相の平均量を１体積％以下又は零にするこ
とが好ましい。The surface layer of the sintered alloy according to the present invention comprises at least one of aluminum oxide and carbides, nitrides, oxides, borides, silicides of the metals of Groups 4a, 5a and 6a of the periodic table and their mutual solid solutions. In some cases, one kind of refractory metal compound is contained, or in addition to aluminum oxide and the refractory metal compound, a binder phase contained in the sintered alloy is contained. Specific examples of the high melting point metal compound constituting the surface layer include TiC,
WC, Ti (C, N), (Ti, W), (Ti, Mo)
C, ZrN, TiN, (Ti, Nb) N, (Cr, A
l) 2 O 3 , Al 2 TiO 5 , TiB 2 , WB, MoSi 2 . When a binder phase is present in the surface layer, it is necessary to make the average amount of the binder phase in the surface layer smaller than the average amount of the binder phase present inside the sintered alloy in order to improve various properties of the sintered alloy. It plays an important role. The average amount of the binder phase in the surface layer varies depending on the application and shape, but is 50% of the average amount of the binder phase present inside the sintered alloy.
The following is preferred. Particularly, when importance is attached to the wear resistance, the average amount of the binder phase in the surface layer is preferably 1% by volume or less or zero.
【００１５】以上のような表面層の組成と共に、表面層
の構成でもう１つ重要な特徴は、表面層を形成している
必須成分として高融点金属化合物の濃度分布が異なって
いることである。具体的には、例えば表面層中に存在す
る高融点金属化合物の含有量が表面層の表面で多く、焼
結合金の内部へ向って漸減している場合、又は高融点金
属化合物である炭化物，窒化物，酸化物，ホウ化物，ケ
イ化物及びこれらの相互固溶体を構成している炭素，窒
素，酸素，ホウ素，ケイ素の中の少なくとも１種の拡散
元素の濃度が表面層の表面で高く、焼結合金の内部へ向
って漸減している場合がある。この内、後者の場合で、
１種の拡散元素の濃度が表面層の表面で高く、焼結合金
の内部へ向って漸減しているのに対し、逆に他の拡散元
素の濃度が相対的に焼結合金の内部との境界面で高く、
表面層の表面へ向って漸減した組合せでなる場合もあ
る。この表面層の厚さが０．０１ｍｍ未満になると、耐
摩耗性，耐熱性，耐酸化性，耐腐食性を向上させる効果
が弱く、上述した表面層の構成及び組成成分により異な
るが、安定に長寿命化するためには、表面層の厚さを
０．０５〜１ｍｍにすることが、特に好ましい。Another important feature in the composition of the surface layer together with the composition of the surface layer as described above is that the concentration distribution of the refractory metal compound as an essential component forming the surface layer is different. . Specifically, for example, when the content of the refractory metal compound present in the surface layer is large on the surface of the surface layer and gradually decreases toward the inside of the sintered alloy, or when the content of the refractory metal compound is carbide, The concentration of at least one diffusing element among carbon, nitrogen, oxygen, boron and silicon constituting nitride, oxide, boride, silicide and their mutual solid solution is high on the surface of the surface layer, and the It may decrease gradually toward the inside of the bond. In the latter case,
While the concentration of one diffusion element is high at the surface of the surface layer and gradually decreases toward the inside of the sintered alloy, the concentration of the other diffusion element is relatively lower than that of the inside of the sintered alloy. High at the boundary,
In some cases, the combination gradually decreases toward the surface of the surface layer. When the thickness of the surface layer is less than 0.01 mm, the effect of improving the wear resistance, heat resistance, oxidation resistance, and corrosion resistance is weak, and depends on the composition and composition of the above-mentioned surface layer. In order to extend the life, it is particularly preferable that the thickness of the surface layer be 0.05 to 1 mm.
