JP5211314B2 - Cr-Cu alloy plate, heat radiating plate for electronic device using the same, and heat radiating component for electronic device - Google Patents
Cr-Cu alloy plate, heat radiating plate for electronic device using the same, and heat radiating component for electronic device Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、電子機器に搭載された半導体素子等の発熱体から発生する熱を速やかに放散させるために用いられ、低い熱膨張率と高い熱伝導率を要求される電子機器用放熱板（すなわちヒートシンク材またはヒートスプレッダー材）や所定の形状に加工された電子機器用放熱部品、ならびにその素材となるCr−Cu合金板に関するものである。
なお、ここでは電子機器用放熱板と電子機器用放熱部品を総称して放熱用材料と記す。
The present invention is used to quickly dissipate heat generated from a heating element such as a semiconductor element mounted on an electronic device, and is a heat sink for electronic devices that requires low thermal expansion coefficient and high thermal conductivity (that is, The present invention relates to a heat sink material or a heat spreader material), a heat radiating component for electronic equipment processed into a predetermined shape, and a Cr—Cu alloy plate as the material.
In addition, here, the heat radiating plate for electronic equipment and the heat radiating component for electronic equipment are collectively referred to as a heat radiating material.
半導体素子等の電子部品を搭載した電子機器を作動させる際には、電子回路への通電に伴い電子部品が発熱する。電子機器の高出力化に伴い、作動時の発熱量はますます増加する傾向にあるが、温度が上昇し過ぎると半導体素子の特性が変化し、電子機器の動作が不安定になる問題が生じる。また長時間にわたって使用することによって過剰な高温に曝されると、電子部品の接合材（たとえばハンダ等）や絶縁材（たとえば合成樹脂等）が変質して、電子機器の故障の原因になる。そのため、電子部品から発熱する熱を速やかに放散させる必要がある。そこで、放熱用材料を介して熱を放散させる技術が種々検討されている。 When an electronic device equipped with an electronic component such as a semiconductor element is operated, the electronic component generates heat as the electronic circuit is energized. As the output of electronic equipment increases, the amount of heat generated during operation tends to increase. However, if the temperature rises too much, the characteristics of the semiconductor element change and the operation of the electronic equipment becomes unstable. . Further, when exposed to an excessively high temperature after being used for a long period of time, a bonding material (for example, solder) or an insulating material (for example, synthetic resin) of an electronic component is altered, causing a failure of the electronic device. Therefore, it is necessary to quickly dissipate the heat generated from the electronic component. Therefore, various techniques for dissipating heat through a heat dissipation material have been studied.
半導体素子は、放熱用材料にハンダ付けまたはロウ付けで直接固定される、あるいはたとえば窒化アルミニウム（AlＮ）にAl電極をダイレクトボンディングした基板（いわゆるＤＢＡ基板）上にハンダ付けまたはロウ付けされた後、そのＤＢＡ基板を放熱用材料の上に同様の方法により固定する。その際、シリコンの熱膨張率は3.5×10-6Ｋ-1であり、ＤＢＡ基板の熱膨張率は５〜７×10-6Ｋ-1であるため、接合される放熱用材料としてはこれらに近い熱膨張率を有することが要求される。現在使用されている放熱用材料としては、Ｗ−Cu系複合材料の熱膨張率が６〜９×10-6Ｋ-1であり、Mo−Cu系複合材料の熱膨張率が７〜14×10-6Ｋ-1である。このように接合される相手材に近い熱膨張率を有することにより、半導体素子の発熱によって発生する熱応力の影響を小さく抑えることができる。 The semiconductor element is directly fixed to the heat dissipation material by soldering or brazing, or after being soldered or brazed on a substrate (so-called DBA substrate) in which an Al electrode is directly bonded to aluminum nitride (AlN), for example, The DBA substrate is fixed on the heat dissipation material by the same method. At that time, the thermal expansion coefficient of silicon is 3.5 × 10 −6 K −1 , and the thermal expansion coefficient of the DBA substrate is 5 to 7 × 10 −6 K −1. It is required to have a coefficient of thermal expansion close to. As heat dissipation materials currently used, the thermal expansion coefficient of W-Cu composite materials is 6-9 × 10 −6 K −1 , and the thermal expansion coefficient of Mo—Cu composite materials is 7-14 ×. 10 −6 K −1 . By having a coefficient of thermal expansion close to that of the counterpart material to be joined in this way, it is possible to suppress the influence of thermal stress generated by heat generation of the semiconductor element.
放熱用材料は、熱膨張が小さいことに加えて、熱伝導率が大きいことが要求されるが、単相材料で両者を同時に達成することは難しい。そのため、熱膨張率の小さい材料と熱伝導率の大きい材料を組み合わせた複合材料が多く用いられている。
このような例として、たとえば特許文献１には、Ｗ−Cu，Mo−Cu等の金属−金属系複合材料が提案されている。Ｗ，Moは熱膨張率が低く、他方、Cuは熱伝導率が高いという特性を利用する技術である。
The heat dissipation material is required to have high thermal conductivity in addition to low thermal expansion, but it is difficult to achieve both simultaneously with a single-phase material. For this reason, a composite material in which a material having a low thermal expansion coefficient and a material having a high thermal conductivity are combined is often used.
As such an example, for example, Patent Document 1 proposes a metal-metal composite material such as W-Cu and Mo-Cu. W and Mo are technologies that utilize the characteristic that the coefficient of thermal expansion is low, while Cu is high in thermal conductivity.
また特許文献２には、SiＣ−Al，Cu2Ｏ−Cu等のセラミックス−金属系の複合材料が開示されている。
さらに特許文献３にはCr−Cu，Nb−Cu等の金属−金属系複合材料が開示されている。この技術は、鋳造した後で熱間圧延し、さらに冷間圧延して所定の形状を得てから溶体化熱処理し、時効熱処理を行なってCuマトリックス中から粒子状Cr相を析出させ、それによって熱膨張率の低減を図るものである。特許文献３は、Cr−Cu系合金について、低熱膨張率と高熱伝導率を共に達成するための技術である。この技術は、２〜50質量％のCrを含有するCu合金について、第２相として存在する凝固の際に析出する初晶Cr相のアスペクト比を10以上とすることによって、複合則から予想されるよりも低い熱膨張率を得ることが可能になるというものである。しかしながら、製造方法は溶解鋳造法を前提としているので、開示されている方法ではCr含有量が増加すると、融点が高くなる上、凝固偏析により均質な合金製造が困難である。これを均質化するためには、高温長時間の均質化熱処理に加えて、熱間鍛造や熱間圧延工程が必要となる。したがって、特許文献３の実施例には、30質量％を超えるCrを含有する例は開示されていない。しかしながら、この方法では凝固の際の１次析出相であるCr相のアスペクト比を100以上として、やっと複合則より10％程度の熱膨張率低下が得られる程度である。Cr相のアスペクト比を100とするだけでも、たとえば冷間圧延では90％以上の圧下を必要とする。その結果、製造コストの上昇を招き、しかも製品として提供できる放熱用材料の寸法が制限されるという問題がある。
Patent Document 2 discloses a ceramic-metal composite material such as SiC-Al and Cu 2 O—Cu.
