JP5939590B2 - High hardness and high heat conductive composite metal material, method for producing high hardness and high heat conductive composite metal material, and mold for molding plastic or fiber reinforced plastic - Google Patents
High hardness and high heat conductive composite metal material, method for producing high hardness and high heat conductive composite metal material, and mold for molding plastic or fiber reinforced plastic Download PDFInfo
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この発明は、高い硬度と良好な熱伝導性を有する高硬度高熱伝導性複合金属材、高硬度高熱伝導性複合金属材の製造方法およびプラスチックまたは繊維強化プラスチック成形用金型に関するものである。 The present invention relates to a high hardness and high thermal conductivity composite metal material having high hardness and good thermal conductivity, a method for producing a high hardness and high thermal conductivity composite metal material, and a mold for plastic or fiber reinforced plastic molding.
プラスチックや繊維強化プラスチック部品を対象とした射出成形及びプレス成形においては、成形時間短縮のために金型の速やかな加熱・冷却が強く求められており、熱伝導性の良好な高熱伝導率材の使用が試行されている。高熱伝導率材として、銅やアルミニウム、黄銅（Ｃｕ−Ｚｎ系）、青銅（Ｃｕ−Ｓｎ系）、ベリリウム銅（Ｂｅ−Ｃｕ系）やコルソン合金（Ｃｕ−Ｎｉ−Ｓｉ系）といった銅合金が知られている。特に、熱伝導とともに強度や硬度が要求されるようなプラスチック射出金型材や航空機部材などには、ベリリウム銅やコルソン合金を用いることが考えられる。一方で、繊維強化プラスチックのような複合材料の成形する場合は、繊維による摩耗が生じることから、これらの成形金型材には高い耐摩耗性が要求されるが、これら銅合金では十分な硬さが得られないため、プラスチックと金型が直接接する意匠面には高硬度金属材を配置し、プラスチックを速やかに固めたい箇所に入れ子の形で銅合金を配置して使用している。しかし、銅合金を入れ子の形で挿入した場合、銅合金と高硬度金属材との間にはエアギャップが生じ、伝熱効率が低下するという問題が生じる。 In injection molding and press molding for plastic and fiber reinforced plastic parts, rapid heating and cooling of the mold is strongly required to shorten the molding time, and high thermal conductivity materials with good thermal conductivity are required. Attempted use. Copper alloys such as copper, aluminum, brass (Cu—Zn), bronze (Cu—Sn), beryllium copper (Be—Cu), and Corson alloy (Cu—Ni—Si) are known as high thermal conductivity materials. It has been. In particular, it is conceivable to use beryllium copper or a Corson alloy for plastic injection mold materials or aircraft members that require strength and hardness as well as heat conduction. On the other hand, when molding composite materials such as fiber reinforced plastics, wear due to fibers occurs, so these mold materials are required to have high wear resistance, but these copper alloys have sufficient hardness. Therefore, a high-hardness metal material is arranged on the design surface where the plastic and the mold are in direct contact with each other, and a copper alloy is arranged in a nesting form at a place where the plastic is to be hardened quickly. However, when a copper alloy is inserted in a nested manner, an air gap is generated between the copper alloy and the high-hardness metal material, resulting in a problem that heat transfer efficiency is lowered.
上記課題を解決する方法として、拡散接合により異種金属同士を隙間なく接合して、金属同士の接合界面での伝熱ロスをなくす方法が提案されている。特許文献１では高熱伝熱材として銅Ｃ１０２０を用いて拡散接合する例が述べられている。また、特許文献２では、高熱伝導性金属層として、純銅、銅合金、純アルミニウム、アルミニウム合金から選択される材種と高硬度金属層を拡散接合するモデルが記載されている。 As a method for solving the above-described problem, a method has been proposed in which dissimilar metals are joined to each other by diffusion joining so as to eliminate heat transfer loss at the joining interface between the metals. Patent Document 1 describes an example of diffusion bonding using copper C1020 as a high heat transfer material. Patent Document 2 describes a model in which a high-hardness metal layer is diffusion-bonded with a material selected from pure copper, a copper alloy, pure aluminum, and an aluminum alloy as a highly thermally conductive metal layer.
高熱伝導性金属の効果を十分に発揮するには、界面でのロスをなくすために拡散接合が好適であり、特許文献２では、拡散接合の実施例として、高硬度金属層にＳＫＤ６１、高熱伝導性金属層に無酸素銅を用いて、加圧下で８００℃、１時間保持する方法が提案されているが、純銅では強度が低く、金型としての剛性が低くなってしまう。これまでに、純銅の代替材として熱伝導性や剛性に優れる銅合金の適用が提案されているが、普及にはいたっていない。 In order to fully exhibit the effect of the high thermal conductivity metal, diffusion bonding is suitable for eliminating loss at the interface. In Patent Document 2, as an example of diffusion bonding, SKD61, high thermal conductivity is applied to the high hardness metal layer. A method has been proposed in which oxygen-free copper is used for the conductive metal layer and held at 800 ° C. for 1 hour under pressure, but pure copper has low strength and low rigidity as a mold. Up to now, the application of a copper alloy having excellent thermal conductivity and rigidity as a substitute for pure copper has been proposed, but it has not been widely used.