【００１６】この表面層は、焼結合金の１部の面に形成
する場合、又は全面に形成する場合、もしくは２面以上
に形成し、１つの面と他の面とが異なった表面層の構
成、具体的には、表面層の厚さが異なる場合、表面層の
組成成分が異なる場合があり、特に、用途や形状に合わ
せて、異なった高融点金属化合物を存在させることは、
特に好ましいことである。具体的な用途例としては、切
削工具、特にスローアウェイチプとして用いる場合、掬
い面と逃げ面にそれぞれ異なった表面層を形成すること
が好ましく、さらに詳述すると、掬い面には、耐溶着
性，耐熱性，耐酸化性を高めるような窒化物，酸化物，
ホウ化物でなる高融点金属化合物の含有した表面層と
し、一方逃げ面には、耐すきとり摩耗性を高める炭化物
でなる高融点金属化合物の含有した表面層とすることが
好ましい。This surface layer may be formed on a part of the surface of the sintered alloy, or may be formed on the entire surface, or may be formed on two or more surfaces, with one surface being different from the other surface. Configuration, specifically, when the thickness of the surface layer is different, the composition component of the surface layer may be different, especially, depending on the application and shape, the presence of different refractory metal compounds,
This is particularly preferred. As a specific application example, when used as a cutting tool, particularly a throwaway chip, it is preferable to form different surface layers on the scooping surface and the flank, respectively.More specifically, the scooping surface has welding resistance. Nitrides, oxides that increase heat resistance and oxidation resistance,
It is preferable to use a surface layer containing a high-melting-point metal compound made of boride, and to provide a surface layer containing a high-melting-point metal compound made of carbide that enhances abrasion resistance on the flank.
【００１７】上述した表面層を有する焼結合金の１部の
面又は全面に、さらに金属，合金，無機化合物の被膜を
被覆させることも好ましく、被膜としては、具体的に
は、例えば周期律表の４ａ，５ａ，６ａ族の金属の炭化
物，窒化物，炭酸化物，窒酸化物、Ａｌの酸化物，窒化
物、Ｓｉの炭化物，窒化物及びこれらの相互固溶体、ダ
イヤモンド、ダイヤモンド状カーボン、立方晶窒化ホウ
素の中の少なくとも１種の単層又は多層でなることが好
ましい。It is preferable that a part or the whole surface of the sintered alloy having the above-mentioned surface layer is further coated with a coating of a metal, an alloy or an inorganic compound. Carbides, nitrides, carbonates, nitrides, oxides and nitrides of Al, carbides and nitrides of Si and their mutual solid solutions, diamond, diamond-like carbon, cubic Preferably, it is formed of at least one kind of a single layer or a multilayer of boron nitride.
【００１８】本発明の焼結合金を作製するには、従来の
粉末冶金法に浸漬法，拡散法，鋳込成形法，遠心成形法
を付加応用して作製することもできるが、次の方法で行
うと表面層の制御が容易で、簡易な製造方法であるこ
と、及び品質管理上からも好ましい方法である。In order to produce the sintered alloy of the present invention, a conventional powder metallurgy method can be applied by additionally applying a dipping method, a diffusion method, a casting method, or a centrifugal molding method. This is a preferable method in that the control of the surface layer is easy and the production method is simple, and also from the viewpoint of quality control.
【００１９】本発明の焼結合金の製造方法は、周期律表
の４ａ，５ａ，６ａ族の金属、Ｎｉ，Ｃｏ，Ｆｅ，Ａｌ
及びこれらの相互合金又はこれらの前駆体の中の少なく
とも１種の結合相形成粉末に酸化アルミニウム又は酸化
アルミニウム５０体積％以上と残り酸化ジルコニウム，
部分安定化酸化ジルコニウム，酸化ハフニウム，酸化ク
ロム，酸化ケイ素，炭化ケイ素，窒化ケイ素，周期律表
の４ａ，５ａ，６ａ族の金属の炭化物，窒化物及びこれ
らの相互固溶体の中の少なくとも１種とでなる硬質相形
成粉末を加えて混合粉砕し、混合粉末とする第１工程、
該混合粉末を所定の形状に成形して粉末圧粉体とする第
２工程、該粉末圧粉体を炭素，窒素，酸素，ホウ素，ケ
イ素の中の少なくとも１種の拡散元素を含む化合物に接
触もしくは付着、あるいは該拡散元素を含むガス雰囲気
中に設置して１４００〜１９００℃に加熱する第３工程
からなる方法である。The method for producing a sintered alloy according to the present invention comprises the steps of forming a group 4a, 5a or 6a metal of the periodic table, Ni, Co, Fe or Al.