Further, Patent Document 3 discloses metal-metal composite materials such as Cr—Cu and Nb—Cu. This technology involves hot rolling after casting, and further cold rolling to obtain a predetermined shape, followed by solution heat treatment, and aging heat treatment to precipitate a particulate Cr phase from the Cu matrix, thereby This is intended to reduce the coefficient of thermal expansion. Patent Document 3 is a technique for achieving both a low thermal expansion coefficient and a high thermal conductivity for a Cr—Cu alloy. This technique is expected from the compound law by setting the aspect ratio of the primary Cr phase that precipitates during solidification existing as the second phase to 10 or more for Cu alloys containing 2 to 50 mass% of Cr. It is possible to obtain a lower coefficient of thermal expansion than the above. However, since the production method is premised on the melt casting method, when the Cr content increases, the melting point increases and the production of a homogeneous alloy is difficult due to solidification segregation. In order to homogenize this, a hot forging or hot rolling process is required in addition to the high temperature and long time homogenization heat treatment. Therefore, the example of Patent Document 3 does not disclose an example containing Cr exceeding 30% by mass. However, with this method, when the aspect ratio of the Cr phase, which is the primary precipitation phase during solidification, is 100 or more, a thermal expansion coefficient reduction of about 10% is finally obtained from the composite law. Even if the aspect ratio of the Cr phase is only 100, for example, cold rolling requires a reduction of 90% or more. As a result, there is a problem in that the manufacturing cost is increased and the size of the heat dissipating material that can be provided as a product is limited.
非特許文献１には、30質量％以上のCrを含むCr−Cu合金を溶解と冷間加工によって均一に製造する技術が開示されている。すなわち、CrとCuの混合粉末を焼結したものを消耗電極として用い、高価なアーク放電を用いた溶解鋳造法で鋳造し、さらに室温での延性が不十分なCrが変形し易いように押出し法によって丸棒を製造する方法である。押出し法は、Crに対してCuマトリックスからの静水圧が働くため、加工が容易となることを利用したものである。この技術では、アーク放電による溶解鋳造が高価である等、経済性に問題があり、かつ放熱材料のような薄い板状の材料の製造には適していない。 Non-Patent Document 1 discloses a technique for uniformly producing a Cr—Cu alloy containing 30 mass% or more of Cr by melting and cold working. In other words, a sintered powder of mixed powder of Cr and Cu is used as a consumable electrode, cast by melt casting using expensive arc discharge, and extruded so that Cr with insufficient ductility at room temperature is easily deformed. It is a method of manufacturing a round bar by the method. The extrusion method utilizes the fact that processing is easy because the hydrostatic pressure from the Cu matrix acts on Cr. This technique has a problem in economy such as high cost for melt casting by arc discharge, and is not suitable for manufacturing a thin plate-like material such as a heat dissipation material.
非特許文献２には、15質量％のCrを含み、20μｍ程度の微細Cr相を析出させたCr−Cu合金に対し、冷間で強加工を施すことにより、低い熱膨張率を達成する技術が開示されている。この技術では、Cr相を１μｍほどの厚さとなるまで強加工を行なう必要があり、経済性に問題がある。また、たとえば30質量％以上のCrを含む場合に、このような強加工を行なうことは困難であると考えられる。 Non-Patent Document 2 discloses a technique for achieving a low coefficient of thermal expansion by subjecting a Cr-Cu alloy containing 15 mass% of Cr and having a fine Cr phase of about 20 μm to cold processing. Is disclosed. In this technique, it is necessary to perform strong processing until the Cr phase has a thickness of about 1 μm. In addition, for example, when 30% by mass or more of Cr is included, it is considered difficult to perform such strong processing.
また発明者らは、特許文献４に、熱処理によって熱膨張率を調整したCr−Cu材を放熱用材料に適用する技術を開示している。特許文献４に開示した粉末冶金法では、Cr粉末を使用し、Cuと焼結あるいは溶浸を行なって合金化し、同様に時効熱処理を行なってCrマトリックス中から粒子状Cr相の析出を図るものである。これらの方法では、粒子状Cr相の析出は３次元でランダムであり、どの方向に対しても膨張率は一定である。一方、半導体用放熱材料では、一般的に薄板形状が多く、この場合、板面上に半導体が接合されるので、半導体の接合部を含む面、つまり板の面内の方向の熱膨張率を小さくすることが要求される。 Moreover, the inventors have disclosed a technique in which a Cr—Cu material whose thermal expansion coefficient is adjusted by heat treatment is applied to a heat dissipation material in Patent Document 4. In the powder metallurgy method disclosed in Patent Document 4, Cr powder is used, alloyed by sintering or infiltration with Cu, and similarly subjected to aging heat treatment to precipitate a particulate Cr phase from the Cr matrix. It is. In these methods, the precipitation of the particulate Cr phase is random in three dimensions, and the expansion coefficient is constant in any direction. On the other hand, semiconductor heat-dissipating materials generally have many thin plate shapes. In this case, since the semiconductor is bonded onto the plate surface, the coefficient of thermal expansion in the direction including the semiconductor junction, that is, in the direction of the plate surface, is increased. It is required to be small.
また、特許文献４に開示されたCr−Cu材では、微細析出物の析出形態を制御することのみで、熱膨張率を低減させる技術であるため、ロウ付け接合のような750℃以上の高温に加熱する接合方法では、微細析出物が変化してしまう惧れがあり、低い熱膨張率が安定して得られない。
また放熱板の場合、放熱板用材料の表面を、フライス盤等の切削加工，平面度を得るための両頭研削盤による研削，あるいはラッピングを行ない、仕上げた上で、そのまま、あるいはさらにNiめっきを施して製品となる。したがって、圧延板表面をそのまま製品表面として、あるいはそのままメッキ仕上げして製品とすることができれば、コスト上非常に大きな利点となる。特許文献３，４や非特許文献１，２に開示されたCr−Cu合金は、熱特性中心の記載で、冷間圧延板表面をそのまま使用する点に関する記載はない。また、冷間圧延が容易ではなかった。Crは脆い金属であり、表面のCr相が冷間で強加工されると表面Cr相が破壊される懸念がある。そこで発明者らは、Cr−Cu材の圧延板表面をそのまま使用することを配慮しながら、冷間圧延により偏平したCr相とCuマトリックスからなる熱伝導性が大きく、さらに面内の方向の熱膨張率が小さく、高温に加熱する接合の後も低い熱膨張率を保持できるCr−Cu合金の発明（特許文献５）に至った。しかしながら特許文献５の方法では、適度なCr配合量，圧延前の素材の厚さ，圧下率であれば問題はないが、Cr配合量，圧延前の素材の厚さ，圧下率が大きくなるにつれて、冷間圧延した圧延板の側面には肉眼でも明瞭に確認できる耳割れを生じ、材料歩留りの点で好ましくないことが判明した。また、圧延板の表面には熱特性や表面粗さ等の形状面での問題はないものの、肉眼では見えない微小なクラックが発生する場合があり、その場合、圧延板の表面に直接めっきを施すと、ロウ付け接合のように高温で熱処理する際に、めっきに数μｍ〜数十μｍ程度の微小なふくれ（以下、めっきふくれという）が発生する場合があることが判明し、放熱用材料として使用するのに支障をきたすという問題が生じる。
In the case of a heat sink, the surface of the heat sink material is cut with a milling machine, etc., ground with a double-headed grinder to obtain flatness, or lapped and finished, and then Ni plating is applied as it is. Product. Therefore, if the surface of the rolled plate can be used as it is as the product surface or can be plated as it is to obtain a product, it is a great advantage in terms of cost. The Cr-Cu alloys disclosed in Patent Documents 3 and 4 and Non-Patent Documents 1 and 2 are described with a focus on the thermal characteristics, and there is no description regarding the point of using the cold rolled sheet surface as it is. Moreover, cold rolling was not easy. Cr is a brittle metal, and there is a concern that the surface Cr phase is destroyed when the surface Cr phase is strongly processed cold. Therefore, the inventors consider that the rolled plate surface of the Cr-Cu material is used as it is, and the thermal conductivity of the Cr phase and Cu matrix flattened by cold rolling is large, and the heat in the in-plane direction is further increased. The invention has led to the invention of a Cr—Cu alloy (Patent Document 5) that has a low expansion coefficient and can maintain a low coefficient of thermal expansion even after bonding heated to a high temperature. However, in the method of Patent Document 5, there is no problem as long as the Cr content is appropriate, the thickness of the material before rolling, and the rolling reduction, but as the Cr content, the thickness of the material before rolling, and the rolling reduction are increased. As a result, it was found that an ear crack that can be clearly recognized with the naked eye was generated on the side surface of the cold-rolled rolled plate, which was not preferable in terms of material yield. In addition, although there are no problems in terms of shape such as thermal characteristics and surface roughness on the surface of the rolled plate, micro cracks that cannot be seen with the naked eye may occur. When it is applied, it has been found that, when heat treatment is performed at a high temperature such as brazing, minute blisters (hereinafter referred to as plating blisters) of several μm to several tens of μm may be generated in the plating. As a result, there arises a problem that the use is difficult.
