JPH06330101A - Production of cu-cr based composite material - Google Patents
Production of cu-cr based composite materialInfo
- Publication number
- JPH06330101A JPH06330101A JP5146948A JP14694893A JPH06330101A JP H06330101 A JPH06330101 A JP H06330101A JP 5146948 A JP5146948 A JP 5146948A JP 14694893 A JP14694893 A JP 14694893A JP H06330101 A JPH06330101 A JP H06330101A
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- JP
- Japan
- Prior art keywords
- powder
- composite material
- sintered
- sintering
- cold
- 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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Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、真空遮断器の電極材料
等として有用な、微細な析出相からなる組織を持つＣｕ
−Ｃｒ系複合材料の製造方法に関する。BACKGROUND OF THE INVENTION The present invention relates to Cu having a structure composed of a fine precipitation phase, which is useful as an electrode material for a vacuum circuit breaker.
-A method for manufacturing a Cr-based composite material.
【０００２】[0002]
【従来の技術】平衡状態図において互いに非固溶の２相
以上が共存する組成の合金又は複合材料を作製するため
の従来からの技術としては、鋳造法や粉末冶金法があ
る。例えば、真空遮断器の電極材料として最近提案され
ているＣｕ−Ｃｒ系合金は、ＣｕとＣｒが互いに殆ど固
溶しない２相分離型の合金系であり、鋳造法か粉末冶金
法によって製造される。2. Description of the Related Art Conventional techniques for producing an alloy or composite material having a composition in which two or more non-solid solution phases coexist in an equilibrium diagram include a casting method and a powder metallurgy method. For example, a Cu-Cr alloy recently proposed as an electrode material for a vacuum circuit breaker is a two-phase separation type alloy system in which Cu and Cr hardly form a solid solution with each other, and is manufactured by a casting method or a powder metallurgy method. .
【０００３】しかし、鋳造法によると、溶解凝固の過程
を取るため析出した組織が粗くなってしまう欠点があっ
た。これは、ＣｕとＣｒが互いに殆ど固溶しないため、
冷却速度が遅いと鋳造凝固過程で安定な合金組成、即ち
ほぼ純Ｃｕと純Ｃｒとが粗大に混合した組成を形成して
しまう事に原因がある。このため、真空遮断器の電極材
料では微細なＣｒ粒構造を持つことが、接触抵抗、截断
値、硬度等の電極として優れた特性を得るうえで必要な
事は判っていても、そのような微細な組織を実現出来な
かった。However, according to the casting method, there is a drawback that the deposited structure becomes coarse because of the process of melting and solidification. This is because Cu and Cr hardly form a solid solution with each other.
A slow cooling rate causes a stable alloy composition during the casting and solidification process, that is, a composition in which substantially pure Cu and pure Cr are coarsely mixed. Therefore, even though it is known that the electrode material of the vacuum circuit breaker has a fine Cr grain structure in order to obtain excellent characteristics such as contact resistance, cutoff value and hardness, as an electrode, I could not realize a fine structure.
【０００４】又、粉末冶金法によりＣｕ−Ｃｒ系の複合
合金を作製する場合には、Ｃｕ粉末とＣｒ粉末を混合
し、成形した後に焼結するが、焼結材には気孔が多く残
留するために密度が上がり難かったり、より困難な問題
としてＣｒ粉の表面が酸化物で覆われているために、焼
結してもＣｒ粒とＣｕマトリックスの間の結合が十分で
なかった。従って、真空遮断器の電極材料としてアーク
による衝撃や開閉負荷に耐え得るだけの強度及び硬度が
得られなかった。つまり、ＣｕマトリックスからＣｒ粒
子が脱離し、電極表面の肌荒れの原因となったり、接触
抵抗値が劣化したり、截断値が安定しない等の原因とな
っていた。When a Cu-Cr-based composite alloy is produced by powder metallurgy, Cu powder and Cr powder are mixed, molded and then sintered, but many pores remain in the sintered material. Therefore, it is difficult to increase the density, and as a more difficult problem, the surface of the Cr powder is covered with an oxide, so that the bond between the Cr particles and the Cu matrix was not sufficient even if sintered. Therefore, as the electrode material of the vacuum circuit breaker, it is not possible to obtain the strength and hardness enough to withstand the impact by the arc and the switching load. That is, Cr particles are detached from the Cu matrix, which causes the surface of the electrode to be rough, the contact resistance value is deteriorated, and the cut value is not stable.
【０００５】粉末冶金法の一つとして、Ｃｒ粉末を焼結
して気孔率の高いスケルトンを作製した後、低融点のＣ
ｕをスケルトンの気孔内に溶融含浸させる方法がある。
しかしながら、この溶浸法では微細なＣｒ粒子からなる
構造のスケルトンを得る事が難しいうえ、Ｃｕを溶浸さ
せたスケルトンの気孔内に空隙が残り易いので緻密且つ
強固な組織を得ることが難しく、従って真空遮断器の電
極材料として優れた特性を実現する事は難しかった。As one of powder metallurgy methods, Cr powder is sintered to prepare a skeleton having a high porosity, and then a C having a low melting point is added.
There is a method of melt impregnating u into the pores of the skeleton.
However, with this infiltration method, it is difficult to obtain a skeleton of a structure composed of fine Cr particles, and since voids are likely to remain in the pores of the skeleton infiltrated with Cu, it is difficult to obtain a dense and strong structure, Therefore, it was difficult to realize excellent characteristics as an electrode material for a vacuum circuit breaker.
