JP2012126971A - Alloy steel powder for powder metallurgy, iron-based sintered material, and method for producing the same - Google Patents

Alloy steel powder for powder metallurgy, iron-based sintered material, and method for producing the same Download PDF

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JP2012126971A
JP2012126971A JP2010280614A JP2010280614A JP2012126971A JP 2012126971 A JP2012126971 A JP 2012126971A JP 2010280614 A JP2010280614 A JP 2010280614A JP 2010280614 A JP2010280614 A JP 2010280614A JP 2012126971 A JP2012126971 A JP 2012126971A
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powder
iron
alloy steel
sintered
steel powder
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Shigeru Unami
繁 宇波
Yukiko Ozaki
由紀子 尾▲崎▼
Naomichi Nakamura
尚道 中村
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JFE Steel Corp
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Abstract

PROBLEM TO BE SOLVED: To provide alloy steel powder for powder metallurgy capable of reconciling strength with wear resistance.SOLUTION: The alloy steel powder is diffused and stuck 0.05-0.5 mass% Cr-containing powder on the surface of steel powder obtained by prealloying 0.02-0.4 mass% Nb.

Description

本発明は、粉末冶金技術に供して好適な粉末冶金用合金鋼粉に関し、特にかかる合金鋼粉を用いて焼結材料を製造した場合に、その強度と共に、耐摩耗性の向上を図ろうとするものである。
また、本発明は、上記の粉末冶金用合金鋼粉を用いて製造した強度および耐摩耗性に優れた焼結材料およびその製造方法に関するものである。
The present invention relates to an alloy steel powder for powder metallurgy that is suitable for use in powder metallurgy technology, and in particular, when a sintered material is produced using such alloy steel powder, it is intended to improve the wear resistance as well as its strength. Is.
Moreover, this invention relates to the sintered material excellent in the intensity | strength and abrasion resistance manufactured using said alloy steel powder for powder metallurgy, and its manufacturing method.

粉末冶金技術は、複雑な形状の部品を、製品形状に極めて近い形状(いわゆるニアネット形状)でしかも高い寸法精度で製造できることから、大幅な切削コストの低減が可能となる。このため、粉末冶金製品が各種の機械や部品として、多方面に利用されている。
さらに、最近では、部品の小型化、軽量化のために、粉末冶金製品の強度の向上が強く要望されている。とくに、鉄基粉末製品(鉄基焼結体)に対する高強度化の要求が強い。
The powder metallurgy technique can manufacture parts having a complicated shape in a shape very close to a product shape (so-called near net shape) and with high dimensional accuracy, so that the cutting cost can be greatly reduced. For this reason, powder metallurgy products are used in various fields as various machines and parts.
Furthermore, recently, there has been a strong demand for improving the strength of powder metallurgy products in order to reduce the size and weight of parts. In particular, there is a strong demand for higher strength for iron-based powder products (iron-based sintered bodies).

粉末冶金用鉄基粉末成形体は、一般に、鉄基粉末に、銅粉,黒鉛粉などの合金用粉末と、ステアリン酸,ステアリン酸リチウム等の潤滑剤を混合して鉄基粉末混合粉とし、これを金型に充填し、加圧成形することにより製造される。鉄基粉末は、成分に応じて、鉄粉(たとえば純鉄粉等)、合金鋼粉等に分類される。また、製法による分類では、アトマイズ鉄粉,還元鉄粉等があり、これらの分類では鉄粉は合金鋼粉を含む広い意味で用いられる。   An iron-based powder compact for powder metallurgy is generally an iron-based powder mixed powder obtained by mixing an iron-based powder with an alloy powder such as copper powder and graphite powder and a lubricant such as stearic acid and lithium stearate, This is manufactured by filling a mold and press-molding it. Iron-based powders are classified into iron powder (for example, pure iron powder), alloy steel powder, and the like, depending on the components. Moreover, in the classification according to the manufacturing method, there are atomized iron powder, reduced iron powder, and the like. In these classifications, iron powder is used in a broad sense including alloy steel powder.

通常の粉末冶金工程で得られる成形体の密度は、6.6〜7.1 Mg/m3程度が一般的である。これら鉄基粉末成形体は、その後に焼結処理が施されて焼結体とされ、さらに必要に応じてサイジングや切削加工が施されて、粉末冶金製品とされる。また、さらに高い強度が必要な場合は、焼結後に浸炭熱処理や光輝熱処理が施されることもある。 As for the density of the molded object obtained by a normal powder metallurgy process, about 6.6-7.1 Mg / m < 3 > is common. These iron-based powder compacts are subsequently subjected to a sintering treatment to obtain sintered bodies, and further subjected to sizing and cutting as necessary to obtain powder metal products. Further, when higher strength is required, carburizing heat treatment or bright heat treatment may be performed after sintering.

原料粉の段階で、合金元素を加えた粉末として、
(1) 純鉄粉に各合金元素粉末を配合した混合粉、
(2) 完全に各元素を合金化した予合金鋼粉、
(3) 純鉄粉や予合金鋼粉の表面に各合金元素粉末を部分的に付着拡散させた部分拡散合金鋼粉(複合合金鋼粉ともいう)
等が知られている。
At the raw material powder stage, as an alloy element added powder,
(1) Mixed powder in which each alloy element powder is mixed with pure iron powder,
(2) Pre-alloyed steel powder completely alloyed with each element,
(3) Partially diffused alloy steel powder (also called composite alloy steel powder) in which each alloy element powder is partially adhered and diffused on the surface of pure iron powder or prealloyed steel powder
Etc. are known.