その理由としては、高硬度金属と高熱伝導性金属の線膨張差が挙げられる。金型向けの一般的な高硬度金属としては工具鋼があるが、その室温〜２００℃における線膨張係数は１．０〜１．２×１０−５／℃程度である。一方、一般的な銅合金の線膨張係数は１．６〜１．８×１０−５／℃程度である。上述した通り、金型全体の剛性を高くするためには高熱伝導性金属もある程度強度が高い必要がある。 The reason for this is the difference in linear expansion between the high hardness metal and the high thermal conductivity metal. As a general hard metal for molds, there is tool steel, and its linear expansion coefficient from room temperature to 200 ° C. is about 1.0 to 1.2 × 10 −5 / ° C. On the other hand, the linear expansion coefficient of a general copper alloy is about 1.6 to 1.8 × 10 −5 / ° C. As described above, in order to increase the rigidity of the entire mold, the high thermal conductivity metal also needs to have a certain degree of strength.
特許文献２では、線膨張係数の差が接合性に影響することを課題として熱変形を拘束することが記載されている（段落００２４、００２５）。
しかし、高硬度金属、高熱伝導性金属ともに強度が高く、その分延靭性が低い素材を用いると、接合後に、両者の線膨張係数の違いから金型使用時に接合界面にひずみが蓄積した際に、クラックが容易に生じて熱伝導性が劣化したり、最悪の場合には金型が破壊してしまうという問題がある。
Patent Document 2 describes that thermal deformation is constrained on the subject that the difference in linear expansion coefficient affects the bondability (paragraphs 0024 and 0025).
However, when materials with high strength and low thermal toughness are used for both high-hardness metal and high thermal conductivity metal, when the strain accumulates at the joint interface during die use due to the difference in linear expansion coefficient between the two after joining. In addition, there is a problem that cracks are easily generated and thermal conductivity is deteriorated, or in the worst case, the mold is destroyed.
本発明は、上記事情を背景としてなされたものであり、熱伝導性に優れたＣｕ−Ｎｉ−Ｓｉ系銅合金と、高硬度金属材とが界面接合によってエアギャップを有することなく良好に接合されており、しかも、両者の材料の線膨張係数差に起因する問題を緩和して接合性を高めた高硬度高熱伝導性複合金属材、高硬度高熱伝導性複合金属材の製造方法およびプラスチックまたは繊維強化プラスチック成形用金型を提供することを目的とする。 The present invention has been made against the background of the above circumstances, and a Cu-Ni-Si-based copper alloy having excellent thermal conductivity and a high-hardness metal material are satisfactorily bonded without having an air gap by interfacial bonding. In addition, a high-hardness and high-heat-conductivity composite metal material that has improved the bondability by alleviating the problem caused by the difference in linear expansion coefficient between the two materials, a method for producing a high-hardness and high-heat-conductivity composite metal material, and plastic or fiber An object is to provide a mold for reinforced plastic molding.
本発明者らは、高硬度金属とＣｕ−Ｎｉ−Ｓｉ系銅合金を界面接合した後に高温処理を施すと、接合界面の高硬度金属側にＣｕ−Ｎｉ−Ｓｉ系銅合金からＮｉとＳｉが拡散し、高硬度金属とＣｕ−Ｎｉ−Ｓｉ系銅合金の中間的な線膨張係数を有する層が生成することを見出した。なお、高温処理の温度はＣｕ−Ｎｉ−Ｓｉ系銅合金に析出するＮｉ２Ｓｉを固溶化する処理と高硬度金属の焼入処理を兼ねた温度を採用できることもわかった。高温処理の後には、Ｃｕ−Ｎｉ−Ｓｉ系銅合金におけるＮｉ２Ｓｉを微細かつ大量に析出させる時効処理と、高硬度金属の焼戻処理を兼ねた低温処理を行うと、高硬度金属、Ｃｕ−Ｎｉ−Ｓｉ系銅合金ともに硬度を高めることができる。 When the present inventors perform high-temperature treatment after interfacial bonding of a high-hardness metal and a Cu-Ni-Si-based copper alloy, Ni and Si are formed from the Cu-Ni-Si-based copper alloy on the high-hardness metal side of the bonding interface. It has been found that a layer that diffuses and has an intermediate linear expansion coefficient between a hard metal and a Cu—Ni—Si based copper alloy is formed. It has also been found that the temperature for the high temperature treatment can be a temperature that combines the treatment for solidifying Ni 2 Si deposited on the Cu—Ni—Si based copper alloy and the quenching treatment for the high hardness metal. After the high temperature treatment, when performing a low temperature treatment that combines Ni 2 Si in Cu—Ni—Si based copper alloy in a fine and large amount and a tempering treatment of the hard metal, the high hardness metal, Cu -Ni-Si type copper alloy can raise hardness.
すなわち、本発明の高硬度高熱伝導性複合金属材のうち、第１の本発明は、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材と高硬度金属材とが界面接合されており、接合界面に、Ｎｉ、Ｓｉの拡散層が形成されていることを特徴とする。 That is, among the high hardness and high thermal conductivity composite metal materials of the present invention, the first present invention is such that a Cu-Ni-Si based copper alloy material and a high hardness metal material are interface bonded, and Ni is bonded to the bonding interface. A Si diffusion layer is formed.
第２の本発明の高硬度高熱伝導性複合金属材は、前記第１の本発明において、前記Ｃｕ−Ｎｉ−Ｓｉ系銅合金材が、質量％でＮｉを３〜７．５％、Ｓｉを０．７〜１．８％含有する組成を有することを特徴とする。 The high hardness and high thermal conductivity composite metal material of the second aspect of the present invention is the above-mentioned first aspect of the present invention, wherein the Cu-Ni-Si based copper alloy material contains 3 to 7.5% Ni and Si in mass%. It has a composition containing 0.7 to 1.8%.