【０００６】更に、電極特性の改善にＢｉの添加が有効
である事は知られているが、前記した従来の方法では、
Ｂｉが低融点であるためにＣｕ−Ｃｒ系合金の焼結過程
や電極材料のロウ付け過程でＢｉが流出し、電極表面に
流出による空孔を残したり、ロウ付け自体も難しくなる
という問題があった。Further, it is known that the addition of Bi is effective for improving the electrode characteristics, but in the above-mentioned conventional method,
Since Bi has a low melting point, Bi flows out during the sintering process of the Cu-Cr alloy or the brazing process of the electrode material, leaving holes due to the outflow on the electrode surface, and the brazing itself becomes difficult. there were.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、かかる従来
の事情に鑑み、互いに非固溶のＣｕとＣｒとの微細な析
出相からなる組織を有し、真空遮断器の電極材料等とし
て優れた特性を持つＣｕ−Ｃｒ系複合材料を、経済的に
製造する方法を提供することを目的とする。In view of such conventional circumstances, the present invention has a structure composed of fine precipitation phases of insoluble Cu and Cr, and is excellent as an electrode material for a vacuum circuit breaker or the like. It is an object of the present invention to provide a method for economically producing a Cu-Cr based composite material having the above characteristics.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するた
め、本発明が提供するＣｕ−Ｃｒ系複合材料の製造方法
においては、Ｃｕ粉末とＣｒ粉末とをＣｒ粉末が５〜５
０重量％となるように配合し、不活性ガス中でメカニカ
ルアロイングし、得られたメカニカルアロイング粉末を
冷間成形し、成形体を水素ガス中又は真空中において５
００℃以上で焼結し、焼結材を１００℃以下で冷間鍛造
し、次に鍛造材を５００℃以上で再焼結することを特徴
とする。In order to achieve the above object, in the method for producing a Cu-Cr composite material provided by the present invention, the Cu powder and the Cr powder are 5 to 5%.
0% by weight, and mechanically alloyed in an inert gas, the resulting mechanically alloyed powder is cold-molded, and the molded body is placed in hydrogen gas or in a vacuum.
It is characterized by sintering at 00 ° C or higher, cold forging the sintered material at 100 ° C or lower, and then re-sintering the forged material at 500 ° C or higher.
【０００９】[0009]
【作用】ＣｕとＣｒは互いに非固溶であるが、Ｃｕ粉末
とＣｒ粉末のメカニカルアロイング（ＭＡと略記する）
によって、均一な強制固溶体に近い状態を実現すること
が出来る。この状態は非平衡な状態であり、熱力学的に
安定な状態に移ろうとする。本発明者等は、このドライ
ビングフォースを利用し、その合金の融点の１／３以上
の温度で焼鈍することによって、前記強制固溶体から原
子の移動度が制限された状態で析出が起こるため、微細
な組織が得られることを見いだした。尚、ここで合金の
融点とは、マトリックス相を形成するＣｕの融点を指
す。Function: Cu and Cr are non-solid solutions with each other, but mechanical alloying of Cu powder and Cr powder (abbreviated as MA)
By this, a state close to a uniform forced solid solution can be realized. This state is a non-equilibrium state and attempts to move to a thermodynamically stable state. The inventors of the present invention utilized this driving force and annealed it at a temperature of ⅓ or more of the melting point of the alloy to cause precipitation in the state in which the mobility of atoms was restricted from the forced solid solution. I found that a different organization could be obtained. Here, the melting point of the alloy means the melting point of Cu forming the matrix phase.
【００１０】従って、ＭＡ粉末の合金組成における融点
の１／３以上の温度でＭＡ粉末を焼鈍した後、冷間成形
して焼結すれば、極めて微細な組織を有するＣｕ−Ｃｒ
系複合材料が得られる。尚、この焼鈍は焼結を兼ねても
良く、即ちＭＡ粉末をそのまま冷間成形し、融点の１／
３以上更に望ましくは１／２以上の温度で且つ焼結可能
な温度、具体的には５００℃以上の温度でそのまま焼結
しても良い。焼鈍又は焼結雰囲気は、酸化物や窒化物の
生成を抑制するため、水素ガス又は真空雰囲気を使用す
る。Therefore, if the MA powder is annealed at a temperature of 1/3 or more of the melting point in the alloy composition of the MA powder, and then cold-formed and sintered, Cu-Cr having an extremely fine structure is obtained.
A composite material is obtained. This annealing may also serve as sintering, that is, the MA powder is cold-formed as it is,
The temperature may be 3 or more, more preferably 1/2 or more and at a temperature at which sintering is possible, specifically, 500 ° C. or more, and the sintering may be performed as it is. As the annealing or sintering atmosphere, hydrogen gas or a vacuum atmosphere is used in order to suppress the formation of oxides and nitrides.
【００１１】真空遮断器の電極材料は真空中で用いるた
め、酸素濃度を極力抑える必要がある。従って、Ｃｕ粉
末とＣｒ粉末のＭＡはＡｒ等の不活性ガス中で行い且つ
焼結は水素ガス中又は真空中で行う。しかし、この様に
してＭＡ粉末を焼結しただけでは、ＭＡ粉末は高硬度で
焼結性が悪いために粉末同士の良好な焼結状態が得るこ
とが難しく、密度や電気電導度等の点で真空遮断器の電
極材料として要求される特性を満たすことが困難である
ことが判った。Since the electrode material of the vacuum circuit breaker is used in vacuum, it is necessary to suppress the oxygen concentration as much as possible. Therefore, MA of Cu powder and Cr powder is performed in an inert gas such as Ar, and sintering is performed in hydrogen gas or in vacuum. However, by simply sintering the MA powder in this manner, it is difficult to obtain a good sintered state between the powders because the MA powder has high hardness and poor sinterability, and it is difficult to obtain the density and the electric conductivity. It was found that it is difficult to satisfy the characteristics required as an electrode material for a vacuum circuit breaker.
【００１２】そこで、得られた焼結材を熱間で押出加工
したが、この方法では内部にブリスターと呼ばれる空孔
が形成され易いうえ、合金の酸素濃度を低く保つ事が困
難であった。酸化を抑えるためには、焼結材を大気にさ
らすことなく熱間で押し出すか、又は低温で押し出すこ
とが考えられる。しかし、低温押出により酸化を抑制し
ようとすると、押出圧力が装置の限界に近い超高圧とな
るため、技術的にも経済的にも難しく、大型の素材作製
も困難である。Therefore, the obtained sintered material was extruded hot, but with this method, it was difficult to keep the oxygen concentration of the alloy low, as well as the formation of voids called blisters inside. In order to suppress the oxidation, it is possible to extrude the sintered material hot without exposing it to the atmosphere, or extruding it at a low temperature. However, when trying to suppress oxidation by low temperature extrusion, the extrusion pressure becomes extremely high pressure close to the limit of the apparatus, which is technically and economically difficult, and it is also difficult to produce a large-sized material.
