JPH02145702A - High strength alloy steel powder for powder metallurgy - Google Patents
High strength alloy steel powder for powder metallurgyInfo
- Publication number
- JPH02145702A JPH02145702A JP63299344A JP29934488A JPH02145702A JP H02145702 A JPH02145702 A JP H02145702A JP 63299344 A JP63299344 A JP 63299344A JP 29934488 A JP29934488 A JP 29934488A JP H02145702 A JPH02145702 A JP H02145702A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- alloy
- iron powder
- strength
- fine
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 93
- 229910000851 Alloy steel Inorganic materials 0.000 title claims abstract description 19
- 238000004663 powder metallurgy Methods 0.000 title claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 238000009792 diffusion process Methods 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 50
- 238000000034 method Methods 0.000 abstract description 23
- 238000005245 sintering Methods 0.000 abstract description 14
- 229910018054 Ni-Cu Inorganic materials 0.000 abstract description 7
- 229910018481 Ni—Cu Inorganic materials 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 229910052748 manganese Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 229910003296 Ni-Mo Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910001182 Mo alloy Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 38
- 238000005275 alloying Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 13
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009692 water atomization Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、例えば歯車、軸受部品等各種の焼結機械部品
の製造に使用される高圧縮性、高強度の粉末冶金用合金
鋼粉に関する。なお、本発明の合金鋼粉は、所望形状に
圧縮成形された後、焼結（合金粉末同士の接合）され、
しかる後ＨＩＰ（熱間静水圧成形）等で各種部品に加工
される。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an alloy steel powder for powder metallurgy with high compressibility and high strength used for manufacturing various sintered machine parts such as gears and bearing parts. . The alloyed steel powder of the present invention is compression-molded into a desired shape and then sintered (bonding of the alloyed powders).
After that, it is processed into various parts by HIP (hot isostatic pressing) or the like.
近年、焼結部品の高強度化の９請がますます高まってお
り、この７請に対して合金化、高密度化等の手法により
、種々の高強度焼結材が開発されている。In recent years, there has been an increasing demand for high strength sintered parts, and various high strength sintered materials have been developed using techniques such as alloying and densification.
この高強度焼結材を得る手法の１つとして、純鉄粉を主
原料とし、これにＮｉ 、Ｃｕ 、Ｈａ等の合金用単体
元素微粉末を混合し、焼結時に合金元素を固溶させる、
いわゆるプレミックス法がある。One method for obtaining this high-strength sintered material is to use pure iron powder as the main raw material, mix it with fine powder of single elements for alloying such as Ni, Cu, Ha, etc., and dissolve the alloying elements as a solid solution during sintering. ,
There is a so-called premix method.
しかし、このプレミックス法ではプレス成形時に、鉄粉
と合金用微粉末とが比重差によって分離、偏析したり、
焼結中に合金用微粉末の拡散が不十分であったりして組
織が不均一化し、その結果、強度や寸法のバラツキが生
じるといった問題がある。However, with this premix method, during press forming, iron powder and fine alloy powder may separate and segregate due to the difference in specific gravity.
There is a problem in that during sintering, the fine powder for alloying is not sufficiently diffused, and the structure becomes non-uniform, resulting in variations in strength and dimensions.
また他の手法として、アトマイズ法の発達により、上記
Ｎｉ、Ｃｕ、Ｍｏ等の合金元素をＦｅ中に固溶させた合
金鋼粉が製造されるようになり、この合金鋼粉を用いる
、いわゆるプレアロイ法が提案されている。この合金鋼
粉の場合、ＭＪ織の不均−化の問題は解消できるものの
、粒子の硬度が高くなるため圧縮性が低下し、従って高
密度の焼結材が得られず、十分な強度が得られない。As another method, with the development of the atomization method, it has become possible to produce alloy steel powder in which alloying elements such as Ni, Cu, Mo, etc. are dissolved in Fe. A law is proposed. In the case of this alloy steel powder, although the problem of unevenness in the MJ weave can be solved, the hardness of the particles increases and the compressibility decreases, so a high-density sintered material cannot be obtained and sufficient strength is not obtained. I can't get it.
そこで上記問題点を解消して高密度、高強度の焼結材料
を得る他の手法として、従来例えば特公昭４５−９６４
９号公報に記載されているように、純鉄粉にＮｌ 、
Ｃｕ 、 Ｍｏ等の単体元素の微粉末を部分的に拡散
付着させた、いわゆる部分拡散合金鋼粉がある（第２図
参照）、この公報記載の手法による鋼粉は、圧縮性は純
鉄粉と同等であり、かつ高い焼結体強度を有している。Therefore, as another method for solving the above problems and obtaining a high-density, high-strength sintered material, for example, Japanese Patent Publication No. 45-964
As described in Publication No. 9, pure iron powder contains Nl,
There is a so-called partially diffused alloy steel powder in which fine powders of simple elements such as Cu and Mo are partially diffused and attached (see Figure 2).The steel powder produced by the method described in this publication has a compressibility comparable to that of pure iron powder , and has high sintered body strength.