第３の本発明の高硬度高熱伝導性複合金属材は、前記第１または第２の本発明において、前記Ｃｕ−Ｎｉ−Ｓｉ系銅合金材は、前記組成において質量％でＮｉ／Ｓｉが３．７〜４．７であることを特徴とする。 The high hardness and high thermal conductivity composite metal material of the third aspect of the present invention is the first or second aspect of the present invention, wherein the Cu—Ni—Si based copper alloy material has a Ni / Si ratio of 3% by mass in the composition. .7 to 4.7.
第４の本発明の高硬度高熱伝導性複合金属材は、前記第１〜第３の本発明のいずれかにおいて、前記高硬度金属材がＨＲＣ３０以上であり、前記Ｃｕ−Ｎｉ−Ｓｉ系銅合金材がＨＲＣ２０以上であることを特徴とする。 The high hardness and high thermal conductivity composite metal material according to the fourth aspect of the present invention is the Cu—Ni—Si based copper alloy according to any one of the first to third aspects, wherein the high hardness metal material is HRC30 or more. The material is HRC20 or more.
第５の本発明の高硬度高熱伝導性複合金属材は、前記第１〜第４の本発明のいずれかにおいて、前記拡散層の厚さが１０μｍ以上であることを特徴とする。 The high hardness and high thermal conductive composite metal material of the fifth aspect of the present invention is characterized in that, in any of the first to fourth aspects of the present invention, the thickness of the diffusion layer is 10 μm or more.
第６の本発明の高硬度高熱伝導性複合金属材は、前記第１〜第５の本発明のいずれかにおいて、前記Ｃｕ−Ｎｉ−Ｓｉ系銅合金材の室温〜２００℃における線膨張率が１．６〜１．８×１０−５／℃であり、前記高硬度金属材の室温〜２００℃における線膨張率が１．０〜１．２×１０−５／℃であり、前記拡散層の室温〜２００℃における線膨張率が１．２〜１．６×１０−５／℃であることを特徴とする。 The high hardness and high thermal conductivity composite metal material according to the sixth aspect of the present invention, in any one of the first to fifth aspects of the present invention, has a linear expansion coefficient at room temperature to 200 ° C. of the Cu—Ni—Si based copper alloy material. 1.6 to 1.8 × 10 −5 / ° C., and the linear expansion coefficient of the high-hardness metal material at room temperature to 200 ° C. is 1.0 to 1.2 × 10 −5 / ° C., and the diffusion layer The linear expansion coefficient at room temperature to 200 ° C. is 1.2 to 1.6 × 10 −5 / ° C.
第７の本発明の高硬度高熱伝導性複合金属材は、前記第１〜第６の本発明のいずれかにおいて、前記高硬度金属材が析出硬化型鋼であることを特徴とする。 The high hardness and high thermal conductivity composite metal material of the seventh aspect of the present invention is characterized in that, in any of the first to sixth aspects of the present invention, the high hardness metal material is precipitation hardening type steel.
第８の本発明の高硬度高熱伝導性複合金属材の製造方法は、界面接合されたＣｕ−Ｎｉ−Ｓｉ系銅合金材と高硬度金属材を加熱してＣｕ−Ｎｉ−Ｓｉ系銅合金材のＮｉ、Ｓｉを高硬度金属側に拡散させて界面にＮｉ、Ｓｉの拡散層を形成することを特徴とする。 According to an eighth aspect of the present invention, there is provided a method for producing a high hardness and high thermal conductivity composite metal material comprising heating a Cu—Ni—Si based copper alloy material and a high hardness metal material which are interface bonded to each other to form a Cu—Ni—Si based copper alloy material. Ni and Si are diffused to the high hardness metal side to form a Ni and Si diffusion layer at the interface.
第９の本発明の高硬度高熱伝導性複合金属材の製造方法は、前記第８の本発明において、
前記高硬度高熱伝導性複合金属材を相対的に高い温度で加熱してＣｕ−Ｎｉ−Ｓｉ系銅合金材のＮｉ、Ｓｉを高硬度金属材側に拡散させるとともに、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材中のＮｉ、Ｓｉを固溶化させ、その後、前記高硬度高熱伝導性複合金属材を相対的に低い温度で加熱して前記Ｃｕ−Ｎｉ−Ｓｉ系銅合金材中にＮｉ２Ｓｉを分散析出させることを特徴とする。
In the ninth aspect of the present invention, the manufacturing method of the high hardness and high thermal conductivity composite metal material of the ninth aspect of the present invention is as follows.
The high hardness and high thermal conductivity composite metal material is heated at a relatively high temperature to diffuse Ni and Si of the Cu-Ni-Si based copper alloy material to the high hardness metal material side, and Cu-Ni-Si based copper. Ni and Si in the alloy material are dissolved, and then the high hardness and high thermal conductivity composite metal material is heated at a relatively low temperature to disperse Ni 2 Si in the Cu—Ni—Si based copper alloy material. It is made to precipitate.