【００１３】又、ＭＡ粉末の酸化を抑えるため、ＭＡ粉
末の固化法として一般に採用されているように、ＭＡ粉
末を真空容器中に封入して押出加工しても良いが、この
方法は非常にコスト高であるため、実用的ではない。即
ち、容器が高価であるうえ、粉末を入れた容器を真空に
脱気するためのパイプの溶接や容器の加工組み立て、粉
末を入れた容器を高温に加熱しての脱気や気密封止、更
には押出後の容器の除去が必要であるため、コスト高と
なる。しかも、製造工程が繁雑化するため品質のコント
ロールが不充分となり、製品の信頼性保証が難しい。Further, in order to suppress the oxidation of the MA powder, the MA powder may be enclosed in a vacuum container and extruded as is generally adopted as a solidification method of the MA powder, but this method is very difficult. High cost makes it impractical. That is, the container is expensive, welding of pipes for degassing the container containing the powder to vacuum, processing and assembly of the container, degassing and hermetic sealing by heating the container containing the powder to a high temperature, Furthermore, since the container after extrusion must be removed, the cost becomes high. Moreover, since the manufacturing process becomes complicated, quality control becomes insufficient, and it is difficult to guarantee product reliability.
【００１４】本発明者等は、この様な制約がある中で、
経済的であり、真空遮断器の電極材料とするため酸素濃
度の上昇を抑えながら、Ｃｕ−Ｃｒ系のＭＡ粉末の焼結
材を緻密化する方法を検討した。その結果、ＭＡ粉末
のＣｒ粒子が小さいほど焼結材中に空孔が発生しにくい
傾向があること、ＭＡ粉末の焼結材は常温において通
常の非ＭＡ粉末の焼結材より硬く且つ変形能が小さいこ
とが常識であるが、Ｃｕ−Ｃｒ系では必ずしもそうでな
いこと、ＭＡ粉末は高硬度であるため成形時には密度
が上がりにくいが、一度焼結した後には鍛造によって密
度が上がり易いことが判明した。The present inventors, in spite of such restrictions,
A method for densifying a sintered material of Cu-Cr-based MA powder while suppressing an increase in oxygen concentration in order to use it as an electrode material for a vacuum circuit breaker was studied. As a result, the smaller the Cr particles of the MA powder, the less likely voids are formed in the sintered material, and the sintered material of the MA powder is harder and deformable than the normal non-MA powder sintered material at room temperature. It is common knowledge that is small, but it is not necessarily the case in Cu-Cr system, and it is found that the density is difficult to increase during molding because MA powder has high hardness, but the density tends to increase by forging after sintering once. did.
【００１５】これらの事実は本発明者等の研究により初
めて明らかにされたものであり、特には焼結によりＭ
Ａ粉末の微細Ｃｒ粒子の硬度が推定で焼結前の６００ｍ
ＨVから焼結後に２００ｍＨVまで低下し、軟化の程度が
極めて大きい事実を発見したことによるものである。こ
れら〜の理由により、前記のＣｕ−Ｃｒ系のＭＡ粉
末の焼結材を鍛造することにより緻密化が可能であり、
しかも鍛造は１００℃以下の低温での冷間鍛造で良いこ
とを見いだした。更に、焼結材の空孔を予め少なくして
おくため、ＭＡ粉末中のＣｒ粒子の大きさが平均粒径で
３０μｍ以下となるようにメカニカルアロイングするこ
とが好ましいことも判った。These facts have been clarified for the first time by the study of the present inventors, and in particular, M is obtained by sintering.
The hardness of the fine Cr particles of the A powder is estimated to be 600 m before sintering.
This is due to the discovery of the fact that the degree of softening was extremely high, decreasing from H V to 200 mH V after sintering. For these reasons, densification is possible by forging the Cu-Cr-based MA powder sintered material.
Moreover, they have found that cold forging at a low temperature of 100 ° C. or less is good. Further, it has been found that it is preferable to mechanically alloy the Cr particles in the MA powder so that the average particle size of the Cr particles is 30 μm or less in order to reduce the pores of the sintered material in advance.
【００１６】ところが、この冷間鍛造により密度は上昇
するものの、電気電導度の上昇は不充分である。そこで
更に検討した結果、真空遮断器の電極材料としての要求
を満たす電気電導度を得るためには、冷間鍛造後に再焼
結することが有効であった。再焼結により材料強度が上
昇することが認められ、結合力の向上によって電気電導
度が高められていると考えられる。この再焼結の温度は
５００℃以上、好ましくは７００℃以上である。又、再
焼結の雰囲気は特に制限はないが、非酸化性雰囲気であ
ることが好ましく、焼結方法は常圧焼結のほかＨＩＰ、
ホットプレス等の方法を用いることも出来る。However, although the density is increased by this cold forging, the increase in electric conductivity is insufficient. As a result of further study, it was found that re-sintering after cold forging was effective in order to obtain electric conductivity satisfying the requirements as an electrode material for a vacuum circuit breaker. It is recognized that the material strength is increased by the re-sintering, and it is considered that the electric conductivity is increased by the improvement of the bonding force. The temperature of this re-sintering is 500 ° C. or higher, preferably 700 ° C. or higher. The atmosphere for re-sintering is not particularly limited, but a non-oxidizing atmosphere is preferable, and the sintering method includes atmospheric pressure sintering, HIP,
A method such as hot pressing can also be used.
【００１７】真空遮断器の電極材料として好ましい特性
を得るためＢｉの含有が有効であることは知られてい
る。従来の方法では低融点のＢｉが流出して空孔が形成
される問題点があったが、本発明方法によりＣｕ粉末と
Ｃｒ粉末にＢｉ粉末を加えてメカニカルアロイングした
ＭＡ粉末を使用すれば、Ｂｉの流出を防止し、ロウ付け
を容易にすることが出来る。Ｂｉ粉末の添加量は粉末全
体の０.０１〜５重量％が好ましい。It is known that the inclusion of Bi is effective in order to obtain preferable characteristics as an electrode material for a vacuum circuit breaker. In the conventional method, there is a problem that Bi having a low melting point flows out to form vacancies. However, if MA powder mechanically alloyed with Cu powder and Cr powder with Bi powder is used according to the method of the present invention, , Bi can be prevented and brazing can be facilitated. The amount of the Bi powder added is preferably 0.01 to 5% by weight based on the whole powder.