(1) の純鉄粉に各合金元素粉末を配合した混合粉は、純鉄粉並みの高圧縮性を確保できるという利点がある。しかしながら、焼結に際し、Feよりも活性金属であるMn,Cr,V,Si,Nb,Tiなどは、焼結雰囲気や浸炭雰囲気中におけるCO2濃度や露点を低く厳密に制御 しないと酸化を起こしての低酸素量化を図れず、また各合金元素がFe中に十分に拡散せず、不均質組織のままとなっての基地強化を達成できないという問題があった。
このために、(1) の純鉄粉に各合金元素粉末を配合した混合粉は、近年の高強度化の要求に対応できず、使用されない状態に至っている。
The mixed powder obtained by blending each alloying element powder with the pure iron powder of (1) has an advantage that high compressibility comparable to that of the pure iron powder can be secured. However, during sintering, Mn, Cr, V, Si, Nb, Ti, etc., which are more active metals than Fe, oxidize unless the CO 2 concentration and dew point in the sintering atmosphere and carburizing atmosphere are low and strictly controlled. However, there is a problem in that it is impossible to achieve a low oxygen content, and each alloy element does not sufficiently diffuse into Fe, thereby making it impossible to achieve base strengthening while maintaining a heterogeneous structure.
For this reason, the mixed powder in which each alloy element powder is blended with the pure iron powder of (1) cannot meet the recent demand for higher strength and has not been used.

これに対し、(2) の各元素を完全に合金化した予合金鋼粉は、溶鋼をアトマイズして製造するため、溶鋼のアトマイズ工程での酸化と完全合金化による固溶硬化作用を生じるものの、Mn,Cr,V,Si,Nb,Tiなどの合金元素の種類と量を限定することにより、低酸素量化と純鉄粉並みの高圧縮性とを確保できる利点がある。また、完全合金化による基地強化の可能性があり、高強度用の予合金鋼粉として開発が行われている。   On the other hand, prealloyed steel powder in which each element of (2) is completely alloyed is produced by atomizing molten steel, so that it causes solid solution hardening by oxidation and complete alloying in the atomizing process of molten steel. By limiting the kind and amount of alloy elements such as Mn, Cr, V, Si, Nb, and Ti, there is an advantage that low oxygen content and high compressibility comparable to pure iron powder can be secured. In addition, there is a possibility of strengthening the base by complete alloying, and it has been developed as a pre-alloyed steel powder for high strength.

また、(3) の部分拡散合金鋼粉は、純鉄粉や予合金鋼粉に各元素の金属粉末を配合し、非酸化性または還元性の雰囲気の下で加熱して、純鉄粉や予合金鋼粉の表面に各金属粉末を部分的に拡散接合して製造することから、(1) の鉄基混合粉および(2) の予合金鋼粉の良い点を組み合わせることができる。したがって、低酸素量化と純鉄粉並みの高圧縮性とを確保でき、完全合金相と部分的な濃化相からなる複合組織となっての基地強化の可能性があり、高強度用の部分拡散予合金鋼粉として開発が行われている。   In addition, the partial diffusion alloy steel powder (3) contains pure iron powder and pre-alloy steel powder mixed with metal powders of each element and heated in a non-oxidizing or reducing atmosphere to produce pure iron powder or Since each metal powder is partially diffusion bonded to the surface of the prealloyed steel powder, the advantages of the iron-based mixed powder (1) and the prealloyed steel powder (2) can be combined. Therefore, low oxygen content and high compressibility comparable to pure iron powder can be secured, and there is a possibility of strengthening the base as a composite structure consisting of a complete alloy phase and a partially concentrated phase, and a high strength part It is being developed as a diffusion prealloyed steel powder.

ところで、上記した予合金鋼粉および部分拡散合金鋼粉の基本的な合金成分として、MoやCrが多くの場合用いられている。これは鉄鋼材料の強化元素としてMoやCrが用いられるのと同じ理由による。すなわち、MoやCrは、鉄鋼材料において母相(マトリックス)を変態強化するだけでなく、母相と炭化物に分配して母相を固溶強化し、さらには微細炭化物となって母相を析出強化するからである。
その他、V,Nb,Tiなどの炭化物形成能の強い元素も、炭化物の析出強化によって、焼結材料を強化することから、添加されている。
By the way, Mo and Cr are often used as basic alloy components of the above-mentioned prealloyed steel powder and partially diffused alloyed steel powder. This is due to the same reason that Mo and Cr are used as strengthening elements in steel materials. In other words, Mo and Cr not only transform and strengthen the matrix (matrix) in steel materials, but also partition the matrix and carbides to strengthen the matrix by solid solution strengthening, and further precipitate the matrix as fine carbides. Because it strengthens.
In addition, elements having strong carbide forming ability such as V, Nb, and Ti are added because the sintered material is strengthened by precipitation strengthening of carbide.

例えば、特許文献1では、Mo:0.1 〜6.0%、V:0.05〜2.0 %と、さらにNb:0.10% 以下を予合金して含み、Mo量:4%以下を部分的に拡散付着させた粉末冶金用合金鋼粉が開示されている。この合金鋼粉は、粉末の段階における低酸素量化と純鉄粉並みの高圧縮性とを確保し、かつ焼結材または浸炭焼入れ材における低酸素量化と基地強化を達成するとされている。   For example, in Patent Document 1, Mo: 0.1 to 6.0%, V: 0.05 to 2.0%, and Nb: 0.10% or less are pre-alloyed, and Mo amount: 4% or less is partially diffused and adhered. An alloy steel powder for metallurgy is disclosed. This alloy steel powder is said to ensure low oxygen content at the powder stage and high compressibility comparable to that of pure iron powder, and to achieve low oxygen content and base strengthening in sintered or carburized and quenched materials.