第１０の本発明の高硬度高熱伝導性複合金属材の製造方法は、前記第９の本発明において、前記高硬度高熱伝導性複合金属材の加熱を、８５０〜１０００℃で１〜１０時間加熱して前記Ｎｉ、Ｓｉの前記拡散と前記固溶化を行い、その後、３７５〜５００℃で１〜５０時間加熱して前記Ｎｉ２Ｓｉを分散析出させることを特徴とする。 The method for producing a high hardness and high thermal conductivity composite metal material according to the tenth aspect of the present invention is the method according to the ninth aspect, wherein the high hardness and high thermal conductivity composite metal material is heated at 850 to 1000 ° C. for 1 to 10 hours. Then, the diffusion of Ni and Si and the solid solution are performed, and then the Ni 2 Si is dispersed and precipitated by heating at 375 to 500 ° C. for 1 to 50 hours.
第１１の本発明の高硬度高熱伝導性複合金属材の製造方法は、前記第１０の本発明において、前記拡散と前記固溶化の処理後、前記分散析出の処理前に、加熱された前記高硬度高熱伝導性複合金属材を５℃／秒以上の冷却速度で冷却することを特徴とする。 The method for producing a high hardness and high thermal conductivity composite metal material of the eleventh aspect of the present invention is the method according to the tenth aspect of the present invention, wherein the high temperature heated after the diffusion and solution treatment and before the dispersion precipitation process. The hard metal composite metal material having high hardness is cooled at a cooling rate of 5 ° C./second or more.
第１２の本発明の高硬度高熱伝導性複合金属材の製造方法は、前記第９〜第１１の本発明のいずれかにおいて、前記高硬度金属材が析出硬化型鋼からなることを特徴とする。 According to a twelfth aspect of the present invention, there is provided a method for producing a high hardness and high thermal conductivity composite metal material according to any one of the ninth to eleventh aspects, wherein the high hardness metal material is made of precipitation hardening type steel.
第１３の本発明のプラスチックまたは繊維強化プラスチック成形用金型は、前記第１〜第７の本発明のいずれかに記載した高硬度高熱伝導性複合金属材を用いてなることを特徴とする。 A plastic or fiber-reinforced plastic molding die according to a thirteenth aspect of the present invention is characterized by using the high hardness and high heat conductive composite metal material described in any of the first to seventh aspects of the present invention.
以上説明したように、本発明によれば、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材と高硬度金属材とが界面接合されて良好な接合状態が得られるとともに、界面にＮｉ、Ｓｉの拡散層が形成されているので、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材と高硬度金属材との線膨張係数差による弊害を防止して良好な接合状態を維持することができ、結果的に高い硬度面を有するとともに良好な熱伝導性を有する。該材料を金型に用いる場合、金型全体として高熱伝導率を維持しつつ、金型の意匠面に耐摩耗性や鏡面性を付与した金属材を供給することが可能となる。この結果、本発明の高硬度高熱伝導性複合金属材は、プラスチック射出成形金型材、特に複合材料向けの金型材として最適であり、従来の金型よりもプラスチック製品射出のサイクルタイムを短縮するとともに、使用中の劣化を低減できる。 As described above, according to the present invention, a Cu—Ni—Si based copper alloy material and a high-hardness metal material are interface bonded to obtain a good bonded state, and Ni and Si diffusion layers are formed at the interface. Since it is formed, it is possible to prevent adverse effects due to the difference in linear expansion coefficient between the Cu-Ni-Si-based copper alloy material and the high-hardness metal material, and maintain a good bonding state, resulting in a high hardness surface. And good thermal conductivity. When the material is used for a mold, it is possible to supply a metal material that imparts wear resistance and specularity to the design surface of the mold while maintaining high thermal conductivity as a whole mold. As a result, the high hardness and high thermal conductivity composite metal material of the present invention is optimal as a plastic injection mold material, particularly a mold material for composite materials, and shortens the cycle time of plastic product injection than conventional molds. Deterioration during use can be reduced.
以下に、本発明の実施形態を説明する。
本発明に用いる高硬度金属材としては、プラスチック金型用鋼、工具鋼、析出硬化型ステンレスなどプラスチック成形金型として従来から使用されている鋼を用いることができる。ただし、Ｃｕ−Ｎｉ−Ｓｉ系合金からＮｉ、Ｓｉを拡散させるため、Ｎｉ、Ｓｉ添加量がＣｕ−Ｎｉ−Ｓｉ系合金の１．２倍以下とするのが望ましい。１．２倍以下であれば銅合金から鋼へＮｉ、Ｓｉが拡散することが実験で確かめられている。なお、以下では、高硬度金属材としては、高硬度を有する金属材の他、高硬度化される前の金属材を総称していうものである。
Hereinafter, embodiments of the present invention will be described.
As the high-hardness metal material used in the present invention, steels conventionally used as plastic molds such as plastic mold steel, tool steel, precipitation hardening stainless steel, and the like can be used. However, in order to diffuse Ni and Si from the Cu—Ni—Si based alloy, it is desirable that the amount of Ni and Si added is 1.2 times or less that of the Cu—Ni—Si based alloy. Experiments have confirmed that Ni and Si diffuse from a copper alloy to steel if it is 1.2 times or less. In the following description, the high-hardness metal material is a generic term for a metal material having a high hardness and a metal material before being hardened.