本発明は上記のような問題を解消し、熱膨張率が小さく、熱伝導率が大きいという特性を有し、かつ耳割れの発生を抑制したCr−Cu合金板およびそれを用いた放熱材料（すなわち電子機器用放熱板，電子機器用放熱部品）を提供することを目的とする。
また本発明のCr−Cu合金板は、めっきふくれも抑制するので、めっきを施して高機能の放熱用材料として好適に使用できる。
The present invention solves the above problems, has a characteristic that the coefficient of thermal expansion is small, the thermal conductivity is large, and the Cr-Cu alloy plate that suppresses the occurrence of ear cracks and a heat dissipation material using the same ( That is, it aims at providing the heat sink for electronic devices, the heat radiating component for electronic devices).
Moreover, since the Cr-Cu alloy plate of the present invention also suppresses plating blistering, it can be suitably used as a high-functional heat dissipation material after plating.
発明者らは、Cr−Cu合金板の耳割れとめっきふくれの発生原因について検討した。その結果、冷間圧延によってCr−Cu合金板の表面に発生する微小なクラックが耳割れの主たる原因であることが分かった。また、Cr−Cu合金板にめっきを施す際に、Cr−Cu合金板の表面に存在する微小なクラックにめっき液等のめっき処理で使用される液体が浸入し、その後、ハンダ付けやロウ付けの際にめっき液が高温に曝されて気化することによって、めっきふくれが発生することが分かった。したがって、微小なクラックの発生を防止すれば、Cr−Cu合金板の耳割れとめっきふくれを防止できる。 The inventors investigated the cause of the occurrence of ear cracks and plating blisters in the Cr—Cu alloy plate. As a result, it was found that the minute cracks generated on the surface of the Cr-Cu alloy sheet by cold rolling were the main cause of the ear cracks. Also, when plating Cr-Cu alloy plate, the liquid used in the plating process such as plating solution enters micro cracks existing on the surface of Cr-Cu alloy plate, and then soldering or brazing It has been found that plating blisters are generated when the plating solution is exposed to high temperatures and vaporizes. Therefore, if the generation of minute cracks is prevented, the ear cracks and plating blisters of the Cr—Cu alloy plate can be prevented.
そこで、冷間圧延によってCr−Cu合金板に生じる微小なクラックについて、さらに調査した。その結果、
(a)冷間圧延ではCrとCuの剛性が異なるので圧延時にCrとCuの界面に高い応力歪が発生する。またCrは脆いのに対して、Cuは優れた延性を有するので、Cr−Cu合金板の表面に露出したCr相とCu相の界面から微小なクラックが発生する、あるいはCr相内で微小なクラックが発生する、
(b)Cr−Cu合金板の内部では、Cu相がCr相を包むので、クラックは発生しないということが分かった。つまり、微小なクラックはCr−Cu合金板の内部には存在せず、表層部のみに発生する、
(c)溶浸後、表面に残留したCu相を除去し、圧延素材として厚さを調整するための加工で、溶浸体表面を傷付けないように適切な方法で切削加工あるいは研削加工した場合は、めっきふくれは生じない、
(d)冷間圧延を行なわず、Crに延性を付与するためにCr−Cu合金素材を40〜300℃の温度範囲とする温間圧延を行なうことによって、微小なクラックが発生するのを防止できる
ということが判明した。
Therefore, further investigation was made on minute cracks generated in the Cr-Cu alloy sheet by cold rolling. as a result,
(a) In cold rolling, the Cr and Cu have different rigidity, so high stress strain occurs at the Cr / Cu interface during rolling. In addition, Cr is brittle, while Cu has excellent ductility, so minute cracks are generated from the interface between the Cr phase and the Cu phase exposed on the surface of the Cr-Cu alloy plate, or minute in the Cr phase. Cracks occur,
(b) Inside the Cr-Cu alloy plate, it was found that the Cu phase envelops the Cr phase, so that no cracks occurred. In other words, minute cracks do not exist inside the Cr-Cu alloy plate, but occur only in the surface layer part.
(c) After infiltration, the Cu phase remaining on the surface is removed and the thickness is adjusted as a rolling material. When the surface of the infiltrated body is cut or ground by an appropriate method so as not to be damaged. No plating blisters,
(d) Preventing the occurrence of minute cracks by performing warm rolling with a Cr-Cu alloy material in the temperature range of 40 to 300 ° C in order to impart ductility to Cr without cold rolling. It turns out that you can.
本発明は、これらの知見に基づいてなされたものである。
すなわち本発明は、質量％で、Crを30％超え80％以下含有し、残部がCuおよび不可避的不純物からなる組成を有し、Cr粉末を用い、これを単独で、あるいはCu粉末と混合して型に充填して焼結した多孔質体にCuを溶浸させることによって得た溶浸体に切削加工や研削加工を施して、溶浸体の表面に残留するCuを除去したのち、40〜300℃の範囲内で温間圧延を施して得た、Cuマトリックスと偏平したCr相とからなる組織を有し、Cr相の平均アスペクト比が1.0超えであり、かつ表面に存在するクラックが2.5個／cm2 以下であるCr−Cu合金板である。
The present invention has been made based on these findings.
That is, the present invention contains, by mass%, Cr exceeding 30% and not more than 80%, with the balance consisting of Cu and inevitable impurities , using Cr powder, which is used alone or mixed with Cu powder. After removing Cu remaining on the surface of the infiltrant by cutting or grinding the infiltrated by infiltrating Cu into the porous body that has been filled and sintered in the mold, 40 obtained by applying warm rolling within the range of to 300 ° C., it has a tissue consisting of Cu matrix and flattened the Cr phase, and an average aspect ratio of Cr phases is more than 1.0, and torque exists on the surface It is a Cr—Cu alloy plate having a rack of 2.5 pieces / cm 2 or less .
また本発明は、上記のCr−Cu合金板を使用した電子機器用放熱板あるいは電子機器用放熱部品である。
また本発明は、上記のCr−Cu合金板の表面にNiめっき層を形成して使用した電子機器用放熱板あるいは電子機器用放熱部品である。
Moreover, this invention is a heat sink for electronic devices or the heat radiating component for electronic devices which uses said Cr-Cu alloy plate.