また、特許文献2では、重量比でCr:0.5〜2%、Mn:0.08%以下、Mo:0.1〜0.6%、 V:0.05〜0.5%を含み、さらにNb:0.01〜0.08%、Ti:0.01〜0.08%の1種又は2種を 含み、さらにMo:0.05〜3.5%を拡散付着した高強度焼結体用合金鋼粉が開示されている 。この技術では、圧縮性のよい、適度な焼入れ性に制御された合金鋼粉が得られ、さらにこの合金鋼粉を用いて焼結後の冷却速度を制御することにより、焼結体に粗大な上部ベイナイト組織を生成させずに微細なパーライト組織にすることができ、焼結のままで高強度を得られるとされている。   Patent Document 2 includes Cr: 0.5 to 2% by weight, Mn: 0.08% or less, Mo: 0.1 to 0.6%, V: 0.05 to 0.5%, and Nb: 0.01 to 0.08%, Ti: 0.01. An alloy steel powder for a high-strength sintered body is disclosed that contains one or two of ˜0.08%, and further has Mo: 0.05 to 3.5% diffused and adhered. In this technique, alloy steel powder having good compressibility and controlled to an appropriate hardenability is obtained, and further, by controlling the cooling rate after sintering using this alloy steel powder, the sintered body is coarsened. It is said that a fine pearlite structure can be obtained without generating an upper bainite structure, and a high strength can be obtained as it is sintered.

特開平8−49047号公報JP-A-8-49047 特開平7−331395号公報JP 7-331395 A

しかしながら、発明者らの研究では、上記した特許文献1および特許文献2いずれの合金鋼粉を用いた焼結材料でも、強度と耐摩耗性を両立させるのは困難であることが分かった。
本発明は、上記した従来技術の問題点を克服し、強度と耐摩耗性の両立が可能な粉末冶金用合金鋼粉を提案することを目的とする。
また、本発明は、上記の粉末冶金用合金鋼粉を用いて製造した、強度および耐摩耗性に優れた焼結材料を、その有利な製造方法と共に提案することを目的とする。
However, the inventors' research has revealed that it is difficult to achieve both strength and wear resistance in the sintered materials using the alloy steel powders of Patent Document 1 and Patent Document 2 described above.
The object of the present invention is to overcome the above-mentioned problems of the prior art and propose an alloy steel powder for powder metallurgy capable of achieving both strength and wear resistance.
Another object of the present invention is to propose a sintered material that is manufactured using the above-mentioned alloy steel powder for powder metallurgy and has excellent strength and wear resistance together with its advantageous manufacturing method.

さて、発明者等は、上記の目的を達成するために、鉄基粉末の合金成分およびその添加手段について種々検討を重ねた結果、以下に述べる知見を得た。
鉄粉中にNbなどの炭化物形成元素を予合金化し、Crのみを拡散付着させた鉄基粉末を、炭素粉末と混合し、成形体にして、焼結した場合、鉄基粉末粒子間の焼結ネック部では合金元素Crが高濃度となる。このため、焼結ネック部には、CrとNbなどの炭化物形成元素およびCが存在し、CrとNb等を含む炭化物が析出、分散することになる。
焼結ネック部には、気孔が多く存在するため、この部分の強度は低下する傾向にあるが、気孔の周囲にかような炭化物が析出すると、焼結ネック部が強化されることになる。
一方、基地部には、Crが含まれていないため、焼結ネック部に比べると、炭化物が生成し難く、強度に優れた組織となる。
本発明は、上記の知見に立脚するものである。
Now, in order to achieve the above object, the inventors have made various studies on the alloy components of the iron-based powder and the means for adding the same, and as a result, have obtained the following knowledge.
When iron-based powders pre-alloyed with carbide-forming elements such as Nb in iron powder and only Cr is diffused and adhering are mixed with carbon powder to form a compact and sintered, sintering between iron-based powder particles The alloying element Cr has a high concentration at the neck. For this reason, carbide forming elements such as Cr and Nb and C are present in the sintered neck portion, and carbides including Cr and Nb are precipitated and dispersed.
Since there are many pores in the sintered neck portion, the strength of this portion tends to decrease. However, when such carbides are deposited around the pores, the sintered neck portion is strengthened.
On the other hand, since the base portion does not contain Cr, compared to the sintered neck portion, carbides are less likely to be formed, and the structure is excellent in strength.
The present invention is based on the above findings.

すなわち、本発明の要旨構成は次のとおりである。
1.0.02〜0.4質量%のNbを予合金化した鋼粉の表面に、0.05〜0.5質量%のCr含有粉末を拡散付着させてなる粉末冶金用合金鋼粉。
That is, the gist configuration of the present invention is as follows.
1. Alloy steel powder for powder metallurgy in which 0.05 to 0.5% by mass of Cr-containing powder is diffused and adhered to the surface of steel powder prealloyed with 0.02 to 0.4% by mass of Nb.

2.0.02〜0.4質量%のNbと、0.01〜0.4質量%のVおよび0.01〜0.4質量%のTiのうちから 選んだ一種または二種とを予合金化した鋼粉の表面に、0.05〜0.5質量%のCr含有粉末を拡散付着させてなる粉末冶金用合金鋼粉。 2. On the surface of steel powder pre-alloyed with 0.02 to 0.4 mass% Nb, one or two selected from 0.01 to 0.4 mass% V and 0.01 to 0.4 mass% Ti, Alloy steel powder for powder metallurgy, formed by diffusion-attaching a mass% Cr-containing powder.

3.前記1または2に記載の粉末冶金用合金鋼粉を、圧粉成形後、焼結して得た鉄基焼結材料であって、該焼結材料の気孔の周囲に少なくともNbとCrを含む炭化物を析出させてなる鉄基焼結材料。 3. An iron-based sintered material obtained by sintering the powder metallurgy alloy steel powder according to 1 or 2 after compacting and including at least Nb and Cr around pores of the sintered material An iron-based sintered material obtained by depositing carbide.