高熱伝導性合金としてはＮｉ、Ｓｉの高硬度金属への拡散が必要であるため、Ｎｉ、Ｓｉを含むＣｕ−Ｎｉ−Ｓｉ系銅合金材が最適である。金型に必要な剛性を得るためには、Ｎｉを３％以上、Ｓｉを０．７％以上添加するのが望ましい。ＮｉとＳｉの比は硬さ上昇能の高いＮｉ２Ｓｉを析出させるために重量比でＮｉ／Ｓｉ＝３．７〜４．７に調整するのが望ましい。Ｎｉ、Ｓｉの含有量が多過ぎると凝固中にＮｉ２Ｓｉなどの晶出物が大量に生じて鋼との接合性を低下させるため、Ｎｉは７．５％以下、Ｓｉは１．８％以下が望ましい。
なお、以下では、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材としては、高硬度高熱伝導性複合金属材に含まれて使用可能な状態のＣｕ−Ｎｉ−Ｓｉ系銅合金材の他、処理前の材料を総称していうものである。
As the high thermal conductivity alloy, Ni and Si need to be diffused into a hard metal, and therefore, a Cu—Ni—Si based copper alloy material containing Ni and Si is optimal. In order to obtain the rigidity required for the mold, it is desirable to add 3% or more of Ni and 0.7% or more of Si. The ratio of Ni and Si is preferably adjusted to Ni / Si = 3.7 to 4.7 by weight ratio in order to precipitate Ni 2 Si having a high hardness increasing ability. If the content of Ni and Si is too large, a large amount of crystallized materials such as Ni 2 Si are generated during solidification and the bondability with steel is lowered. Therefore, Ni is 7.5% or less, and Si is 1.8%. The following is desirable.
In the following, as the Cu—Ni—Si based copper alloy material, the Cu—Ni—Si based copper alloy material in a state of being usable by being included in the high hardness and high thermal conductive composite metal material, and the material before the processing Is a collective term.
Ｎｉ、Ｓｉ以外の元素については、一般的に銅合金に添加されているＢｅ、Ｐ、Ｃｒ、Ｍｎ、Ｃｏ、Ｚｎ、Ａｇ、Ｓｎの１種以上をそれぞれ単独で１％以下、合計で３％以下含有しても問題ない。酸化物形成傾向が強いあるいは鉄と金属間化合物を形成しやすい元素であるＭｇ、Ａｌ、Ｔｉ、Ｚｒの１種以上を含有してもよく、その場合、それぞれ単独で０．２％以下、合計で０．５％以下が望ましい。 For elements other than Ni and Si, one or more of Be, P, Cr, Mn, Co, Zn, Ag, and Sn generally added to copper alloys are each 1% or less, and 3% in total. Even if it contains below, there is no problem. It may contain one or more of Mg, Al, Ti, and Zr, which are elements that have a strong tendency to form oxides or easily form intermetallic compounds with iron. And 0.5% or less is desirable.
両素材の製造方法については限定しない。鋼の溶解方法としては高炉、電気炉、誘導溶解炉、真空誘導溶解炉など、精錬方法としては取鍋精錬、ＲＨ真空脱ガスなど、鋳込み方法としては真空脱ガス鋳込み、連続鋳造法など常法を採用できる。エレクトロスラグ再溶解や真空アーク再溶解といった二次溶解も採用できる。また、金型に要求される特性を有しているならば、粉末冶金手法で製造しても問題ない。一方、銅合金の溶解方法としては誘導溶解炉、真空誘導溶解炉など、鋳込み方法としてはダービル法、連続鋳造法など常法を、エレクトロスラグ再溶解といった二次溶解も採用できる。
また、両素材の厚さも互いに特に限定されるものではない。
The manufacturing method of both materials is not limited. Steel melting methods include blast furnace, electric furnace, induction melting furnace, vacuum induction melting furnace, refining methods such as ladle refining, RH vacuum degassing, etc. Conventional methods such as vacuum degassing casting and continuous casting methods Can be adopted. Secondary melting such as electroslag remelting or vacuum arc remelting can also be employed. Moreover, if it has the characteristic requested | required of a metal mold | die, even if it manufactures with a powder metallurgy technique, there is no problem. On the other hand, as a melting method of the copper alloy, an induction melting furnace, a vacuum induction melting furnace or the like can be used. As a casting method, a conventional method such as the Darville method or a continuous casting method can be used, and secondary melting such as electroslag remelting can be employed.
Further, the thicknesses of both materials are not particularly limited to each other.
Ｃｕ−Ｎｉ−Ｓｉ系銅合金材と高硬度金属材の接合方法は、真空下で加熱・加圧して実施する拡散接合が最適ではある。適切に接合するためには１〜２０ＭＰａの圧力下で、８５０〜９５０℃に保持して１０分〜１０時間保持する。圧力は低過ぎると界面が密着しないため１ＭＰａ以上、高過ぎるとＣｕ−Ｎｉ−Ｓｉ系合金が変形するため２０ＭＰａ以下が望ましい。保持温度は界面の元素の移動を盛んにするため８５０℃以上、Ｃｕ−Ｎｉ−Ｓｉ系合金の変形を防止するために９５０℃以下が望ましい。保持時間は界面の元素の移動を確実にするために１０分以上、Ｃｕ−Ｎｉ−Ｓｉ系合金のクリープ変形を防止するために１０時間以下が望ましい。加熱時の昇温速度や接合後の冷却速度は限定する必要はない。なお、界面接合方法は、本発明としては特に限定されるものではなく、加熱後の圧延、室温での爆着など、両者の界面を隙間なく接合させる方法であれば限定しない。 As a method for joining the Cu—Ni—Si copper alloy material and the high hardness metal material, diffusion joining performed by heating and pressurizing under vacuum is optimal. In order to join appropriately, it hold | maintains at 850-950 degreeC under the pressure of 1-20 Mpa, and hold | maintains for 10 minutes-10 hours. If the pressure is too low, the interface does not adhere, so that it is 1 MPa or more, and if it is too high, the Cu—Ni—Si alloy is deformed, so 20 MPa or less is desirable. The holding temperature is desirably 850 ° C. or higher for increasing the movement of elements at the interface, and 950 ° C. or lower for preventing deformation of the Cu—Ni—Si alloy. The holding time is desirably 10 minutes or longer to ensure the movement of elements at the interface, and 10 hours or shorter to prevent creep deformation of the Cu—Ni—Si alloy. There is no need to limit the heating rate during heating and the cooling rate after bonding. The interface bonding method is not particularly limited as the present invention, and is not limited as long as it is a method of bonding the interfaces of both without gaps, such as rolling after heating and explosion at room temperature.