And at least one binder phase forming powder in these mutual alloys or precursors thereof contains at least 50% by volume of aluminum oxide or aluminum oxide and the remaining zirconium oxide;
Partially stabilized zirconium oxide, hafnium oxide, chromium oxide, silicon oxide, silicon carbide, silicon nitride, at least one of carbides, nitrides, and mutual solid solutions of metals of groups 4a, 5a, and 6a of the periodic table A first step of adding a hard phase forming powder consisting of
A second step of forming the mixed powder into a predetermined shape to form a powder compact, contacting the powder compact with a compound containing at least one diffusion element among carbon, nitrogen, oxygen, boron and silicon Alternatively, it is a method comprising a third step of heating in a gas atmosphere containing the diffusion element or in a gas atmosphere containing the diffusion element and heating to 1400 to 1900 ° C.
【００２０】本発明の製造方法における結合相形成粉末
は、例えば２μｍ以下の微細な金属又は合金粉末を用い
ることもできるが、第３工程の加熱時に熱分解して金属
もしくは合金を生成する前駆体、具体的には、例えばＴ
ｉＨ2，ＺｒＨ2，ＴａＨ2，ＮｂＨ2，の水素化物、Ｃｒ
Ｎ，Ｍｏ2Ｎ，ＴｉＮ，の窒化物を用いると、第１工程
の混合粉砕時に微細になりやすく、かつ付着及び吸着酸
素の影響が少なく緻密で高強度な焼結合金を得ることが
できるので好ましい。結合相形成粉末に、出発原料とし
て用いる硬質相形成粉末は、従来から粉末冶金法で用い
られている粉末、例えば粒径１０μｍ以下の粉末、好ま
しくは粒径３μｍ以下の粉末を用いればよく、特に酸化
物粉末の場合には、サブミクロンの粒径粉末を用いる
と、緻密で高強度な焼結合金を得ることができるので好
ましい。As the binder phase forming powder in the production method of the present invention, for example, a fine metal or alloy powder having a size of 2 μm or less can be used. Specifically, for example, T
hydride of iH 2 , ZrH 2 , TaH 2 , NbH 2 , Cr
When a nitride of N, Mo 2 N, TiN, is used, a dense and high-strength sintered alloy can be obtained, which tends to be fine during mixing and pulverization in the first step, and is less affected by adhesion and adsorbed oxygen. preferable. For the binder phase forming powder, the hard phase forming powder used as a starting material may be a powder conventionally used in powder metallurgy, for example, a powder having a particle size of 10 μm or less, preferably a powder having a particle size of 3 μm or less. In the case of oxide powder, it is preferable to use a submicron particle size powder because a dense and high-strength sintered alloy can be obtained.
【００２１】結合相形成粉末と硬質相形成粉末とを混合
粉砕して混合粉末とする第１工程は、従来の粉末冶金法
で行われている混合方法で行い、次の粉末圧粉体とする
第２工程も従来の粉末冶金法で行われている方法、例え
ば金型成形，押出し成形，射出成形，鋳込成形，遠心成
形による方法を適時行えばよい。The first step of mixing and pulverizing the binder phase forming powder and the hard phase forming powder to form a mixed powder is performed by the mixing method used in the conventional powder metallurgy method to obtain the next powder compact. In the second step, a method performed by a conventional powder metallurgy method, for example, a method by die molding, extrusion molding, injection molding, cast molding, or centrifugal molding may be appropriately performed.