4.前記少なくともNbとCrを含む炭化物が、(Nb,Cr)C、(Nb,V,Cr)C、(Nb,Ti,Cr)Cおよび(Nb,Ti,V,Cr)Cのいずれかである前記3に記載の鉄基焼結材料。 4). The carbide containing at least Nb and Cr is any one of (Nb, Cr) C, (Nb, V, Cr) C, (Nb, Ti, Cr) C, and (Nb, Ti, V, Cr) C. 4. The iron-based sintered material as described in 3 above.

5.前記1または2に記載の粉末冶金用合金鋼粉を、0.1〜1.0質量%の炭素粉末と混合したのち、400〜1000MPaの加圧力で圧粉成形後、1100〜1300℃の温度で焼結し、得られる焼結材料の気孔の周囲に少なくともNbとCrを含む炭化物を析出させることを特徴とする鉄基焼結材料の製造方法。 5). After the alloy steel powder for powder metallurgy described in 1 or 2 above is mixed with 0.1 to 1.0% by mass of carbon powder, it is compacted at a pressure of 400 to 1000MPa and then sintered at a temperature of 1100 to 1300 ° C. A method for producing an iron-based sintered material, comprising depositing a carbide containing at least Nb and Cr around pores of the obtained sintered material.

6.前記少なくともNbとCrを含む炭化物が、(Nb,Cr)C、(Nb,V,Cr)C、(Nb,Ti,Cr)Cおよび(Nb,Ti,V,Cr)Cのいずれかである前記5に記載の鉄基焼結材料の製造方法。 6). The carbide containing at least Nb and Cr is any one of (Nb, Cr) C, (Nb, V, Cr) C, (Nb, Ti, Cr) C, and (Nb, Ti, V, Cr) C. 6. The method for producing an iron-based sintered material as described in 5 above.

本発明に従い、NbやV,Tiを予合金化し、Crのみを拡散付着させた粉末冶金用合金鋼粉を使用することにより、高強度のみならず、高耐摩耗性を兼ね備えた焼結材料を得ることができる。   According to the present invention, by using alloy steel powder for powder metallurgy in which Nb, V, and Ti are pre-alloyed and only Cr is diffused and adhered, a sintered material having not only high strength but also high wear resistance is obtained. Obtainable.

本発明により得られた焼結体の焼結ネック部を含む焼結組織を示す模式図である。It is a schematic diagram which shows the sintered structure containing the sintering neck part of the sintered compact obtained by this invention.

以下、本発明を具体的に説明する。
本発明の粉末冶金用合金鋼粉は、NbあるいはさらにVやTiを予合金化した鋼粉の表面に、Cr含有粉末を拡散付着させたものである。
上記した本発明の鉄基粉末を、炭素粉末と混合し、成形体として、焼結することにより、鉄基粉末粒子間の焼結ネック部で合金元素Crが高濃度となる。このため、焼結ネック部には、CrとNb,V,TiおよびCが存在し、Cr とNb,V,Ti等を含む炭化物が析出、分散することになる。
Hereinafter, the present invention will be specifically described.
The alloy steel powder for powder metallurgy according to the present invention is obtained by diffusing and adhering Cr-containing powder to the surface of steel powder prealloyed with Nb or V or Ti.
The above-described iron-based powder of the present invention is mixed with carbon powder and sintered as a molded body, so that the alloy element Cr has a high concentration at the sintering neck portion between the iron-based powder particles. For this reason, Cr, Nb, V, Ti, and C exist in the sintered neck portion, and carbides including Cr, Nb, V, Ti, and the like are precipitated and dispersed.

焼結ネック部には、気孔が多く存在するため、この部分の強度は低下する傾向にあるが、気孔の周囲にかような炭化物が析出すると、焼結ネック部が強化されることになる。
一方、基地部には、Crが含まれていないため、焼結ネック部に比べると、炭化物が生成し難く、高強度の組織となる。
上述したように、炭化物の生成領域を制御することにより、高強度と高耐摩耗性の両立が可能になったものと考えられる。
Since there are many pores in the sintered neck portion, the strength of this portion tends to decrease. However, when such carbides are deposited around the pores, the sintered neck portion is strengthened.
On the other hand, since the base portion does not contain Cr, carbide is less likely to be produced than the sintered neck portion, and a high-strength structure is obtained.
As described above, it is considered that both high strength and high wear resistance can be achieved by controlling the carbide generation region.

以下、本発明において、Nb,V,Tiを前記の組成範囲で予合金化させた理由について説明する。なお、以下に示す「%」は、本発明の粉末冶金用合金鋼粉全体に対する比率(質量%)である。
Nb:0.02〜0.4%
Nbは、基地中に炭化物として析出させることにより、強度の向上に極めて有効に作用する。しかしながら、含有量が0.02%に満たないと炭化物の生成量が不十分となって、焼結体の十分な高強度化が望めず、一方0.4%を超えると炭化物が粗大化して、強度向上効果が低下し、しかも合金鋼粉粒子の硬化により圧縮性の低下を招くだけでなく、経済的な観点からも不利となる。
Hereinafter, the reason why Nb, V, and Ti are pre-alloyed within the above composition range in the present invention will be described. In addition, "%" shown below is a ratio (mass%) with respect to the whole alloy steel powder for powder metallurgy of this invention.
Nb: 0.02-0.4%
Nb acts extremely effectively for improving the strength by precipitating as carbide in the matrix. However, if the content is less than 0.02%, the amount of carbide generated becomes insufficient, and sufficient strength of the sintered body cannot be expected. On the other hand, if it exceeds 0.4%, the carbide becomes coarse and the strength is improved. In addition, the hardening of the alloy steel powder particles not only causes a decrease in compressibility, but is also disadvantageous from an economical viewpoint.

