JP2018076580A - Precipitation hardening type copper alloy and manufacturing method therefor - Google Patents
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 33
- 238000004881 precipitation hardening Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 230000032683 aging Effects 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 210000001787 dendrite Anatomy 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 28
- 239000000956 alloy Substances 0.000 abstract description 28
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 229910000967 As alloy Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007712 rapid solidification Methods 0.000 description 8
- 238000010583 slow cooling Methods 0.000 description 6
- 229910052735 hafnium Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 229910017813 Cu—Cr Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、耐摩耗性に優れる析出硬化型銅合金及びその製造方法に関し、特に、Ｎｉ及びＳｉを合金成分に含み組織制御を与えて得られる析出硬化型銅合金及びその製造方法に関する。 The present invention relates to a precipitation hardening type copper alloy having excellent wear resistance and a method for producing the same, and more particularly, to a precipitation hardening type copper alloy obtained by imparting microstructure control to Ni and Si contained in an alloy component and a method for producing the same.
ベリリウム銅は、機械加工性に優れるとともに耐熱性、耐食性、及び耐疲労強度にも優れ、高い電気伝導性を有することから、コネクタ、スイッチ、リレー等の各種電気部品の接点や端子、ばねなどに広く用いられている。一方で、元素としてのベリリウムの毒性からこれを含まない代替銅合金として、Ｎｉ及びＳｉを添加した銅合金、いわゆるコルソン系合金の開発が行われている。 Beryllium copper has excellent machinability, heat resistance, corrosion resistance, fatigue resistance, and high electrical conductivity, so it can be used as contacts, terminals and springs for various electrical components such as connectors, switches, and relays. Widely used. On the other hand, a copper alloy to which Ni and Si are added, that is, a so-called Corson-based alloy has been developed as an alternative copper alloy not containing this because of the toxicity of beryllium as an element.
例えば、特許文献１では、ベリリウム銅鋳造品並みの引張強さ及び伸びを有するとともに、機械加工性に優れたコルソン系合金を開示している。主成分として、Ｎｉ：６．０〜９．０ｗｔ％、Ｓｉ：１．４〜２．４ｗｔ％、Ｃｒ：０．２〜１．３ｗｔ％、Ｚｎ：０．５〜１０．０ｗｔ％をＣｕ中に含有する成分組成を有し、９２０℃で溶体化処理後、４３０℃〜４９０℃の温度範囲で所定時間だけ時効熱処理することで、引張強さが６００ＭＰａ以上、伸びが２％以上、硬さがＨＲＣで２５以上、導電率がＩＡＣＳで２０％以上を得られるとしている。 For example, Patent Document 1 discloses a Corson alloy having a tensile strength and elongation comparable to those of a beryllium copper cast product and excellent in machinability. As main components, Ni: 6.0-9.0 wt%, Si: 1.4-2.4 wt%, Cr: 0.2-1.3 wt%, Zn: 0.5-10.0 wt% in Cu The component composition contained in the composition, after solution treatment at 920 ° C., aging heat treatment for a predetermined time in a temperature range of 430 ° C. to 490 ° C., tensile strength is 600 MPa or more, elongation is 2% or more, hardness The HRC can obtain 25 or more by HRC, and the electrical conductivity can obtain 20% or more by IACS.
ところで、析出硬化型の銅合金では、析出相の分散状態を組織制御することで機械特性を大幅に変化させることができる。上記した特許文献１でも、母相としてのα固溶体中にＮｉ及びＣｒとＳｉとの金属間化合物からなる析出相を所定粒径且つ所定アスペクト比で与えて機械強度の向上を図っている。一方で、凝固由来の組織制御による機械特性の制御についても提案されている。 By the way, in the precipitation hardening type copper alloy, the mechanical properties can be significantly changed by controlling the structure of the dispersed state of the precipitated phase. Also in Patent Document 1 described above, the mechanical strength is improved by giving a precipitated phase composed of an intermetallic compound of Ni and Cr and Si to the α solid solution as a matrix phase with a predetermined particle size and a predetermined aspect ratio. On the other hand, control of mechanical properties by coagulation-derived tissue control has also been proposed.
