JP2003003201A - Powder mixture for powder metallurgy - Google Patents
Powder mixture for powder metallurgyInfo
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- JP2003003201A JP2003003201A JP2001189028A JP2001189028A JP2003003201A JP 2003003201 A JP2003003201 A JP 2003003201A JP 2001189028 A JP2001189028 A JP 2001189028A JP 2001189028 A JP2001189028 A JP 2001189028A JP 2003003201 A JP2003003201 A JP 2003003201A
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- Prior art keywords
- powder
- metal
- mixed
- metallurgy
- stearate
- 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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- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、焼結部品、刷子等
に製造に用いる粉末冶金用混合粉に関し、特に固体潤滑
剤等として使用する防錆性に優れた焼結部品等の製造に
適した粉末冶金用混合粉に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder mixture for powder metallurgy used for manufacturing sintered parts, brushes, etc., and is particularly suitable for manufacturing sintered parts etc. which are used as solid lubricants and have excellent rust resistance. Mixed powder for powder metallurgy.
【０００２】[0002]
【従来の技術】一般に、焼結機械部品、焼結含油軸受、
金属黒鉛刷子等の用途に使用されている銅粉は、錆び易
く、一般にはベンゾトリアゾールなどの有機防錆剤を混
ぜて使用されている。しかし、これらの有機防錆剤は一
時的な防錆効果を有しているが、５００°Ｃ以上では分
解又は揮発するため、通常使用される７００°Ｃ以上の
焼結温度では無くなってしまう。したがって、焼結後は
防錆していない場合と同様の状態となり、非常に錆び易
くなるという問題がある。2. Description of the Related Art Generally, sintered machine parts, sintered oil-impregnated bearings,
Copper powder used for applications such as metal graphite brushes easily rusts, and is generally used by mixing with an organic rust inhibitor such as benzotriazole. However, although these organic rust preventives have a temporary rust preventive effect, they decompose or volatilize at a temperature of 500 ° C or higher, and therefore disappear at a sintering temperature of 700 ° C or higher, which is usually used. Therefore, there is a problem in that after sintering, the state is the same as that in the case where rust prevention is not performed, and it becomes very easy to rust.
【０００３】一方、焼結後の防錆性を得るために、微量
のビスマス（Ｂｉ）や鉛（Ｐｎ）の金属粉末を銅等の冶
金用粉末に混合したり、又はこれらの蒸気を焼結時のガ
スに混合して複合粉末焼結体とする提案がなされてい
る。しかし、これらは新たな工程を増やすこととなり、
製造工程が複雑になり、またそれだけ品質にばらつきを
生ずるという問題がある。またビスマスや鉛の金属粉末
を混合しても、小さな粒子が分散しているだけで均一に
分布しているとは言い難く、さらに金属インジウムは軟
らかい金属であるために金属粉末とすることが困難であ
った。On the other hand, in order to obtain rust prevention after sintering, a small amount of metal powder of bismuth (Bi) or lead (Pn) is mixed with metallurgical powder such as copper, or the vapor of these is sintered. Proposals have been made to prepare a composite powder sintered body by mixing with the gas at the time. However, these will add new processes,
There is a problem that the manufacturing process becomes complicated and the quality varies accordingly. Even if metal powders of bismuth and lead are mixed, it is difficult to say that they are uniformly distributed because only small particles are dispersed. Furthermore, since indium metal is a soft metal, it is difficult to make metal powders. Met.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、従来の工程
を殆ど変更せずに、簡単に防錆効果を高めることができ
る粉末冶金用混合粉を得ることを課題とする。SUMMARY OF THE INVENTION It is an object of the present invention to obtain a powdered metallurgical mixture whose rust-preventing effect can be easily enhanced without changing the conventional steps.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記問題
点を解決するために種々検討した結果、特定の添加材を
銅粉の成形時に混合することにより、成形時の潤滑剤と
しての効果がありかつ特定の金属成分が均一に分散する
ことで、焼結後の部品においても著しく防錆効果を高め
ることができるとの知見を得た。本発明はこの知見に基
づいて、
１．銅粉などの粉末冶金用金属粉末に低温揮発性金属の
金属石鹸を添加したことを特徴とする粉末冶金用混合粉
２．低温揮発性金属がビスマス、インジウム又は鉛であ
ることを特徴とする上記１記載の粉末冶金用混合粉
３．金属石鹸がステアリン酸ビスマスであることを特徴
とする上記１記載の粉末冶金用混合粉
を提供する。As a result of various studies to solve the above-mentioned problems, the present inventors have found that a specific additive is mixed at the time of molding of copper powder to obtain a lubricant as a molding agent. It was found that the effect and the specific metal component are uniformly dispersed to remarkably enhance the rust preventive effect even in the sintered part. The present invention is based on this finding. 1. A mixed powder for powder metallurgy, characterized in that a metal soap for low-temperature volatile metal is added to a metal powder for powder metallurgy such as copper powder. 2. The low temperature volatile metal is bismuth, indium or lead, and the mixed powder for powder metallurgy according to the above item 1. There is provided a powder mixture for powder metallurgy according to the above 1, wherein the metal soap is bismuth stearate.