V:0.01〜0.4%およびTi:0.01〜0.4%のいずれか一種または二種
VおよびTiは、Nbの次に炭化物形成元素として有用であるので、Nbと複合含有させることにより、強度の向上に一層寄与する。しかしながら、いずれの元素も、下限に満たないとその添加硬化に乏しく、一方上限を超えて添加すると、やはり炭化物が粗大化してしまい、強度向上効果の低下や、圧縮性の低下を招くので、それぞれ上記の範囲で含有させるものとする。
V: 0.01 to 0.4% and Ti: 0.01 to 0.4%, either one or two types V and Ti are useful as carbide-forming elements next to Nb. Contribute further. However, if any element is less than the lower limit, its addition hardening is poor.On the other hand, if it is added in excess of the upper limit, the carbide is also coarsened, resulting in a decrease in strength improvement effect and a decrease in compressibility. It shall contain in said range.

次に、本発明の粉末冶金用合金鋼粉の製造方法について説明する。
まず、所定量の合金元素を予め合金成分として(すなわち予合金として)含有する鉄基粉末(原料としての鉄基粉末)とCr含有粉末の原料であるCr原料粉末を準備する。
鉄基粉末としては、いわゆるアトマイズ鉄粉が好ましい。アトマイズ鉄粉とは、合金成分を目的に応じて調整した溶鋼を水ないしガスで噴霧して得られる鉄基粉末である。アトマイズ鉄粉は、通常、アトマイズ後に還元性雰囲気(例えば水素雰囲気)や真空中で加熱して鉄粉中からCとOを低減させる処理を施す。しかし、本発明の原料としての鉄基粉末にはこのような熱処理を施さない、いわゆる「アトマイズまま」の鉄粉を用いることも可能である。
Next, the manufacturing method of the alloy steel powder for powder metallurgy of this invention is demonstrated.
First, an iron-based powder (iron-based powder as a raw material) containing a predetermined amount of an alloy element as an alloy component (that is, as a pre-alloy) and a Cr raw material powder as a raw material for the Cr-containing powder are prepared.
As the iron-based powder, so-called atomized iron powder is preferable. Atomized iron powder is an iron-based powder obtained by spraying molten steel with alloy components adjusted according to the purpose with water or gas. The atomized iron powder is usually subjected to a treatment for reducing C and O from the iron powder by heating in a reducing atmosphere (for example, hydrogen atmosphere) or vacuum after atomization. However, it is also possible to use so-called “as-atomized” iron powder that is not subjected to such heat treatment for the iron-based powder as the raw material of the present invention.

Cr原料粉末としては、目的とするCr含有粉末そのものを用いても良いし、あるいはCr含有粉末に還元可能なCrの化合物を用いても良い。
ここに、Cr含有粉末としては、Crの純金属粉末をはじめとして、酸化Cr粉末、あるいはFeCr(フェロクロム)粉末などのCr合金粉末が有利に適合する。また、Crの化合物としては、Cr炭化物、Cr硫化物、Cr窒化物などが好適である。
As the Cr raw material powder, the target Cr-containing powder itself may be used, or a Cr compound that can be reduced to the Cr-containing powder may be used.
Here, as the Cr-containing powder, Cr alloy powder such as Cr pure metal powder, Cr oxide powder, or FeCr (ferrochrome) powder is advantageously suitable. As the Cr compound, Cr carbide, Cr sulfide, Cr nitride and the like are suitable.

ついで、上記した鉄基粉末とCr原料粉末を、所定の比率で混合する。混合方法については特に制限はなく、例えばヘンシェルミキサーやコーン型ミキサーなどを用いることができる。   Next, the above iron-based powder and Cr raw material powder are mixed at a predetermined ratio. There is no restriction | limiting in particular about a mixing method, For example, a Henschel mixer, a cone type mixer, etc. can be used.

ついで、この混合物を高温で保持し、鉄基粉末とCr原料粉末の接触面でCrを鉄中に拡散させて接合することにより、本発明の粉末冶金用合金鋼粉が得られる。
ここに、熱処理の雰囲気としては、還元性雰囲気や水素含有雰囲気が好適であり、とりわけ水素雰囲気が適している。なお、真空下で熱処理を加えても良い。また、好適な熱処理の温度は800〜1200℃の範囲である。
なお、アトマイズままの鉄粉を鉄基粉末として使用した場合には、CやOの含有量が高いので、熱処理を真空下とすることでCとOとを低減することが好ましい。この低減作用により鉄基粉末表面が活性になり、Cr含有粉末の拡散による付着が低温(800〜1000℃程度)でも確実に起こるようになる。
Subsequently, this mixture is held at a high temperature, and Cr is diffused into the iron at the contact surface between the iron-based powder and the Cr raw material powder, thereby joining the alloy steel powder for powder metallurgy of the present invention.
Here, as the atmosphere for the heat treatment, a reducing atmosphere or a hydrogen-containing atmosphere is suitable, and a hydrogen atmosphere is particularly suitable. Note that heat treatment may be applied under vacuum. Moreover, the temperature of suitable heat processing is the range of 800-1200 degreeC.
In addition, when the atomized iron powder is used as the iron-based powder, the content of C and O is high. Therefore, it is preferable to reduce C and O by making the heat treatment under vacuum. This reduction action makes the surface of the iron-based powder active, and adhesion due to diffusion of the Cr-containing powder surely occurs even at low temperatures (about 800 to 1000 ° C.).