例えば、特許文献２では、（Ｚｒ，Ｈｆ）からなる群、（Ｃｒ，Ｎｉ，Ｍｎ，Ｔａ）からなる群、（Ｔｉ，Ａｌ）からなる群のそれぞれから１種又は２種以上の合金元素を組み合わせた析出硬化型銅合金において、急冷凝固によって組織制御したベリリウム銅の代替銅合金を開示している。母合金の急冷凝固と時効処理によって、平均二次デンドライトアーム間隔を２μｍ以下のＣｕ初晶と、準安定Ｃｕ５（Ｚｒ，Ｈｆ）化合物相及びＣｕ相で構成されたラメラ間隔を０．２μｍ以下とした共晶マトリックスとを形成することで機械加工性に優れるとともに優れた機械強度と高い電気伝導性とを得られるとしている。 For example, in Patent Document 2, one or more alloy elements are selected from each of a group consisting of (Zr, Hf), a group consisting of (Cr, Ni, Mn, Ta), and a group consisting of (Ti, Al). In the combined precipitation hardening type copper alloy, an alternative copper alloy for beryllium copper whose structure is controlled by rapid solidification is disclosed. By rapid solidification and aging treatment of the mother alloy, the lamellar spacing composed of a Cu primary crystal having an average secondary dendrite arm spacing of 2 μm or less, a metastable Cu 5 (Zr, Hf) compound phase, and a Cu phase is 0.2 μm or less. By forming the eutectic matrix, excellent machinability and excellent mechanical strength and high electrical conductivity can be obtained.
いわゆるコルソン系合金において、耐摩耗性の一層の向上が求められている。これには上記したように、時効処理による析出相の析出形態の制御、例えば、析出母相の組織制御を考慮できる。この点、特許文献２では、ＺｒやＨｆがＣｕに対して負の混合熱を有することを利用して融点を降下させ、初晶としての平均二次デンドライトアーム間隔を狭くする制御を行っている。つまり、かかる方法は、ＺｒやＨｆを合金成分に含むことが必須となる。 In so-called Corson alloys, further improvement in wear resistance is required. For this purpose, as described above, control of the precipitation form of the precipitated phase by aging treatment, for example, control of the structure of the precipitated mother phase can be considered. In this regard, in Patent Document 2, Zr and Hf have a negative heat of mixing with respect to Cu, and the melting point is lowered to control the average secondary dendrite arm interval as the primary crystal to be narrowed. . That is, in this method, it is essential that Zr or Hf is included in the alloy component.
本発明は、以上のような状況に鑑みてなされたものであって、その目的とするところは、Ｎｉ及びＳｉを合金成分に含むいわゆるコルソン系合金において、特殊な合金元素を含まず、組織制御を与えて耐摩耗性に優れる析出硬化型銅合金を与える製造方法及び析出硬化型銅合金を提供することにある。 The present invention has been made in view of the situation as described above, and the object thereof is a so-called Corson alloy containing Ni and Si as an alloy component, which does not contain a special alloy element, and has a structure control. It is providing the manufacturing method and precipitation hardening type copper alloy which give precipitation hardening type copper alloy which is excellent in abrasion resistance by giving it.
本発明による析出硬化型銅合金は、質量％で、Ｎｉを６．５〜８．８％、Ｓｉを１．５〜２．５％、Ｃｒを０．３〜１．３％、Ｎｉ／Ｓｉ比を３．３〜４．８で残部をＣｕ及び不可避的不純物とした成分組成を有する析出硬化型銅合金であって、Ｃｕ母相の＜１１０＞方向に伸長した析出物を分散させて２００Ｈｖ以上の硬さを有することを特徴とする。 The precipitation hardening type copper alloy according to the present invention is mass%, Ni is 6.5 to 8.8%, Si is 1.5 to 2.5%, Cr is 0.3 to 1.3%, Ni / Si It is a precipitation hardening type copper alloy having a component composition in which the ratio is 3.3 to 4.8 and the balance is Cu and inevitable impurities, and the precipitate elongated in the <110> direction of the Cu matrix is dispersed to give 200 Hv It has the above hardness.
