JP2013237887A - Method for producing copper-iron alloy - Google Patents
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本発明は、Ｃｕを主成分とするＣｕ基質中にＣｕとＦｅの金属間化合物（以下、「Ｃｕ／Ｆｅ間化合物」と記す。）が分散した銅鉄合金の製造方法に関する。 The present invention relates to a method for producing a copper-iron alloy in which an intermetallic compound of Cu and Fe (hereinafter referred to as “Cu / Fe intermetallic compound”) is dispersed in a Cu substrate containing Cu as a main component.
従来の銅鉄合金の製造方法は、炉内へＦｅを投入し、Ｆｅが完全に溶けたところでＣｕを装入し、晶化反応させ、反応溶湯をインゴットケースに注湯する（例えば、特許文献１参照。）。 In a conventional method for producing a copper-iron alloy, Fe is introduced into a furnace, Cu is charged when the Fe is completely melted, a crystallization reaction is performed, and the reaction molten metal is poured into an ingot case (for example, Patent Documents). 1).
得られたインゴットは、Ｃｕを主成分とする基質中にＣｕ／Ｆｅ間化合物の晶体片（以下、「Ｃｕ／Ｆｅ晶体片」と記す。）が均一に分布しており、押出し、圧延、引き抜きなどの塑性加工により、様々な工業材料となる。このような複合材料は、Ｃｕ基質中に高透磁性体であるＣｕ／Ｆｅ晶体片が分散されているため、例えば、電磁波に対するシールド材として非常に優れた特性を有する。 In the obtained ingot, Cu / Fe compound crystal pieces (hereinafter referred to as “Cu / Fe crystal pieces”) are uniformly distributed in a substrate containing Cu as a main component, and are extruded, rolled, and drawn. It becomes various industrial materials by plastic working such as. Such a composite material has very excellent characteristics as a shielding material against electromagnetic waves, for example, because a Cu / Fe crystal piece, which is a highly permeable material, is dispersed in a Cu substrate.
しかしながら、特許文献１の製法では、Ｆｅ溶湯中に固体のＣｕを装入するため、溶湯面の乱れが大きく、気泡が紛れ込み易い。また、直ぐにＣｕとＦｅの晶化反応が開始し、液相中に固相が析出し、液相に対して固相の占める割合が増大し、溶湯の粘度が高くなるため、真空炉で脱気してもすべての気泡を除去することはできない。 However, in the manufacturing method of Patent Document 1, since solid Cu is charged into the molten Fe, the molten metal surface is greatly disturbed, and bubbles are easily mixed. In addition, the crystallization reaction of Cu and Fe starts immediately, the solid phase precipitates in the liquid phase, the proportion of the solid phase in the liquid phase increases, and the viscosity of the molten metal increases. You can't remove all the bubbles even if you care.
また、溶湯には、空気だけでなく、原料に付着した油脂汚れの微細な分解ガスも紛れ込む。溶湯中に紛れ込んだ微細な気泡は、鍛造や押し出しによる加工でも潰すことができない。 Moreover, not only air but also fine cracked gas of oil and fat dirt adhering to the raw material is mixed in the molten metal. The fine bubbles mixed in the molten metal cannot be crushed by forging or extrusion.
溶湯中に気泡が紛れ込み、インゴット、ビレットなどの鋳塊に気孔として混入した場合、塑性加工に大きな障害となる。特に直径０．１ｍｍオーダの細線の引き抜きでは、鋳塊中の微細な気孔でも断線の原因となる。このため、銅鉄合金の製造では、溶湯中の気泡を完全に脱気する方法が望まれている。 When bubbles are mixed into the molten metal and mixed as pores in an ingot such as an ingot or billet, it becomes a major obstacle to plastic working. In particular, when a thin wire having a diameter of 0.1 mm is drawn, even fine pores in the ingot cause disconnection. For this reason, in the manufacture of a copper-iron alloy, a method of completely degassing bubbles in the molten metal is desired.
本発明は、このような従来の実情に鑑みて提案されたものであり、気孔の混入を低減し、高品質な鋳塊を得ることができる銅鉄合金の製造方法を提供する。 The present invention has been proposed in view of such a conventional situation, and provides a method for producing a copper-iron alloy capable of reducing the mixing of pores and obtaining a high-quality ingot.
本発明に係る銅鉄合金の製造方法は、電解銅と、純鉄の粒片を溶解炉に投入する投入工程と、前記電解銅を溶解させ、銅溶湯中のガスを脱気させる脱気工程と、前記純鉄を溶解させ、銅と鉄とを晶化反応させる反応工程と、前記晶化反応させた反応溶湯を鋳型に注湯する注湯工程とを有することを特徴とする。 The method for producing a copper-iron alloy according to the present invention includes electrolytic copper and a step of introducing pure iron particles into a melting furnace, and a degassing step of dissolving the electrolytic copper and degassing the gas in the molten copper. And a reaction step in which the pure iron is dissolved to cause crystallization reaction between copper and iron, and a pouring step in which the reaction molten metal obtained by the crystallization reaction is poured into a mold.