上記のようにして拡散付着処理を行った場合、通常は、鉄基粉末とCr含有粉末が焼結して固まった状態となるので、所望の粒径に粉砕・分級し、必要に応じてさらに焼鈍を施して粉末冶金用合金鋼粉とする。   When the diffusion adhesion treatment is performed as described above, the iron-based powder and the Cr-containing powder are usually sintered and solidified, and thus pulverized and classified to a desired particle size, and further if necessary. Annealing is performed to obtain alloy steel powder for powder metallurgy.

本発明において、Cr含有粉末の微細な粒子は、均一に鉄基粉末表面に付着していることが好ましい。均一に付着していない場合、粉末冶金用合金鋼粉を付着処理後に粉砕する際や、運搬等の際に、鉄基粉末表面から脱落しやすいので、遊離状態のCr含有粉末が特に増加しやすい。そのような状態の合金鋼粉から成形体を焼結すると、炭化物の分散状態が偏析してしまう傾向にある。したがって、焼結体の強度、耐摩耗性を高めるためには、鉄基粉末の表面にCr含有粉末を均一に付着させ、脱落などにより発生する遊離状態のCr含有粉末を低減することが好ましい。   In the present invention, it is preferable that the fine particles of the Cr-containing powder are uniformly attached to the surface of the iron-based powder. If it is not uniformly adhered, it is easy to drop off from the iron-based powder surface when pulverizing the alloy steel powder for powder metallurgy after adhesion treatment or during transportation, etc., so free Cr-containing powder is particularly likely to increase . When the compact is sintered from the alloy steel powder in such a state, the dispersion state of the carbide tends to segregate. Therefore, in order to increase the strength and wear resistance of the sintered body, it is preferable to uniformly deposit the Cr-containing powder on the surface of the iron-based powder and reduce the free Cr-containing powder generated by dropping off.

拡散付着させるCr量は、0.05〜0.5%である。0.05%を下回ると、炭化物生成効果が少なく、強度向上効果も少ない。一方、0.5%を超えると、炭化物生成効果は飽和し、むしろ焼結体の組織が不均一となるため、強度向上効果が得られなくなる。したがって、拡散付着させるCr量は0.05〜0.5%とする。好ましくは0.1〜0.5%の範囲である。   The amount of Cr to be diffused is 0.05 to 0.5%. If it is less than 0.05%, the carbide generation effect is small and the strength improvement effect is also small. On the other hand, if it exceeds 0.5%, the carbide generating effect is saturated, and the structure of the sintered body is rather non-uniform, so that the effect of improving the strength cannot be obtained. Therefore, the Cr amount to be diffused is 0.05 to 0.5%. Preferably it is 0.1 to 0.5% of range.

上記した複合合金鋼粉を原料として焼結体を製造する場合、黒鉛などの炭素粉末は、高強度化および高疲労強度化に有効であるので、加圧成形に先立ち、C換算で0.1〜1.0%を添加し、混合する。上記したC換算量は、混合後の合金鋼粉混合粉に対する質量比率である。
なお、合金鋼粉混合粉に含有される不純物としては、CやO,N,S等が挙げられるが、これらはそれぞれC:0.02%以下,O:0.2%以下,N:0.004%以下,S:0.03%以下であれば特に問題はない。
In the case of producing a sintered body using the above composite alloy steel powder as a raw material, carbon powder such as graphite is effective in increasing strength and increasing fatigue strength. Therefore, prior to pressure forming, 0.1 to 1.0 in terms of C. Add% and mix. The above-mentioned C conversion amount is a mass ratio with respect to the mixed alloy steel powder after mixing.
Examples of impurities contained in the alloy steel powder mixed powder include C, O, N, and S. These are C: 0.02% or less, O: 0.2% or less, N: 0.004% or less, S : If it is 0.03% or less, there is no particular problem.

次に、本発明の粉末冶金用合金鋼粉を用いて焼結体を製造する際に好適な焼結条件について説明する。
加圧成形に際しては、他に、粉末状の潤滑剤を混合しても良い。また、金型に潤滑剤を塗布あるいは付着させることもできる。いずれの場合であっても、潤滑剤としては、ステアリン酸亜鉛などの金属石鹸、エチレンビスステアリン酸アミドなどのアミド系ワックスなどの公知の潤滑剤を好適に用いることができる。潤滑剤を混合する場合、合金鋼粉混合粉:100質量部に対して0.1〜1.2質量部程度とすることが好ましい。
Next, the sintering conditions suitable for producing a sintered body using the alloy steel powder for powder metallurgy according to the present invention will be described.
In the press molding, a powdery lubricant may be mixed. Also, a lubricant can be applied or adhered to the mold. In any case, known lubricants such as metal soaps such as zinc stearate and amide waxes such as ethylenebisstearic acid amide can be suitably used as the lubricant. When the lubricant is mixed, the alloy steel powder mixed powder is preferably about 0.1 to 1.2 parts by mass with respect to 100 parts by mass.

加圧成形に際しては、400〜1000MPaの加圧力で行う必要がある。というのは、加圧力が400MPaに満たないと得られる成形体の密度が低くなり、焼結体の特性が低下するからであり、一方1000MPaを超えると金型の寿命が短くなり、経済的に不利になるからである。な お、加圧の際の温度は、常温(約20℃)〜約160℃の範囲とすることが好ましい。
また、焼結は、1100〜1300℃の温度域で行う必要がある。というのは、焼結温度が1100℃に満たないと焼結が進行しなくなり、焼結体の特性が低下するからであり、一方1300℃を超えると焼結炉の寿命が短くなり、経済的に不利になるからである。なお、焼結時間は10〜180分の範囲とすることが好ましい。
The pressure molding must be performed with a pressure of 400 to 1000 MPa. This is because if the applied pressure is less than 400 MPa, the density of the resulting molded body will be low and the properties of the sintered body will be reduced.On the other hand, if it exceeds 1000 MPa, the life of the mold will be shortened and economically. Because it becomes disadvantageous. The temperature at the time of pressurization is preferably in the range of room temperature (about 20 ° C.) to about 160 ° C.
Moreover, it is necessary to perform sintering in the temperature range of 1100-1300 degreeC. This is because if the sintering temperature is less than 1100 ° C, the sintering does not proceed and the characteristics of the sintered body deteriorate, whereas if it exceeds 1300 ° C, the life of the sintering furnace is shortened and economical. It is because it becomes disadvantageous. The sintering time is preferably in the range of 10 to 180 minutes.