かかる発明によれば、特殊な合金元素を含まないコルソン系合金において高い耐摩耗性を得られるのである。 According to this invention, high wear resistance can be obtained in a Corson alloy that does not contain a special alloy element.
また、本発明による析出効果型合金の製造方法によれば、質量％で、Ｎｉを６．５〜８．８％、Ｓｉを１．５〜２．５％、Ｃｒを０．３〜１．３％、Ｎｉ／Ｓｉ比を３．３〜４．８で残部をＣｕ及び不可避的不純物とした成分組成を有する析出硬化型銅合金の製造方法であって、平均二次デンドライトアーム間隔を２０μｍ以下となるように急冷凝固後、少なくとも９００℃以上に加熱することなく４００〜５００℃の温度範囲内の温度で保持する時効熱処理によって２００Ｈｖ以上の硬さを与えることを特徴とする。 Further, according to the method for producing a precipitation effect type alloy according to the present invention, by mass, Ni is 6.5 to 8.8%, Si is 1.5 to 2.5%, and Cr is 0.3 to 1. A method for producing a precipitation hardening type copper alloy having a composition of 3%, a Ni / Si ratio of 3.3 to 4.8, the remainder being Cu and inevitable impurities, and having an average secondary dendrite arm spacing of 20 μm or less Thus, after rapid solidification, a hardness of 200 Hv or more is given by aging heat treatment that is held at a temperature within a temperature range of 400 to 500 ° C. without heating to at least 900 ° C. or more.
かかる発明によれば、特殊な合金元素を含まず、組織制御を与えて耐摩耗性に優れる析出硬化型銅合金を得られるのである。 According to this invention, it is possible to obtain a precipitation hardening type copper alloy which does not contain a special alloy element and gives a structure control and is excellent in wear resistance.
以下に、本発明による析出硬化型銅合金の製造方法の１つの実施例について、図１及び図２を用いて説明する。 Below, one Example of the manufacturing method of the precipitation hardening type copper alloy by this invention is described using FIG.1 and FIG.2.
図１に示すように、本実施例における析出硬化型銅合金は、組織制御を与えることで耐摩耗性を高めた銅合金であって、いわゆるコルソン系合金の一種であり、質量％で、Ｎｉを６．５〜８．８％、Ｓｉを１．５〜２．５％、Ｃｒを０．３〜１．３％、Ｎｉ／Ｓｉ比を３．３〜４．８で残部をＣｕ及び不可避的不純物とした成分組成を有する。 As shown in FIG. 1, the precipitation hardening type copper alloy in this example is a copper alloy whose wear resistance is improved by giving a structure control, and is a kind of so-called Corson alloy, which is Ni Of 6.5 to 8.8%, Si of 1.5 to 2.5%, Cr of 0.3 to 1.3%, Ni / Si ratio of 3.3 to 4.8 and the balance of Cu and inevitable It has a component composition that is regarded as a typical impurity.
図２に示すように、上記した成分組成を与える銅合金の溶湯を準備する（Ｓ１）。 As shown in FIG. 2, a molten copper alloy that provides the above-described component composition is prepared (S1).
次いで、合金溶湯を鋳込んで急冷凝固させる（Ｓ２）。急冷凝固においては、平均二次デンドライトアーム間隔を２０μｍ以下となるように冷却速度を制御する。つまり、このような冷却速度の急冷凝固を可能とするように、鋳造の方法や鋳型の形状を選択する。例えば、急冷凝固を可能とする連続鋳造などを用いることができる。 Next, molten alloy is cast and rapidly solidified (S2). In the rapid solidification, the cooling rate is controlled so that the average secondary dendrite arm spacing is 20 μm or less. That is, the casting method and the shape of the mold are selected so that rapid solidification at such a cooling rate is possible. For example, continuous casting that enables rapid solidification can be used.
なお、得られた合金は、これ以降、少なくとも９００℃以上に加熱されない。通常であれば後述する時効熱処理の前に、例えば９２０℃程度で溶体化熱処理を行うが、このような高温の熱処理を省略するのである。 The obtained alloy is not heated to at least 900 ° C. or higher thereafter. Usually, a solution heat treatment is performed at about 920 ° C., for example, before the aging heat treatment described later, but such a high temperature heat treatment is omitted.