接合した後の高温処理の温度は、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材から高硬度金属材へのＮｉ、Ｓｉの拡散を促進するために８５０℃以上が望ましく、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材の部分溶融を避けるために１０００℃以下が望ましい。高温処理の保持時間は、Ｃｕ−Ｎｉ−Ｓｉ系合金におけるＮｉ２Ｓｉの固溶化を促進するために１時間以上が望ましく、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材の結晶粒粗大化を防ぐために１０時間以下が望ましい。
処理時の昇温速度は限定する必要はないが、冷却速度は水冷かそれに準じた速度であるのが望ましい。コルソン合金におけるＮｉ２Ｓｉの固溶を確実にするために５℃／秒以上の冷却速度とすることが望ましい。
低温処理はＣｕ−Ｎｉ−Ｓｉ系銅合金材においてＮｉ２Ｓｉが微細かつ大量に析出する３７５〜５００℃で１時間〜５０時間保持するのが望ましい。処理時の昇温速度と冷却速度は限定する必要はない。
The temperature of the high temperature treatment after joining is preferably 850 ° C. or more in order to promote the diffusion of Ni and Si from the Cu—Ni—Si based copper alloy material to the high hardness metal material, and the Cu—Ni—Si based copper alloy. In order to avoid partial melting of the material, 1000 ° C. or lower is desirable. The holding time of the high temperature treatment is desirably 1 hour or more in order to promote the solid solution of Ni 2 Si in the Cu—Ni—Si based alloy, and 10 in order to prevent the crystal grain coarsening of the Cu—Ni—Si based copper alloy material. Less than an hour is desirable.
The rate of temperature increase during the treatment need not be limited, but the cooling rate is preferably water cooling or a similar rate. In order to ensure the solid solution of Ni 2 Si in the Corson alloy, a cooling rate of 5 ° C./second or more is desirable.
The low temperature treatment is desirably held at 375 to 500 ° C. for 1 to 50 hours at which Ni 2 Si precipitates finely and in large quantities in the Cu—Ni—Si based copper alloy material. There is no need to limit the heating rate and cooling rate during the treatment.
図１は、上記工程の例Ａ、Ｂを示すものである。
工程Ａでは、高硬度金属材２とＣｕ−Ｎｉ−Ｓｉ系銅合金材３とが界面接合によって接合され、高硬度高熱伝導性複合金属材１が得られる。
両素材が界面接合された高硬度高熱伝導性複合金属材１は、好適には８５０〜１０００℃で１時間〜１０時間加熱されてＣｕ−Ｎｉ−Ｓｉ系銅合金材３の一部のＮｉ、Ｓｉが高硬度金属材２側に拡散してＮｉ、Ｓｉ拡散層４が得られ、また、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材３中のＮｉ、Ｓｉが固溶化する。この際に、高硬度金属材２の溶体化処理を併せて行うことができる。
加熱された高硬度高熱伝導性複合金属材１は、水冷やこれに準ずる方法で冷却し、その際の冷却速度を５℃／秒以上とするのが望ましい。なお、この冷却速度による冷却は、少なくとも３００℃まで行われればよい。
FIG. 1 shows examples A and B of the above process.
In step A, the high-hardness metal material 2 and the Cu—Ni—Si-based copper alloy material 3 are joined by interfacial bonding, and the high-hardness and high-heat conductive composite metal material 1 is obtained.
The high hardness and high thermal conductivity composite metal material 1 in which both materials are interface-bonded is preferably heated at 850 to 1000 ° C. for 1 hour to 10 hours to form a part of Ni in the Cu—Ni—Si based copper alloy material 3, Si diffuses to the high hardness metal material 2 side to obtain a Ni / Si diffusion layer 4, and Ni and Si in the Cu—Ni—Si based copper alloy material 3 are solidified. At this time, the solution treatment of the high-hardness metal material 2 can be performed together.
The heated high hardness and high thermal conductivity composite metal material 1 is preferably cooled by water cooling or a method equivalent thereto, and the cooling rate at that time is preferably 5 ° C./second or more. The cooling at this cooling rate may be performed up to at least 300 ° C.
冷却された高硬度高熱伝導性複合金属材１は、好適には３７５〜５００℃で、１〜５０時間の加熱を行う。この加熱により、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材３中に固溶したＮｉ、ＳｉからＮｉ２Ｓｉ粒子が微細かつ大量に生成したＣｕ−Ｎｉ−Ｓｉ系銅合金材３０が得られる。なお、Ｎｉ２Ｓｉ粒子の大きさや分散密度は特に限定されるものではない。
なお、この加熱の際に、高硬度金属材２の焼戻しが行われるものであってもよい。
The cooled high hardness and high thermal conductive composite metal material 1 is preferably heated at 375 to 500 ° C. for 1 to 50 hours. By this heating, a Cu—Ni—Si based copper alloy material 30 in which Ni 2 Si particles are finely and produced in large quantities from Ni and Si dissolved in the Cu—Ni—Si based copper alloy material 3 is obtained. The size and dispersion density of the Ni 2 Si particles is not particularly limited.
