JP6736869B2 - Copper alloy material - Google Patents
Copper alloy material Download PDFInfo
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- JP6736869B2 JP6736869B2 JP2015219851A JP2015219851A JP6736869B2 JP 6736869 B2 JP6736869 B2 JP 6736869B2 JP 2015219851 A JP2015219851 A JP 2015219851A JP 2015219851 A JP2015219851 A JP 2015219851A JP 6736869 B2 JP6736869 B2 JP 6736869B2
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- 239000000956 alloy Substances 0.000 title claims description 41
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 71
- 239000013078 crystal Substances 0.000 claims description 39
- 229910052698 phosphorus Inorganic materials 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 description 28
- 230000032683 aging Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 7
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000004453 electron probe microanalysis Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 238000005098 hot rolling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/06—Permanent moulds for shaped castings
- B22C9/061—Materials which make up the mould
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Description
本発明は、例えば鋳造用モールド材やコンタクトチップ等の溶接用部材等の高温環境下で使用される部材に適した銅合金素材に関するものである。 The present invention relates to a copper alloy material suitable for a member used in a high temperature environment such as a casting mold material and a welding member such as a contact tip.
従来、C18150等のCu−Cr−Zr系合金は、優れた耐熱性及び導電性を備えていることから、特許文献1−3に示すように、使用環境が高温となる鋳造用モールド材や溶接用部材の素材として利用されている。
このようなCu−Cr−Zr系合金は、通常、Cu−Cr−Zr系合金鋳塊に塑性加工を施し、例えば保持温度が950〜1050℃、保持時間が0.5〜1.5時間の溶体化処理と、例えば保持温度が400〜500℃、保持時間が2〜4時間の時効処理と、を行い、最後に機械加工により所定の形状に仕上げる製造工程によって製造される。また、Cu−Cr−Zr系合金における溶体化処理工程は、塑性加工工程と併せて行うことも可能であり、熱間圧延加工と同時に溶体化処理を行う、いわゆるインライン溶体化処理に替えて製造されることもある。
そして、Cu−Cr−Zr系合金においては、溶体化処理でCr及びZrをCuの母相中に固溶し、時効処理によってCrやZrの析出物を微細分散させることで、強度及び導電率の向上を図っている。
Conventionally, Cu-Cr-Zr-based alloys such as C18150 have excellent heat resistance and electrical conductivity, and therefore, as shown in Patent Documents 1-3, casting mold materials and welding in which the use environment becomes high temperature. It is used as a material for manufacturing materials.
Such a Cu-Cr-Zr-based alloy is usually obtained by subjecting a Cu-Cr-Zr-based alloy ingot to plastic working, for example, a holding temperature of 950 to 1050°C and a holding time of 0.5 to 1.5 hours. It is manufactured by a manufacturing process in which a solution treatment and, for example, an aging treatment with a holding temperature of 400 to 500° C. and a holding time of 2 to 4 hours are performed, and finally a predetermined shape is finished by machining. Further, the solution treatment step in the Cu-Cr-Zr alloy can be performed in combination with the plastic working step, and the solution treatment is performed instead of the so-called in-line solution treatment in which the solution treatment is performed simultaneously with the hot rolling. It may be done.
Then, in the Cu-Cr-Zr-based alloy, Cr and Zr are solid-solved in the matrix of Cu by the solution treatment, and the precipitates of Cr and Zr are finely dispersed by the aging treatment. We are trying to improve
ところで、上述のCu−Cr−Zr系合金においては、優れた耐熱性を有しているが、ピーク温度が500℃以上の使用環境にさらされると、析出物の再固溶が始まり、それにともなって強度及び導電率が低下するとともに結晶粒の粗大化が発生することがある。
結晶粒の粗大化が起きた場合には、亀裂の伝播速度が増大し、製品寿命が短くなるおそれがあった。また、結晶粒の粗大化が局所的に発生することで、強度及び伸び等の機械的特性が著しく低下するといった問題があった。
By the way, although the above-mentioned Cu-Cr-Zr-based alloy has excellent heat resistance, when it is exposed to a use environment having a peak temperature of 500°C or higher, re-dissolution of precipitates starts, and accordingly. As a result, the strength and the conductivity may decrease and the crystal grains may become coarse.