【００２２】本発明の製造方法における第３工程は、例
えばカーボン，グラファイト，金属ホウ素，ケイ素，炭
化ホウ素，炭化ケイ素，酸化ホウ素，窒化ケイ素等の粉
末からなる拡散元素を含む化合物を有機溶媒に分散させ
てスラリー状物質とし、上述の粉末圧粉体の必要な表面
にスラリー状物質を吹付け又は塗付して付着する方法、
またグラファイト板等に上述のスラリー状物質を塗付
し、その上に粉末圧粉体を接触させる方法、さらに粉末
圧粉体の成形時に、その表面部を拡散元素を含む化合物
の層で一体成形する方法、粉末圧粉体を拡散元素を含む
化合物の粉末中に埋設する方法等でもって行った後、加
熱すればよい。また、第３工程の別の方法としては、例
えばＣＨ4，Ｎ2，Ｏ2，ＣＯ，ＣＯ2，ＢＣｌ4，ＳｉＨ4
の拡散元素を含むガス雰囲気中で粉末圧粉体を設置して
加熱することもできる。この場合、粉末圧粉体が焼結さ
れて緻密になる温度までは真空又は不活性ガス中で加熱
した後、拡散元素を含むガス雰囲気に切換えて焼結する
ことが好ましい。The third step in the production method of the present invention is to disperse a compound containing a diffusing element such as carbon, graphite, metallic boron, silicon, boron carbide, silicon carbide, boron oxide, silicon nitride or the like in an organic solvent. A method of applying a slurry material to the necessary surface of the powder compact by spraying or applying the slurry material to the slurry material,
A method in which the above-mentioned slurry-like substance is applied to a graphite plate or the like, and a powder compact is brought into contact therewith. Further, when the powder compact is formed, its surface is integrally formed with a layer of a compound containing a diffusion element. After that, the method may be performed by embedding the powder compact in the powder of the compound containing the diffusing element, and then heating. As another method in the third step, for example, CH 4 , N 2 , O 2 , CO, CO 2 , BCl 4 , SiH 4
Alternatively, the powder compact may be placed and heated in a gas atmosphere containing the above diffusion element. In this case, it is preferable that the powder compact is heated in a vacuum or an inert gas to a temperature at which the powder compact is sintered and densified, and then switched to a gas atmosphere containing a diffusion element for sintering.
【００２３】本発明の焼結合金の表面層の制御、特に表
面層の組成，厚み及び拡散元素の濃度勾配の制御は、上
述の製造方法の中でも拡散元素を含む化合物の量、ガス
雰囲気中の拡散元素ガス分圧、焼結温度及び時間によっ
て行うことができる。The control of the surface layer of the sintered alloy of the present invention, in particular, the control of the composition and thickness of the surface layer and the concentration gradient of the diffusion element include the amount of the compound containing the diffusion element and the concentration of the diffusion element in the gas atmosphere. It can be performed by the partial pressure of the diffusion element gas, the sintering temperature and the time.
【００２４】以上の製造方法で得た焼結合金をさらに熱
間静水圧処理（ＨＩＰ処理）を行うことは、緻密で高強
度な焼結合金を得るために好ましいことである。また、
本発明の焼結合金の表面に、さらに被膜を被覆させる場
合には、従来から行われている化学蒸着法又は物理蒸着
法でもって行うことができる。It is preferable to further subject the sintered alloy obtained by the above-described production method to hot isostatic pressure treatment (HIP treatment) in order to obtain a dense and high-strength sintered alloy. Also,
When the surface of the sintered alloy of the present invention is further coated with a film, it can be performed by a conventional chemical vapor deposition method or physical vapor deposition method.
【００２５】[0025]
【作用】本発明の焼結合金は、焼結合金の内部、具体的
には焼結合金の内部を構成している主として結合相が強
度及び靭性を高める作用をし、表面層を構成している主
として高融点金属化合物及び結合相濃度が耐摩耗性，耐
熱性，耐酸化性，耐腐食性を高める作用をし、表面層に
おける拡散元素の濃度勾配が表面層と焼結合金の内部と
の境界面近傍における熱応力緩和を高める作用をしてい
るものである。In the sintered alloy of the present invention, the bonding phase constituting the inside of the sintered alloy, specifically, the inside of the sintered alloy mainly acts to increase the strength and toughness, and forms the surface layer. The concentration of the refractory metal compound and the binder phase mainly acts to enhance wear resistance, heat resistance, oxidation resistance, and corrosion resistance, and the concentration gradient of the diffusion element in the surface layer between the surface layer and the inside of the sintered alloy. It acts to enhance thermal stress relaxation near the interface.