得られた焼結体には必要に応じて浸炭焼入れ(ガス浸炭、真空浸炭)、光輝焼入れ、高周波焼入れおよび浸炭窒化処理等の強化処理を施すことができるが、強化処理を施さない場合でも、従来の焼結体(強化処理を施さないもの)に比べて強度および靭性が改善される。なお、各強化処理は常法に従って施せば良い。   The obtained sintered body can be subjected to tempering treatment such as carburizing and quenching (gas carburizing, vacuum carburizing), bright quenching, induction quenching and carbonitriding as required. Strength and toughness are improved as compared with conventional sintered bodies (those not subjected to strengthening treatment). In addition, what is necessary is just to give each reinforcement | strengthening process according to a conventional method.

上記の焼結を施した場合、鉄基粉末粒子間の焼結ネック部にはCr濃度が高い領域が形成されるが、この領域には、Nbなどの炭化物形成元素と共にCが存在するので、CrとNb等を含む炭化物が析出、分散することになる。気孔の周囲にかような炭化物が析出すると、焼結ネック部が強化されるので、強度のみならず、耐摩耗性に優れた組織が得られるのである。
図1に、本発明により得られた焼結体の焼結ネック部を含む焼結組織を模式で示す。図中、符号1が鉄基粉末、2が焼結ネック部である。
When the above sintering is performed, a region having a high Cr concentration is formed in the sintering neck portion between the iron-based powder particles, but in this region, C is present together with a carbide forming element such as Nb. Carbides including Cr and Nb are precipitated and dispersed. When such carbides are deposited around the pores, the sintered neck portion is strengthened, so that a structure excellent not only in strength but also in wear resistance can be obtained.
In FIG. 1, the sintered structure containing the sintering neck part of the sintered compact obtained by this invention is shown typically. In the figure, reference numeral 1 is an iron-based powder, and 2 is a sintered neck portion.

ここに、CrとNb等を含む炭化物としては、(Nb,Cr)C、(Nb,V,Cr)C、(Nb,Ti,Cr)Cおよび(Nb,Ti,V,Cr)Cが挙げられる。
また、かような炭化物は、焼結ネック部のCr濃化領域において、単位面積1μm2当たり1〜100個程度の割合で析出させることが好ましい。なお、Cr濃化領域とは、焼結ネック部の周辺10μm 程度の領域を意味する。
Here, examples of the carbide containing Cr and Nb include (Nb, Cr) C, (Nb, V, Cr) C, (Nb, Ti, Cr) C, and (Nb, Ti, V, Cr) C. It is done.
Moreover, it is preferable to deposit such carbides at a rate of about 1 to 100 per unit area of 1 μm 2 in the Cr concentrated region of the sintered neck portion. The Cr-enriched area means an area of about 10 μm around the sintered neck.

以下、実施例により、本発明をさらに詳細にするが、 本発明は、以下の例に何ら限定されるものではない。
実施例1
表1のNo.1〜15に示す合金元素を含む溶鋼を水アトマイズ法によって噴霧した後、露点:30℃の水素雰囲気中で熱処理(保持温度:950℃,保持時間:1h)し、鉄基粉末とした。この鉄基粉末に、Cr粉末を所定の比率で添加し、V型混合器で15分間混合したのち、真空中で熱処理(保持温度:1000℃,保持時間:1h)して、鉄基粉末の表面に所定量のCrを拡散付着させた粉末冶金用合金鋼粉を製造した。
ついで、これらの粉末冶金用合金鋼粉に対して、表1に示す量の黒鉛を添加し、さらに得られた合金鋼粉混合粉:100質量部に対しエチレンビスステアリン酸アミドを0.6質量部添加したのち、V型混合機で15分間混合した。その後、圧力:686MPaで加圧成形して長さ:55mm、幅:10mm、厚さ:10mmの成形体を作製した。
この成形体に焼結を施して、焼結体とした。この焼結は、N2−10%H2雰囲気中にて、焼結温度:1250℃,焼結時間:20分の条件で行った。
得られた焼結体を、引張試験用に平行部径:5mmの丸棒引張試験片に加工した。
また、耐摩耗試験用としては、焼結したままの形状のものを用いた。
それぞれの試験片を、カーボンポテンシャル0.8%でガス浸炭(保持温度:870℃,保持時間:60分)した後、焼入れ(60℃,油焼入れ)および焼戻し(180℃,60分)を行った。 これらの焼結体の引張強度TS(MPa)および耐摩耗性について調査した結果を、表1に併せて示す。
なお、耐摩耗試験は、大越式摩耗試験装置を用いて、下記の条件で行い、摩耗体積を測定し、それを摩耗量とした。
荷重:12.6kgf、摩擦速度:4.21m/s、摩擦距離:15000m
湿式:ATFオイル、1滴/s、相手材:SUF−2
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to the following examples at all.
Example 1
After spraying molten steel containing the alloy elements shown in Nos. 1 to 15 in Table 1 by the water atomization method, heat treatment was performed in a hydrogen atmosphere with a dew point of 30 ° C. (holding temperature: 950 ° C., holding time: 1 h). Powdered. To this iron-based powder, Cr powder was added at a predetermined ratio, mixed for 15 minutes with a V-type mixer, and then heat-treated in a vacuum (holding temperature: 1000 ° C., holding time: 1 h). An alloy steel powder for powder metallurgy having a predetermined amount of Cr diffused and adhered to the surface was produced.
Next, graphite in the amount shown in Table 1 is added to these alloy steel powders for powder metallurgy, and 0.6 parts by mass of ethylenebisstearic acid amide is added to 100 parts by mass of the obtained alloy steel powder mixed powder. After that, it was mixed for 15 minutes with a V-type mixer. Then, it pressure-molded with pressure: 686MPa, and produced the molded object of length: 55mm, width: 10mm, thickness: 10mm.
The molded body was sintered to obtain a sintered body. This sintering was performed in a N 2 -10% H 2 atmosphere under conditions of sintering temperature: 1250 ° C. and sintering time: 20 minutes.
The obtained sintered body was processed into a round bar tensile test piece having a parallel part diameter of 5 mm for a tensile test.
Moreover, the thing of the shape as sintered was used for an abrasion-resistant test.
Each test piece was subjected to gas carburization (retention temperature: 870 ° C., retention time: 60 minutes) at a carbon potential of 0.8%, followed by quenching (60 ° C., oil quenching) and tempering (180 ° C., 60 minutes). Table 1 also shows the results of investigations on the tensile strength TS (MPa) and the wear resistance of these sintered bodies.
The wear resistance test was performed using the Ogoshi type wear test apparatus under the following conditions, the wear volume was measured, and this was used as the wear amount.
Load: 12.6kgf, friction speed: 4.21m / s, friction distance: 15000m
Wet: ATF oil, 1 drop / s, mating material: SUF-2