しかしながら上記公報記載の手法により、例えば６〜ｌ
ｏｗｔ％Ｎｉを含有するような高Ｎｉ合金鋼粉を製造す
る場合、この合金用元素の融点が高く、また鉄粉中への
拡散速度が遅いことから、未拡散の合金用元素が多く残
り、十分な強度が得られない、また十分に拡散させるた
めには高温で長時間の焼結が必要となり、コスト高とな
る問題点がある。However, by the method described in the above publication, for example, 6 to 1
When producing high Ni alloy steel powder containing owt%Ni, since the melting point of this alloying element is high and the rate of diffusion into the iron powder is slow, a large amount of undiffused alloying element remains. There are problems in that sufficient strength cannot be obtained, and sintering at high temperatures and for a long time is required for sufficient diffusion, resulting in high costs.
そこで本発明者等は、上記問題点を解消できる粉末冶金
用高強度合金鋼粉として、高純度純鉄粉に、Ｎｉ 、Ｃ
ｕ 、Ｍｏの内２種類以上の元素を予め合金化した合金
微粉末を拡散付着させたものを開発している（特願昭６
２−１３６９３４号参照）。Therefore, the present inventors have developed a high-strength alloy steel powder for powder metallurgy that can solve the above problems by adding Ni and C to high-purity pure iron powder.
We have developed a product in which fine alloy powder made by pre-alloying two or more elements of u and Mo is diffused and adhered (patent application filed in 1983).
2-136934).
上記開発に係る合金鋼粉は、第１図に示すように、純鉄
粉にＮｔ−Ｃｕ粉末、Ｎｔ−Ｍｏ粉末、あるいはＮｉ−
Ｃｕ−Ｍｏ粉末等の何れかが拡散付着しているものであ
る。なお、この合金鋼粉は、上記合金微粉末の他に上記
元素の単体微粉末が拡散付着していても良い、ここで拡
散付着（ディフェージョンボンディング）とは、上記合
金微粉末が完全に固溶しているのではなく、該合金微粉
末の例えばＣｕ成分が鉄粉中に拡散し、両者の界面では
一部が合金化し、この状態で付着していることを言う。As shown in Fig. 1, the developed alloy steel powder includes pure iron powder, Nt-Cu powder, Nt-Mo powder, or Ni-
Either Cu-Mo powder or the like is diffused and adhered thereto. In addition to the above-mentioned alloy fine powder, this alloy steel powder may also have a single fine powder of the above elements diffused and adhered thereto. Here, diffusion bonding means that the above-mentioned alloy fine powder is completely bonded. Rather than being in a solid solution, for example, the Cu component of the alloy fine powder is diffused into the iron powder, and at the interface between the two, a portion is alloyed and adhered in this state.
上記開発に係る合金鋼粉では、Ｎｉ、Ｃｕ、ＭＯの合金
微粉末を拡散付着させるようにしたので、これらの単体
元素の微粉末の場合に比較して融点を低下させることが
でき、高温長時間焼結を要することなく、短時間で十分
に拡散させることができ、焼結強度を向上できる。In the alloy steel powder developed above, fine alloy powders of Ni, Cu, and MO are diffused and adhered, so the melting point can be lowered compared to the case of fine powders of these single elements, and it can be used for long periods at high temperatures. It can be sufficiently diffused in a short time without requiring time-consuming sintering, and the sintering strength can be improved.
ところがその後の実験研究により、上述の合金微粉末を
採用しても、その母粉に対する成分割合の如何によって
は上述の効果が十分に現れない、あるいは逆に製品の寸
法変化のばらつきが大きくなる等の問題が生じる場合が
あることが判明した。However, subsequent experimental research has shown that even if the above-mentioned alloy fine powder is used, the above-mentioned effects may not be fully manifested depending on the proportion of the components in the mother powder, or conversely, the variation in dimensional changes of the product may increase. It has been found that problems may occur.
そこで本発明は、上記状況に鑑みてなされたもので、添
加元素が最適成分範囲になるように合金用微粉末を拡散
付着させることにより、確実十分な拡散を実現し、焼結
体強度の向上及び寸法変化率のばらつきの抑制が図れる
粉末冶金用高強度合金鋼粉を提供することを目的として
いる。Therefore, the present invention was made in view of the above situation, and by diffusing and adhering the fine powder for alloying so that the added elements fall within the optimum range, it is possible to ensure sufficient diffusion and improve the strength of the sintered body. Another object of the present invention is to provide a high-strength alloy steel powder for powder metallurgy that can suppress variations in dimensional change rate.
本発明は、Ｃ： ０．０１ｗｔ％以下、Ｓ ｉ ：
０．０２ｗｔ％以下、Ｍｎ ：０．１０ｗｔ％以下、
Ｐ ： ０．０１ｗｔ％以下、Ｓ ： ０．０１０ ｗ
ｔ％ｔ％以下 ： ０．１５ｗｔ％以下で残部鉄及び不
可避的不純物からなる高純度純鉄粉に、Ｎｉ、Ｃｕ、Ｍ
ｏのうち２種類以上の元素を予め合金化した合金微粉末
を、上記純鉄粉に対してＮｉ：６〜８ｗｔ％、 Ｃｕ：
Ｏ〜２ｉｉｔ％、Ｍｏ ：０．５〜１゜Ｏｗｔ％Ｍｏ
になるように拡散付着させることを特徴とする焼結合金
用高強度合金鋼粉である。In the present invention, C: 0.01 wt% or less, S i :
0.02wt% or less, Mn: 0.10wt% or less,
P: 0.01wt% or less, S: 0.010w
t% or less: 0.15wt% or less of high-purity pure iron powder consisting of the balance iron and unavoidable impurities, Ni, Cu, M
Fine alloy powder prepared by pre-alloying two or more elements of o is added to the above pure iron powder with Ni: 6 to 8 wt% and Cu:
O~2iit%, Mo: 0.5~1°Owt%Mo
This is a high-strength alloy steel powder for sintered alloys, which is characterized by being diffused and adhered so that it becomes sintered.