【００２６】[0026]
【実施例１】平均粒径がそれぞれ０．３μｍのα−アル
ミナ粉末、０．５μｍのＭｏ，Ｗ，ＷＣの粉末、１〜３
μｍのＴｉ（Ｃ0.5，Ｎ0.5），ＴｉＨ2，ＺｒＨ2，Ｎｂ
Ｈ2，ＴａＨ2，ＣｒＮ，Ｎｉの粉末、０．１μｍのＡ
ｌ，ＺｒＯ2（含３モル％Ｙ2Ｏ3）粉末を用いて、表１
に示す組成成分に配合し、ウレタン内張りしたステンレ
ス製ポットにメタノールとアルミナ製ボールと共に配合
粉末を装入して４８時間混合粉砕し、乾燥後８０℃に加
熱しながら６ｗｔ％のパラフィンワックスを添加混合し
て混合粉末を得た。次に、金型を用いて、それぞれの混
合粉末を１ｔｏｎ／ｃｍ2で加圧成形して粉末成形体を
作製した。次いで、表１に併記した粉末圧粉体の表面へ
の処理方法でもって処理した後、表１に併記した焼結条
件（但し、焼結雰囲気は、１５００℃までは全て１０-3
Ｔｏｒｒの真空とした）でもって焼結し、形状がＩＳＯ
規格のＳＮＭＮ１２０４０８相当からなる本発明品１〜
１０及び比較品１〜３の焼結合金を得た。Example 1 α-alumina powder having an average particle diameter of 0.3 μm, Mo, W, and WC powders having an average particle diameter of 0.5 μm;
μm of Ti (C 0.5 , N 0.5 ), TiH 2 , ZrH 2 , Nb
H 2 , TaH 2 , CrN, Ni powder, 0.1 μm A
l, ZrO 2 (containing 3 mol% Y 2 O 3 ) powder,
The mixed powder was charged into a urethane-lined stainless steel pot together with methanol and alumina balls and mixed and ground for 48 hours. After drying, 6 wt% of paraffin wax was added while heating to 80 ° C. Thus, a mixed powder was obtained. Next, using a mold, each mixed powder was press-formed at 1 ton / cm 2 to prepare a powder compact. Next, after the powder compact was treated by the treatment method for the surface of the powder compact shown in Table 1, the sintering conditions shown in Table 1 (however, the sintering atmosphere was 10 −3 until 1500 ° C.)
(Torr vacuum) and the shape is ISO
The present invention product 1 which is equivalent to the standard SNMN120408
Sintered alloys No. 10 and Comparative products 1 to 3 were obtained.
【００２７】[0027]
【表１】 本発明品１〜１０及び比較品１〜３の焼結合金を切断
し、それぞれの表面層の厚さ、焼結合金の表面層の表面
より０．０１ｍｍ内部の点（表面層）と焼結合金の表面
層の表面より２．０ｍｍ内部の点（焼結合金の内部）に
おける、それぞれの微少部Ｘ線回折、金属顕微鏡，走査
型電子顕微鏡による組成成分及びマイクロビッカース硬
さ（５００ｇ荷重）を調べて、その結果を表２に示し
た。（但し、表面層がない場合は、焼結合金の表面よ
り、０．０１ｍｍ及び２．０ｍｍの各点を調べた）[Table 1] The sintered alloys of the present invention products 1 to 10 and the comparative products 1 to 3 are cut, and the thickness of each surface layer, and the point (surface layer) within 0.01 mm from the surface of the surface layer of the sintered alloy are sintered and bonded. At a point within 2.0 mm from the surface of the gold surface layer (inside of the sintered alloy), the composition of each microscopic part by X-ray diffraction, metallographic microscope, and scanning electron microscope and micro Vickers hardness (500 g load) were measured. Upon examination, the results are shown in Table 2. (However, when there is no surface layer, points of 0.01 mm and 2.0 mm were examined from the surface of the sintered alloy)
【００２８】[0028]
【表２】 こうして得た表２の焼結合金の内、本発明品３，５，
７，１０、比較品１，２と、さらに同様の形状に作製し
た市販の純アルミナ系セラミックス、アルミナ−炭化チ
タン系セラミックスを用いて、被削材Ｓ４８Ｃ，切削速
度４００ｍ／ｍｉｎ，送り０．２ｍｍ／ｒｅｖ，切込み
１．５ｍｍ，チップ形状ＳＮＭＮ１２０４０８（ブレー
カ付き，０．１５×−２５°ＰＨ付），切削時間１０
分，評価平均逃げ面摩耗幅（ＶB）による乾式旋削試験
と、被削材Ｓ４８Ｃ（外周に４本溝入り）切削速度１０
０ｍ／ｍｉｎ，送り０．１２ｍｍ／ｒｅｖ，切込み１．
５ｍｍ，チップ形状同上，切削時間欠損又はチッピング
による寿命まで、評価３コーナーの平均寿命時間による
乾式断続旋削試験を行い、その結果を表３に示した。[Table 2] Of the sintered alloys in Table 2 thus obtained, the products of the present invention 3, 5,
7, S4C, cutting speed 400 m / min, feed 0.2 mm using commercially available pure alumina-based ceramics and alumina-titanium carbide-based ceramics manufactured in the same shape as Comparative Examples 1 and 2 and Comparative Products 1 and 2. / Rev, depth of cut 1.5mm, chip shape SNMN120408 (with breaker, with 0.15x-25 ° PH), cutting time 10
Min., Evaluation Dry turning test based on average flank wear width (V B ) and work material S48C (with four grooves on the outer periphery) Cutting speed 10
0 m / min, feed 0.12 mm / rev, depth of cut 1.