In addition, the high-hardness metal material 2 may be tempered during this heating.
工程Ｂでは、界面接合として拡散接合が行われる工程である。拡散接合では、１〜２０ＭＰａの加圧状態で、８５０〜９５０℃、１０分〜１０時間の加熱が行われる。この際にＣｕ−Ｎｉ−Ｓｉ系銅合金材３の一部のＮｉ、Ｓｉが高硬度金属材２側に拡散してＮｉ、Ｓｉ拡散層４ａが得られるが、拡散量は十分ではない。なお、拡散に際し、熱拘束する手段を講じてもよい。 In step B, diffusion bonding is performed as interface bonding. In diffusion bonding, heating is performed at 850 to 950 ° C. for 10 minutes to 10 hours in a pressurized state of 1 to 20 MPa. At this time, a part of Ni and Si in the Cu—Ni—Si based copper alloy material 3 is diffused to the high hardness metal material 2 side to obtain the Ni and Si diffusion layer 4a, but the diffusion amount is not sufficient. Note that a means for thermally constraining the diffusion may be taken.
次いで、高硬度高熱伝導性複合金属材１は、好適には８５０〜１０００℃で１時間〜１０時間加熱されてＣｕ−Ｎｉ−Ｓｉ系銅合金材３の一部のＮｉ、Ｓｉが高硬度金属材２側に拡散してＮｉ、Ｓｉ拡散層４が得られ、また、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材３中のＮｉ、Ｓｉが固溶化する。この際に、高硬度金属材２の溶体化が行われ、所望の特性を有する高硬度金属材２０が得られる。この際に加熱によって、Ｎｉ、Ｓｉ拡散層４では、十分な量のＮｉ、Ｓｉ拡散が得られる。
加熱された高硬度高熱伝導性複合金属材１は、その後、上記工程Ａと同様に冷却され、さらに、加熱により、Ｃｕ−Ｎｉ−Ｓｉ系銅合金材３中に固溶したＮｉ、ＳｉをＮｉ２Ｓｉ粒子として析出、分散させる。
Next, the high hardness and high thermal conductivity composite metal material 1 is preferably heated at 850 to 1000 ° C. for 1 to 10 hours, and a part of the Cu—Ni—Si-based copper alloy material 3 Ni and Si is a high hardness metal. The Ni and Si diffusion layers 4 are obtained by diffusing to the material 2 side, and Ni and Si in the Cu—Ni—Si based copper alloy material 3 are solidified. At this time, the high-hardness metal material 2 is formed into a solution, and the high-hardness metal material 20 having desired characteristics is obtained. At this time, a sufficient amount of Ni and Si diffusion is obtained in the Ni and Si diffusion layer 4 by heating.
The heated high hardness and high thermal conductivity composite metal material 1 is then cooled in the same manner as in the above step A, and further, Ni and Si dissolved in the Cu—Ni—Si based copper alloy material 3 by heating are converted into Ni. 2 Precipitate and disperse as Si particles.
以下に、本発明の実施例について説明する。
２０ｋｇ真空溶解炉で溶製し、鍛造成形したＣｕ−Ｎｉ−Ｓｉ系合金のコルソン合金と、５０ｋｇＶＩＭで溶製し、鍛造成形したプラスチック金型用鋼であるＡＩＳＩ Ｐ２１系鋼ならびに市販の析出硬化型ステンレスＳＵＳ６３０を用いた。これら素材の成分を表１に示す。いずれの成分も質量％を示しており、ＳＵＳ６３０およびＰ２１系鋼では、残部がＦｅおよび不可避不純物からなる。コルソン合金では、残部がＣｕおよび不可避不純物からなる。
Examples of the present invention will be described below.
A Cu-Ni-Si alloy Corson alloy melted and forged in a 20 kg vacuum melting furnace, AISI P21 steel as a plastic mold steel melted and forged and molded in 50 kg VIM, and a commercially available precipitation hardening die Stainless steel SUS630 was used. Table 1 shows the components of these materials. All the components show mass%, and the balance of SUS630 and P21 steel is Fe and inevitable impurities. In the Corson alloy, the balance consists of Cu and inevitable impurities.
真空下で９００℃、加圧力５ＭＰａ、保持時間１時間４０分の条件で、コルソン合金とＰ２１系鋼あるいはＳＵＳ６３０との拡散接合を行った。その後、一体化した高強度高熱伝導性複合金属に高温処理および低温処理を施した。
高温処理は、９００℃×４時間で行い、その後、水冷によって冷却速度１０℃／秒で ２００℃まで冷却した。低温処理は、４５０℃×１０時間で行った。
Diffusion bonding between the Corson alloy and P21 steel or SUS630 was performed under the conditions of 900 ° C., pressure of 5 MPa, and holding time of 1 hour and 40 minutes under vacuum. Thereafter, the integrated high strength and high thermal conductive composite metal was subjected to high temperature treatment and low temperature treatment.