Figure 2012126971
Figure 2012126971

表1に示したとおり、発明例と比較例の引張強度および耐摩耗性を比べると、発明例はいずれも引張強度: 1250MPa以上、耐摩耗性:摩耗量0.010mm3以下と高強度と耐摩耗性を両立できたのに対し、比較例はいずれも、発明例に比べると引張強度と耐摩耗性の少なくともいずれかが劣っていた。 As shown in Table 1, when comparing the tensile strength and wear resistance of the inventive example and the comparative example, the inventive example has high tensile strength: 1250 MPa or more, wear resistance: wear amount of 0.010 mm 3 or less, high strength and wear resistance In contrast, all of the comparative examples were inferior in tensile strength and wear resistance compared to the inventive examples.

1 鉄基粉末
2 焼結ネック部
1 Iron-based powder 2 Sintered neck

Claims (6)

0.02〜0.4質量%のNbを予合金化した鋼粉の表面に、0.05〜0.5質量%のCr含有粉末を拡散付着させてなる粉末冶金用合金鋼粉。   Alloy steel powder for powder metallurgy obtained by diffusing and adhering 0.05 to 0.5 mass% of Cr-containing powder to the surface of steel powder pre-alloyed with 0.02 to 0.4 mass% of Nb. 0.02〜0.4質量%のNbと、0.01〜0.4質量%のVおよび0.01〜0.4質量%のTiのうちから 選んだ一種または二種とを予合金化した鋼粉の表面に、0.05〜0.5質量%のCr含有粉末を拡散付着させてなる粉末冶金用合金鋼粉。   On the surface of the steel powder prealloyed with 0.02 to 0.4 mass% Nb, 0.01 to 0.4 mass% V or 0.01 to 0.4 mass% Ti or one selected from Ti, 0.05 to 0.5 mass% Alloy steel powder for powder metallurgy, formed by diffusion-adhering Cr-containing powder. 請求項1または2に記載の粉末冶金用合金鋼粉を、圧粉成形後、焼結して得た鉄基焼結材料であって、該焼結材料の気孔の周囲に少なくともNbとCr を含む炭化物を析出させてなる鉄基焼結材料。   An iron-based sintered material obtained by sintering the alloy steel powder for powder metallurgy according to claim 1 or 2 after compacting and comprising at least Nb and Cr around the pores of the sintered material. An iron-based sintered material obtained by precipitating carbide containing it. 前記少なくともNbとCrを含む炭化物が、(Nb,Cr)C、(Nb,V,Cr)C、(Nb,Ti,Cr )Cおよび(Nb,Ti,V,Cr)Cのいずれかである請求項3に記載の鉄基焼結材料。   The carbide containing at least Nb and Cr is any one of (Nb, Cr) C, (Nb, V, Cr) C, (Nb, Ti, Cr) C and (Nb, Ti, V, Cr) C. The iron-based sintered material according to claim 3. 請求項1または2に記載の粉末冶金用合金鋼粉を、0.1〜1.0質量%の炭素粉末と混合したのち、400〜1000MPaの加圧力で圧粉成形後、1100〜1300℃の温度で焼結し、得られる焼結材料の気孔の周囲に少なくともNbとCrを含む炭化物を析出させることを特徴とする鉄基焼結材料の製造方法。   The alloy steel powder for powder metallurgy according to claim 1 or 2 is mixed with 0.1 to 1.0% by mass of carbon powder, compacted with a pressure of 400 to 1000MPa, and then sintered at a temperature of 1100 to 1300 ° C. And a carbide containing at least Nb and Cr is precipitated around the pores of the obtained sintered material. 前記少なくともNbとCrを含む炭化物が、(Nb,Cr)C、(Nb,V,Cr)C、(Nb,Ti,Cr)Cおよび(Nb,Ti,V,Cr)Cのいずれかである請求項5に記載の鉄基焼結材料の製造方法。   The carbide containing at least Nb and Cr is any one of (Nb, Cr) C, (Nb, V, Cr) C, (Nb, Ti, Cr) C, and (Nb, Ti, V, Cr) C. A method for producing an iron-based sintered material according to claim 5.
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