The present invention also relates to a heat radiating plate for electronic equipment or a heat radiating component for electronic equipment, which is used by forming a Ni plating layer on the surface of the Cr-Cu alloy plate.
本発明によれば、熱膨張率が小さく、かつ熱伝導率が大きいという特性を有し、かつ耳割れの発生を抑制した歩留りの高い圧延板からCr−Cu合金板およびそれを用いた放熱材料を得ることができる。
また本発明のCr−Cu合金板は表面の微小なクラックが極めて少なく、めっきふくれも抑制するので、研削等の表面加工の必要はなく、合金板の表面に直接めっきを施して高機能の放熱用材料として好適に使用できる。
According to the present invention, a Cr-Cu alloy plate and a heat dissipating material using the same from a rolled plate having a low thermal expansion coefficient and a high thermal conductivity and having a high yield that suppresses the occurrence of ear cracks. Can be obtained.
In addition, the Cr-Cu alloy plate of the present invention has very few surface cracks and suppresses plating blistering, so there is no need for surface treatment such as grinding. It can be suitably used as a material for use.
まず、本発明を適用して得られるCr−Cu合金板におけるCr含有量の限定理由を説明する。なお各元素の含有量の単位は、いずれも質量％である。
Crは、本発明のCr−Cu合金において、熱膨張率の低減を達成するための重要な元素である。Cr含有量が30％以下では、放熱用材料（すなわち電子機器用放熱板，電子機器用放熱部品）に要求される低熱膨張率（約14×10-6Ｋ-1以下）が得られない。一方、80％を超えると、熱伝導率が低下し、放熱用材料として十分な放熱効果が得られない。したがって、Crは30％超え80％以下とする。好ましくは40％以上70％以下である。なお、より好ましくは45％以上65％以下であり、50％超え65％以下が一層好ましい。
First, the reason for limiting the Cr content in the Cr—Cu alloy sheet obtained by applying the present invention will be described. The unit of the content of each element is mass%.
Cr is an important element for achieving a reduction in the coefficient of thermal expansion in the Cr—Cu alloy of the present invention. When the Cr content is 30% or less, the low coefficient of thermal expansion (about 14 × 10 −6 K −1 or less) required for a heat radiating material (that is, a heat radiating plate for electronic equipment and a heat radiating component for electronic equipment) cannot be obtained. On the other hand, if it exceeds 80%, the thermal conductivity decreases, and a sufficient heat dissipation effect as a heat dissipation material cannot be obtained. Therefore, Cr is over 30% and 80% or less. Preferably they are 40% or more and 70% or less. More preferably, it is 45% or more and 65% or less, and more preferably more than 50% and 65% or less.
本発明では、Crの原料をCr粉末として粉末冶金法を適用する。粉末冶金法の採用によって、Cr粉末を用い、これを単独で、あるいはCu粉末と混合して型に充填して焼結した多孔質体にCuを溶浸させることによって、30％を超えるCrを均一に分布させたCr−Cu合金の製造が可能になった。多孔質体に求められる好ましい気孔率としては、水銀圧下法（ＪＩＳ規格R1655：2003）で得られる値で15〜65体積％程度である。なお多孔質体を得るにあたって、Cr粉末を単独で、またはCr粉末をCu粉末と混合して型に充填した後、圧力を加えて成形（いわゆる加圧成形）して焼結しても良いし、あるいは圧力を加えず充填したまま（いわゆる自然充填）で焼結しても良い。 In the present invention, the powder metallurgy method is applied using Cr powder as the Cr raw material. By adopting powder metallurgy method, Cr powder is used alone, or mixed with Cu powder and infiltrated into a porous body sintered by filling Cu and exceeding 30% Cr The production of uniformly distributed Cr-Cu alloys has become possible. A preferable porosity required for the porous body is about 15 to 65% by volume as a value obtained by a mercury reduction method (JIS standard R1655: 2003). In order to obtain a porous body, Cr powder may be used alone or mixed with Cu powder and filled in a mold, and then pressed (so-called pressure molding) and then sintered. Alternatively, sintering may be performed while filling without applying pressure (so-called natural filling).
使用するCr粉末は、純度99％以上、ＪＩＳ規格Z2510:2004に準拠して篩分けした粒度10〜250μｍ（ＪＩＳ規格Z8801-1:2006に規定される公称目開き寸法）が好ましい。ただし、粒度が大きくなると、粉末を均一に充填することが困難になるほか、圧延後に板厚方向で十分な熱伝導率が得られ難いという傾向がある。また、粒度が小さくなるとCr粉末の表面積が増大して酸化し易くなり、焼結して得た多孔質体にCuを溶浸することが困難になる上、酸素含有量が増加して、後述する温間圧延等の加工性にも悪影響を及ぼす傾向がある。したがって、より好ましい粒度は30〜250μｍであり、50〜200μｍが一層好ましい。 The Cr powder to be used preferably has a purity of 99% or more and a particle size of 10 to 250 μm (nominal opening size defined in JIS standard Z8801-1: 2006) sieved according to JIS standard Z2510: 2004. However, when the particle size becomes large, it becomes difficult to uniformly fill the powder, and it is difficult to obtain sufficient thermal conductivity in the plate thickness direction after rolling. In addition, when the particle size is reduced, the surface area of the Cr powder increases and it becomes easy to oxidize, it becomes difficult to infiltrate Cu into the porous body obtained by sintering, and the oxygen content increases, which will be described later. There is also a tendency to adversely affect workability such as warm rolling. Therefore, a more preferable particle size is 30 to 250 μm, and more preferably 50 to 200 μm.
またCr粉末中の不純物は、多孔質体にCuを溶浸した溶浸体の加工性向上の観点から、可能な限り低減することが好ましい。特にＯ，Ｎ，Ｃは多大な影響を及ぼし、大きい加工を施す場合には、Ｏ含有量を0.15％以下，Ｎ含有量を0.1％以下，Ｃ含有量を0.1％以下とすることが好ましい。より好ましくは、Ｏ含有量：0.08％以下，Ｎ含有量：0.03％以下，Ｃ含有量：0.03％以下である。 Moreover, it is preferable to reduce impurities in the Cr powder as much as possible from the viewpoint of improving the workability of the infiltrated body in which Cu is infiltrated into the porous body. In particular, O, N, and C have a great influence, and when large processing is performed, it is preferable that the O content is 0.15% or less, the N content is 0.1% or less, and the C content is 0.1% or less. More preferably, the O content is 0.08% or less, the N content is 0.03% or less, and the C content is 0.03% or less.
Cu粉末は、工業的に生産される電解銅粉，アトマイズ銅粉等を使用することが好ましい。
Cr粉末を焼結して得た多孔質体に溶浸させるCuは、工業的に製造されるタフピッチ銅，りん脱酸銅，無酸素銅等の金属Cu板、あるいは電解銅粉，アトマイズ銅粉等のCu粉末を使用するのが好ましい。
The Cu powder is preferably an industrially produced electrolytic copper powder, atomized copper powder or the like.
Cu to be infiltrated into a porous body obtained by sintering Cr powder is an industrially manufactured metal Cu plate such as tough pitch copper, phosphorous deoxidized copper, oxygen-free copper, or electrolytic copper powder, atomized copper powder. It is preferable to use Cu powder such as.