次いで、時効熱処理を行う（Ｓ３）。時効熱処理では、４００〜５００℃の温度範囲内の所定の温度で保持する。本実施例では４７０℃で３時間保持し、炉冷した。かかる時効熱処理によって得られた銅合金には、２００Ｈｖ以上、好ましくは２５０Ｈｖ以上、さらに好ましくは３００Ｈｖ以上の硬さを与えることができる。このような硬さによって、耐摩耗性に優れるのである。また、得られた銅合金においては、Ｃｕ母相の＜１１０＞方向に伸長した析出物が分散しており、これによって高い耐摩耗性を得ているものと考えられる。 Next, an aging heat treatment is performed (S3). In the aging heat treatment, it is held at a predetermined temperature within a temperature range of 400 to 500 ° C. In this example, the temperature was maintained at 470 ° C. for 3 hours and the furnace was cooled. The copper alloy obtained by such aging heat treatment can be given a hardness of 200 Hv or higher, preferably 250 Hv or higher, more preferably 300 Hv or higher. This hardness is excellent in wear resistance. Further, in the obtained copper alloy, precipitates elongated in the <110> direction of the Cu matrix phase are dispersed, and it is considered that high wear resistance is obtained thereby.
なお、導電率については、従来の鋳込み時に徐冷して溶体化熱処理及び時効熱処理する方法に比べて若干の低下傾向にあるが、特に、耐摩耗性を必要とする電気部材においても本実施例による析出硬化型合金は有効である。 The electrical conductivity tends to be slightly lower than the conventional methods of annealing and solution heat treatment and aging heat treatment at the time of casting, especially in the case of electrical members that require wear resistance. The precipitation hardening type alloy is effective.
以上述べてきたように、コルソン系合金において、例えばＺｒやＨｆのような特殊な合金元素を含まずとも、急冷凝固（Ｓ２）させて時効熱処理を行う熱履歴により、すなわち溶体化熱処理を省略しても、必要な硬さを得られる組織制御を与えて、耐摩耗性に優れる析出硬化型銅合金を得ることができる。 As described above, in the Corson alloy, even if it does not contain a special alloy element such as Zr or Hf, for example, it omits the solution heat treatment by the heat history in which it is rapidly solidified (S2) to perform the aging heat treatment. However, it is possible to obtain a precipitation hardening type copper alloy having excellent wear resistance by giving the structure control capable of obtaining the necessary hardness.
上記した製造方法により銅合金を作製するとともに、急冷凝固後の平均二次デンドライトアーム間隔を測定し、時効熱処理後の硬さ及び導電率を測定したのでその結果について図１乃至図５を用いて説明する。 While producing a copper alloy by the above-described manufacturing method, the average secondary dendrite arm interval after rapid solidification was measured, and the hardness and conductivity after aging heat treatment were measured, so the results are shown in FIGS. explain.
図１に示すように、ここでは、質量％で、Ｎｉを６．８％、Ｓｉを１．８３％、Ｃｒを０．５５％含有するとともに、さらに不可避的不純物としてＭｎを０．０４％、Ｍｇを０．００５％含有する銅合金の溶湯を準備した。 As shown in FIG. 1, here, in mass%, Ni is 6.8%, Si is 1.83%, Cr is 0.55%, and Mn is 0.04% as an inevitable impurity, A molten copper alloy containing 0.005% Mg was prepared.
図２に示すように、急冷凝固（Ｓ１）においては、上記したように平均二次デンドライトアーム間隔を２０μｍ以下とする冷却速度を得られるように、溶湯を急冷凝固させる。ここで平均二次デンドライトアームは、断面組織についてデンドライト晶の一次枝に垂直な二次枝の先端部をプロットし、その５点の単純算術平均を得たものである。 As shown in FIG. 2, in the rapid solidification (S1), as described above, the molten metal is rapidly solidified to obtain a cooling rate with an average secondary dendrite arm interval of 20 μm or less. Here, the average secondary dendrite arm is obtained by plotting the tip of the secondary branch perpendicular to the primary branch of the dendrite crystal with respect to the cross-sectional structure, and obtaining a simple arithmetic average of the five points.