【０００６】[0006]
【発明の実施の形態】本発明をなすに当たって、粉末を
成形する際に潤滑剤として微量添加するステアリン酸亜
鉛に着目した。しかし、このステアリン酸亜鉛のみでは
防錆効果を高めることはできないことは、すでに認識し
ていたことである。 上記の通り、このステアリン酸亜
鉛は専ら成形する際の潤滑剤として使用されるものであ
るが、このステアリン酸亜鉛と同等の潤滑機能を持つと
同時に、該ステアリン酸亜鉛にはない防錆効果を高め得
る材料を検討した。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, attention was paid to zinc stearate, which is added in a trace amount as a lubricant when molding powder. However, it has already been recognized that this zinc stearate alone cannot enhance the anticorrosion effect. As described above, this zinc stearate is used exclusively as a lubricant when molding, but it has a lubricating function equivalent to that of this zinc stearate, and at the same time, has an anticorrosive effect not found in the zinc stearate. Considered materials that can be improved.
【０００７】ここで、得られたのがステアリン酸亜鉛と
同等の成形用潤滑剤としての機能を持ち、かつ焼結後に
おいても該ステアリン酸亜鉛にはない防錆効果を高める
ことができる低温揮発性金属の金属石鹸を粉末冶金用粉
末に添加することである。これによって、従来の焼結体
製造の工程を変更することなく、焼結体の防錆効果を飛
躍的に高めることが可能となった。低温揮発性金属とし
てはビスマス、インジウム又は鉛を使用することができ
る。特に、ステアリン酸ビスマスの金属石鹸が非常に優
れた防錆効果を得ることができる。[0007] Here, what was obtained is a low-temperature volatilization which has the same function as a molding lubricant as zinc stearate and which can enhance the rust-preventing effect which zinc stearate does not have even after sintering. The addition of a metallic soap of a positive metal to the powder for powder metallurgy. As a result, it has become possible to dramatically improve the rust preventive effect of the sintered body without changing the conventional manufacturing process of the sintered body. Bismuth, indium or lead can be used as the low temperature volatile metal. In particular, the metal soap of bismuth stearate can obtain a very excellent anticorrosion effect.
【０００８】これらの金属石鹸は、銅等の粉末冶金用金
属粉末１００重量部に対して、０．１〜２．０重量部を
添加するのが望ましい。しかし、焼結体の種類に応じて
この添加量を変えることができ、必ずしも上記添加量に
制限されなくても良い。すなわち、目的とする焼結体の
特性を維持できる範囲において、任意に設定できる。ま
た、添加する粉末冶金用粉末は必ずしも銅に制限され
ず、他の金属粉に銅をコーティングした複合銅粉やその
他の金属粉にも防錆効果を高めるために同様に適用でき
る。It is desirable to add 0.1 to 2.0 parts by weight of these metal soaps to 100 parts by weight of metal powder for powder metallurgy such as copper. However, the addition amount can be changed according to the type of the sintered body, and the addition amount is not necessarily limited to the above addition amount. That is, it can be arbitrarily set within a range in which the desired characteristics of the sintered body can be maintained. Further, the powder for powder metallurgy to be added is not necessarily limited to copper, and the same can be applied to composite copper powder obtained by coating other metal powder with copper or other metal powder in order to enhance the rust preventive effect.