【００１８】又、Ｃｕ粉末とＣｒ粉末に、Ｚｒ粉末、Ｂ
粉末、酸化クロム粉末又は炭化クロム粉末を加え、メカ
ニカルアロイングすることによって、複合材料の高温強
度を向上させ、電極特性を更に改善する効果が得られ
る。特に酸化クロム粉末又は炭化クロム粉末を加えるこ
とにより、メカニカルアロイングの進行が促進され、よ
り微細なＣｒ粒子が得られる。これらの粉末の添加量も
粉末全体の０.０１〜５重量％とすることが好ましい。In addition, Cu powder and Cr powder, Zr powder, B
By adding powder, chromium oxide powder or chromium carbide powder and mechanically alloying, the effect of improving the high temperature strength of the composite material and further improving the electrode characteristics can be obtained. In particular, by adding chromium oxide powder or chromium carbide powder, the progress of mechanical alloying is promoted and finer Cr particles can be obtained. The addition amount of these powders is also preferably 0.01 to 5% by weight based on the whole powder.
【００１９】本発明の複合材料においては、冷間鍛造又
は再焼結により得られた再焼結材を非酸化性雰囲気中に
おいて３００〜８５０℃で時効処理することにより、時
効硬化させることが出来る。又、鍛造材又は再焼結材を
押出加工又はＨＩＰ処理して更に緻密化させることも可
能である。この場合の押出やＨＩＰ処理では、鍛造材及
び再焼結材が既に９５％以上の密度を有し、表面がほぼ
封孔されているので、これを更に容器に真空封入する必
要はなく、鍛造材又は再焼結材をそのままの状態で押出
又はＨＩＰ処理して良い。The composite material of the present invention can be age-hardened by subjecting the re-sintered material obtained by cold forging or re-sintering to an aging treatment at 300 to 850 ° C. in a non-oxidizing atmosphere. . Further, it is possible to further densify the forged material or the re-sintered material by extrusion processing or HIP processing. In the extrusion and HIP processing in this case, since the forged material and the re-sintered material already have a density of 95% or more and the surface is almost sealed, it is not necessary to further vacuum-seal it in the container, The material or the re-sintered material may be extruded or HIPed as it is.
【００２０】[0020]
【実施例】実施例１ 電解法による粒径２０μｍ以下の純Ｃｕ粉末と、粒径７
４μｍ以下の電解純Ｃｒ粉末を重量比でＣｕ：Ｃｒ＝５
３：４７となるように配合し、予備混合後、ボールミル
によりＡｒガス中で４０時間のメカニカルアロイング
（ＭＡ）を行った。得られたＭＡ粉末中のＣｒ粒子の平
均粒径は７μｍであった。このＭＡ粉末を６ｔ／ｃｍ2
で冷間成形した後、水素雰囲気中において１０００℃で
３時間焼結した。更に、この焼結材を常温にて６ｔ／ｃ
ｍ2の圧力で冷間鍛造を行った後、水素雰囲気中にて１
０００℃で３時間再焼結することによりＣｕ−Ｃｒ系複
合材料を得た。EXAMPLES Example 1 Pure Cu powder having a particle size of 20 μm or less by an electrolysis method and a particle size of 7
Cu: Cr = 5 by weight ratio of electrolytic pure Cr powder of 4 μm or less
The mixture was blended so as to be 3:47, preliminarily mixed, and then mechanically alloyed (MA) for 40 hours in Ar gas by a ball mill. The average particle size of Cr particles in the obtained MA powder was 7 μm. This MA powder was added at 6 t / cm 2
After cold-forming at 1000 ° C., it was sintered in a hydrogen atmosphere at 1000 ° C. for 3 hours. Furthermore, this sintered material is 6 t / c at room temperature.
After cold forging at a pressure of m 2 , 1 in a hydrogen atmosphere
A Cu—Cr based composite material was obtained by re-sintering at 000 ° C. for 3 hours.
【００２１】焼結材、鍛造材及び再焼結材とも、組織中
のＣｒ粒子は粒径が１〜１５μｍの範囲内にある微細な
組織であることが判った。又、各工程における真密度比
と電気電導度（％ＩＡＣＳ）の変化を図１及び図２に示
した。焼結→冷間鍛造→再焼結と工程を進めるに従っ
て、密度及び電気電導度が向上することが判る。尚、冷
間鍛造材を４００℃で５時間時効焼鈍したところ、電気
電導度は鍛造材の電気電導度よりも３〜６％ＩＡＣＳ増
加した。It has been found that the Cr particles in the structure of each of the sintered material, the forged material and the re-sintered material have a fine structure having a grain size in the range of 1 to 15 μm. 1 and 2 show changes in the true density ratio and the electric conductivity (% IACS) in each process. It can be seen that the density and electric conductivity improve as the process proceeds from sintering to cold forging to re-sintering. When the cold forged material was annealed at 400 ° C. for 5 hours, the electric conductivity increased by 3 to 6% IACS over the electric conductivity of the forged material.
【００２２】得られたＣｕ−Ｃｒ系複合材料を真空遮断
器の電極材料として用いたところ、截断値は１Ａと低い
値を示した。これに対して、従来の溶浸法によりＣｒ粉
末を焼結して気孔率の高いスケルトンを作製し、このス
ケルトンの気孔内に低融点のＣｕを溶融含浸させて製造
したＣｕ−Ｃｒ系溶浸材の場合、截断値は５Ａと高かっ
た。又、溶浸材では切削加工面が脆く、その表面は凹凸
が激しく亀裂も認められたが、本発明の複合材料では切
削加工面が美しく、亀裂もなかった。これらの事実か
ら、本発明のＣｕ−Ｃｒ系複合材料は真空遮断器の電極
材料として優れていることが理解できる。When the obtained Cu--Cr composite material was used as an electrode material for a vacuum circuit breaker, the cutoff value was as low as 1A. On the other hand, Cu-Cr infiltration produced by sintering Cr powder by a conventional infiltration method to produce a skeleton having a high porosity and melt-impregnating the low melting point Cu into the pores of the skeleton. In the case of wood, the cutoff value was as high as 5A. Further, the infiltrated material had a fragile cutting surface, and the surface had severe irregularities and cracks were observed, but the composite material of the present invention had a beautiful cutting surface and had no cracks. From these facts, it can be understood that the Cu—Cr composite material of the present invention is excellent as an electrode material for a vacuum circuit breaker.