また、本発明に係る銅鉄合金の製造方法は、電解銅を第１の溶解炉で溶解させ、銅溶湯中のガスを脱気させる銅溶湯脱気工程と、純鉄を第２の溶解炉で溶解させ、鉄溶湯中のガスを脱気させる鉄溶湯脱気工程と、前記第１の溶解炉の銅溶湯と前記第２の溶解炉の鉄溶湯とを混合し、銅と鉄とを晶化反応させる反応工程と、前記晶化反応させた反応溶湯を鋳型に注湯する注湯工程とを有することを特徴とする。 Moreover, the manufacturing method of the copper iron alloy which concerns on this invention melts | dissolves electrolytic copper with a 1st melting furnace, and degasses the gas in a molten copper, and the 2nd melting furnace with pure iron The molten iron degassing step for degassing the gas in the molten iron, mixing the molten copper in the first melting furnace with the molten iron in the second melting furnace, and crystallizing copper and iron. A crystallization reaction step and a pouring step of pouring the crystallization reaction reaction molten metal into a mold.
本発明によれば、溶湯の粘度が高くなるＣｕ／Ｆｅ間の晶化反応の前に、溶湯中のガスを十分に脱気することができるため、気孔の混入が極めて少ない、高品質な鋳塊を得ることができる。 According to the present invention, the gas in the molten metal can be sufficiently degassed before the crystallization reaction between Cu / Fe in which the viscosity of the molten metal becomes high. A lump can be obtained.
以下、本発明の実施の形態について、図面を参照しながら下記順序にて詳細に説明する。
１．第１の実施の形態
２．第２の実施の形態
３．実施例
Hereinafter, embodiments of the present invention will be described in detail in the following order with reference to the drawings.
1. First Embodiment 2. FIG. Second Embodiment 3. FIG. Example
＜１．第１の実施の形態＞
図１は、第１の実施の形態における銅鉄合金の製造方法を示すフローチャートである。図１に示すように、第１の実施の形態における銅鉄合金の製造方法は、電解銅と、純鉄の粒片を溶解炉に投入する投入工程Ｓ１１と、電解銅を溶解させ、銅溶湯中のガスを脱気させる脱気工程Ｓ１２と、純鉄を溶解させ、Ｃｕ／Ｆｅ間に晶化反応させる反応工程Ｓ１３と、晶化反応させた反応溶湯を鋳型に注湯する注湯工程Ｓ１４と、加工工程Ｓ１５とを有する。
<1. First Embodiment>
FIG. 1 is a flowchart showing a method for producing a copper-iron alloy in the first embodiment. As shown in FIG. 1, the method for producing a copper-iron alloy in the first embodiment includes electrolytic copper, a charging step S <b> 11 in which pure iron particles are charged into a melting furnace, and electrolytic copper is melted to obtain a molten copper. Degassing step S12 for degassing the gas therein, reaction step S13 for dissolving pure iron and crystallization reaction between Cu / Fe, and pouring step S14 for pouring the crystallization reaction reaction molten metal into the mold And processing step S15.
投入工程Ｓ１１では、電解銅と、純鉄の粒片を溶解炉に投入する。電解銅は、粗銅を電解精錬することによって得られる、いわゆる電気銅であり、純度が９９．９９％以上の純銅である。純鉄は、炭素含有量が０．０２％以下であり、その他の不純物元素が非常に少ない鉄である。また、純鉄の粒片は、焼鈍などにより球状化処理された球状であることが好ましい。また、純鉄の粒片の粒径は、網ふるいの目開き（JIS Z 8801）で０．５ｍｍ以上２．０ｍｍ以下であることが好ましい。純鉄の粒片が網ふるいの目開きで０．５ｍｍ未満である場合、酸化反応により粉塵爆発が起こる虞がある。一方、純鉄の粒片が目開きで２．０ｍｍより大きい場合、次の脱気工程Ｓ１２において、Ｆｅの溶融時間とＣｕ／Ｆｅの晶化時間が長くなり、結果として結晶の成長に差異がでる虞がある。また、原料投入工程Ｓ１１において、例えば、優れた電磁波遮蔽効果を得るために、電解銅と、純鉄の粒片と共に、コバルト、ニッケル、マンガンクロムなどを少量添加してもよい。 In the charging step S11, electrolytic copper and pure iron particles are charged into a melting furnace. The electrolytic copper is so-called electrolytic copper obtained by electrolytic refining of crude copper, and is pure copper having a purity of 99.99% or more. Pure iron is iron with a carbon content of 0.02% or less and very little other impurity elements. Moreover, it is preferable that the particle pieces of pure iron have a spherical shape that has been spheroidized by annealing or the like. The particle diameter of the pure iron particles is preferably 0.5 mm or more and 2.0 mm or less in terms of mesh sieve openings (JIS Z 8801). If the pure iron particles are less than 0.5 mm with a mesh sieve opening, dust explosion may occur due to the oxidation reaction. On the other hand, when the pure iron particles are larger than 2.0 mm with an opening, in the next degassing step S12, the melting time of Fe and the crystallization time of Cu / Fe become long, resulting in a difference in crystal growth. There is a risk of going out. Further, in the raw material charging step S11, for example, in order to obtain an excellent electromagnetic wave shielding effect, a small amount of cobalt, nickel, manganese chromium, etc. may be added together with electrolytic copper and pure iron particles.