ここで本発明における各構成要件の限定理由について説
明する。Here, the reason for limiting each component in the present invention will be explained.
（１）母籾である純鉄粉の組成を、Ｃ： ０．０１ｗｔ
％以下、Ｓ ｉ １０．０２ｗｔ％以下、Ｍｎ ：
０．１０ｗ４ｔ％以下、Ｐ ：０．０１ｗｔ％以下、
Ｓ ： ０．０１０ ｗｔ％ｔ％以下：０゜１５−ｔ％
以下で残部鉄及び不可避的不純物からなる、として許容
限界を定めたのは優れた圧縮性を確保するためである。(1) The composition of pure iron powder, which is the mother rice, is C: 0.01wt.
% or less, Si 10.02wt% or less, Mn:
0.10w4t% or less, P: 0.01wt% or less,
S: 0.010 wt% or less: 0°15-t%
The reason why the allowable limit is defined below as consisting of the remainder iron and unavoidable impurities is to ensure excellent compressibility.
Ｓｉ、Ｍｎ＋純鉄粉の製造過程において溶鋼の脱酸を行
うために、少量のＳｔあるいはＭｎを添加するが、これ
らの０との親和力の強い元素は、水アトマイズ時に酸化
され、酸化介在物となって鉄粉中に残存して圧縮性を阻
害する。従ってＭｎ、Ｓｉの添加量が多くなると酸化介
在物も多くなつり、次の還元行程においてもこれらの酸
化介在物は還元されずに残存して圧縮性を低下させるこ
とから、Ｓｌは０．０２ｗｔ％以下、Ｍｎは０．１ ｗ
ｔ％以下と極力少なくすることが望ましい。A small amount of St or Mn is added to deoxidize the molten steel in the process of producing Si, Mn + pure iron powder, but these elements, which have a strong affinity for 0, are oxidized during water atomization and form oxidized inclusions. It remains in the iron powder and inhibits compressibility. Therefore, as the amount of Mn and Si added increases, the number of oxidized inclusions increases, and even in the next reduction process, these oxidized inclusions remain without being reduced and reduce compressibility, so Sl is 0.02wt. % or less, Mn is 0.1 w
It is desirable to reduce it to t% or less as much as possible.
ｐ、ｓ： 溶鋼の精練時にＰ、 Ｓが残存すると鉄
粉粒子を硬化させ、圧縮性を低下させる。そしてこのＰ
、Ｓが多いと、還元処理後においても粒子が軟らか（な
らない、この鉄粉粒子の硬化を防止するため、Ｐ、Ｓ共
に０．０１０ ｗｔ％以下とした。p, s: If P and S remain during smelting of molten steel, they harden iron powder particles and reduce compressibility. And this P
If the iron powder particles contain a large amount of S, the particles will remain soft even after reduction treatment.In order to prevent the iron powder particles from hardening, the contents of both P and S were set to 0.010 wt% or less.
Ｃ，Ｏ：このＣ２０については還元雰囲気中で加熱する
還元行程において、脱炭、脱酸反応により低減すること
が可能であるが、還元後の鉄粉中にＣが多量に残存する
と圧縮性を著しく低下させることから、Ｃは０．０１ｗ
ｔ％以下とした。またＯが多いと圧縮性を低下させるだ
けでなく、通常の粉末冶金法において混合使用される黒
鉛粉の歩留を低下させ、さらにＭｉ織のばらつきの原因
になることから、Ｏは０．１５ｗｔ％以下とした。C, O: This C20 can be reduced through decarburization and deoxidation reactions during the reduction process of heating in a reducing atmosphere, but if a large amount of C remains in the iron powder after reduction, it will reduce compressibility. C is 0.01w because it significantly reduces
It was set to t% or less. Furthermore, if there is a large amount of O, it not only reduces compressibility but also reduces the yield of graphite powder mixed and used in normal powder metallurgy, and also causes variations in the Mi weave. % or less.
（２）上記母親に、Ｎｉ 、Ｃｕ 、Ｍｏのうち２種類
以上の元素を予め合金化した合金微粉末を、上記母親に
対してＮｉが６〜８ｗｔ％、Ｃｕが０〜２−仁％、Ｍｏ
が０．５〜１．Ｑ ｗｔ％となるように拡散付着させる
ようにしたのは、以下の理由による。(2) Add to the above mother an alloy fine powder pre-alloyed with two or more elements among Ni, Cu, and Mo; 6 to 8 wt% of Ni and 0 to 2 wt% of Cu; Mo
is 0.5 to 1. The reason why the diffusion and adhesion was made to achieve Q wt% is as follows.
■ Ｎｉ は靭性、焼入性を改善する効果があり、Ｍｏ
は焼入性を高め、焼入、焼戻処理時の軟化を防止する。■ Ni has the effect of improving toughness and hardenability, and Mo
improves hardenability and prevents softening during hardening and tempering treatments.
またＣｕは強度を向上させる効果がある。Further, Cu has the effect of improving strength.