このようにして得た溶浸体に切削加工や研削加工を施して、溶浸体の表面に残留するCuを除去するとともに、所定の厚みのCr−Cu合金板を得る。
切削加工を行なう場合は、作業効率の観点から超硬チップによるフライス加工が好ましい。ただし、超硬チップが欠損するとCr−Cu合金板の表面に疵を誘発する原因になるので、超硬チップの保守点検が重要である。超硬チップの耐用性を高めるために、CrＮ等でコーティングした超硬チップを使用することが好ましい。
The infiltrated body thus obtained is subjected to cutting and grinding to remove Cu remaining on the surface of the infiltrated body, and a Cr—Cu alloy plate having a predetermined thickness is obtained.
When cutting is performed, milling with a carbide tip is preferable from the viewpoint of work efficiency. However, if the carbide tip is damaged, it will cause wrinkles on the surface of the Cr-Cu alloy plate, so maintenance inspection of the carbide tip is important. In order to increase the durability of the carbide tip, it is preferable to use a carbide tip coated with CrN or the like.
研削加工を行なう場合は、砥粒（たとえばAl2Ｏ3 ，SiＣ等）がCr−Cu合金板の表面に食い込むと疵を誘発する原因になるので、砥粒の選択および押圧力の調整が重要である。
あるいは、溶浸体の表面に残留するCuを除去した後、温間圧延を施して所定の厚みのCr−Cu合金板を得ることが好ましい。温間で圧延することによって、Cr相に延性が付与され、クラックの発生を防止できる。
When grinding, abrasive grains (for example, Al 2 O 3 , SiC, etc.) bite into the surface of the Cr-Cu alloy plate, causing wrinkles. Therefore, it is important to select the abrasive grains and adjust the pressing force. It is.
Alternatively, after removing Cu remaining on the surface of the infiltrated body, it is preferable to perform warm rolling to obtain a Cr—Cu alloy plate having a predetermined thickness. Rolling warmly imparts ductility to the Cr phase and prevents cracks from occurring.
Crは、その純度や結晶粒の大きさ，熱処理によって延性−脆性遷移温度（いわゆるＤＢＴＴ）が大きく変化することが知られており（非特許文献３参照）、状況によって30〜40℃の室温に近い温度でＤＢＴＴが発現する（非特許文献４，５参照）。Cr−Cu合金も、Cr粉末の純度を高める（特にＯ，Ｃ，Ｎを低減する）ことによって低いＤＢＴＴのCr相を得ることができる。Cr−Cu材の圧延試験の結果、Cr相の延性向上が圧延板表面の微小クラック発生を抑える効果のあることが判明した。したがって、温間圧延におけるCr−Cu合金素材の温度は40℃以上とすることが好ましい。さらに好ましくは60℃以上である。80℃以上が一層好ましい。 It is known that Cr has a ductile-brittle transition temperature (so-called DBTT) that varies greatly depending on its purity, crystal grain size, and heat treatment (see Non-Patent Document 3). DBTT develops at near temperatures (see Non-Patent Documents 4 and 5). Cr-Cu alloys can also obtain a low DBTT Cr phase by increasing the purity of Cr powder (especially by reducing O, C, and N). As a result of the rolling test of the Cr-Cu material, it was found that the improvement of the ductility of the Cr phase has the effect of suppressing the occurrence of microcracks on the surface of the rolled sheet. Therefore, the temperature of the Cr—Cu alloy material in the warm rolling is preferably 40 ° C. or higher. More preferably, it is 60 ° C. or higher. 80 ° C. or higher is more preferable.
一方、温間圧延におけるCr−Cu合金素材の温度が300℃を超えると、Cr−Cu合金板の表面にスケールが発生し、めっきの前処理にてスケールを除去する際にCrとCuの酸化物の溶解速度の相違により段差を生じて表面が粗くなる。また、CrとCuの界面が過剰にエッチングされて亀裂を生じる等、めっき不良（たとえば密着不良，変色等）が発生する原因となる。したがって、温間圧延におけるCr−Cu合金素材の加熱温度は300℃以下が好ましい。より好ましくは200℃以下である。150℃以下が一層好ましい。 On the other hand, when the temperature of the Cr-Cu alloy material in warm rolling exceeds 300 ° C, scale is generated on the surface of the Cr-Cu alloy plate, and oxidation of Cr and Cu occurs when the scale is removed in the pretreatment of plating. Due to the difference in the dissolution rate of the object, a step is generated and the surface becomes rough. Further, the interface between Cr and Cu is excessively etched to cause cracks and the like, which causes plating defects (for example, poor adhesion, discoloration, etc.). Therefore, the heating temperature of the Cr—Cu alloy material in warm rolling is preferably 300 ° C. or less. More preferably, it is 200 ° C. or lower. 150 ° C. or less is more preferable.
つまり、温間圧延におけるCr−Cu合金素材の温度が40〜300℃の範囲内となるようにCr−Cu合金素材を加熱する。好ましくは40〜200℃，80〜200℃である。80〜150℃が一層好ましい。この温度範囲では、表面の酸化膜を軽度のエッチングで除去でき、通常のめっき前処理でめっきできるため、大気中で温間圧延を行なうことが可能である。 That is, the temperature of the Cr-Cu alloy material in warm rolling heat the Cr-Cu alloy material to be within a range of 40 to 300 ° C.. Preferably they are 40-200 degreeC and 80-200 degreeC. 80-150 degreeC is still more preferable. In this temperature range, the oxide film on the surface can be removed by light etching, and plating can be performed by normal plating pretreatment, so that warm rolling can be performed in the atmosphere.
Crに含有される不純物が増加すると、ＤＢＴＴが高くなるので、温間圧延における溶浸体の温度を上昇せざるを得なくなる。不純物としては、Ｏ，Ｎ，ＣがＤＢＴＴに多大な影響を及ぼす。ただし、温間圧延が施される溶浸体におけるＯ含有量：0.08質量％以下，Ｎ含有量：0.05質量％以下，Ｃ含有量：0.05質量％以下（好ましくはＯ含有量：0.03質量％以下，Ｎ含有量：0.02質量％以下，Ｃ含有量：0.01質量％以下）の範囲内であれば、上記の温度範囲で温間圧延する上で問題はない。 When impurities contained in Cr increase, DBTT becomes high, and thus the temperature of the infiltrated body in warm rolling must be increased. As impurities, O, N, and C greatly affect DBTT. However, the O content in the infiltrate subjected to warm rolling: 0.08 mass% or less, N content: 0.05 mass% or less, C content: 0.05 mass% or less (preferably O content: 0.03 mass% or less , N content: 0.02 mass% or less, C content: 0.01 mass% or less), there is no problem in warm rolling in the above temperature range.
なお、不可避的不純物は通常の範囲（たとえば合計で約１質量％以下）で問題ない。主な不可避的不純物として、たとえば0.03質量％以下のＳ，0.02質量％以下のＰ，0.3質量％以下のFeを含んでも良い。
温間圧延を行なうにあたって、溶浸体を所定の温度に加熱する方法は、加熱装置を用いて溶浸体を予め加熱する、溶浸体と圧延ロールに温風を吹き付ける、あるいは加熱装置（たとえばヒーター等）を備えた圧延ロールを使用する等の方法が好ましい。
Inevitable impurities are not a problem in a normal range (for example, about 1 mass% or less in total). As main inevitable impurities, for example, 0.03% by mass or less of S, 0.02% by mass or less of P, and 0.3% by mass or less of Fe may be included.