【００２３】比較例１ 実施例１と同じ比率でＣｕ粉末とＣｒ粉末を混合し、Ｍ
Ａを行わない変わりにＶ型ミキサーで３０分間混合した
混合粉末を使用し、それ以外は実施例１と同様にしてＣ
ｕ−Ｃｒ系複合材料を製造した。 Comparative Example 1 Cu powder and Cr powder were mixed in the same ratio as in Example 1, and M
Instead of performing A, the mixed powder obtained by mixing with a V-type mixer for 30 minutes was used, and otherwise C was the same as in Example 1.
A u-Cr composite material was manufactured.
【００２４】比較例の混合粉末はＣｒ粒子の大きさがほ
ぼ原料粉末と同じ大きさで極めて粗大であり、得られた
Ｃｕ−Ｃｒ系複合材料においても本発明法による冷間鍛
造後の鍛造材よりも空孔が２倍以上多いことが判った。
又、焼結後、鍛造後、再焼結後のいずれの状態において
も、密度が本発明法の場合よりも真密度比で３〜５％低
く、電気電導度も１〜３％ＩＡＣＳ低かった。The mixed powder of the comparative example had Cr particles of almost the same size as the raw material powder and was extremely coarse, and the obtained Cu--Cr composite material was also a forged material after cold forging according to the method of the present invention. It was found that there were more than twice as many holes as
Further, in any state after sintering, after forging, and after re-sintering, the density was 3 to 5% lower in true density ratio and the electric conductivity was 1 to 3% IACS lower than in the case of the method of the present invention. .
【００２５】実施例２ 実施例１と同じ純Ｃｕ粉末と純Ｃｒ粉末に、粒径１４９
μｍ以下の純Ｂｉ粉末を重量比でＣｕ：Ｃｒ：Ｂｉ＝７
５：２３：２となるように配合し、予備混合後、アトラ
イターによりＡｒガス中で４時間のＭＡを行った。得ら
れたＭＡ粉末中のＣｒ粒子の平均粒径は４μｍであっ
た。このＭＡ粉末を６ｔ／ｃｍ2で冷間成形した後、１
０-3Ｔｏｒｒの真空中において１０００℃で３時間焼結
したところ真密度比は８７％となり、焼結材の電気電導
度は３５％ＩＡＣＳであった。 Example 2 The same pure Cu powder and pure Cr powder as in Example 1 were added with a particle size of 149
Cu: Cr: Bi = 7 in weight ratio of pure Bi powder having a size of μm or less
The ingredients were blended in a ratio of 5: 23: 2, premixed, and then MA was performed in an Ar gas in an Ar gas for 4 hours. The average particle size of Cr particles in the obtained MA powder was 4 μm. After cold molding this MA powder at 6 t / cm 2 , 1
When sintered at 1000 ° C. for 3 hours in a vacuum of 0 −3 Torr, the true density ratio was 87%, and the electric conductivity of the sintered material was 35% IACS.
【００２６】この焼結材を更に１００℃において６ｔ／
ｃｍ2の圧力で冷間鍛造を行ったところ、真密度比は９
６％に向上した。その後、鍛造材を真空中において１０
００℃で３時間再焼結したところ、電気電導度は５４％
ＩＡＣＳまで向上した。又、再焼結により得られたＣｕ
−Ｃｒ系複合材料中のＣｒ粒子の粒径は１〜１４μｍの
範囲内であり、微細組織となっていることが確認され
た。This sintered material was further subjected to 6 t / 100 ° C.
When cold forging was performed at a pressure of cm 2 , the true density ratio was 9
It improved to 6%. Then, the forged material is vacuumed for 10
When re-sintered at 00 ° C for 3 hours, the electric conductivity is 54%.
It improved to IACS. Also, Cu obtained by re-sintering
It was confirmed that the grain size of the Cr particles in the -Cr composite material was within the range of 1 to 14 µm, and that it had a fine structure.
【００２７】次に、Ｃｒ粉末の比率を２３重量％とした
まま、Ｂｉ粉末の比率を０、０.００５、０.０１、０.
０５、０.２、０.５、０.１、１.５、５.０、１０重量
％と変化させ、上記と同様に本発明によるＣｕ−Ｃｒ系
複合材料を製造した。比較のために、同様にＢｉ粉末の
比率を変え、ＭＡを行わない変わりにＶ型ミキサーで３
０分間混合した混合粉末を使用し、それ以外は実施例２
と同様にしてＣｕ−Ｃｒ系複合材料を製造した。Next, with the Cr powder ratio kept at 23% by weight, the Bi powder ratios were changed to 0, 0.005, 0.01, and 0.0.
The Cu-Cr-based composite material according to the present invention was manufactured in the same manner as above by changing the amount to 05, 0.2, 0.5, 0.1, 1.5, 5.0 and 10% by weight. For comparison, the ratio of Bi powder was changed in the same manner, and the V-type mixer was used instead of MA instead of 3
Example 2 was used except that the mixed powder was mixed for 0 minutes.
A Cu-Cr composite material was manufactured in the same manner as in.
【００２８】いずれのＢｉ濃度においても、ＭＡなしの
Ｃｕ−Ｃｒ系複合材料はＣｒ粒子の粒径が２０μｍ以上
であったが、本発明のＭＡを実施した複合材料では１〜
１４μｍの微細組織になっていることが判った。又、Ｂ
ｉ濃度が０.０１重量％以上になると、ＭＡなしの複合
材料はＭＡを行った本発明の複合材料より５倍以上も空
孔が多く存在し、ロウ付け性が劣化するなど機械加工性
が低下した。このことから、Ｂｉの電極材料に与える効
果が期待される０.２重量％以上の濃度では、本発明に
よるＭＡを行ったＣｕ−Ｃｒ系複合材料が優れているこ
とが判る。At any Bi concentration, the Cu--Cr based composite material without MA had a grain size of Cr particles of 20 μm or more.