A dry intermittent turning test was performed with an average life time of three evaluation corners until a life of 5 mm, the same shape of the insert, and a cutting time defect or chipping, and the results are shown in Table 3.
【００２９】[0029]
【表３】 [Table 3]
【００３０】[0030]
【実施例２】実施例１で得た本発明品３，５，７、比較
品１，２の焼結合金及び市販のＡｌ2Ｏ3系セラミック
ス，Ａｌ2Ｏ3−ＴｉＣ系セラミックスを用いて、従来か
ら行われている化学蒸着法でもって、それぞれの焼結合
金又はセラミックスの表面に０．５μｍ厚さのＴｉＣ、
１μｍ厚さのＴｉ（Ｃ，Ｎ）、０．５μｍ厚さのＴｉＮ
を順次被覆して、それぞれ本発明品１１，１２，１３、
比較品４，５，及び被覆Ａｌ2Ｏ3系セラミックス，被覆
Ａｌ2Ｏ3−ＴｉＣ系セラミックスを得た。こうして得た
被覆焼結合金及び被覆セラミックスを用いて実施例１で
行った旋削試験と断続試験を行った結果、本発明品１
１，１２，１３は、それぞれ実施例１の本発明品３，
５，７に対し、約５０〜１５０％向上したのに対し、比
較品４，５及び被覆セラミックスは、それぞれ実施例１
の比較品１，２及び市販セラミックスと殆んど同等であ
った。Example 2 Using the sintered alloys of the products 3, 5, 7 of the present invention and the comparative products 1 and 2 obtained in Example 1, and commercially available Al 2 O 3 -based ceramics and Al 2 O 3 -TiC-based ceramics By the conventional chemical vapor deposition method, a 0.5 μm thick TiC,
1 μm thick Ti (C, N), 0.5 μm thick TiN
Are sequentially coated, and the products of the present invention 11, 12, 13,
Comparative products 4 and 5, coated Al 2 O 3 ceramics, and coated Al 2 O 3 —TiC ceramics were obtained. The turning test and the intermittent test performed in Example 1 were performed using the coated sintered alloy and the coated ceramics thus obtained.
1, 12 and 13 are the products of the present invention 3 of Example 1, respectively.
Compared to Examples 5 and 7, the products of Comparative Examples 4 and 5 and the coated ceramics were improved by about 50 to 150%, respectively.
Comparative products 1 and 2 and commercial ceramics were almost equivalent.
【００３１】[0031]
【発明の効果】本発明の焼結合金は、表面層の硬さが焼
結合金の内部に比べて、４％〜３４％高く、従来の酸化
アルミニウム系焼結合金に比べて、耐摩耗性において
３．３倍以上、耐欠損性による寿命において５．６倍〜
６３倍も向上するという効果、また従来の酸化アルミニ
ウム系セラミックスに比べて、耐摩耗性において７％〜
５２％、耐欠損性による寿命において８３％〜６３倍も
向上するという効果がある。According to the present invention, the hardness of the surface layer of the sintered alloy is 4% to 34% higher than that of the inside of the sintered alloy, and the wear resistance is higher than that of the conventional aluminum oxide based sintered alloy. 3.3 times or more, and 5.6 times or more in life due to fracture resistance
63% improvement in effect, and 7% ~ in abrasion resistance compared to conventional aluminum oxide ceramics
There is an effect that the life is improved by 52% and 83% to 63 times in the life due to the fracture resistance.
【００３２】さらに、硬質被膜を被覆した本発明の被覆
焼結合金は、被膜が被覆されない本発明の焼結合金に比
べて、耐摩耗性及び耐欠損性において５０〜１５０％も
向上するという効果がある。Furthermore, the coated sintered alloy of the present invention coated with a hard coating has an effect of improving the wear resistance and chipping resistance by 50 to 150% as compared with the sintered alloy of the present invention not coated with the coating. There is.