In performing the warm rolling, the infiltrant is heated to a predetermined temperature by preheating the infiltrant using a heating device, blowing hot air on the infiltrant and the roll, or a heating device (for example, A method such as using a rolling roll equipped with a heater or the like is preferable.
温間圧延は、圧下率を10％以上として行なうことが好ましい。圧下率が10％未満では、温間圧延によってCr相が熱膨張率の低減に有利な方向に配向しない。ここで圧下率は、100×〔ｔ0−ｔ〕／ｔ0（ｔ0：圧延前の板厚，ｔ：圧延後の板厚）とする。
溶浸体の加工性を改善するために、温間圧延を行なうに先立って、必要に応じて溶浸体（すなわちCr−Cu合金素材）を還元雰囲気あるいは真空中で300〜1050℃の温度範囲に熱処理することが好ましい。その温度が300℃未満では、加工性の改善効果が乏しい。一方、1050℃を超えると、Cu相が一部溶解する。こうしてCr−Cu合金素材を加熱した後、一旦冷却して、所定の温度で温間圧延を行なう。
The warm rolling is preferably performed at a rolling reduction of 10% or more. When the rolling reduction is less than 10%, the Cr phase is not oriented in a direction advantageous for reducing the thermal expansion coefficient by warm rolling. Here, the rolling reduction is 100 × [t 0 −t] / t 0 (t 0 : plate thickness before rolling, t: plate thickness after rolling).
In order to improve the workability of the infiltrated body, the temperature of the infiltrated body (that is, Cr-Cu alloy material) is 300 to 1050 ° C in a reducing atmosphere or vacuum as necessary prior to warm rolling. It is preferable to heat-treat. If the temperature is less than 300 ° C, the effect of improving workability is poor. On the other hand, when it exceeds 1050 ° C., a part of the Cu phase is dissolved. After heating the Cr—Cu alloy material in this way, it is once cooled and warm-rolled at a predetermined temperature.
一方、温間圧延が終了した後、Cr−Cu合金板を還元雰囲気，不活性ガスあるいは真空中で300〜900℃の温度範囲で熱処理を施すことが好ましい。この熱処理は、圧延後のCr−Cu合金板を軟質化するために行なうものである。熱処理の温度が300℃未満では、軟質化の効果が得られない。一方、900℃を超えると、溶浸したCuが溶解する等のため、圧延板が大きく変形する。 On the other hand, after the warm rolling is completed, it is preferable to heat-treat the Cr—Cu alloy sheet in a reducing atmosphere, an inert gas, or a vacuum at a temperature range of 300 to 900 ° C. This heat treatment is performed to soften the Cr—Cu alloy sheet after rolling. If the temperature of the heat treatment is less than 300 ° C., the effect of softening cannot be obtained. On the other hand, when the temperature exceeds 900 ° C., the infiltrated Cu dissolves and the rolled plate is greatly deformed.
このようにして、得られた溶浸体に切削加工や研削加工を施す、あるいは溶浸体に温間圧延を施すことによって、表層部の微小なクラックが１cm2 あたり2.5個以下のCr−Cu合金板を得ることができる。微小なクラックが2.5個／cm2 以下であれば、Cr−Cu合金板にめっきを施した後、ハンダ付けやロウ付けの際に高温に曝されて発生するめっきふくれは極めて少ないので、放熱用材料として支障なく使用できる。 In this way, the obtained infiltrant is subjected to cutting and grinding, or the infiltrant is warm-rolled, so that the number of microcracks in the surface layer portion is 2.5 or less per cm 2. An alloy plate can be obtained. If the number of micro cracks is 2.5 / cm 2 or less, there are very few plating blisters that occur when exposed to high temperatures during soldering or brazing after plating on a Cr-Cu alloy plate. Can be used as a material without any problems.
なお、温間圧延を行なうことによってCuマトリックス中のCr相は偏平になる。圧下率の増加とともにCr相のアスペクト比は大きくなる。そのCr相のアスペクト比が1.0以下では、さらなる熱膨張率の低減効果が得られない。したがって、Cr相のアスペクト比は1.0超えとする。より好ましくは4.0以上である。
なお、圧下率10％未満の圧延加工では、Cr−Cu合金板の断面全体にわたってはCr相の偏平化を生じないので、熱膨張率のさらなる低減効果が得られないものと考えられる。
Note that the Cr phase in the Cu matrix becomes flat by performing warm rolling. As the reduction ratio increases, the aspect ratio of the Cr phase increases. If the aspect ratio of the Cr phase is 1.0 or less, a further effect of reducing the coefficient of thermal expansion cannot be obtained. Therefore, the aspect ratio of the Cr phase is set to exceed 1.0. More preferably, it is 4.0 or more.
In addition, in the rolling process with a rolling reduction of less than 10%, since the Cr phase is not flattened over the entire cross section of the Cr—Cu alloy sheet, it is considered that the effect of further reducing the thermal expansion coefficient cannot be obtained.
Cr相のアスペクト比は、Cr−Cu合金板の厚み方向を含む断面のうち、偏平したCr相の長径が最大となる方向を含む断面、さらに具体的には溶浸体を温間圧延した後の断面（圧延方向および圧下方向を含む断面）を光学顕微鏡で観察して求められ、下記の(1)式で算出される値である。そして、50〜100倍の光学顕微鏡で観察した任意の１視野の平均値を求める。なお、観察した視野に全体が入っているCr相について測定する。また複数のCr相が合体して形成されているように見えるものは、複数のCr相に分解し、分解した各Cr相のアスペクト比を求める。 The aspect ratio of the Cr phase is the cross section including the direction in which the major axis of the flattened Cr phase is maximized among the cross sections including the thickness direction of the Cr-Cu alloy sheet, and more specifically, after warm rolling the infiltrant This is a value calculated by observing the cross section (cross section including the rolling direction and the rolling direction) with an optical microscope and calculated by the following equation (1). And the average value of arbitrary 1 visual fields observed with the optical microscope 50-100 times is calculated | required. In addition, it measures about the Cr phase in which the whole is in the observed visual field. In addition, what appears to be formed by combining a plurality of Cr phases is decomposed into a plurality of Cr phases, and the aspect ratio of each decomposed Cr phase is obtained.
アスペクト比＝Ｌ1／Ｌ2 ・・・(1)
なお(1)式において、Ｌ1は、Cr−Cu合金板の厚み方向を含む断面のうち、偏平したCr相の長径が最大となる方向を含む断面において長径が最大となる方向の最大長さを指し、Ｌ2は、Cr−Cu合金の厚み方向を含む断面のうち、偏平したCr相の長径が最大となる方向を含む断面において厚み方向の最大長さを指す。温間圧延を施して得られるCr−Cu合金板の場合には、上記の偏平したCr相の長径が最大となる方向は圧延方向である。また、２方向への圧延を行なう場合には、２方向のうち偏平したCr相の長径が最大となる圧延方向である。
Aspect ratio = L 1 / L 2 (1)
In the formula (1), L 1 is the maximum length in the direction in which the major axis becomes the maximum in the cross section including the direction in which the major axis of the flat Cr phase is the maximum among the cross sections including the thickness direction of the Cr—Cu alloy plate. L 2 indicates the maximum length in the thickness direction in the cross section including the direction in which the major axis of the flat Cr phase is the maximum among the cross sections including the thickness direction of the Cr—Cu alloy. In the case of a Cr—Cu alloy sheet obtained by performing warm rolling, the direction in which the major axis of the flat Cr phase becomes the maximum is the rolling direction. In addition, when rolling in two directions, it is the rolling direction in which the major axis of the flat Cr phase in the two directions is maximized.