【０００９】[0009]
【実施例及び比較例】次に、本発明の実施例について説
明する。なお、本実施例はあくまで１例であり、この例
に制限されるものではない。すなわち、本発明の技術思
想の範囲内で、実施例以外の態様あるいは変形を全て包
含するものである。Examples and Comparative Examples Next, examples of the present invention will be described. It should be noted that this embodiment is merely an example, and the present invention is not limited to this example. That is, it includes all aspects or modifications other than the examples within the scope of the technical idea of the present invention.
【００１０】（実施例１）実験室で合成したステアリン
酸ビスマス（Ｂｉ含有量１９．１重量％）を細かく粉砕
し、篩いを通して２５０メッシュ以下の白色微粉を得
た。銅粉＃３４−２０（日鉱マテリアルズ製）１００重
量部に対して前記ステアリン酸ビスマスを０．５重量部
の比で混合した。この混合粉を成形圧１ｔ／ｃｍ２、
１．５ｔ／ｃｍ２、２ｔ／ｃｍ２、３ｔ／ｃｍ２で約１
１．３φ×１１．３ｍｍＨの試験片に成形した。成形性
を判断するために、各成形体の成形密度と成形圧力の関
係を図１及び図２に示す。さらに、成形圧２ｔ／ｃｍ２
で約１１．３φ×１１．３ｍｍＨの試験片に成形した成
形体をメッシュベルト炉にて焼結温度７８０°Ｃ、焼結
時間３０ｍｉｎ、水素ガス雰囲気下で焼結した。この焼
結体を恒温恒湿槽内にセットし、温度８０°Ｃ、湿度８
０％雰囲気で１６８時間放置し、耐湿酸化試験を実施し
た。この結果を表１に示す。(Example 1) Bismuth stearate (Bi content 19.1% by weight) synthesized in a laboratory was finely pulverized and passed through a sieve to obtain a white fine powder having a size of 250 mesh or less. The bismuth stearate was mixed at a ratio of 0.5 parts by weight to 100 parts by weight of copper powder # 34-20 (manufactured by Nikko Materials). This mixed powder was molded at a molding pressure of 1 t / cm 2 ,
About 1 at 1.5 t / cm 2 , 2 t / cm 2 , and 3 t / cm 2.
It was molded into a test piece of 1.3φ × 11.3 mmH. The relationship between the molding density and the molding pressure of each molded product is shown in FIGS. 1 and 2 in order to judge the moldability. Further, the molding pressure is 2 t / cm 2
The molded body formed into a test piece of about 11.3φ × 11.3 mmH was sintered in a mesh belt furnace at a sintering temperature of 780 ° C. for a sintering time of 30 min in a hydrogen gas atmosphere. This sintered body was set in a constant temperature and humidity chamber, and the temperature was 80 ° C and the humidity was 8
The sample was allowed to stand in a 0% atmosphere for 168 hours to carry out a moisture oxidation resistance test. The results are shown in Table 1.
【００１１】（実施例２）実験室で合成したステアリン
酸インジウム（Ｉｎ含有量５．４重量％）を細かく粉砕
し、篩いを通して２５０メッシュ以下の白色微粉を得
た。銅粉＃３４−２０（日鉱マテリアルズ製）１００重
量部に対して前記ステアリン酸インジウムを０．５重量
部の比で混合した。この混合粉を成形圧１ｔ／ｃｍ ２、
１．５ｔ／ｃｍ２、２ｔ／ｃｍ２、３ｔ／ｃｍ２で約１
１．３φ×１１．３ｍｍＨの試験片に成形した。この試
験片について、実施例１と同条件で混合粉の成形性の評
価を行い、さらに成形圧２ｔ／ｃｍ２で約１１．３φ×
１１．３ｍｍＨの試験片に成形した成形体をメッシュベ
ルト炉にて焼結温度７８０°Ｃ、焼結時間３０ｍｉｎ、
水素ガス雰囲気下で焼結して耐酸化性試験を実施した。
この結果を同様に、図１と表１に示す。(Example 2) Stearin synthesized in the laboratory
Fine grinding of indium acid (In content 5.4% by weight)
And pass through a sieve to obtain a white fine powder of 250 mesh or less.
It was Copper powder # 34-20 (manufactured by Nikko Materials) 100 weight
0.5 parts by weight of the above indium stearate per part by weight
Mixed in parts ratio. Forming pressure of this mixed powder is 1 t / cm Two,
1.5t / cmTwo2t / cmTwo3t / cmTwoAbout 1
It was molded into a test piece of 1.3φ × 11.3 mmH. This trial
Evaluation of the moldability of the mixed powder for the test piece under the same conditions as in Example 1.