溶解炉としては、燃焼炉又は電気炉を使用することができるが、高品質な鋳塊を製造する観点から、電気炉の一つである高周波誘導炉を使用することが好ましい。高周波溶解炉は、誘導電力によって溶湯を活発に攪拌するため、次の銅溶湯脱気工程Ｓ１２において、銅溶湯中の純鉄の粒片を均一に分散させ、銅溶湯の粘度を低下させ、ガスの脱気を十分に行うことができる。また、溶解炉の炉材は、グラファイト系を避け、シリカ系又はマグネシア系を採用することが望ましい。グラファイト系の炉材を使用し、溶湯中に炭素が溶け込んでしまうと、Ｆｅの融点が低下してＣｕ／Ｆｅ間の晶化反応が乱され、また、Ｆｅ／Ｃ合金が生じて偏析の原因となる。 As the melting furnace, a combustion furnace or an electric furnace can be used, but from the viewpoint of producing a high quality ingot, it is preferable to use a high frequency induction furnace which is one of electric furnaces. The high frequency melting furnace vigorously agitates the molten metal by induction power, so in the next molten copper degassing step S12, the particles of pure iron in the molten copper are uniformly dispersed, the viscosity of the molten copper is reduced, Can be sufficiently deaerated. Further, it is desirable that the melting furnace material be a silica-based or magnesia-based material, avoiding a graphite-based material. When graphite furnace material is used and carbon dissolves in the molten metal, the melting point of Fe is lowered and the crystallization reaction between Cu / Fe is disturbed, and the Fe / C alloy is produced, causing segregation. It becomes.
脱気工程Ｓ１２では、溶解炉の温度をＣｕの融点（１０８３℃）以上、Ｆｅの融点（１５３５℃）以下にし、電解銅を溶解させる。溶解炉の温度は、脱気促進の観点から、なるべく高温域である方が好ましい。 In the deaeration step S12, the melting furnace temperature is set to a melting point of Cu (1083 ° C.) or higher and a melting point of Fe (1535 ° C.) or lower to dissolve electrolytic copper. The temperature of the melting furnace is preferably as high as possible from the viewpoint of promoting degassing.
電解銅を溶解させた後、溶解炉の温度を保ち、銅溶湯中のガスを十分に脱気させる。脱気時間は、原料の投入量によるが、例えば合計１００ｋｇを投入した場合、２０〜５０分程度である。 After the electrolytic copper is dissolved, the temperature of the melting furnace is maintained, and the gas in the molten copper is sufficiently degassed. Although the deaeration time depends on the amount of raw material charged, for example, when a total of 100 kg is charged, it is about 20 to 50 minutes.
脱気工程Ｓ１２における銅溶湯は、Ｃｕ液相に未融解のＦｅ固体が分散した混相であり、Ｃｕ液体の密度とＦｅ固体の密度は、それぞれ７９４０ｋｇ／ｍ３と７８７４ｋｇ／ｍ３とほぼ同じ値である。このため、粗粒のＦｅ固体は、Ｃｕ液相中に浮遊し、相互干渉が少ないため、溶湯は低粘度となる。したがって、溶解炉の温度を一定時間保つことにより、溶湯中のガスを容易に脱気させることができる。また、原料投入工程Ｓ１１において、網ふるいの目開き（JIS Z 8801）で０．５ｍｍ以上２．０ｍｍ以下の純鉄の粒片を投入することにより、溶湯の粘度を低下させることができるため、溶湯中のガスをより容易に脱気させることができる。 Molten copper in degassing step S12, a mixed phase of Fe solid is dispersed unmelted in Cu liquid phase, the density of the density and Fe solid Cu liquid, respectively almost the same value as 7940kg / m 3 and 7874kg / m 3 It is. For this reason, since the coarse Fe solid floats in the Cu liquid phase and there is little mutual interference, the molten metal has a low viscosity. Therefore, the gas in the molten metal can be easily degassed by maintaining the temperature of the melting furnace for a certain time. Moreover, in the raw material charging step S11, the viscosity of the molten metal can be reduced by introducing particles of pure iron of 0.5 mm or more and 2.0 mm or less with a mesh sieve opening (JIS Z 8801). The gas in the molten metal can be degassed more easily.
また、銅溶湯中にケイ素（Ｓｉ）、リン（Ｐ）、リチウム（Ｌｉ）などを含むＣｕ脱酸剤を添加することが好ましい。これにより、銅溶湯中のガスの脱気を促進させ、銅溶湯中の気泡の紛れ込みを確実に低減することができる。 Moreover, it is preferable to add Cu deoxidizer containing silicon (Si), phosphorus (P), lithium (Li) etc. in a molten copper. Thereby, the deaeration of the gas in the molten copper can be promoted, and the intrusion of bubbles in the molten copper can be reliably reduced.
晶化反応工程Ｓ１３では、溶解炉の温度をＦｅの融点（１５３５℃）以上にし、純鉄を溶解させ、銅と鉄とを晶化反応させる。溶解炉の温度は、晶化反応の促進と完結の観点から、なるべく高温域の方が好ましい。なお、晶化反応時間は、原料の投入量によるが、例えば合計１００ｋｇを投入した場合、５〜４０分程度である。 In the crystallization reaction step S13, the temperature of the melting furnace is set to the melting point of Fe (1535 ° C.) or more, pure iron is dissolved, and copper and iron are crystallized. The temperature of the melting furnace is preferably as high as possible from the viewpoint of promoting and completing the crystallization reaction. The crystallization reaction time depends on the amount of raw material charged, but is about 5 to 40 minutes when a total of 100 kg is charged, for example.