It was found that the microstructure was 14 μm. Also, B
When the i concentration was 0.01% by weight or more, the composite material without MA had more than 5 times more pores than the composite material of the present invention in which MA was performed, resulting in poor machinability such as deterioration in brazing property. Fell. From this, it is understood that the Cu-Cr-based composite material obtained by MA according to the present invention is excellent at a concentration of 0.2% by weight or more, which is expected to have the effect of Bi on the electrode material.
【００２９】比較例２ 実施例２と同様にＣｕ−２３重量％Ｃｒ−２重量％Ｂｉ
に配合した原料粉末をメカニカルアロイング（ＭＡ）
し、次に焼結した後、得られた焼結材を実施例２の冷間
鍛造の代わりに下記のａ〜ｅの各加工処理を行った。 Comparative Example 2 As in Example 2, Cu-23% by weight Cr-2% by weight Bi
Mechanical alloying (MA)
Then, after sintering, the obtained sintered material was subjected to the following respective processing treatments of a to e instead of the cold forging of Example 2.
【００３０】ａ：焼結材をＣｕ容器に入れ、２００℃で
１０-3Ｔｏｒｒの真空中にて封止した後、８００℃にて
押出比８で押出加工 ｂ：焼結材をそのまま８００℃にて押出比８で押出加工 ｃ：焼結材をそのまま常温にて押出比８で押出加工 ｄ：焼結材をａと同様に容器中に封止した後、８００℃
×２０００ｋｇｆ／ｃｍ2×１時間の条件でＡｒガス中
でＨＩＰ加工 ｅ：焼結材をそのままｄと同じ条件でＨＩＰ加工A: Sintered material is put in a Cu container, sealed at 200 ° C. in a vacuum of 10 −3 Torr, and then extruded at 800 ° C. with an extrusion ratio of 8 b: Sintered material as it is at 800 ° C. Extruding with an extrusion ratio of 8 c: Extruding the sintered material as it is at room temperature with an extrusion ratio of 8 d: Sealing the sintered material in a container in the same manner as a, then 800 ° C
HIP processing in Ar gas under the condition of × 2000 kgf / cm 2 × 1 hour e: HIP processing of the sintered material as it is under the same conditions as d
【００３１】ａ及びｄの加工処理で得られた複合材料は
実施例２の場合とほぼ同様に密度及び電気電導度が向上
し、真密度比は９５％及び電気電導度は約３０％ＩＡＣ
Ｓになった。しかし、ａ及びｄの加工処理は真空容器の
作製と真空封入作業が必要であるため、コストが非常に
高くなる欠点がある。一方、ｂの加工処理で得られた複
合材料は真密度比が９２％であったが、加熱中の酸化反
応によるブリスター状の空孔が数多く発生した。又、ｅ
の加工処理による複合材料ではブリスターの発生はなか
ったが、真密度比が約８６％で焼結材の密度から殆ど向
上していなかった。更に、ｃの加工処理は最も簡便で経
済的であるが、押出圧力が押出機の限界に近くなるため
圧し詰まりを起こすことが多いうえ、押出材に割れが多
く発生するため良好な材料の回収率は鍛造材の１／１０
以下と極めて低かった。The composite material obtained by the processing of a and d improved in density and electric conductivity in substantially the same manner as in Example 2, the true density ratio was 95% and the electric conductivity was about 30% IAC.
It became S. However, since the processing of a and d requires the production of a vacuum container and the vacuum sealing work, there is a drawback that the cost becomes very high. On the other hand, the composite material obtained by the processing of b had a true density ratio of 92%, but many blister-shaped holes were generated due to the oxidation reaction during heating. Also, e
Although the blister did not occur in the composite material by the processing of (1), the true density ratio was about 86%, which was almost not improved from the density of the sintered material. Further, the processing of c is the simplest and most economical, but the extrusion pressure is close to the limit of the extruder, so that it is often pressed and clogged. In addition, many cracks occur in the extruded material and good recovery of the material. Ratio is 1/10 of forged material
It was extremely low as below.
【００３２】次に、同じＣｕ−２３重量％Ｃｒ−２重量
％Ｂｉに配合した原料粉末をＭＡした後、ＭＡ粉末を成
形及び焼結する代わりに、下記に示すｆ及びｇの各加工
処理を行った。Next, after the raw material powder blended with the same Cu-23 wt% Cr-2 wt% Bi was MA, instead of molding and sintering the MA powder, the respective processings of f and g shown below were performed. went.
【００３３】ｆ：ＭＡ粉末をＣｕ容器に入れ、２００℃
で１０-3Ｔｏｒｒの真空中にて封止した後、９００℃に
て押出比８で押出加工 ｇ：ＭＡ粉末をｆと同様に容器中に封止した後、９００
℃×２０００ｋｇｆ／ｃｍ2×１時間の条件でＡｒガス
中でＨＩＰ加工F: MA powder was placed in a Cu container and the temperature was 200 ° C.
And then sealed in a vacuum of 10 −3 Torr at 900 ° C. and extruded at an extrusion ratio of 8 g: MA powder was sealed in a container in the same manner as f, and then 900
HIP processing in Ar gas under the condition of ℃ × 2000kgf / cm 2 × 1 hour
【００３４】ｆ及びｇの加工処理で得られた複合材料
は、共に真密度比が９５％及び電気電導度が２８〜３１
％ＩＡＣＳと高かったが、ＭＡ粉末を容器中に真空封入
する必要があるので、本発明方法に比べると極めて非生
産的である。The composite materials obtained by the processing of f and g both have a true density ratio of 95% and an electric conductivity of 28 to 31.
Although it was as high as% IACS, it is extremely unproductive as compared with the method of the present invention because the MA powder needs to be vacuum-sealed in the container.