この場合、Ｎｉが６ｗｔ％未満の場合は強度が不十分で
あり、一方８ｗｔ％を越えると残留オーステナイトの増
加により強度が劣化する。Ｍｏが０．５ｗｔ％未満場合
は焼入性向上効果が得られず、１．０ｗｔ％を越えると
靭性（ｉｌｌ値）が低下する。またＣｕが２％を越える
と焼結時の寸法変化率のばらつき（標準偏差）が大幅に
増加する。従ってＮｌ：６〜８ｗｔ％、Ｃｕ：０〜２ｗ
ｔ％、Ｍｏ ： ０．５〜１、Ｑ ｗｔ％とする必要が
ある。In this case, if the Ni content is less than 6 wt%, the strength will be insufficient, while if it exceeds 8 wt%, the strength will deteriorate due to an increase in retained austenite. If Mo is less than 0.5 wt%, the effect of improving hardenability cannot be obtained, and if it exceeds 1.0 wt%, the toughness (ill value) decreases. Moreover, when Cu exceeds 2%, the variation (standard deviation) in the dimensional change rate during sintering increases significantly. Therefore, Nl: 6-8wt%, Cu: 0-2w
t%, Mo: 0.5 to 1, Q wt%.
■ 上述のようにＮｉ、Ｍｏは鉄粉中に拡散固溶される
と、焼結材、あるいは熱処理材の強度を著しく向上でき
る。しかしこのＮｉ、Ｍｏは融点が高く、また鉄粉中へ
の拡散速度が遅く、そのため十分な拡散を得るには、高
温かつ長時間の焼結処理が必要となる。また、Ｎｉ 、
Ｃｕ 、Ｍｏをそれぞれ単体元素粉末のまま使用した場
合、ある場所にそれぞれの元素粉末が存在する場合と、
ある元素粉末だけが存在する場合とがある確率で発生し
、組織的に不均一となるやさらにＣｕを単体粉末として
添加すると、Ｃｕの溶出による異常膨張が発生し、製品
の寸法精度が低下する。(2) As mentioned above, when Ni and Mo are diffused and dissolved in iron powder, the strength of sintered materials or heat-treated materials can be significantly improved. However, Ni and Mo have a high melting point and a slow diffusion rate into iron powder, so a high temperature and long sintering process is required to achieve sufficient diffusion. Also, Ni,
When Cu and Mo are used as single element powders, when each element powder exists in a certain place,
It occurs with a certain probability that only a certain elemental powder exists, and when the structure becomes non-uniform, if Cu is added as a single powder, abnormal expansion will occur due to Cu elution, and the dimensional accuracy of the product will decrease. .
そこで本発明では、Ｎｉ、Ｃｕ、ＭｏＯ内２種顆以上の
元素を予め合金化した合金微粉末、例えばＮｉ−Ｍｏ粉
末、Ｎｉ−Ｃｕ粉末、あるいはＮｉ −Ｃｕ−Ｍｏ粉末
を使用するようにしたものであり、この合金化された微
粉末は、Ｎｉ、Ｍｏの単体粉末の場合より融点を低下さ
せることとなり、また拡散性を向上できる。Therefore, in the present invention, a fine alloy powder in which Ni, Cu, and two or more elements in MoO are alloyed in advance, such as Ni-Mo powder, Ni-Cu powder, or Ni-Cu-Mo powder, is used. This alloyed fine powder has a lower melting point than the case of single powders of Ni and Mo, and can also improve diffusivity.
またＣｕを合金微粉末として添加することにより、単体
添加時に見られるＣｕの溶出による異常膨張がないため
、寸法精度が向上し、焼結後の密度も上昇し強度が向上
する。Furthermore, by adding Cu as an alloy fine powder, there is no abnormal expansion due to elution of Cu, which occurs when Cu is added alone, so dimensional accuracy is improved, density after sintering is also increased, and strength is improved.
ここで本発明に使用される合金微粉末自体の成分割合は
特に限定されるものではないが、以下の組成か好ましい
。Although the component ratio of the fine alloy powder used in the present invention itself is not particularly limited, the following composition is preferred.
Ｎｉ−Ｍｏ系二Ｍｏの高融点をＮｉ−Ｍｏ合金粉とする
ことににより低下させ、鉄粉中への拡散性を向上させる
ことができる。しかしＭｏがｓｏｗｔ％以上になると、
この融点低下効果がほとんどなくなるので、Ｍｏは５０
ｗ ｔ％以下にするのが望ましい。The high melting point of Ni-Mo based di-Mo can be lowered by forming Ni-Mo alloy powder, and the diffusibility into iron powder can be improved. However, when Mo becomes more than sowt%,
Since this melting point lowering effect is almost eliminated, Mo is 50
It is desirable to keep it below wt%.
Ｎｉ −Ｃｕ系：この系では全固溶型の合金粉が得られ
、Ｃｕ ｗｔ％が増加するほど融点を下げることができ
、鉄粉中への拡散を容易化できる。しかしＣ，ｕが４０
ｗ ｔ％以上になると焼結後の寸法が膨張するため実用
性の点で効果がな（なる、従ってＣＵは４０ｗｔ％以下
が望ましい。Ni-Cu system: In this system, an all-solid solution type alloy powder can be obtained, and as the Cu wt% increases, the melting point can be lowered and diffusion into the iron powder can be facilitated. However, C, u is 40
If it exceeds wt%, the dimensions after sintering will expand, making it ineffective in terms of practicality (therefore, it is desirable that CU be 40wt% or less).