Ｆｅは、Ｃｕに対する溶解度が２％と低いため、大半が過飽和成分となり、直ぐにＣｕと結合し、さらに、これらの結合単位は、晶化反応を繰り返してＣｕ／Ｆｅ間化合物に成長する。このＣｕ／Ｆｅ間化合物は、極めて安定な物質であり、その融点は、Ｆｅの融点（１５３５℃）よりも高くなる。また、金属間化合物の密度は、Ｃｕ液相と同程度であるから、これらの晶体粒片もＣｕの分散媒に懸濁する。晶体粒片の粒径は、１０−９〜１０−７ｍと微細である。また、晶体粒片の一部は球状化しているが、大半は扁平な紐状を呈している。晶化反応を繰り返して晶体粒片の濃度が高くなると、混相は容易に分散コロイドになり、流動抵抗が増大し、高粘度を発現する。この結果、晶化反応は、阻害され、停留する。 Since Fe has a low solubility in Cu of 2%, most of it becomes a supersaturated component and immediately bonds to Cu, and these bond units grow into a Cu / Fe compound by repeating the crystallization reaction. This Cu / Fe compound is a very stable substance, and its melting point is higher than the melting point of Fe (1535 ° C.). Further, since the density of the intermetallic compound is approximately the same as that of the Cu liquid phase, these crystal grain pieces are also suspended in the Cu dispersion medium. The grain size of the crystal grains is as small as 10 −9 to 10 −7 m. In addition, some of the crystal grain pieces are spheroidized, but most of them have a flat string shape. When the crystallization reaction is repeated to increase the concentration of the crystal grain fragments, the mixed phase easily becomes a dispersed colloid, the flow resistance increases, and a high viscosity is developed. As a result, the crystallization reaction is inhibited and stops.
Ｃｕ／Ｆｅ間の晶化反応を完結するためには、Ｆｅの過飽和度、反応温度、及び反応時間を最適化し、さらには反応溶湯の粘度の変化によって進行度を判定し、反応の停留を防ぐことが肝要である。ＣｕとＦｅの晶化反応が停留すると、Ｆｅの過飽和成分が局所的に析出し、偏析が発生し易くなる。 In order to complete the Cu / Fe crystallization reaction, the degree of supersaturation of Fe, the reaction temperature, and the reaction time are optimized, and the degree of progress is judged by the change in viscosity of the molten metal to prevent the reaction from stopping. It is important. When the crystallization reaction between Cu and Fe stops, the supersaturated component of Fe is locally precipitated and segregation is likely to occur.
注湯工程Ｓ１４では、反応溶湯を鋳型に注湯し、急冷する。このとき、超音波発振器などによって鋳型に振動を与えることが好ましい。これにより、微結晶体粒片が均一に分散した銅鉄合金インゴットを得ることができる。 In the pouring step S14, the reaction molten metal is poured into a mold and rapidly cooled. At this time, it is preferable to apply vibration to the mold by an ultrasonic oscillator or the like. Thereby, it is possible to obtain a copper iron alloy ingot in which fine crystal particles are uniformly dispersed.
加工工程Ｓ１５では、鋳塊（インゴット）に対して、塑性加工（熱間加工・冷間加工）、焼鈍などを行い、製品化する。例えば、線材に加工する場合、インゴットを鍛造して丸棒材にし、熱間ロール圧延して線材とし、この線材を複数回冷間線引きすることにより、直径０．１ｍｍオーダの細線まで伸線することができる。 In the processing step S15, the ingot (ingot) is subjected to plastic processing (hot processing / cold processing), annealing, and the like to produce a product. For example, when processing into a wire rod, the ingot is forged into a round bar, hot rolled to obtain a wire rod, and the wire rod is drawn to a thin wire having a diameter of 0.1 mm by cold drawing a plurality of times. be able to.
また、鋳塊（インゴット）は、純銅を追加、調合した上で、１３００℃以上１５００℃以下の温度で再溶融させてもよい。再溶融させた調合溶湯は、連続鋳造方式で鋳片（ビレット）にし、鋳片を熱間加工（押出し、圧延、引き抜きなど）、熱処理することにより、安定した材料に製品化することができる。 Further, the ingot may be remelted at a temperature of 1300 ° C. or higher and 1500 ° C. or lower after pure copper is added and mixed. The remelted mixed molten metal is made into a slab (billet) by a continuous casting method, and the slab can be commercialized into a stable material by hot working (extrusion, rolling, drawing, etc.) and heat treatment.