【００３５】実施例３ 実施例２と同じ純Ｃｕ粉末と純Ｃｒ粉末と純Ｂｉ粉末を
重量比でＣｕ：Ｃｒ：Ｂｉ＝７５：２１：４となるよう
に配合し、予備混合後、振動ミルによりＡｒガス中で２
０時間のメカニカルアロイングを行った。得られたＭＡ
粉末中のＣｒ粒子の平均粒径は５μｍであった。このＭ
Ａ粉末を６ｔ／ｃｍ2で冷間成形した後、水素雰囲気中
において１０００℃で３時間焼結した。得られた焼結材
を常温にて６ｔ／ｃｍ2の圧力で冷間鍛造を行った後、
鍛造材を真空中にて８００℃で３時間再焼結した。 Example 3 The same pure Cu powder, pure Cr powder and pure Bi powder as in Example 2 were blended in a weight ratio of Cu: Cr: Bi = 75: 21: 4, premixed and then vibrated. 2 in Ar gas
I did mechanical alloying for 0 hours. MA obtained
The average particle size of Cr particles in the powder was 5 μm. This M
The powder A was cold-molded at 6 t / cm 2 and then sintered in a hydrogen atmosphere at 1000 ° C. for 3 hours. After cold forging the obtained sintered material at a pressure of 6 t / cm 2 at room temperature,
The forged material was re-sintered in vacuum at 800 ° C. for 3 hours.
【００３６】得られた再焼結材のＣｕ−Ｃｒ複合材料
は、Ｃｒ粒子の粒径１〜１５μｍの微細組織を有し、電
気電導度は５４％ＩＡＣＳであって、４００℃で５時間
焼鈍したところ電気電導度が約１〜４％ＩＡＣＳ増加し
た。又、再焼結材と再焼結なしの鍛造材の引張強度を比
較したところ、再焼結材はＣｒ粒子とＣｕマトリックス
の界面が強固なため２８ｋｇ／ｍｍ2の引張強度を示し
たが、再焼結なしの鍛造材はその７０％以下の引張強度
しか示さなかった。The obtained Cu--Cr composite material of the re-sintered material had a fine structure of Cr particles having a particle size of 1 to 15 μm, an electric conductivity of 54% IACS, and was annealed at 400 ° C. for 5 hours. Then, the electric conductivity was increased by about 1 to 4% IACS. When the tensile strengths of the re-sintered material and the forged material without re-sintering were compared, the re-sintered material showed a tensile strength of 28 kg / mm 2 due to the strong interface between the Cr particles and the Cu matrix. The forged material without resintering exhibited a tensile strength of 70% or less.
【００３７】実施例４ 実施例２と同じ純Ｃｕ粉末と純Ｃｒ粉末と純Ｂｉ粉末に
Ｚ粉末を加え、重量比でＣｕ：Ｃｒ：Ｂｉ：Ｚｒ＝５
４.８：４４：０.２：１となるように配合した。更に、
Ｃｒ2Ｏ3粉末とＣｒ3Ｃ2粉末をそれぞれ０〜７重量％加
え、予備混合後、振動ミルによりＡｒガス中で２０時間
のＭＡを行った。Ｃｒ2Ｏ3粉末又はＣｒ3Ｃ2粉末を加え
た場合はＭＡの進行が早く、これらの添加量が増えるに
従って得られたＭＡ粉末中のＣｒ粒子は小さくなること
が判った。 Example 4 Z powder was added to the same pure Cu powder, pure Cr powder, and pure Bi powder as in Example 2, and Cu: Cr: Bi: Zr = 5 by weight ratio.
It was blended so as to be 4.8: 44: 0.2: 1. Furthermore,
Each of Cr 2 O 3 powder and Cr 3 C 2 powder was added in an amount of 0 to 7% by weight, and after premixing, MA was performed for 20 hours in Ar gas by a vibration mill. It was found that when the Cr 2 O 3 powder or the Cr 3 C 2 powder was added, MA proceeded quickly, and the Cr particles in the MA powder obtained became smaller as the addition amount of these increased.
【００３８】各ＭＡ粉末を６ｔ／ｃｍ2で冷間成形した
後、真空中において１０００℃で３時間焼結した。得ら
れた焼結材を常温にて６ｔ／ｃｍ2の圧力で冷間鍛造を
行った後、鍛造材を真空中にて８００℃で３時間再焼結
した。再焼結材はいずれも１２μｍ以下の微細なＣｒ粒
子を含む組織となっており、ＭＡにより微細組織が得ら
れることが判る。Each MA powder was cold-formed at 6 t / cm 2 and then sintered in vacuum at 1000 ° C. for 3 hours. The obtained sintered material was cold forged at room temperature under a pressure of 6 t / cm 2 , and then the forged material was re-sintered in vacuum at 800 ° C. for 3 hours. Each of the re-sintered materials has a structure containing fine Cr particles of 12 μm or less, and it can be seen that a fine structure can be obtained by MA.
【００３９】しかし、得られる複合材料の強度はＣｒ2
Ｏ3粉末とＣｒ3Ｃ2粉末の添加量が増えると共に低下
し、Ｃｕ−４４重量％Ｃｒ−１重量％Ｚｒ−０.２重量
％Ｂｉの系での引張強度は２７ｋｇ／ｍｍ2であるのに
対して、Ｃｕ−４４重量％Ｃｒ−１重量％Ｚｒ−０.２
重量％Ｂｉ−５重量％Ｃｒ2Ｏ3の系では１４ｋｇ／ｍｍ
2及びＣｕ−４４重量％Ｃｒ−１重量％Ｚｒ−０.２重量
％Ｂｉ−７重量％Ｃｒ2Ｏ3の系では８.９ｋｇ／ｍｍ2と
なり、構造材としては強度的に使用に適しないことが判
った。However, the strength of the obtained composite material is Cr 2
The amount of O 3 powder and Cr 3 C 2 powder added increased and decreased, and the tensile strength in the system of Cu-44 wt% Cr-1 wt% Zr-0.2 wt% Bi was 27 kg / mm 2 . On the other hand, Cu-44 wt% Cr-1 wt% Zr-0.2
14 kg / mm in the system of wt% Bi-5 wt% Cr 2 O 3
2 and Cu-44 wt% Cr-1 wt% Zr-0.2 wt% Bi-7 wt% Cr 2 O 3 system has 8.9 kg / mm 2 , which is not suitable for use as a structural material in terms of strength. I knew that.
【００４０】[0040]
【発明の効果】本発明によれば、互いに非固溶のＣｕと
Ｃｒとの微細な析出相からなる組織を有し、真空遮断器
の電極材料等として優れた特性を持つＣｕ−Ｃｒ系複合
材料を経済的に提供することが出来る。EFFECTS OF THE INVENTION According to the present invention, a Cu-Cr-based composite having a structure composed of fine precipitation phases of Cu and Cr which are insoluble with each other and having excellent characteristics as an electrode material for a vacuum circuit breaker, etc. Materials can be provided economically.