Ｎｉ Ｃｕ−Ｍｏ系： この系においては、上述の点
から、Ｍｏは５０ｗ ｔ％以下、Ｃｕは４０ｗｔ％以下
の組成にするのが望ましい。Ni Cu-Mo system: In this system, from the above point, it is desirable that the composition of Mo be 50 wt% or less and Cu be 40 wt% or less.
ところで本発明の合金鋼粉は例えば以下の方法で製造す
ることができる。即ち、上記高純度純鉄粉と、上記合金
微粉末とを有機溶媒中にて湿式混合し、しかる後該混合
粉を還元性雰囲気中にて７５０℃を越え、かつ１０００
℃未満の温度で還元焼鈍し、上記純鉄粉に上記合金微粉
末及び単体元素微粉末を拡散付着させることを特徴とし
ている。By the way, the alloy steel powder of the present invention can be produced, for example, by the following method. That is, the above-mentioned high-purity pure iron powder and the above-mentioned alloy fine powder are wet mixed in an organic solvent, and then the mixed powder is heated in a reducing atmosphere at a temperature exceeding 750°C and at a temperature of 1000°C.
The method is characterized in that reduction annealing is performed at a temperature below .degree. C., and the fine alloy powder and fine single element powder are diffused and adhered to the pure iron powder.
ここで上記製造方法において、純鉄粉と合金粉とを有機
溶媒中で湿式混合するようにしたのは、純鉄粉の表面に
合金粉末を均一かつ十分に付着させるためである。金属
粉末の混合には、金属粉末を一対の円錐型コーンの底面
同士を接続してなるダブルコーン型混合機内に装入し、
該コーンを水平軸廻りに回転させるようにした乾式混合
法があるが、この方法では、各金属粉の比重差によって
層状に分離され易く、均一な混合は困難である。Here, in the above manufacturing method, the pure iron powder and the alloy powder are wet mixed in an organic solvent in order to uniformly and sufficiently adhere the alloy powder to the surface of the pure iron powder. To mix metal powder, the metal powder is charged into a double cone mixer made by connecting the bottoms of a pair of cones.
There is a dry mixing method in which the cone is rotated around a horizontal axis, but in this method, metal powders tend to separate into layers due to differences in specific gravity, making uniform mixing difficult.
これに対して上記製造方法では、例えばエチルアルコー
ル等の有機溶媒に合金粉末を分散させたものと、母親の
純鉄粉とを混合攪拌する湿式混合法を採用したので、純
鉄粉末に合金粉末が均一に分散され、かつ各粉末の表面
に形成された溶媒の薄膜の濡れ性により、均一に分散さ
れた状態で付着する。従って上記乾式の場合のような比
重差で各粉末が分離することはない、その結果次の還元
工程での拡散付着が均一かつ十分に行われ、焼結強度が
向上する。On the other hand, in the above manufacturing method, a wet mixing method is adopted in which alloy powder is dispersed in an organic solvent such as ethyl alcohol and mother pure iron powder is mixed and stirred. are uniformly dispersed and adhere to each powder in a uniformly dispersed state due to the wettability of the thin film of solvent formed on the surface of each powder. Therefore, the powders do not separate due to the difference in specific gravity as in the case of the dry method, and as a result, the diffusion adhesion in the next reduction step is uniform and sufficient, and the sintering strength is improved.
なお、上記湿式混合法を工業化した場合、混合後、次の
還元工程までの間にある程度時間が経過し、上記溶媒が
蒸発し、上記付着した合金粉が分離してしまう恐れがあ
る。そこで上記付着状態を保持するために、上記溶媒中
にレジン等の結合剤を添加しておくことが望ましい。In addition, when the wet mixing method is industrialized, there is a risk that a certain amount of time will elapse between mixing and the next reduction step, and the solvent will evaporate and the adhered alloy powder will separate. Therefore, in order to maintain the above-mentioned adhesion state, it is desirable to add a binder such as a resin to the above-mentioned solvent.
また上記還元焼鈍温度を７５０〜１０００℃としたのは
以下の理由による。Further, the reason why the reduction annealing temperature is set to 750 to 1000°C is as follows.
還元焼鈍温度が７５０℃より低い場合は、還元ケーキが
硬くならないため見掛は密度の高いものが得られ、成形
体密度も優れているが、焼結強度が若干低くなる。これ
は処理温度が低いため合金粉末の拡散付着（合金化）が
少ないためと思われる。When the reduction annealing temperature is lower than 750° C., the reduction cake does not become hard, so a product with high apparent density is obtained, and the compact density is also excellent, but the sintering strength is slightly lower. This is thought to be due to the low processing temperature, which causes less diffusion and adhesion (alloying) of the alloy powder.
一方、１０００℃より高くなると、成形体密度が低くな
る。これは合金元素の鉄粉中への拡散固溶が進み、鉄粉
粒子が硬くなり、圧縮性が低下するためであると考えら
れる。On the other hand, when the temperature is higher than 1000°C, the density of the compact becomes low. This is thought to be because the alloying elements diffuse into the iron powder as a solid solution, making the iron powder particles harder and reducing compressibility.
本発明に係る粉末冶金用高強度合金鋼粉によれば、高純
度純鉄粉に拡散付着させる強化用粉末としてＮｉ 、Ｃ
ｕ 、Ｍｏのうち２種以上の元素を予め合金化１．でな
る合金微粉末を採用したので、合金微粉末の融点が合金
元素単体の微粉末より低くなることから、鉄粉への拡散
、即ち合金化が容易確実に行われる。According to the high-strength alloy steel powder for powder metallurgy according to the present invention, Ni, C can be used as the reinforcing powder to be diffused and adhered to the high-purity pure iron powder.