The high temperature treatment was performed at 900 ° C. for 4 hours, and then cooled to 200 ° C. at a cooling rate of 10 ° C./second by water cooling. The low temperature treatment was performed at 450 ° C. × 10 hours.
界面接合部の界面直角方向で、引張強さはどちらも６５０ＭＰａであり、コルソン合金（６５０ＭＰａ）と同等であった。
処理後のコルソン合金はＪＩＳＺ２２４４に基づき、荷重５ｋｇでビッカース硬さと、ヴィーデマン＝フランツ則に示されるように熱伝導率とほぼ比例関係にある導電率を測定した。コルソン合金のビッカース硬さはＨＶ２４０、導電率は４５％ＩＡＣＳであった。
In the direction perpendicular to the interface of the interface joint, both tensile strengths were 650 MPa, which was equivalent to the Corson alloy (650 MPa).
Based on JISZ2244, the Corson alloy after the treatment was measured for Vickers hardness at a load of 5 kg and conductivity substantially proportional to the thermal conductivity as shown by Wiedemann-Franz rule. The Corson alloy had a Vickers hardness of HV240 and an electrical conductivity of 45% IACS.
ＡＩＳ ＩＰ２１系鋼の硬さはＨＶ３７０、ＳＵＳ６３０の硬さはＨＶ４２０であった。
Ｐ２１系鋼、ＳＵＳ６３０ともに接合界面には拡散層が確認された。ＳＵＳ６３０を用いた供試材について走査型電子顕微鏡（ＳＥＭ）とエネルギー分散型Ｘ線分光法（ＥＤＸ）で分析した結果、拡散層にはＮｉ、Ｓｉの濃化が認められた。
The hardness of the AIS IP21 steel was HV370, and the hardness of SUS630 was HV420.
A diffusion layer was confirmed at the bonding interface for both P21 steel and SUS630. As a result of analyzing the test material using SUS630 with a scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX), enrichment of Ni and Si was observed in the diffusion layer.
アーク溶解により本拡散層の成分で溶製した素材の室温〜２００℃の線膨張係数を測定した。線膨張係数はＪＩＳ Ｚ ２２８５に準拠して測定した。Ｐ２１系鋼の界面は１．２×１０−５／℃、ＳＵＳ６３０の界面は１．３×１０−５／℃であり、コルソン合金（１．７×１０−５／℃）と鋼（Ｐ２１系鋼：１．１×１０−５／℃、ＳＵＳ６３０：１．１×１０−５／℃）の中間に位置する値が得られた。
また、拡散層の厚さは、ＡＩＳ ＩＰ２１系鋼で１０〜２０μｍ、ＳＵＳ６３０で１０〜３０μｍであった。
The linear expansion coefficient from room temperature to 200 ° C. of the material melted with the components of this diffusion layer by arc melting was measured. The linear expansion coefficient was measured according to JIS Z 2285. The interface of P21 steel is 1.2 × 10 −5 / ° C., and the interface of SUS630 is 1.3 × 10 −5 / ° C .. Corson alloy (1.7 × 10 −5 / ° C.) and steel (P21 steel) steel: the value located in the middle of 1.1 × 10 -5 /℃,SUS630:1.1×10 -5 / ℃ ) was obtained.
The thickness of the diffusion layer was 10 to 20 μm for AIS IP21 steel and 10 to 30 μm for SUS630.
以上、本発明について上記実施形態および上記実施例に基づいて説明を行ったが、本発明の範囲を逸脱しない限りは適宜の変更が可能である。 As described above, the present invention has been described based on the above embodiment and the above examples, but appropriate modifications can be made without departing from the scope of the present invention.
１ 高硬度高熱伝導性複合金属材
２ 高硬度金属材
３ Ｃｕ−Ｎｉ−Ｓｉ系銅合金材
４ Ｎｉ、Ｓｉ拡散層
２０ 高硬度金属材
３０ Ｃｕ−Ｎｉ−Ｓｉ系銅合金材
DESCRIPTION OF SYMBOLS 1 High hardness high heat conductive composite metal material 2 High hardness metal material 3 Cu-Ni-Si type copper alloy material 4 Ni, Si diffusion layer 20 High hardness metal material 30 Cu-Ni-Si type copper alloy material
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| JPS6024750B2 (en) * | 1977-09-05 | 1985-06-14 | 三菱重工業株式会社 | Diffusion welding of copper and stainless steel |
| JPS60197834A (en) * | 1984-03-17 | 1985-10-07 | Ngk Insulators Ltd | Cladding material of iron or steel base alloy and copper alloy material |
| JPH0938785A (en) * | 1995-07-26 | 1997-02-10 | Chuetsu Gokin Chuko Kk | Method for joining copper alloy to ferrous material |
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| FI114691B (en) * | 2000-02-23 | 2004-12-15 | Outokumpu Oy | A method for forming a connection between copper and stainless steel |
| JP4819148B2 (en) * | 2009-03-31 | 2011-11-24 | 新日本製鐵株式会社 | Material for metal outer case and metal outer case of lithium ion battery with little voltage drop due to metal elution and lithium ion battery |
| JP5706193B2 (en) * | 2011-03-02 | 2015-04-22 | 株式会社タカコ | Manufacturing method of sliding member |
| CN202087919U (en) * | 2011-04-19 | 2011-12-28 | 大连海事大学 | Copper and steel dual-metal pipe end head structure |
| JP2013154399A (en) * | 2012-01-05 | 2013-08-15 | Hitachi Metals Ltd | Dissimilar metal joined body |
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