【図１】本発明方法による成形、焼結、冷間鍛造、及び
再焼結の各工程におけるＣｕ−Ｃｒ系複合材料の真密度
の変化を示すグラフである。FIG. 1 is a graph showing changes in true density of a Cu—Cr based composite material in each step of forming, sintering, cold forging, and re-sintering according to the method of the present invention.
【図２】本発明方法による焼結、冷間鍛造、及び再焼結
の各工程におけるＣｕ−Ｃｒ系複合材料の電気電導度の
変化を示すグラフである。FIG. 2 is a graph showing changes in electric conductivity of a Cu—Cr based composite material in each step of sintering, cold forging, and re-sintering according to the method of the present invention.
Claims (6)
５０重量％となるように配合し、不活性ガス雰囲気中で
メカニカルアロイングし、得られたメカニカルアロイン
グ粉末を冷間成形し、成形体を水素ガス中又は真空中に
おいて５００℃以上で焼結し、焼結材を１００℃以下で
冷間鍛造し、次に鍛造材を５００℃以上で再焼結するこ
とを特徴とするＣｕ−Ｃｒ系複合材料の製造方法。1. A Cu powder and a Cr powder containing 5 to 5 Cr powders.
50% by weight is blended, mechanically alloyed in an inert gas atmosphere, the resulting mechanically alloyed powder is cold-molded, and the molded body is sintered in hydrogen gas or vacuum at 500 ° C. or higher. Then, the sintered material is cold forged at 100 ° C. or lower, and then the forged material is re-sintered at 500 ° C. or higher, and a method for producing a Cu—Cr based composite material.
るようにメカニカルアロイングすることを特徴とする、
請求項１に記載のＣｕ−Ｃｒ系複合材料の製造方法。2. Mechanical alloying so that the average particle diameter of Cr particles is 30 μm or less,
The method for producing the Cu-Cr composite material according to claim 1.
Ｚｒ粉末、Ｂ粉末、酸化クロム粉末又は炭化クロム粉末
を全体の０.０１〜５重量％となるように配合した後、
メカニカルアロイングすることを特徴とする、請求項１
又は２に記載のＣｕ−Ｃｒ系複合材料の製造方法。3. In addition to Cu powder and Cr powder, Bi powder,
After blending Zr powder, B powder, chromium oxide powder or chromium carbide powder so as to be 0.01 to 5% by weight of the whole,
2. Mechanical alloying
Or the manufacturing method of Cu-Cr type composite material as described in 2.
その合金組成における融点の１／３以上の温度で焼鈍す
ることを特徴とする、請求項１〜３のいずれかに記載の
Ｃｕ−Ｃｒ系複合材料の製造方法。4. The Cu—Cr alloy according to claim 1, wherein the mechanical alloying powder is annealed at a temperature of 1/3 or more of the melting point of its alloy composition before sintering. Method for manufacturing a composite material.
材料を、更に非酸化性雰囲気中において３００〜８５０
℃で時効処理することを特徴とする、請求項１ないし４
のいずれかに記載のＣｕ−Ｃｒ系複合材料の製造方法。5. The composite material obtained by cold forging or re-sintering is further subjected to 300 to 850 in a non-oxidizing atmosphere.
5. Aging treatment at 0 ° C. 5.
5. A method for producing a Cu-Cr composite material according to any one of 1.
材料を、更に押出加工又はＨＩＰ処理することを特徴と
する、請求項１ないし４のいずれかに記載のＣｕ−Ｃｒ
系複合材料の製造方法。6. The Cu—Cr according to claim 1, wherein the composite material obtained by cold forging or re-sintering is further subjected to extrusion processing or HIP processing.
Method for manufacturing a composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14694893A JP3321906B2 (en) | 1993-05-26 | 1993-05-26 | Method for producing Cu-Cr based composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14694893A JP3321906B2 (en) | 1993-05-26 | 1993-05-26 | Method for producing Cu-Cr based composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06330101A true JPH06330101A (en) | 1994-11-29 |
| JP3321906B2 JP3321906B2 (en) | 2002-09-09 |
Family
ID=15419200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14694893A Expired - Fee Related JP3321906B2 (en) | 1993-05-26 | 1993-05-26 | Method for producing Cu-Cr based composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3321906B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006015149A (en) * | 2004-06-30 | 2006-01-19 | Cordis Corp | Improved magnetic resonance imaging compatibility alloy for implantable medical devices |
| CN107604200A (en) * | 2017-09-06 | 2018-01-19 | 西安理工大学 | A kind of preparation method of the enhanced CuCr alloys of timeliness |
| CN112589101A (en) * | 2020-10-21 | 2021-04-02 | 陕西斯瑞新材料股份有限公司 | Preparation method of copper-chromium shielding case for vacuum arc-extinguishing chamber |
| CN115522096A (en) * | 2022-10-11 | 2022-12-27 | 江西理工大学 | Preparation method of copper-chromium alloy with heterogeneous lamellar structure |
-
1993
- 1993-05-26 JP JP14694893A patent/JP3321906B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006015149A (en) * | 2004-06-30 | 2006-01-19 | Cordis Corp | Improved magnetic resonance imaging compatibility alloy for implantable medical devices |
| CN107604200A (en) * | 2017-09-06 | 2018-01-19 | 西安理工大学 | A kind of preparation method of the enhanced CuCr alloys of timeliness |
| CN112589101A (en) * | 2020-10-21 | 2021-04-02 | 陕西斯瑞新材料股份有限公司 | Preparation method of copper-chromium shielding case for vacuum arc-extinguishing chamber |
| CN112589101B (en) * | 2020-10-21 | 2022-09-09 | 陕西斯瑞新材料股份有限公司 | Preparation method of copper-chromium shielding case for vacuum arc-extinguishing chamber |
| CN115522096A (en) * | 2022-10-11 | 2022-12-27 | 江西理工大学 | Preparation method of copper-chromium alloy with heterogeneous lamellar structure |
| CN115522096B (en) * | 2022-10-11 | 2023-04-07 | 江西理工大学 | Preparation method of copper-chromium alloy with heterogeneous lamellar structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3321906B2 (en) | 2002-09-09 |
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