Pre-alloying two or more elements among u and Mo1. Since the alloy fine powder consisting of the above is used, the melting point of the alloy fine powder is lower than that of the fine powder of a single alloying element, so that diffusion into iron powder, that is, alloying, can be easily and reliably performed.
また、上記合金元素を添加するにあたって、該合金元素
の純鉄粉に対する成分割合を所定範囲に規制したので、
Ｎｉ、Ｃｕによる強度向上効果（実施例！参照）、ＭＯ
による靭性（衝ＩＩ値）向上効果（実施例２参照）が得
られ、また、Ｃｕの単体添加時に見られるＣｕ溶出によ
る異常膨張を抑制できる効果（実施例３参照）が得られ
る。In addition, when adding the alloying element, the proportion of the alloying element to the pure iron powder was regulated within a predetermined range.
Strength improvement effect by Ni and Cu (see examples!), MO
(see Example 2), and the effect of suppressing abnormal expansion due to Cu elution, which is observed when Cu is added alone (see Example 3).
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
大差層上
本実施例は、予めＮｉをＣｕと合金化した微粉末を、Ｎ
ｉが所定の成分範囲になるよう純鉄粉に拡散付着させる
本発明の焼結体強度向上効果を効果を確認するために、
以下の手順で行った。In this example, a fine powder in which Ni is alloyed with Cu in advance is
In order to confirm the effect of improving the strength of the sintered compact of the present invention by diffusing and adhering it to pure iron powder so that i is within a predetermined component range,
The procedure was as follows.
■ Ｎｉ−Ｃｕ合金微粉およびＮｌ、Ｃｕ、Ｍｏの単体
粉末を第１表のＡ−Ｆに示す組成になるように高純度純
鉄粉に湿式混合した後、該混合粉をＡＸガス（アンモニ
ア分解ガス−Ｈ１ニア５％、Ｎ２・２５％）雰囲気中で
８５０℃×３０分間還元焼鈍処理し、しかる後に解粒し
た。また比較のため、ＮｉＣｕ 、Ｍｏの単体粉末だけ
を使用して、第１表のＧ−１に示す組成になるように湿
式混合し、還元焼鈍熱処理５解粒を行った。■ After wet-mixing Ni-Cu alloy fine powder and single powders of Nl, Cu, and Mo into high-purity pure iron powder so as to have the composition shown in Table 1, A-F, the mixed powder was heated with AX gas (ammonia decomposition Reduction annealing was performed at 850° C. for 30 minutes in a gas-H1 (5% near gas, 25% N2) atmosphere, followed by disintegration. For comparison, only single powders of NiCu and Mo were wet-mixed to obtain the composition shown in G-1 in Table 1, and subjected to reduction annealing heat treatment and granulation.
■ 上記解粒した各銅粉に黒鉛わ）未０．６ ｗｔ％と
潤滑剤としてのステアリン酸亜鉛粉末０．７５ｗｔ％と
を添加した後、Ｖ型混合器により３０分間混合し、この
混合粉末を金型を用いて６ ＴＯＮ／ｃｄの圧力で成形
して１０ Ｘ １０ Ｘ ５５ｇｍの成形体を得た。■ After adding 0.6 wt% of graphite powder and 0.75 wt% of zinc stearate powder as a lubricant to each of the above disintegrated copper powders, the mixed powder was mixed for 30 minutes using a V-type mixer. was molded using a mold at a pressure of 6 TON/cd to obtain a molded product of 10 x 10 x 55 gm.
■上記成形体をＡＸガス雰囲気中で１１２０℃×３０分
間焼結した。この焼結体から平行部６φの引張り試験片
を形成し、これの引張り強度を測定した。(2) The above molded body was sintered at 1120° C. for 30 minutes in an AX gas atmosphere. A tensile test piece with a parallel portion of 6φ was formed from this sintered body, and its tensile strength was measured.
以上の実験より、得られたデータを第２表に示す。The data obtained from the above experiments are shown in Table 2.
同表から明らかなように、本発明二こ従った銅粉（Ａ−
Ｆａ）に比較して、比較例鋼粉（Ｇ〜■欄）は若干Ｎｉ
成分が低くなっており、本発明の予め合金化したＮｉ−
Ｃｕ合金微粉を用いる方法が、Ｎｉ 、Ｃｕの単体微粉
末を用いた場合より拡散付着性に優れていることが判る
。As is clear from the same table, the copper powder (A-
Compared to Fa), the comparative example steel powder (G~■ column) has a slight amount of Ni.
The pre-alloyed Ni-
It can be seen that the method using fine Cu alloy powder has better diffusion adhesion than the method using single fine powder of Ni and Cu.
また例えば８ＮＬ１．５ Ｃｕ−１，０Ｍｏ （Ｂ、
Ｅ。Also, for example, 8NL1.5 Cu-1,0Mo (B,
E.
Ｈａ）を見ると、焼結体強度はＢ＞Ｅ＞Ｈとなっており
、合金微粉の使用比率を高くすると強度が向上すること
を示している。またＮｉが８％時において強度が最高と
なり、６％より少なく１０％より多くなると強震は著し
く低下することが理解できる。Looking at Ha), the strength of the sintered body is B>E>H, indicating that the strength improves as the ratio of alloy fine powder used increases. It can also be seen that the strength is highest when the Ni content is 8%, and that when the Ni content is less than 6% and more than 10%, the strong earthquakes decrease significantly.