If the crystal grains become coarse, the propagation speed of cracks may increase and the product life may be shortened. Further, there is a problem that mechanical properties such as strength and elongation are remarkably reduced due to local coarsening of crystal grains.
この発明は、前述した事情に鑑みてなされたものであって、500℃以上の高温環境下で使用された場合であっても、結晶粒の粗大化を抑制でき、特性が安定し、かつ、使用寿命に優れた銅合金素材を提供することを目的とする。 The present invention has been made in view of the above-mentioned circumstances, and even when used in a high temperature environment of 500°C or higher, coarsening of crystal grains can be suppressed, characteristics are stable, and The object is to provide a copper alloy material having an excellent service life.
上記の課題を解決するために、本発明の銅合金素材は、Crを0.1mass%以上1.5mass%以下、Zrを0.05mass%以上0.25mass%以下、Pを0.005mass%以上0.10mass%以下、Coを0.02mass%以上0.15mass%以下の範囲内で含み、残部がCu及び不可避不純物からなる組成を有し、CoとPの質量比〔Co〕/〔P〕が、0.5≦〔Co〕/〔P〕≦5.0の範囲内とされており、CrとZrとPを含むCr−Zr−P化合物が存在し、組織観察において前記Cr−Zr−P化合物の面積率が0.5%以上5.0%以下の範囲内とされており、
前記Cr−Zr−P化合物は、針状もしくは粒状の形態をとり、最長となる辺の長さが100μm以下とされていることを特徴としている。
In order to solve the above problems, the copper alloy material of the present invention has a Cr content of 0.1 mass% or more and 1.5 mass% or less, a Zr content of 0.05 mass% or more and 0.25 mass% or less, and a P content of 0.005 mass% or more. 0.10 mass% or less, Co in the range of 0.02 mass% or more and 0.15 mass% or less, and the balance of Cu and inevitable impurities, and the mass ratio [Co]/[P] of Co and P. Is within the range of 0.5≦[Co]/[P]≦5.0, and there is a Cr—Zr—P compound containing Cr, Zr, and P. The area ratio of the P compound is in the range of 0.5% or more and 5.0% or less,
The Cr-Zr-P compound is in the form of needles or particles, and is characterized in that the longest side length is 100 μm or less.
この構成の銅合金素材においては、Crを0.1mass%以上1.5mass%以下、Zrを0.05mass%以上0.25mass%以下、Pを0.005mass%以上0.10mass%以下、Coを0.02mass%以上0.15mass%以下の範囲内で含み、残部がCu及び不可避不純物からなる組成とされているので、時効処理によって微細な析出物を析出させることにより、強度(硬さ)及び導電率を向上させることができる。
そして、本発明の銅合金素材においては、CrとZrとPを含むCr−Zr−P化合物が存在し、組織観察において前記Cr−Zr−P化合物の面積率が0.5%以上5.0%以下の範囲内とされている。このCrとZrとPを含むCr−Zr−P化合物は、1000℃程度の高温条件においても消失しないことから、高温環境下で使用した場合であっても、Cr−Zr−P化合物による結晶粒界のピン止め効果によって、結晶粒の粗大化を抑制することができる。
また、Cr−Zr−P化合物が、針状もしくは粒状の形態をとり、最長となる辺の長さが100μm以下とされているので、上述のピン止め効果を確実に奏功せしめることが可能となる。
さらに、Cr及びZrに加えてさらにCoを0.02mass%以上0.15mass%以下の範囲内で含んでいるので、CoP化合物及びCo 2 P化合物が存在することになり、上述のCr−Zr−P化合物とともに、結晶粒界のピン止め効果を発揮することができ、高温環境下で使用した場合であっても結晶粒の粗大化を確実に抑制することができる。
また、CoとPの原子比〔Co〕/〔P〕が、0.5≦〔Co〕/〔P〕≦5.0の範囲内とされているので、余剰のCoやPが母相中に固溶することを抑制でき、導電率の低下を抑制することができる。
In the copper alloy material of this configuration, Cr is 0.1 mass% or more and 1.5 mass% or less, Zr is 0.05 mass% or more and 0.25 mass% or less, P is 0.005 mass% or more and 0.10 mass% or less, and Co is It is contained in the range of 0.02 mass% or more and 0.15 mass% or less, and the balance is composed of Cu and unavoidable impurities. Therefore, by precipitating fine precipitates by aging treatment, strength (hardness) and The conductivity can be improved.