すなわち、図３（ａ）に示すように、上部の開口した略円筒形の断熱材２の周囲をＣｕ−Ｃｒ合金製の金型１で保持した鋳型に溶湯３を鋳込み、断熱材の開口部にＣｕ−Ｃｒ合金製の冷却金型４を載せるとともにプレス５で押さえて溶湯３から熱を急速に奪って冷却させる（急冷）。なお、鋳型の寸法は、内径φ３８ｍｍ、高さ１１ｍｍ又は１７ｍｍである。 That is, as shown in FIG. 3A, the molten metal 3 is cast into a mold in which the periphery of a substantially cylindrical heat insulating material 2 having an upper opening is held by a mold 1 made of Cu—Cr alloy, and an opening portion of the heat insulating material. A cooling mold 4 made of a Cu—Cr alloy is placed on the metal and pressed by a press 5 to quickly take heat from the molten metal 3 and cool it (rapid cooling). The mold has an inner diameter of 38 mm and a height of 11 mm or 17 mm.
また、図３（ｂ）に示すように、より速い冷却方法として、平板状のＣｕ−Ｃｒ合金製の金型１’の上に溶湯３を滴下し、これをプレス５で押さえて溶湯３から熱をさらに急速に奪って冷却させる（最急冷）。 Further, as shown in FIG. 3B, as a faster cooling method, the molten metal 3 is dropped on a flat plate-shaped Cu—Cr alloy mold 1 ′, and this is pressed by a press 5 from the molten metal 3. Heat is taken away more quickly and cooled (rapid cooling).
これに対して、図３（ｃ）に示すように、溶湯を徐冷して凝固させる比較例としての冷却方法では、上部の開口した略円筒形の断熱材２の周囲をＣｕ−Ｃｒ合金製の金型１で保持した鋳型に溶湯３を鋳込み、そのまま空冷した（徐冷）。なお、鋳型の寸法は上記した「急冷」と同様である。 On the other hand, as shown in FIG. 3C, in the cooling method as a comparative example in which the molten metal is gradually cooled and solidified, the periphery of the substantially cylindrical heat insulating material 2 having an upper opening is made of a Cu—Cr alloy. The molten metal 3 was poured into a mold held by the mold 1 and air-cooled as it was (slow cooling). The dimensions of the mold are the same as the above-mentioned “rapid cooling”.
図４に示すように、このようにして得た鋳放しの試料について、それぞれ断面組織観察を行い、平均二次デンドライトアーム間隔（ＤＡＳ ＩＩ、以降ＤＡＳと称する）を測定し、記録した。なお、実施例１が「急冷」において鋳型の高さを１１ｍｍとしたもの、実施例２が「急冷」において鋳型の高さを１７ｍｍとしたもの、実施例３が「最急冷」によるものである。また、参考例として、溶湯３を水槽中に滴下して凝固させた試料についてもＤＡＳを測定した。さらに、比較例１が「徐冷」において鋳型の高さを１１ｍｍとしたもの、比較例２が「徐冷」において鋳型の高さを１７ｍｍとしたものである。ここで、最表層のチル層よりも中心寄りの測定結果を「上部」として、中心部近傍の測定結果を「中心部」としてそれぞれ示した。 As shown in FIG. 4, the as-cast samples thus obtained were each subjected to cross-sectional structure observation, and the average secondary dendrite arm interval (DAS II, hereinafter referred to as DAS) was measured and recorded. In Example 1, the height of the mold was 11 mm in “rapid cooling”, in Example 2, the height of the mold was 17 mm in “quick cooling”, and in Example 3, the “fastest cooling” was performed. . As a reference example, DAS was also measured for a sample obtained by dripping the molten metal 3 into a water bath and solidifying it. Further, Comparative Example 1 is “Slow Cooling” with a mold height of 11 mm, and Comparative Example 2 is “Slow Cooling” with a mold height of 17 mm. Here, the measurement result closer to the center than the outermost chill layer is indicated as “upper part”, and the measurement result near the center part is indicated as “central part”.