このような二段階溶解法によれば、溶湯の粘度が高くなるＣｕ／Ｆｅ間の晶化反応の前の脱気工程Ｓ１２において、銅溶湯中のガスを十分に脱気することができる。また、投入工程Ｓ１１において、球状の純鉄の粒片を投入することにより、脱気工程Ｓ１２の銅溶湯の粘度を低くすることができ、銅溶湯中のガスをさらに脱気することができる。また、脱気工程１２において、銅溶湯中にケイ素、リン、又はリチウムのうち少なくとも１種を含む脱酸剤を添加することにより、銅溶湯中のガスの脱気を促進させ、銅溶湯中への気泡の紛れ込みを確実に低減させることができる。
According to such a two-stage melting method, the gas in the molten copper can be sufficiently degassed in the degassing step S12 before the crystallization reaction between Cu / Fe in which the viscosity of the molten metal increases. In addition, in the charging step S11, by introducing spherical pure iron particles, the viscosity of the molten copper in the degassing step S12 can be lowered, and the gas in the molten copper can be further degassed. Further, in the
＜２．第２の実施の形態＞
図２は、第２の実施の形態における銅鉄合金の製造方法を示すフローチャートである。図２に示すように、第２の実施の形態における銅鉄合金の製造方法は、電解銅を第１の溶解炉で溶解させ、銅溶湯中のガスを脱気させる銅溶湯脱気工程Ｓ２１と、純鉄を第２の溶解炉で溶解させ、鉄溶湯中のガスを脱気させる鉄溶湯脱気工程Ｓ２２と、第１の溶解炉の銅溶湯と第２の溶解炉の鉄溶湯とを混合し、銅と鉄とを晶化反応させる反応工程Ｓ２３と、晶化反応させた反応溶湯を鋳型に注湯する注湯工程Ｓ２４と、加工工程２５とを有する。
<2. Second Embodiment>
FIG. 2 is a flowchart showing a method for producing a copper-iron alloy according to the second embodiment. As shown in FIG. 2, the method for producing a copper-iron alloy in the second embodiment includes a molten copper degassing step S21 in which electrolytic copper is melted in a first melting furnace and gas in the molten copper is degassed. The molten iron degassing step S22 for melting pure iron in the second melting furnace and degassing the gas in the molten iron, and the molten copper in the first melting furnace and the molten iron in the second melting furnace are mixed. And a reaction step S23 for crystallization reaction of copper and iron, a pouring step S24 for pouring the reaction melt obtained by the crystallization reaction into a mold, and a processing step 25.
銅溶湯脱気工程Ｓ２１では、電解銅を第１の溶解炉で溶解させ、銅溶湯中のガスを脱気させる。電解銅は、粗銅を電解精錬することによって得られる、いわゆる電気銅であり、純度が９９．９９％以上の純銅である。第１の溶解炉としては、燃焼炉又は電気炉を使用することができるが、高品質な鋳塊を製造する観点から、電気炉の一つである高周波誘導炉を使用することが好ましい。また、第１の溶解炉の炉材は、グラファイト系を避け、シリカ系又はマグネシア系を採用することが望ましい。グラファイト系の炉材を使用し、溶湯中に炭素が溶け込んでしまうと、Ｆｅの融点が低下してＣｕ／Ｆｅ間の晶化反応が乱され、また、Ｆｅ／Ｃ合金が生じて偏析の原因となる。 In the molten copper degassing step S21, electrolytic copper is melted in the first melting furnace, and the gas in the molten copper is degassed. The electrolytic copper is so-called electrolytic copper obtained by electrolytic refining of crude copper, and is pure copper having a purity of 99.99% or more. Although a combustion furnace or an electric furnace can be used as the first melting furnace, it is preferable to use a high-frequency induction furnace, which is one of electric furnaces, from the viewpoint of manufacturing a high-quality ingot. Moreover, it is desirable that the furnace material of the first melting furnace avoids the graphite system and adopts the silica system or the magnesia system. When graphite furnace material is used and carbon dissolves in the molten metal, the melting point of Fe is lowered and the crystallization reaction between Cu / Fe is disturbed, and the Fe / C alloy is produced, causing segregation. It becomes.
電解銅の溶解は、第１の溶解炉の温度をＣｕの融点（１０８３℃）以上、Ｆｅの融点（１５３５℃）以下にして行われる。溶解炉の温度は、脱気促進の観点から、なるべく高温域の方が好ましい。 The electrolytic copper is melted at a temperature of the first melting furnace not lower than the melting point of Cu (1083 ° C.) and not higher than the melting point of Fe (1535 ° C.). The temperature of the melting furnace is preferably as high as possible from the viewpoint of promoting degassing.
電解銅を溶解させた後、第１の溶解炉の温度を保ち、銅溶湯中のガスを十分に脱気させる。脱気時間は、電解銅の投入量によるが、例えば１００ｋｇを投入した場合、２０〜５０分程度である。 After the electrolytic copper is dissolved, the temperature of the first melting furnace is maintained, and the gas in the molten copper is sufficiently degassed. Although the deaeration time depends on the amount of electrolytic copper added, for example, when 100 kg is added, it is about 20 to 50 minutes.
また、銅溶湯中にケイ素（Ｓｉ）、リン（Ｐ）、リチウム（Ｌｉ）などを含むＣｕ脱酸剤を添加することが好ましい。これにより、銅溶湯中のガスの脱気を促進させ、銅溶湯中への気泡の紛れ込みを確実に低減させることができる。 Moreover, it is preferable to add Cu deoxidizer containing silicon (Si), phosphorus (P), lithium (Li) etc. in a molten copper. Thereby, the deaeration of the gas in the molten copper can be promoted, and bubbles can be reliably reduced in the molten copper.
鉄溶湯脱気工程Ｓ２２では、純鉄を第２の溶解炉で溶解させ、鉄溶湯中のガスを脱気させる。純鉄は、炭素含有量が０．０２％以下であり、その他の不純物元素が非常に少ない鉄である。第２の溶解炉は、第１の溶解炉と同様のものを用いることができる。 In the molten iron degassing step S22, pure iron is melted in the second melting furnace, and the gas in the molten iron is degassed. Pure iron is iron with a carbon content of 0.02% or less and very little other impurity elements. As the second melting furnace, the same one as the first melting furnace can be used.