以上のようにして得られたCr−Cu合金板は、微小なクラックが大幅に減少するので、耳割れが大幅に減少する。その結果、Cr−Cu合金板の歩留りが向上する。特に温間圧延を施すことによって得られたCr−Cu合金板の表面は、切削加工，研削加工あるいはラッピングを行なって仕上げた表面と同等の清浄度を有するので、温間圧延後、そのまま、又は直接Niめっきを施して放熱用材料とすることが可能となる。また、そのCr−Cu合金板は、めっきを施した後、高温に曝されても、めっきふくれが大幅に減少する。そのため、放熱用材料として好適に使用できる。 In the Cr—Cu alloy sheet obtained as described above, since micro cracks are greatly reduced, ear cracks are greatly reduced. As a result, the yield of the Cr—Cu alloy plate is improved. In particular, the surface of the Cr-Cu alloy plate obtained by performing the warm rolling has the same cleanliness as the surface finished by cutting, grinding or lapping, so that it remains as it is after the warm rolling, or It becomes possible to apply Ni plating directly to make a material for heat dissipation. Moreover, even if the Cr-Cu alloy plate is subjected to high temperature after plating, plating blistering is greatly reduced. Therefore, it can be suitably used as a heat dissipation material.
Ｏ含有量：0.04〜0.15％，Ｎ含有量：0.01〜0.08％，Ｃ含有量：0.01〜0.08％のCr粉末（粒度50〜200μｍ）を型に自然充填して真空中で焼結し、気孔率41体積％の焼結体（70×70×10mm）を作製した。焼結温度は1200〜1500℃とし、焼結時間は90分とした。この気孔率41体積％の焼結体（すなわち多孔質体）のCr量は、Cuを溶浸した後のCr含有量に換算すると54％に相当する。なお、各元素の含有量の単位は質量％である。 Oxygen content: 0.04-0.15%, N content: 0.01-0.08%, C content: 0.01-0.08% Cr powder (particle size 50-200μm) is naturally filled into a mold and sintered in a vacuum. A sintered body (70 × 70 × 10 mm) with a rate of 41% by volume was produced. The sintering temperature was 1200-1500 ° C., and the sintering time was 90 minutes. The amount of Cr in the sintered body (that is, the porous body) having a porosity of 41% by volume corresponds to 54% in terms of the Cr content after infiltrating Cu. The unit of the content of each element is mass%.
得られた多孔質体の上面にCu板を載置し、さらに真空中で1200℃に加熱（保持時間1.5時間）してCu板を溶解し、多孔質体にCuを溶浸させた。次いで、冷却する過程で、1200〜200℃の温度範囲を200〜600℃／時間の冷却速度で冷却した。
得られた溶浸体のＯ含有量は0.01〜0.07％，Ｎ含有量は0.004〜0.04％，Ｃ含有量は0.004〜0.04％であった。
A Cu plate was placed on the upper surface of the obtained porous body, and further heated to 1200 ° C. in a vacuum (holding time 1.5 hours) to dissolve the Cu plate, and Cu was infiltrated into the porous body. Next, in the cooling process, the temperature range of 1200 to 200 ° C. was cooled at a cooling rate of 200 to 600 ° C./hour.
The obtained infiltrant had an O content of 0.01 to 0.07%, an N content of 0.004 to 0.04%, and a C content of 0.004 to 0.04%.
さらにフライス盤を用いて切削加工を施し、溶浸体の表面に残留するCuを除去した。これを予備加工とする。
この予備加工を施した溶浸体（厚み15mm）に仕上げ加工を施して、厚み3.5mmのCr−Cu合金板とした。仕上げ加工は表１に示す通りである。
これらのCr−Cu合金板の表面を実体顕微鏡で観察（倍率40倍）し、表面に発生したクラックの数を測定した。その結果を１cm2あたりの個数に換算して表１に示す。なお、ここで測定したクラックは、Cr−Cu合金板の表面に露出したCr相とCu相の界面から発生するクラック、あるいはCr相内に発生するクラックを指し、長さ数十μｍ程度の微小なクラックである。ただし、切削加工，研削加工，温間圧延，冷間圧延の際に異物を巻き込むことによって発生したクラックは除外した。参考例３、発明例２〜８は、Cr−Cu合金板の表面の微小なクラックの数が本発明の範囲を満足する例、参考例１，２は微小なクラックの数が本発明の範囲を外れる例である。
Further, cutting was performed using a milling machine to remove Cu remaining on the surface of the infiltrated body. This is a preliminary process.
The preliminarily processed infiltrant (thickness 15 mm) was finished to obtain a Cr—Cu alloy plate having a thickness of 3.5 mm. The finishing process is as shown in Table 1.
The surface of these Cr—Cu alloy plates was observed with a stereoscopic microscope (magnification 40 times), and the number of cracks generated on the surface was measured. The results are shown in Table 1 in terms of the number per 1 cm 2 . In addition, the crack measured here refers to the crack which generate | occur | produces from the interface of the Cr phase and Cu phase exposed on the surface of the Cr-Cu alloy plate, or the crack which generate | occur | produces in the Cr phase, and is about micro tens of micrometers in length. Is a crack. However, cracks caused by the inclusion of foreign matters during cutting, grinding, warm rolling, and cold rolling were excluded. Reference Example 3 and Invention Examples 2 to 8 are examples in which the number of minute cracks on the surface of the Cr—Cu alloy plate satisfies the scope of the present invention, and Reference Examples 1 and 2 are in the range where the number of minute cracks is within the scope of the present invention. This is an example that deviates.
さらに前述した方法で、Cr−Cu合金板の厚み方向断面でのCr相のアスペクト比を求めた。
なお、参考例３の仕上げ加工はフライス盤を用いた切削加工である。発明例２〜８の仕上げ加工は温間圧延（圧下率77％）である。ここで温間圧延に用いた圧延ロールはワークロールとして直径80mm，幅200mmの加熱装置を内蔵したものを使用した。また、0.1〜0.2mm／パスの圧下量にて約40パスの圧延を行なった。発明例２では、加熱装置を用いて溶浸体（Cr−Cu合金素材）を予め60℃に加熱しておき、ヒーターを内蔵した圧延ロールの温度を60℃に保持して温間圧延を行なった。発明例３では、加熱装置を用いて溶浸体を予め80℃に加熱しておき、ヒーターを内蔵した圧延ロールの温度を80℃に維持して温間圧延を行なった。発明例３では、加熱装置を用いて溶浸体を予め120℃に加熱しておき、ヒーターを内蔵した圧延ロールの温度を100℃に維持して温間圧延を行なった。発明例５では、加熱装置を用いて溶浸体を予め150℃に加熱しておき、ヒーターを内蔵した圧延ロールの温度を150℃に維持して温間圧延を行なった。発明例６では、加熱装置を用いて溶浸体を予め200℃に加熱しておき、ヒーターを内蔵した圧延ロールの温度を200℃に維持して温間圧延を行なった。発明例７では、加熱装置を用いて溶浸体を予め250℃に加熱しておき、ヒーターを内蔵した圧延ロールの温度を250℃に維持して温間圧延を行なった。発明例８では、加熱装置を用いて溶浸体を予め80℃に加熱しておき、ヒーターを内蔵した圧延ロールの温度を80℃に保持して温間圧延を行なった。
Furthermore, the aspect ratio of the Cr phase in the cross section in the thickness direction of the Cr—Cu alloy plate was determined by the method described above.