図４に示すように、実施例１〜３及び水中に溶湯を滴下した参考例は、いずれも同等程度のＤＡＳとなり、冷却速度も同等程度と考えられる。詳細には、ＤＡＳは「上部」で４．２〜９．５μｍであり、「中心部」で９．３〜１３．０μｍであり、いずれも２０μｍ以下であった。実施例１よりも実施例２においてＤＡＳが大きいが、試料の厚さの差によって冷却速度が遅くなったためと考えられる。これに対し、比較例１及び２では、ＤＡＳが２０μｍより大きく、「上部」で５４．５〜６８．１μｍ、「中心部」で４３．３〜６１．６μｍであった。 As shown in FIG. 4, Examples 1 to 3 and the reference examples in which the molten metal is dropped into water all have the same level of DAS, and the cooling rate is considered to be about the same. Specifically, DAS was 4.2 to 9.5 μm at the “upper part”, 9.3 to 13.0 μm at the “center part”, and both were 20 μm or less. The DAS is larger in Example 2 than in Example 1, but it is considered that the cooling rate was slowed due to the difference in the thickness of the sample. On the other hand, in Comparative Examples 1 and 2, DAS was larger than 20 μm, 54.5 to 68.1 μm at the “upper part”, and 43.3 to 61.6 μm at the “central part”.
なお、ＤＡＳは冷却速度に依存する。そこで、同一の成分組成の銅合金において冷却速度：ｘ（℃／ｓｅｃ）とＤＡＳ：ｙ（μｍ）を複数回測定して両者の関係を導出したところ、次の式１が得られた。
ｌｎ（ｙ）＝−０．３２×ｌｎ（ｘ）＋３．９ （式１）
つまり、測定したＤＡＳから式１により各試料の冷却速度も推定できる。
Note that DAS depends on the cooling rate. Thus, when a cooling rate: x (° C./sec) and DAS: y (μm) were measured a plurality of times in a copper alloy having the same component composition, the relationship between the two was derived, and the following formula 1 was obtained.
ln (y) = − 0.32 × ln (x) +3.9 (Formula 1)
That is, the cooling rate of each sample can also be estimated from the measured DAS according to Equation 1.
上記した実施例１〜３、比較例１及び２について、さらに、時効熱処理（Ｓ３）して、その断面においてビッカース硬さを測定した。時効熱処理においては、４７０℃で３時間保持し、炉冷した。また、硬さは、最表層のチル層を避けて、上端近傍、中心部近傍、下端近傍のそれぞれ３か所において５回ずつ測定した平均値を得て、３か所の平均値をさらに平均した値を示した。 The above-mentioned Examples 1 to 3 and Comparative Examples 1 and 2 were further subjected to aging heat treatment (S3), and the Vickers hardness was measured in the cross section. In the aging heat treatment, it was kept at 470 ° C. for 3 hours and cooled in the furnace. In addition, the hardness is obtained by obtaining an average value measured five times at each of three locations near the upper end, near the center, and near the lower end, avoiding the outermost chill layer, and further averaging the average values at the three locations. Showed the value.
図４に示すように、実施例１〜３において硬さは３０７〜３１６Ｈｖであり、いずれも３００Ｈｖを超えていた。これに対し、比較例１及び２ではいずれも硬さは１７３Ｈｖであり、２００Ｈｖを下回った。つまり、鋳込み時にＤＡＳを２０μｍ以下とするように急冷することで、徐冷する場合と比べて時効熱処理後の硬さが大きく向上するのである。 As shown in FIG. 4, in Examples 1-3, the hardness was 307-316Hv, and all exceeded 300Hv. On the other hand, in Comparative Examples 1 and 2, the hardness was 173 Hv, which was lower than 200 Hv. That is, by rapidly cooling the DAS to 20 μm or less during casting, the hardness after aging heat treatment is greatly improved as compared with the case of slow cooling.