純鉄の溶解は、第２の溶解炉の温度をＦｅの融点（１５３５℃）以上にして行われる。溶解炉の温度は、脱気促進の観点から、なるべく高温域の方が好ましい。 The melting of pure iron is performed by setting the temperature of the second melting furnace to the melting point of Fe (1535 ° C.) or higher. The temperature of the melting furnace is preferably as high as possible from the viewpoint of promoting degassing.
純鉄を溶解させた後、第２の溶解炉の温度を保ち、鉄溶湯中のガスを十分に脱気させる。脱気時間は、純鉄の投入量によるが、例えば１００ｋｇを投入した場合、２０〜５０分程度である。 After melting pure iron, the temperature of the second melting furnace is maintained and the gas in the molten iron is sufficiently degassed. Although the deaeration time depends on the amount of pure iron introduced, for example, when 100 kg is introduced, it is about 20 to 50 minutes.
また、鉄溶湯中にアルミニウム（Ａｌ）、マンガン（Ｍｎ）、チタン（Ｔｉ）、ケイ素（Ｓｉ）などを含むＦｅ脱酸剤を添加することが好ましい。これにより、鉄溶湯中のガスの脱気を促進させ、鉄溶湯中への気泡の紛れ込みの混入を確実に低減させることができる。 Moreover, it is preferable to add Fe deoxidizer containing aluminum (Al), manganese (Mn), titanium (Ti), silicon (Si), etc. in molten iron. Thereby, the deaeration of the gas in the molten iron can be promoted, and the mixing of bubbles into the molten iron can be reliably reduced.
反応工程Ｓ２３では、第１の溶解炉の銅溶湯と第２の溶解炉の鉄溶湯とを混合し、銅と鉄とを晶化反応させる。銅溶湯と鉄溶湯との混合は、略同一の溶湯温度で行い、湯面が乱れないように一方の溶湯を流し込む。混合時の溶解炉の温度は、晶化反応の促進と完結の観点から、なるべく高温域の方が好ましい。なお、晶化反応時間は、原料の投入量によるが、例えば合計２００ｋｇを投入した場合、５〜４０分程度である。 In the reaction step S23, the molten copper of the first melting furnace and the molten iron of the second melting furnace are mixed to cause crystallization reaction between copper and iron. Mixing of the molten copper and the molten iron is performed at substantially the same molten metal temperature, and one molten metal is poured so that the molten metal surface is not disturbed. The temperature of the melting furnace at the time of mixing is preferably as high as possible from the viewpoint of promoting and completing the crystallization reaction. The crystallization reaction time depends on the amount of raw material charged, but is about 5 to 40 minutes when a total of 200 kg is charged, for example.
また、反応工程Ｓ２３において、例えば、優れた電磁波遮蔽効果を得るために、電解銅と、純鉄の粒片と共に、コバルト、ニッケル、マンガンクロムなどを少量添加してもよい。 In the reaction step S23, for example, in order to obtain an excellent electromagnetic wave shielding effect, a small amount of cobalt, nickel, manganese chromium or the like may be added together with electrolytic copper and pure iron particles.
Ｆｅは、Ｃｕに対する溶解度が２％と低いため、大半が過飽和成分となり、直ぐにＣｕと結合し、さらに、これらの結合単位は、晶化反応を繰り返して金属間化合物に成長する。金属間化合物の密度は、Ｃｕ液相と同程度であるから、これらの晶体粒片もＣｕの分散媒に懸濁する。晶体粒片の粒径は１０−９〜１０−７ｍと微細であり、晶体粒片の一部は球状化し、大半が扁平な紐状を呈している。晶化反応を繰り返して分散粒片の濃度が高くなると、Ｃｕ液相との混相は分散コロイドになり、流動抵抗が増大し、高粘度を発現する。 Since Fe has a low solubility in Cu of 2%, most of it becomes a supersaturated component and immediately bonds to Cu, and these bond units grow into an intermetallic compound by repeating the crystallization reaction. Since the density of the intermetallic compound is about the same as that of the Cu liquid phase, these crystal grain pieces are also suspended in the Cu dispersion medium. The grain size of the crystal grain pieces is as small as 10 −9 to 10 −7 m, a part of the crystal grain pieces are spheroidized, and most of them have a flat string shape. When the concentration of the dispersed particle pieces increases by repeating the crystallization reaction, the mixed phase with the Cu liquid phase becomes a dispersed colloid, the flow resistance increases, and high viscosity is developed.
Ｃｕ／Ｆｅ間の晶化反応は、不完全な場合、品質低下となるＦｅ偏析が発生してしまい、結晶の生長により巨晶化した場合、材料の物性が劣化する。このため、反応温度、及び反応時間を最適化し、さらには反応溶湯の粘度の変化によって、反応の進行度を判定することが好ましい。 When the crystallization reaction between Cu / Fe is incomplete, Fe segregation that lowers the quality occurs, and when crystallized due to crystal growth, the physical properties of the material deteriorate. For this reason, it is preferable to determine the progress of the reaction by optimizing the reaction temperature and the reaction time, and further by changing the viscosity of the reaction molten metal.