【００３３】以上本発明の焼結合金は、表面層が耐摩耗
性，耐酸化性，耐熱性，耐腐食性，鉄系材料に対する耐
溶着性及び硬質被膜との密着性を高める効果を発揮し、
焼結合金の内部が強度及び靭性を高める効果を発揮して
いるもので、工具や各種の機械部品に応用できる産業上
有用な材料である。As described above, the sintered alloy of the present invention has the effect of improving the wear resistance, oxidation resistance, heat resistance, corrosion resistance, welding resistance to iron-based materials, and adhesion to hard coatings. ,
The inside of the sintered alloy exhibits the effect of increasing the strength and toughness, and is an industrially useful material that can be applied to tools and various mechanical parts.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−171264（ＪＰ，Ａ) 特開 平５−286754（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/10 C22C 29/12 C22C 1/05 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-171264 (JP, A) JP-A-5-286754 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C04B 35/10 C22C 29/12 C22C 1/05
Claims (4)
Ｎｉ，Ｃｏ，Ｆｅ，Ａｌ及びこれらの相互合金の中の少
なくとも１種の結合相２〜５０体積％と、残部が酸化ア
ルミニウムの硬質相、又は酸化アルミニウム５０体積％
以上と残り酸化ジルコニウム，部分安定化酸化ジルコニ
ウム，酸化ハフニウム，酸化クロム，酸化ケイ素，炭化
ケイ素，窒化ケイ素，周期律表の４ａ，５ａ，６ａ族の
金属の炭化物，窒化物及びこれらの相互固溶体の中の少
なくとも１種とでなる硬質相と不可避不純物とからなる
焼結合金の１部の面もしくは全面に表面から少なくとも
０．０１ｍｍ内部までの厚さでなる表面層が形成されて
おり、該表面層が酸化アルミニウムと周期律表の４ａ，
５ａ，６ａ族の金属の炭化物，窒化物，酸化物，ホウ化
物，ケイ化物及びこれらの相互固溶体の中の少なくとも
１種の高融点金属化合物とでなり、あるいは、酸化アル
ミニウムと該高融点金属化合物と該結合相とでなる表面
層を有する焼結合金であって、該表面層中の該結合相の
平均量が該焼結合金の内部の該結合相の平均量よりも少
なく、かつ該表面層中に存在している炭素，窒素，酸
素，ホウ素，ケイ素，の中の少なくとも１種の拡散元素
が該表面層の表面から該焼結合金の内部に向って漸減し
ていることを特徴とする表面調質焼結合金。1. A metal belonging to groups 4a, 5a and 6a of the periodic table,
2 to 50% by volume of at least one binder phase of Ni, Co, Fe, Al and their alloys, and the balance is a hard phase of aluminum oxide or 50% by volume of aluminum oxide
The above and the remaining zirconium oxide, partially stabilized zirconium oxide, hafnium oxide, chromium oxide, silicon oxide, silicon carbide, silicon nitride, carbides and nitrides of metals of groups 4a, 5a and 6a of the periodic table, and their mutual solid solutions A surface layer having a thickness of at least 0.01 mm from the surface is formed on a part or the whole surface of a sintered alloy comprising a hard phase comprising at least one of the above and an unavoidable impurity; The layer is made of aluminum oxide and 4a of the periodic table,
At least one refractory metal compound among carbides, nitrides, oxides, borides, silicides and mutual solid solutions of metals belonging to the group 5a and 6a, or aluminum oxide and the refractory metal compound And a surface layer comprising the binder phase, wherein the average amount of the binder phase in the surface layer is smaller than the average amount of the binder phase inside the sintered alloy, and At least one diffusion element of carbon, nitrogen, oxygen, boron and silicon present in the layer is gradually reduced from the surface of the surface layer toward the interior of the sintered alloy. Surface refined sintered alloy.
も２つの表面に形成されており、該焼結合金の１つの表
面に形成された該表面層と他の表面に形成された該表面
層には、異なった上記高融点金属化合物が存在している
ことを特徴とする請求項１記載の表面調質焼結合金。2. The surface layer formed on at least two surfaces of the sintered alloy, the surface layer formed on one surface of the sintered alloy and the surface formed on another surface of the sintered alloy. 2. The surface-finished sintered alloy according to claim 1, wherein different layers of the refractory metal compound are present in the layer.