Value and further molding pressure 2t / cmTwoAbout 11.3φ ×
A molded body molded into a 11.3 mmH test piece was
Sintering temperature 780 ° C, sintering time 30min,
The oxidation resistance test was carried out by sintering in a hydrogen gas atmosphere.
The results are similarly shown in FIG. 1 and Table 1.
【００１２】[0012]
【表１】 [Table 1]
【００１３】（比較例１）銅粉＃３４−２０のみを使用
して、実施例１と同様にして銅粉＃３４−２０の成形性
の評価と耐酸化性試験を実施した。この結果を同様に、
図１と表１に示す。Comparative Example 1 The copper powder # 34-20 was evaluated for moldability and subjected to an oxidation resistance test in the same manner as in Example 1 using only the copper powder # 34-20. This result is likewise
It is shown in FIG. 1 and Table 1.
【００１４】（比較例２）ステアリン酸ビスマスの替わ
りに、通常のステアリン酸亜鉛ＳＺ−２０００（堺化学
工業製）を使用して、実施例１と同様に銅粉＃３４−２
０１００重量部に対して前記ステアリン酸亜鉛を０．５
重量部の比で混合した。この混合粉を成形圧１ｔ／ｃｍ
２、１．５ｔ／ｃｍ２、２ｔ／ｃｍ２、３ｔ／ｃｍ２で
約１１．３φ×１１．３ｍｍＨの試験片に成形した。こ
の試験片について実施例１と同条件で混合粉の成形性の
評価を行い、さらに成形圧２ｔ／ｃｍ２で約１１．３φ
×１１．３ｍｍＨの試験片に成形した成形体をメッシュ
ベルト炉にて焼結温度７８０°Ｃ、焼結時間３０ｍｉ
ｎ、水素ガス雰囲気下で焼結して耐酸化性試験を実施し
た。この結果を同様に、図２と表１に示す。Comparative Example 2 Instead of bismuth stearate, ordinary zinc stearate SZ-2000 (manufactured by Sakai Chemical Industry Co., Ltd.) was used, and copper powder # 34-2 was used in the same manner as in Example 1.
0100 parts by weight of the above zinc stearate 0.5
Mixed in parts by weight ratio. Forming pressure of this mixed powder is 1 t / cm
2 , 1.5 t / cm 2 , 2 t / cm 2 , and 3 t / cm 2 were molded into a test piece of about 11.3φ × 11.3 mmH. With respect to this test piece, the moldability of the mixed powder was evaluated under the same conditions as in Example 1, and further about 11.3φ at a molding pressure of 2 t / cm 2.
A compact molded into a test piece of 11.3 mmH was sintered in a mesh belt furnace at a sintering temperature of 780 ° C and a sintering time of 30 mi.
n, sintering was performed in a hydrogen gas atmosphere to carry out an oxidation resistance test. The results are also shown in FIG. 2 and Table 1.
【００１５】（比較例３）ステアリン酸ビスマスの替わ
りに、通常のステアリン酸亜鉛ＺＮＳ−１０００（旭電
化工業製）を使用して、実施例１と同様に銅粉＃３４−
２０１００重量部に対して前記ステアリン酸亜鉛を０．
５重量部の比で混合した。この混合粉を成形圧１ｔ／ｃ
ｍ２、１．５ｔ／ｃｍ２、２ｔ／ｃｍ２、３ｔ／ｃｍ２
で約１１．３φ×１１．３ｍｍＨの試験片に成形した。
この試験片について実施例１と同条件で混合粉の成形性
の評価を行い、さらに成形圧２ｔ／ｃｍ２で約１１．３
φ×１１．３ｍｍＨの試験片に成形した成形体をメッシ
ュベルト炉にて焼結温度７８０°Ｃ、焼結時間３０ｍｉ
ｎ、水素ガス雰囲気下で焼結して耐酸化性試験を実施し
た。この結果を同様に、図２と表１に示す。Comparative Example 3 Instead of bismuth stearate, ordinary zinc stearate ZNS-1000 (manufactured by Asahi Denka Co., Ltd.) was used, and copper powder # 34- was used in the same manner as in Example 1.
20100 parts by weight of the zinc stearate was added in an amount of 0.