次の注湯工程Ｓ２４及び加工工程Ｓ２５は、それぞれ第１の実施の形態の注湯工程Ｓ１４及び加工工程Ｓ１５と同様のため、ここでは説明を省略する。 Since the next pouring step S24 and the processing step S25 are the same as the pouring step S14 and the processing step S15 of the first embodiment, respectively, description thereof is omitted here.
このような別々溶解法によれば、溶湯の粘度が高くなるＣｕ／Ｆｅ間の晶化反応の前の銅溶湯脱気工程Ｓ２１及び鉄溶湯脱気工程Ｓ２２において、銅溶湯中及び鉄溶湯中のガスをそれぞれ十分に脱気することができる。また、銅溶湯脱気工程２１において、銅溶湯中にケイ素、リン、又はリチウムの少なくとも１種を含む脱酸剤を添加することにより、銅溶湯中のガスの脱気を促進させ、銅溶湯中への気泡の紛れ込みを確実に低減させることができる。また、鉄溶湯脱気工程２２において、鉄溶湯中にアルミニウム、マンガン、チタン、又はケイ素のうち少なくとも１種を含む脱酸剤を添加することにより、鉄溶湯中のガスの脱気を促進させ、鉄溶湯中への気泡の紛れ込みを確実に低減させることができる。 According to such a separate melting method, in the molten copper degassing step S21 and the molten iron degassing step S22 before the crystallization reaction between Cu / Fe where the molten metal has a high viscosity, in the molten copper and in the molten iron Each gas can be sufficiently degassed. In addition, in the molten copper degassing step 21, by adding a deoxidizer containing at least one of silicon, phosphorus, or lithium to the molten copper, gas degassing in the molten copper is promoted, It is possible to surely reduce the bubble intrusion. Further, in the molten iron degassing step 22, by adding a deoxidizer containing at least one of aluminum, manganese, titanium, or silicon in the molten iron, the degassing of the gas in the molten iron is promoted, It is possible to surely reduce the bubble intrusion into the molten iron.
＜３．実施例＞
以下、本発明の実施例について説明する。本実施例では、銅鉄合金（５０Ｃｕ−５０Ｆｅ）のインゴット（１００Ｋｇ）を、実施例１（二段階溶解法）、及び実施例２（別々溶解法）によって製造した。なお、本発明はこれらの実施例に限定されるものではない。
<3. Example>
Examples of the present invention will be described below. In this example, copper iron alloy (50Cu-50Fe) ingots (100 Kg) were produced according to Example 1 (two-stage dissolution method) and Example 2 (separate dissolution method). The present invention is not limited to these examples.
［実施例１］
先ず、高周波溶解炉に電解銅（純度９９．９９％以上）を５０ｋｇと、球状化した純鉄（炭素含有量０.０２％以下）の粒片（目開き（JIS Z 8801）１．７ｍｍ）を５０ｋｇ投入した。
[Example 1]
First, 50 kg of electrolytic copper (purity 99.99% or more) in a high-frequency melting furnace, and spherical particles of pure iron (carbon content 0.02% or less) (mesh (JIS Z 8801) 1.7 mm) Of 50 kg.
高周波溶解炉の溶湯温度を１３００℃に上げ、Ｃｕのみを溶融させ、３０分間保持した。また、脱酸剤としてＳｉを添加し、Ｃｕ液相の気泡を完全に脱気させた。また、投入した脱酸剤は、実質的に燃えてなくなった。 The molten metal temperature of the high frequency melting furnace was raised to 1300 ° C., only Cu was melted, and held for 30 minutes. Further, Si was added as a deoxidizing agent, and bubbles in the Cu liquid phase were completely deaerated. In addition, the deoxidizer that was introduced did not substantially burn.
次に、高周波溶解炉の溶湯温度をＦｅの融点以上に上げ、Ｆｅを溶融させるとともに、Ｃｕ／Ｆｅ間に晶化反応を開始させた。晶化反応の終了を溶湯の粘性から判定し、反応溶湯を鋳型に注湯して急冷し、鋳塊を得た。 Next, the molten metal temperature of the high-frequency melting furnace was raised to the melting point of Fe or more to melt Fe, and a crystallization reaction was started between Cu / Fe. The completion of the crystallization reaction was judged from the viscosity of the molten metal, and the molten metal was poured into a mold and rapidly cooled to obtain an ingot.
このインゴット（直径１２０ｍｍ）を鍛造して、直径８０ｍｍの丸棒材にし、熱間ロール圧延して直径２０ｍｍの線材とし、この線材を複数回冷間線引きすることにより、直径０．１ｍｍオーダの線材を得た。この塑性加工において、断線は発生しなかった。 This ingot (diameter: 120 mm) is forged into a round bar with a diameter of 80 mm, hot-rolled into a wire with a diameter of 20 mm, and this wire is cold-drawn several times to obtain a wire with an order of 0.1 mm in diameter. Got. In this plastic working, no disconnection occurred.