金の１部の面又は全面に周期律表の４ａ，５ａ，６ａ族
の金属の炭化物，窒化物，炭酸化物，窒酸化物、Ａｌの
酸化物，窒化物、Ｓｉの炭化物，窒化物及びこれらの相
互固溶体、ダイヤモンド、ダイヤモンド状カーボン、立
方晶窒化ホウ素の中の少なくとも１種の単層もしくは多
層でなる被膜を被覆したことを特徴とする表面調質焼結
合金。3. A carbide, nitride, carbonate, or nitric oxide of a metal belonging to Group 4a, 5a, or 6a of the periodic table on a part or the whole surface of the surface-tempered sintered alloy according to claim 1 or 2. Coated with at least one monolayer or multilayer of at least one of a substance, an oxide, a nitride of Al, a carbide and a nitride of Si and a mutual solid solution thereof, diamond, diamond-like carbon, and cubic boron nitride. Surface-finished sintered alloy characterized by the following.
Ｎｉ，Ｃｏ，Ｆｅ，Ａｌ及びこれらの相互合金又はこれ
らの前駆体の中の少なくとも１種の結合相形成粉末に酸
化アルミニウム、又は酸化アルミニウム５０体積％以上
と残り酸化ジルコニウム，部分安定化酸化ジルコニウ
ム，酸化ハフニウム，酸化クロム，酸化ケイ素，炭化ケ
イ素，窒化ケイ素，周期律表の４ａ，５ａ，６ａ族の金
属の炭化物，窒化物及びこれらの相互固溶体の中の少な
くとも１種とでなる硬質相形成粉末を加えて混合粉砕
し、混合粉末とする第１工程、該混合粉末を所定の形状
に成形して粉末圧粉体とする第２工程、該粉末圧粉体を
炭素，窒素，酸素，ホウ素，ケイ素の中の少なくとも１
種の拡散元素を含む化合物に接触もしくは付着、あるい
は該拡散元素を含むガス雰囲気中に設置して１４００〜
１９００℃に加熱する第３工程を経て請求項１又は２記
載の表面調質焼結合金を作製することを特徴とする表面
調質焼結合金の製造方法。4. A metal of group 4a, 5a, 6a of the periodic table,
At least one binder phase forming powder among Ni, Co, Fe, Al and their alloys or precursors thereof contains aluminum oxide or 50% by volume or more of aluminum oxide and the remaining zirconium oxide, partially stabilized zirconium oxide; Hard phase forming powder comprising hafnium oxide, chromium oxide, silicon oxide, silicon carbide, silicon nitride, carbides and nitrides of metals of groups 4a, 5a and 6a of the periodic table, and at least one of these mutual solid solutions , Followed by mixing and grinding to form a mixed powder, a second step of forming the mixed powder into a predetermined shape to form a powder compact, and forming the powder compact into carbon, nitrogen, oxygen, boron, At least one of the silicon
Contacting or adhering to a compound containing a kind of diffusion element, or installing in a gas atmosphere containing the kind of diffusion element, 1400
The method for producing a surface-finished sintered alloy according to claim 1, wherein the surface-finished sintered alloy according to claim 1 is produced through a third step of heating to 1900 ° C. 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04337974A JP3092887B2 (en) | 1992-11-25 | 1992-11-25 | Surface-finished sintered alloy and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04337974A JP3092887B2 (en) | 1992-11-25 | 1992-11-25 | Surface-finished sintered alloy and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157135A JPH06157135A (en) | 1994-06-03 |
| JP3092887B2 true JP3092887B2 (en) | 2000-09-25 |
Family
ID=18313752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04337974A Expired - Fee Related JP3092887B2 (en) | 1992-11-25 | 1992-11-25 | Surface-finished sintered alloy and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3092887B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4726781B2 (en) * | 2004-03-12 | 2011-07-20 | サンアロイ工業株式会社 | Sintered tool and its manufacturing method |
| JP5967764B2 (en) * | 2012-09-12 | 2016-08-10 | 国立研究開発法人物質・材料研究機構 | Method for producing alloy powder for oxidation-resistant coating, method for producing alloy having excellent oxidation resistance characteristics using the powder, and method for producing member using the alloy |
-
1992
- 1992-11-25 JP JP04337974A patent/JP3092887B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06157135A (en) | 1994-06-03 |
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