The finishing process in Reference Example 3 is a cutting process using a milling machine. The finishing process of Invention Examples 2 to 8 is warm rolling (rolling rate 77%). Here, the roll used for the warm rolling was a work roll with a built-in heating device having a diameter of 80 mm and a width of 200 mm. Further, rolling for about 40 passes was performed at a reduction amount of 0.1 to 0.2 mm / pass. In Invention Example 2, the infiltrated body (Cr—Cu alloy material) is heated to 60 ° C. in advance using a heating device, and the temperature of the rolling roll incorporating the heater is maintained at 60 ° C. to perform warm rolling. It was. In Invention Example 3, the infiltrant was heated to 80 ° C. in advance using a heating device, and the temperature of the rolling roll incorporating the heater was maintained at 80 ° C. to perform warm rolling. In Invention Example 3, the infiltrate was heated to 120 ° C. in advance using a heating device, and the temperature of the rolling roll incorporating the heater was maintained at 100 ° C. to perform warm rolling. In Invention Example 5, the infiltrate was heated to 150 ° C. in advance using a heating device, and the temperature of the rolling roll incorporating the heater was maintained at 150 ° C. to perform warm rolling. In Invention Example 6, the infiltrant was heated to 200 ° C. in advance using a heating device, and the temperature of the rolling roll incorporating the heater was maintained at 200 ° C. to perform warm rolling. In Invention Example 7, the infiltrate was heated to 250 ° C. in advance using a heating device, and the temperature of the rolling roll incorporating the heater was maintained at 250 ° C. to perform warm rolling. In Invention Example 8, the infiltrate was heated to 80 ° C. in advance using a heating device, and the temperature of the rolling roll incorporating the heater was maintained at 80 ° C. to perform warm rolling.
参考例１の仕上げ加工は、溶浸体の予熱とロールの加熱を行なわない冷間圧延（圧下率72％）である。参考例２の仕上げ加工は、夏季日中に圧延を行なったので、加熱は行なわない。 The finishing process of Reference Example 1 is cold rolling (rolling rate 72%) without preheating the infiltrate and heating the roll. The finishing process of Reference Example 2 is not heated because it was rolled during the summer day.
これらのCr−Cu合金板から試験片を切り出し、参考例３は550℃で熱処理した後、圧延方向の平均熱膨張率を常温〜200℃の温度範囲で測定した。それ以外の圧延板は800℃で熱処理した後、圧延方向の平均熱膨張率を常温〜200℃の温度範囲で測定した。その結果、平均熱膨張率は、参考例３が10.8×10-6Ｋ-1であり、その他の圧延材はいずれも9.1〜9.5×10-6Ｋ-1であった。 Test pieces were cut out from these Cr—Cu alloy plates, and in Reference Example 3 , after heat treatment at 550 ° C., the average thermal expansion coefficient in the rolling direction was measured in a temperature range from room temperature to 200 ° C. The other rolled sheets were heat-treated at 800 ° C., and the average coefficient of thermal expansion in the rolling direction was measured in the temperature range from room temperature to 200 ° C. As a result, the average coefficient of thermal expansion was 10.8 × 10 −6 K −1 in Reference Example 3 and 9.1 to 9.5 × 10 −6 K −1 for all other rolled materials.
また耳割れの巾は、Cr−Cu合金板の上下表面において側面から目視で観察される最大クラック長を測定した。その結果を表１に示す。なお、Cr−Cu合金板の板巾は約70mmであった。表１から明らかなように、発明例２〜６では耳割れの巾が１〜２mmであったのに対して、参考例１，２では８〜10mmであった。
次に、Cr−Cu合金板の表面を実体顕微鏡で観察（倍率40倍）し、表面に発生したクラックの数を測定した。その結果を１cm2あたりの個数に換算して表１に示す。なお、ここで測定したクラックは、Cr−Cu合金板の表面に露出したCr相とCu相の界面から発生するクラック、あるいはCu相内に発生するクラックを指し、長さ数十μｍ程度の微小なクラックや試験片の切り出し時に発生したクラックである。ただし、温間圧延の際に異物を巻き込むことによって発生したクラックは除外した。表１から明らかなように、発明例２〜８では微小なクラックの数が0.1〜2.5個／cm2であったのに対して、参考例１，２では8.0〜11.0個／cm2であった。
Moreover, the width | variety of the ear crack measured the maximum crack length observed visually from the side in the upper and lower surfaces of a Cr-Cu alloy board. The results are shown in Table 1. The plate width of the Cr—Cu alloy plate was about 70 mm. As is clear from Table 1, the width of the ear cracks was 1 to 2 mm in Invention Examples 2 to 6, whereas it was 8 to 10 mm in Reference Examples 1 and 2 .
Next, the surface of the Cr—Cu alloy plate was observed with a stereomicroscope (magnification 40 times), and the number of cracks generated on the surface was measured. The results are shown in Table 1 in terms of the number per 1 cm 2 . In addition, the crack measured here refers to the crack which generate | occur | produces from the interface of the Cr phase and Cu phase exposed on the surface of the Cr-Cu alloy plate, or the crack which generate | occur | produces in a Cu phase, and is about tens of micrometers in length. Cracks or cracks that occurred when the test piece was cut out. However, the crack which generate | occur | produced by involving a foreign material in the case of warm rolling was excluded. As apparent from Table 1, the number of micro cracks was 0.1 to 2.5 / cm 2 in Invention Examples 2 to 8, whereas 8.0 to 11.0 / cm 2 in Reference Examples 1 and 2. It was.
次に、Cr−Cu合金板の表面に電解Niめっき（厚さ５μｍ）を施した。さらに水素雰囲気中で800℃に加熱した後、冷却し、表面をそれぞれ200cm2ずつ実体顕微鏡（倍率40倍）で観察して、めっきふくれの数を測定した。その結果を１cm2あたりの個数に換算して表１に示す。なお、めっきふくれは、数μｍ〜数十μｍ程度の直径と高さを有する膨らみである。表１から明らかなように、参考例３、発明例２〜８ではめっきふくれの数が0.0〜0.5個／cm2であったのに対して、参考例１，２では1.0〜1.5個／cm2であった。 Next, electrolytic Ni plating (thickness 5 μm) was applied to the surface of the Cr—Cu alloy plate. Further, after heating to 800 ° C. in a hydrogen atmosphere, the surface was cooled, and each surface was observed with a stereoscopic microscope (magnification 40 times) by 200 cm 2 to measure the number of plating blisters. The results are shown in Table 1 in terms of the number per 1 cm 2 . The plating blister is a bulge having a diameter and height of about several μm to several tens of μm. As is clear from Table 1, the number of plating blisters was 0.0 to 0.5 / cm 2 in Reference Example 3 and Invention Examples 2 to 8, whereas 1.0 to 1.5 / cm 2 in Reference Examples 1 and 2. 2 .
以上の結果から、本発明のCr−Cu合金板は、微小なクラックが大幅に減少し、その結果、耳割れが大幅に減少することが確かめられた。また、そのCr−Cu合金板は、めっきを施した後、高温に曝されて発生するめっきふくれが大幅に減少することが確かめられた。
From the above results, it was confirmed that in the Cr—Cu alloy plate of the present invention, minute cracks were greatly reduced, and as a result, ear cracks were greatly reduced. Moreover, it was confirmed that the plating blisters generated when the Cr-Cu alloy plate was exposed to high temperature after plating were greatly reduced.
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