［実施例２］
先ず、第１の高周波溶解炉に電解銅（純度９９．９９％以上）を１００ｋｇ投入し、第１の高周波溶解炉の溶湯温度を１３００℃に上げてＣｕを溶融させ、３０分間保持した。また、脱酸剤としてＳｉを添加し、Ｃｕ液相の気泡を完全に脱気させた。また、投入した脱酸剤は、実質的に燃えてなくなった。
[Example 2]
First, 100 kg of electrolytic copper (purity 99.99% or more) was charged into the first high-frequency melting furnace, the molten metal temperature of the first high-frequency melting furnace was raised to 1300 ° C., and Cu was melted and held for 30 minutes. Further, Si was added as a deoxidizing agent, and bubbles in the Cu liquid phase were completely deaerated. In addition, the deoxidizer that was introduced did not substantially burn.
また、第２の高周波溶解炉に純鉄（炭素含有量０.０２％以下）を１００ｋｇ投入し、第２の高周波溶解炉の溶湯温度をＦｅの融点以上に上げてＦｅを溶融させ、３０分間保持した。また、脱酸剤としてＡｌを添加し、Ｆｅ液相の気泡を完全に脱気させた。また、投入した脱酸剤は、実質的に燃えてなくなった。 Also, 100 kg of pure iron (carbon content of 0.02% or less) is charged into the second high-frequency melting furnace, and the molten metal temperature of the second high-frequency melting furnace is raised to the melting point of Fe or more to melt Fe for 30 minutes. Retained. In addition, Al was added as a deoxidizer to completely degas the bubbles in the Fe liquid phase. In addition, the deoxidizer that was introduced did not substantially burn.
次に、第１の高周波溶解炉の溶湯温度を上げ、第２の高周波溶解炉の溶湯温度と略等しくした。そして、第１の高周波溶解炉の銅溶湯に第２の高周波溶解炉の鉄溶湯を湯面が乱れないように流し込み、ＣｕとＦｅの間に晶化反応を開始させた。晶化反応の終了を溶湯の粘性から判定し、反応溶湯を鋳型に注湯して急冷し、鋳塊を得た。 Next, the molten metal temperature of the 1st high frequency melting furnace was raised, and it was made substantially equal to the molten metal temperature of the 2nd high frequency melting furnace. Then, the molten iron of the second high frequency melting furnace was poured into the molten copper of the first high frequency melting furnace so that the molten metal surface was not disturbed, and a crystallization reaction was started between Cu and Fe. The completion of the crystallization reaction was judged from the viscosity of the molten metal, and the molten metal was poured into a mold and rapidly cooled to obtain an ingot.
このインゴット（直径１２０ｍｍ）を鍛造して、直径８０ｍｍの丸棒材にし、熱間ロール圧延して直径２０ｍｍの線材とし、この線材を複数回冷間線引きすることにより、直径０．１ｍｍオーダの線材を得た。この塑性加工において、断線は発生しなかった。 This ingot (diameter: 120 mm) is forged into a round bar with a diameter of 80 mm, hot-rolled into a wire with a diameter of 20 mm, and this wire is cold-drawn several times to obtain a wire with an order of 0.1 mm in diameter. Got. In this plastic working, no disconnection occurred.
Claims (6)
前記電解銅を溶解させ、銅溶湯中のガスを脱気させる脱気工程と、
前記純鉄を溶解させ、銅と鉄とを晶化反応させる反応工程と、
前記晶化反応させた反応溶湯を鋳型に注湯する注湯工程と
を有する銅鉄合金の製造方法。 A charging step of charging electrolytic copper and pure iron particles into a melting furnace;
A degassing step of dissolving the electrolytic copper and degassing the molten metal;
A reaction step of dissolving the pure iron and crystallizing copper and iron;
And a pouring step of pouring the crystallization reaction molten metal into a mold.
純鉄を第２の溶解炉で溶解させ、鉄溶湯中のガスを脱気させる鉄溶湯脱気工程と
前記第１の溶解炉の銅溶湯と前記第２の溶解炉の鉄溶湯とを混合し、銅と鉄とを晶化反応させる反応工程と、
前記晶化反応させた反応溶湯を鋳型に注湯する注湯工程と
を有する銅鉄合金の製造方法。 A molten copper deaeration process in which electrolytic copper is melted in the first melting furnace and the gas in the molten copper is degassed and a molten iron in which pure iron is melted in the second melting furnace and the gas in the molten iron is degassed A deaeration step, a reaction step of mixing the molten copper of the first melting furnace and the molten iron of the second melting furnace, and causing a crystallization reaction between copper and iron;
And a pouring step of pouring the crystallization reaction molten metal into a mold.
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| CN115029610A (en) * | 2022-06-30 | 2022-09-09 | 宁波金田铜业(集团)股份有限公司 | Preparation method of iron-copper alloy |
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| JP2004225093A (en) * | 2003-01-22 | 2004-08-12 | Dowa Mining Co Ltd | Copper-base alloy and manufacturing method therefor |
| JP2009148825A (en) * | 2007-11-30 | 2009-07-09 | Furukawa Electric Co Ltd:The | Process for manufacturing copper alloy product and equipment therefor |
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| CN113263161A (en) * | 2021-04-25 | 2021-08-17 | 西安斯瑞先进铜合金科技有限公司 | Preparation method of soldering bit |
| CN113263161B (en) * | 2021-04-25 | 2022-08-26 | 西安斯瑞先进铜合金科技有限公司 | Preparation method of soldering bit |
| CN115029610A (en) * | 2022-06-30 | 2022-09-09 | 宁波金田铜业(集团)股份有限公司 | Preparation method of iron-copper alloy |
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