去Ｗ
本実施例は、Ｍｏを本発明範囲内で添加することによる
靭性向上効果を確認するためのもので、上記実施例１の
手順に従い、ＭＯの含有量が０．５〜２．Ｏｗｔ％の試
験片を作成し、シャルピー衝Ｎ試験（ノツチなし）を行
い、街！！ｌ値を測定した。なお、この試験片の焼結体
密度は７．２０ｇ／ａｍ’であった・
測定結果を第３図に示す、同図からも明らかなように、
ＭＯ添加量が０．５．１．０ｗｔ％の場合は、衝撃値は
高い水準にあるが、１．０ ｓｔ％を越えると急に低下
していることが判る。This example was conducted to confirm the effect of improving toughness by adding Mo within the range of the present invention, and according to the procedure of Example 1 above, the MO content was 0.5 to 2. Owt% test piece was prepared, Charpy impact N test (no notch) was performed, and the town! ! The l value was measured. The sintered body density of this test piece was 7.20 g/am'. The measurement results are shown in Figure 3. As is clear from the figure,
It can be seen that when the amount of MO added is 0.5 and 1.0 wt%, the impact value is at a high level, but when it exceeds 1.0 st%, it suddenly decreases.
大立桝↓
本実施例は、Ｃｕを合金化した微粉末を純鉄む）に本発
明範囲内で拡散付着させることによる寸法変化率のばら
つきの抑制効果を確認するためのもので、上記実施例１
の手順に従い、Ｎｉ−Ｃｕ合金の形で添加したＣｕの含
有量がＯ〜２，５ ｗｔ％の試験片（６４Φ〜２４Φ）
を作成し、焼結時の寸法変化率の標準偏差を求めた。比
較のために、Ｃｕを上記含有量になるよう単体で添加し
た試験片についても同様に測定した。Otachimasu ↓ This example was conducted to confirm the effect of suppressing variations in the dimensional change rate by diffusing and adhering fine powder alloyed with Cu to pure iron within the scope of the present invention. Example 1
A test piece (64Φ~24Φ) with a Cu content of O~2.5 wt% added in the form of Ni-Cu alloy according to the procedure of
was created and the standard deviation of the dimensional change rate during sintering was determined. For comparison, a test piece in which Cu was added alone to the above content was similarly measured.
測定結果を第４図に示す、同図からも明らかなように、
ＣｕをＮｉ−Ｃｕ合金の形で添加した場合はＣｕ単体で
添加した場合に比較して、何れの含有量においても寸法
変化率の標準偏差が小さくなっている。また、添加量が
２．Ｏｗｔ％を越えると、Ｃｕ単体で添加した場合だけ
でな（Ｎｉ−Ｃｕ合金で添加した場合にも、急激に寸法
変化率の標準偏差が大きくなっている。The measurement results are shown in Figure 4.As is clear from the figure,
When Cu is added in the form of a Ni-Cu alloy, the standard deviation of the dimensional change rate is smaller at any content than when Cu is added alone. Also, the amount added is 2. When it exceeds Owt%, the standard deviation of the dimensional change rate suddenly increases not only when Cu is added alone (also when it is added as a Ni-Cu alloy).
以とのように、本発明に係る粉末冶金用高強度合金鋼粉
によれば、Ｎｉ 、Ｃｕ 、Ｍｏのうち２種類以−Ｆの
元素を予め合金化してなる合金微粉末を、それぞれ６〜
８ｗｔ％０〜２ｗｔ％、０．５〜１．０ ｗｔ％の組成
になるように高純度純鉄粉に拡散付着させたので、合金
微粉末の融点が合金元素単体より低いことから、鉄粉へ
の拡散、即ち合金化を容易化でき、圧縮性を向上できる
とともに、焼結体・強度を太き（向上できる効果がある
。As described above, according to the high-strength alloy steel powder for powder metallurgy according to the present invention, alloy fine powder obtained by pre-alloying two or more elements of Ni, Cu, and Mo, respectively
Since the melting point of the fine alloy powder is lower than that of the alloy element alone, the iron powder This has the effect of making it easier to diffuse into the sintered body, that is, to make it into an alloy, improve compressibility, and thicken (improve) the strength of the sintered body.