なお、参考として、時効熱処理前に９２０℃で３時間保持して水冷する溶体化熱処理を行った場合の硬さについても図４に示した（溶体化あり）。つまり、鋳込み時に徐冷した比較例１及び２の「溶体化あり」については従来通りの製造方法を再現している。実施例１〜３の「溶体化あり」の場合、ビッカース硬さは２９５〜３０２Ｈｖ、比較例１及び２の「溶体化あり」の場合、ビッカース硬さは２８６〜２９１とほぼ同等となり、溶体化熱処理を行わなかった実施例１〜３に比べて若干硬さが低かった。つまり、溶体化熱処理をしてしまうと時効熱処理後の硬さは高いが、徐冷したものと同等となってしまう。なお、実施例３の「溶体化あり」においては、上記した時効熱処理の後にさらに４７０℃で６時間保持する２回目の時効熱処理をしたものである。 As a reference, FIG. 4 also shows the hardness when solution heat treatment was performed by holding at 920 ° C. for 3 hours and water cooling before aging heat treatment (with solution heat treatment). That is, the conventional manufacturing method is reproduced for “with solution” in Comparative Examples 1 and 2 that were gradually cooled during casting. In the case of “With solution” in Examples 1 to 3, the Vickers hardness is 295 to 302 Hv, and in the case of “With solution” in Comparative Examples 1 and 2, the Vickers hardness is almost equivalent to 286 to 291. The hardness was slightly lower than in Examples 1 to 3 where heat treatment was not performed. That is, if solution heat treatment is performed, the hardness after the aging heat treatment is high, but it is equivalent to that after slow cooling. In the case of “with solution” in Example 3, after the above aging heat treatment, the second aging heat treatment was further held at 470 ° C. for 6 hours.
また、時効熱処理後の導電率について測定した結果、従来と同じ製造方法を再現した比較例１及び２の「溶体化あり」について両者とも２９．２％ＩＡＣＳであったが、これに対して実施例１及び２については２７．８〜２８．３％ＩＡＣＳとなり、ほぼ同等であった。また、実施例３については１７．６％ＩＡＣＳとやや低い。つまり、溶湯を急冷凝固させた後に時効熱処理により製造する方法においては、溶湯を徐冷後に溶体化熱処理及び時効熱処理する従来の方法に比べて、導電率を若干低下させる傾向にある。 In addition, as a result of measuring the electrical conductivity after the aging heat treatment, both of the “with solution” in Comparative Examples 1 and 2 reproducing the same production method as before were 29.2% IACS. About Example 1 and 2, it became 27.8 to 28.3% IACS, and was substantially equivalent. Moreover, about Example 3, it is a little low with 17.6% IACS. That is, in the method of manufacturing by aging heat treatment after rapidly solidifying the molten metal, the electrical conductivity tends to be slightly lowered as compared with the conventional method in which the molten metal is slowly cooled and then subjected to solution heat treatment and aging heat treatment.
図５には、実施例１〜３と同じ成分組成の合金溶湯を急冷し、（ａ）４７５℃で６時間保持する時効熱処理した試料、及び（ｂ）４７５℃で４８時間保持する時効熱処理した試料、のそれぞれの底面から０．７ｍｍ付近の断面（それぞれビッカース硬さ３２２Ｈｖ及び３１０Ｈｖ）において、透過型電子顕微鏡（ＴＥＭ）による観察を行った顕微鏡写真を示した。なお、＜００１＞方向に電子線を入射させるよう絞りを入れている。これからわかるように、Ｃｕ母相の＜１１０＞方向に伸長した析出物が分散して観察された。なお、図５（ａ）の６時間保持した時効熱処理においては析出物の長径が数ｎｍ程度であったが、図５（ｂ）の４８時間保持した時効熱処理においては析出物の長径が数十ｎｍ程度に粗大化していた。 In FIG. 5, the molten alloy having the same composition as in Examples 1 to 3 was rapidly cooled, (a) a sample heat-treated at 475 ° C. for 6 hours, and (b) a heat-treated heat treated at 475 ° C. for 48 hours. The micrograph which observed by the transmission electron microscope (TEM) in the cross section (Vickers hardness 322Hv and 310Hv, respectively) of 0.7 mm vicinity from each bottom face of a sample was shown. A diaphragm is inserted so that an electron beam is incident in the <001> direction. As can be seen, precipitates elongated in the <110> direction of the Cu matrix were dispersed and observed. In the aging heat treatment held for 6 hours in FIG. 5A, the major axis of the precipitate was about several nanometers. However, in the aging heat treatment held for 48 hours in FIG. 5B, the major axis of the precipitate was several tens of nanometers. It was coarsened to about nm.