Mixed in a ratio of 5 parts by weight. This mixed powder is molded at a molding pressure of 1 t / c.
m 2 , 1.5 t / cm 2 , 2 t / cm 2 , 3 t / cm 2.
Was molded into a test piece of about 11.3φ × 11.3 mmH.
With respect to this test piece, the moldability of the mixed powder was evaluated under the same conditions as in Example 1, and further about 11.3 at a molding pressure of 2 t / cm 2.
A compact molded into a φ × 11.3 mmH test piece is sintered in a mesh belt furnace at a sintering temperature of 780 ° C. and a sintering time of 30 mi.
n, sintering was performed in a hydrogen gas atmosphere to carry out an oxidation resistance test. The results are also shown in FIG. 2 and Table 1.
【００１６】図１及び図２から明らかなように、圧縮性
の評価結果から、潤滑剤を添加しなかった比較例１以外
は、ほぼ同一の圧粉密度を得ている。これはステアリン
酸ビスマスを添加した実施例１やステアリン酸インジウ
ムを添加した実施例２は、従来のステアリン酸亜鉛潤滑
剤を添加した比較例２及び３と同等の潤滑性、成形性を
有することが分かる。As is clear from FIGS. 1 and 2, from the evaluation results of the compressibility, except for Comparative Example 1 in which the lubricant was not added, almost the same green compact density was obtained. This is because Example 1 containing bismuth stearate and Example 2 containing indium stearate have the same lubricity and moldability as Comparative Examples 2 and 3 containing the conventional zinc stearate lubricant. I understand.
【００１７】次に、表１から明らかなように、銅粉に潤
滑剤を添加していない比較例１は焼結後の耐湿、耐酸化
性試験では、２４時間後に変色を生じており、７２時間
後では激しく変色している。これはステアリン酸亜鉛の
潤滑剤を添加した比較例２及び比較例３においても同様
であり、ステアリン酸亜鉛の添加は耐湿、耐酸化性が全
くないことが分かる。Next, as is clear from Table 1, in Comparative Example 1 in which the lubricant was not added to the copper powder, discoloration occurred after 24 hours in the moisture resistance and oxidation resistance test after sintering. The color has changed drastically after hours. This is the same in Comparative Examples 2 and 3 in which a zinc stearate lubricant was added, and it can be seen that the addition of zinc stearate has no humidity resistance and oxidation resistance.
【００１８】これらに対し、ステアリン酸インジウムを
添加した実施例２では、２４時間後の耐湿、耐酸化性試
験ではわずかに変色する程度で、耐湿、耐酸化性がある
ことが分かる。インジウムは金属として低融点で柔らか
いので、微細な金属粉末に加工し難いが、ステアリン酸
インジウムとすることにより微細粉末とすることが容易
となり、銅粉への添加混合が容易となる利点がある。On the other hand, in Example 2 in which indium stearate was added, it was found that in the humidity resistance and oxidation resistance test after 24 hours, there was a slight discoloration, and there was humidity resistance and oxidation resistance. Since indium is a metal having a low melting point and is soft, it is difficult to process it into a fine metal powder. However, when indium stearate is used, it becomes easy to obtain a fine powder, and there is an advantage that it can be easily added to and mixed with copper powder.
【００１９】さらに、表１に示す通り本実施例１のステ
アリン酸ビスマスを添加した銅粉焼結体は、２４時間後
では変色は全く認められず、７２時間後さらには１６８
時間でもわずかに変色する程度であり、優れた耐湿耐酸
化性を示した。以上から、ステアリン酸ビスマスを添加
した銅粉焼結体は最も優れた耐湿耐酸化性を有すること
が分かる。なお、実施例には示していないが、ステアリ
ン酸鉛も実施例１のステアリン酸ビスマスと同様に耐湿
耐酸化性を示すことが分かった。Further, as shown in Table 1, the copper powder sintered body to which bismuth stearate of Example 1 was added did not show any discoloration after 24 hours, and further after 168 hours, 168.
It showed only a slight color change with time, and showed excellent resistance to moisture and oxidation. From the above, it is understood that the copper powder sintered body to which bismuth stearate is added has the best moisture resistance and oxidation resistance. Although not shown in the examples, it was found that lead stearate also showed resistance to moisture and oxidation similarly to the bismuth stearate of Example 1.