嶌１表 本発明による合伶ゴ頭諧すTable 1: Comparison according to the present invention
第１図は本発明に係る合金鋼粉の純鉄粉に合金粉が拡散
付着している状態を示す模式図、第２図は従来の合金鋼
粉の模式図、第３図及び第４図は本発明の詳細な説明す
るための図であり、第３図はＭｏ添加量−衝撃値特性図
、第４図はＣｕ添加量−寸法変化率標準偏差特性図であ
る。
特許出願人 株式会社 神戸製鋼所
代理人 弁理士 下車 努
第３図
第４
図
Ｃｕ
（Ｚ）Fig. 1 is a schematic diagram showing a state in which alloy powder is diffused and adhered to pure iron powder of alloy steel powder according to the present invention, Fig. 2 is a schematic diagram of conventional alloy steel powder, and Figs. 3 and 4. 3 is a diagram for explaining the present invention in detail, FIG. 3 is a characteristic diagram of Mo addition amount vs. impact value, and FIG. 4 is a diagram of Cu addition amount vs. dimensional change rate standard deviation characteristic diagram. Patent Applicant Kobe Steel Co., Ltd. Representative Patent Attorney Tsutomu Tsutomu Figure 3 Figure 4 Cu (Z)
Claims (1)
以下、Ｍｎ：０．１０ｗｔ％以下、Ｐ：０．０１ｗｔ％
以下、Ｓ：０．０１０％ｗｔ％以下、Ｏ：０．１５ｗｔ
％以下で残部Ｆｅ及び不可避的不純物からなる高純度純
鉄粉に、Ｎｉ、Ｃｕ、Ｍｏのうち２種類以上の元素を予
め合金化した合金微粉末を、Ｎｉ：６〜８ｗｔ％、Ｃｕ
：０〜２ｗｔ％、Ｍｏ：０．５〜１．０ｗｔ％になるよ
うに拡散付着（ディフェージョンボンディング）させた
ことを特徴とする粉末冶金用高強度合金鋼粉。(1) C: 0.01wt% or less, Si: 0.02wt%
Below, Mn: 0.10wt% or less, P: 0.01wt%
Below, S: 0.010%wt% or less, O: 0.15wt
% or less, the balance is Fe and unavoidable impurities, and alloy fine powder pre-alloyed with two or more elements among Ni, Cu, and Mo is mixed with Ni: 6 to 8 wt%, Cu
A high-strength alloy steel powder for powder metallurgy, characterized in that it has been bonded by diffusion so that Mo: 0 to 2 wt% and Mo: 0.5 to 1.0 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63299344A JPH0689363B2 (en) | 1988-11-26 | 1988-11-26 | High strength alloy steel powder for powder metallurgy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63299344A JPH0689363B2 (en) | 1988-11-26 | 1988-11-26 | High strength alloy steel powder for powder metallurgy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02145702A true JPH02145702A (en) | 1990-06-05 |
| JPH0689363B2 JPH0689363B2 (en) | 1994-11-09 |
Family
ID=17871336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63299344A Expired - Lifetime JPH0689363B2 (en) | 1988-11-26 | 1988-11-26 | High strength alloy steel powder for powder metallurgy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689363B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09195012A (en) * | 1996-01-19 | 1997-07-29 | Hitachi Powdered Metals Co Ltd | Wear resistant sintered alloy and its production |
| WO2010074634A1 (en) * | 2008-12-23 | 2010-07-01 | Höganäs Ab (Publ) | A method of producing a diffusion alloyed iron or iron-based powder, a diffusion alloyed powder, a composition including the diffusion alloyed powder, and a compacted and sintered part produced from the composition |
| CN102672180A (en) * | 2012-06-07 | 2012-09-19 | 太仓市锦立得粉末冶金有限公司 | Powdery metallurgical finished product process |
| CN106086659A (en) * | 2016-06-24 | 2016-11-09 | 江阴市宝能特种钢线有限公司 | A kind of high-strength alloy steel wire and production method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540851A (en) * | 2013-10-11 | 2014-01-29 | 芜湖市鸿坤汽车零部件有限公司 | High-performance powder metallurgy material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4918740A (en) * | 1972-06-05 | 1974-02-19 | ||
| JPS5049106A (en) * | 1973-09-03 | 1975-05-01 | ||
| JPS61223101A (en) * | 1985-03-28 | 1986-10-03 | Kobe Steel Ltd | Atomized iron powder for green compact magnetic powder and production thereof |
| JPS63297502A (en) * | 1987-05-29 | 1988-12-05 | Kobe Steel Ltd | High-strength alloy steel powder for powder metallurgy and its production |
| JPH01159301A (en) * | 1987-09-30 | 1989-06-22 | Kawasaki Steel Corp | Conjugate steel powder having excellent compressibility and homogeneity |
-
1988
- 1988-11-26 JP JP63299344A patent/JPH0689363B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4918740A (en) * | 1972-06-05 | 1974-02-19 | ||
| JPS5049106A (en) * | 1973-09-03 | 1975-05-01 | ||
| JPS61223101A (en) * | 1985-03-28 | 1986-10-03 | Kobe Steel Ltd | Atomized iron powder for green compact magnetic powder and production thereof |
| JPS63297502A (en) * | 1987-05-29 | 1988-12-05 | Kobe Steel Ltd | High-strength alloy steel powder for powder metallurgy and its production |
| JPH01159301A (en) * | 1987-09-30 | 1989-06-22 | Kawasaki Steel Corp | Conjugate steel powder having excellent compressibility and homogeneity |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09195012A (en) * | 1996-01-19 | 1997-07-29 | Hitachi Powdered Metals Co Ltd | Wear resistant sintered alloy and its production |
| WO2010074634A1 (en) * | 2008-12-23 | 2010-07-01 | Höganäs Ab (Publ) | A method of producing a diffusion alloyed iron or iron-based powder, a diffusion alloyed powder, a composition including the diffusion alloyed powder, and a compacted and sintered part produced from the composition |
| CN102672180A (en) * | 2012-06-07 | 2012-09-19 | 太仓市锦立得粉末冶金有限公司 | Powdery metallurgical finished product process |
| CN106086659A (en) * | 2016-06-24 | 2016-11-09 | 江阴市宝能特种钢线有限公司 | A kind of high-strength alloy steel wire and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0689363B2 (en) | 1994-11-09 |
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