つまり、溶湯を急冷凝固することで、Ｓｉが十分固溶した状態を維持できて、溶体化熱処理を経ずとも時効熱処理において伸長方向を揃えてＮｉ２Ｓｉを分散析出させて硬さを得ること、すなわち、耐摩耗性を高めることができたものと考えられる。 In other words, by rapidly solidifying the molten metal, it is possible to maintain a sufficiently solid Si state, and to obtain hardness by dispersing and precipitating Ni 2 Si in the aging heat treatment without aligning the solution heat treatment. That is, it is considered that the wear resistance could be improved.
以上、本発明による実施例及びこれに基づく変形例を説明したが、本発明は必ずしもこれに限定されるものではなく、当業者であれば、本発明の主旨又は添付した特許請求の範囲を逸脱することなく、様々な代替実施例及び改変例を見出すことができるであろう。例えば、合金の成分組成については、本発明の本質的な特徴を失わない限りにおいて追加の合金成分を与え、追加の効果を得られるようにし得る。 As mentioned above, although the Example by this invention and the modification based on this were demonstrated, this invention is not necessarily limited to this, A person skilled in the art will deviate from the main point of this invention, or the attached claim. Various alternative embodiments and modifications could be found without doing so. For example, the alloy component composition may be provided with additional alloy components so long as the essential features of the present invention are not lost so that additional effects can be obtained.
１ 金型
２ 断熱材
３ 溶湯
1 Mold 2 Heat insulation material 3 Molten metal
Claims (2)
平均二次デンドライトアーム間隔を２０μｍ以下となるように急冷凝固後、少なくとも９００℃以上に加熱することなく４００〜５００℃の温度範囲内の温度で保持する時効熱処理によって２００Ｈｖ以上の硬さを与えることを特徴とする析出硬化型銅合金の製造方法。
In mass%, Ni is 6.5 to 8.8%, Si is 1.5 to 2.5%, Cr is 0.3 to 1.3%, and Ni / Si ratio is 3.3 to 4.8. A method for producing a precipitation hardening copper alloy having a component composition in which the balance is Cu and inevitable impurities,
After quenching and solidifying so that the average secondary dendrite arm spacing is 20 μm or less, a hardness of 200 Hv or more is given by aging heat treatment that is maintained at a temperature within a temperature range of 400 to 500 ° C. without heating to at least 900 ° C. or more. A method for producing a precipitation-hardening type copper alloy.
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| JPS55158246A (en) * | 1979-04-30 | 1980-12-09 | Delta Enfield Metals | Precipitation hardenable copper alloy |
| JPH04247839A (en) * | 1989-12-26 | 1992-09-03 | Ampco Metal Mfg Inc | Copper based alloy and method of its manufac- ture |
| JP2008223069A (en) * | 2007-03-12 | 2008-09-25 | Miyoshi Gokin Kogyo Kk | High-strength, high-conductivity copper alloy and its manufacturing method |
| JP2009235557A (en) * | 2008-03-07 | 2009-10-15 | Miyoshi Gokin Kogyo Kk | High-strength and high-conductivity copper alloy, and method for manufacturing the same |
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| JPS55158246A (en) * | 1979-04-30 | 1980-12-09 | Delta Enfield Metals | Precipitation hardenable copper alloy |
| JPH04247839A (en) * | 1989-12-26 | 1992-09-03 | Ampco Metal Mfg Inc | Copper based alloy and method of its manufac- ture |
| JP2008223069A (en) * | 2007-03-12 | 2008-09-25 | Miyoshi Gokin Kogyo Kk | High-strength, high-conductivity copper alloy and its manufacturing method |
| JP2009235557A (en) * | 2008-03-07 | 2009-10-15 | Miyoshi Gokin Kogyo Kk | High-strength and high-conductivity copper alloy, and method for manufacturing the same |
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