【００２０】[0020]
【発明の効果】以上に示す通り、銅粉などの粉末冶金用
金属粉末に低温揮発性金属の金属石鹸を添加し粉末冶金
用混合粉とすることにより、従来の焼結体製造の工程を
変更することなく、焼結機械部品、焼結含油軸受、金属
黒鉛刷子などの焼結体の防錆効果を飛躍的に高めること
が可能となった。As described above, the conventional process for producing a sintered body is changed by adding a metal soap of a low temperature volatile metal to a metal powder for powder metallurgy such as copper powder to obtain a mixed powder for powder metallurgy. Without doing so, it has become possible to dramatically improve the rust prevention effect of sintered bodies such as sintered machine parts, sintered oil-impregnated bearings, and metal graphite brushes.
【図１】実施例１、実施例２及び比較例１の各成形体の
成形密度と成形圧力の関係を示す図である。FIG. 1 is a diagram showing a relationship between a molding density and a molding pressure of each molded body of Example 1, Example 2 and Comparative Example 1.
【図２】実施例１、比較例２及び比較例３の各成形体の
成形密度と成形圧力の関係を示す図である。FIG. 2 is a diagram showing a relationship between a molding density and a molding pressure of each molded body of Example 1, Comparative Example 2 and Comparative Example 3.
Claims (3)
発性金属の金属石鹸を添加したことを特徴とする粉末冶
金用混合粉。1. A mixed powder for powder metallurgy, comprising a metal soap for powder metallurgy such as copper powder, to which metal soap of a low temperature volatile metal is added.
又は鉛であることを特徴とする請求項１記載の粉末冶金
用混合粉。2. The mixed powder for powder metallurgy according to claim 1, wherein the low temperature volatile metal is bismuth, indium or lead.
ことを特徴とする請求項１記載の粉末冶金用混合粉。3. The mixed powder for powder metallurgy according to claim 1, wherein the metal soap is bismuth stearate.
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| JP2001189028A JP3641222B2 (en) | 2001-06-22 | 2001-06-22 | Mixed powder for powder metallurgy |
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|---|---|---|---|
| JP2001189028A JP3641222B2 (en) | 2001-06-22 | 2001-06-22 | Mixed powder for powder metallurgy |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004024375A1 (en) * | 2002-09-10 | 2004-03-25 | Nikko Materials Co., Ltd. | Iron-based sintered compact and method for production thereof |
| WO2004024372A1 (en) * | 2002-09-10 | 2004-03-25 | Nikko Materials Co., Ltd. | Metal powder for powder metallurgy and iron-based sintered compact |
| US7666245B2 (en) | 2004-08-30 | 2010-02-23 | Nippon Mining & Metals Co., Ltd. | Metallic powder for powder metallurgy whose main component is iron and iron-based sintered body |
| US7691172B2 (en) | 2004-08-30 | 2010-04-06 | Nippon Mining & Metals Co., Ltd. | Metallic powder for powder metallurgy whose main component is iron and iron-based sintered body |
-
2001
- 2001-06-22 JP JP2001189028A patent/JP3641222B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004024375A1 (en) * | 2002-09-10 | 2004-03-25 | Nikko Materials Co., Ltd. | Iron-based sintered compact and method for production thereof |
| WO2004024372A1 (en) * | 2002-09-10 | 2004-03-25 | Nikko Materials Co., Ltd. | Metal powder for powder metallurgy and iron-based sintered compact |
| US7217310B2 (en) | 2002-09-10 | 2007-05-15 | Nippon Mining & Metals Co., Ltd. | Metal powder for powder metallurgy and iron-based sintered compact |
| US7347969B2 (en) | 2002-09-10 | 2008-03-25 | Nippon Mining & Metals Co., Ltd | Iron-based sintered compact and method for production thereof |
| US7727639B2 (en) | 2002-09-10 | 2010-06-01 | Nippon Mining & Metals Co., Ltd | Iron-based sintered compact and method for production thereof |
| US7666245B2 (en) | 2004-08-30 | 2010-02-23 | Nippon Mining & Metals Co., Ltd. | Metallic powder for powder metallurgy whose main component is iron and iron-based sintered body |
| US7691172B2 (en) | 2004-08-30 | 2010-04-06 | Nippon Mining & Metals Co., Ltd. | Metallic powder for powder metallurgy whose main component is iron and iron-based sintered body |
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