In the copper alloy material of the present invention, a Cr-Zr-P compound containing Cr, Zr, and P is present, and the area ratio of the Cr-Zr-P compound is 0.5% or more and 5.0 in the structure observation. It is within the range of% or less. Since the Cr-Zr-P compound containing Cr, Zr, and P does not disappear even under a high temperature condition of about 1000°C, even when used in a high temperature environment, the crystal grains of the Cr-Zr-P compound The grain pinning effect can suppress the coarsening of crystal grains.
In addition, since the Cr-Zr-P compound has a needle-like or granular form and the length of the longest side is 100 μm or less, the pinning effect described above can be reliably achieved. ..
Further, in addition to Cr and Zr, it further contains Co in the range of 0.02 mass% or more and 0.15 mass% or less, so that the CoP compound and the Co 2 P compound are present, and the above-mentioned Cr-Zr- Along with the P compound, the pinning effect of the crystal grain boundaries can be exhibited, and the coarsening of the crystal grains can be surely suppressed even when used in a high temperature environment.
Further, since the atomic ratio [Co]/[P] of Co and P is within the range of 0.5≦[Co]/[P]≦5.0, surplus Co and P are present in the parent phase. The solid solution can be suppressed, and the decrease in conductivity can be suppressed.
ここで、本発明の銅合金素材においては、1000℃で30分保持の熱処理を実施した後の平均結晶粒径が200μm以下とされていることが好ましい。
この場合、1000℃で30分保持の熱処理を実施した後でも、結晶粒が粗大化しておらず、500℃以上の高温環境下で使用された場合であっても、機械的特性や導電率が安定している。
Here, in the copper alloy material of the present invention, it is preferable that the average crystal grain size after the heat treatment of holding at 1000° C. for 30 minutes is 200 μm or less.
In this case, even after the heat treatment of holding at 1000° C. for 30 minutes, the crystal grains were not coarsened, and even when used in a high temperature environment of 500° C. or higher, the mechanical properties and conductivity were stable.
さらに、Coを含有する本発明の銅合金素材においては、不可避不純物であるTi、Hfの含有量の合計が0.10mass%以下とされていることが好ましい。
この場合、Pと化合物を形成する元素であるTi及びHfの合計含有量が0.10mass%以下に制限されているので、CoP化合物及びCo2P化合物が確実に形成され、結晶粒界のピン止め効果を効果的に発揮させることができ、結晶粒の粗大化を抑制することが可能となる。
Furthermore, in the copper alloy material of the present invention containing Co, it is preferable that the total content of Ti and Hf which are inevitable impurities is 0.10 mass% or less.
In this case, since the total content of Ti and Hf, which are elements forming a compound with P, is limited to 0.10 mass% or less, the CoP compound and the Co 2 P compound are reliably formed, and the crystal grain boundary pin is formed. The stopping effect can be effectively exhibited, and the coarsening of crystal grains can be suppressed.
本発明によれば、500℃以上の高温環境下で使用された場合であっても、結晶粒の粗大化を抑制でき、特性が安定し、かつ、使用寿命に優れた銅合金素材を提供することができる。 According to the present invention, it is possible to provide a copper alloy material that can suppress the coarsening of crystal grains even when used in a high temperature environment of 500° C. or higher, has stable characteristics, and has an excellent service life. be able to.
以下に、本発明の一実施形態である銅合金素材について説明する。
本実施形態である銅合金素材は、例えば鋳造用モールドや溶接用部材等の高温環境下で使用される部材に用いられるものである。
Below, the copper alloy material which is one embodiment of the present invention is explained.
The copper alloy material according to the present embodiment is used for a member used in a high temperature environment such as a casting mold or a welding member.
本実施形態である銅合金素材は、Crを0.1mass%以上1.5mass%以下、Zrを0.05mass%以上0.25mass%以下、Pを0.005mass%以上0.10mass%以下、含み、残部がCu及び不可避不純物からなる組成を有する。
なお、本実施形態である銅合金素材においては、必要に応じて、さらにCoを0.02mass%以上0.15mass%以下の範囲内で含み、CoとPの質量比〔Co〕/〔P〕が、0.5≦〔Co〕/〔P〕≦5.0の範囲内とされていてもよい。また、Coを含有する場合には、不可避不純物であるTi、Hfの含有量の合計が0.10mass%以下であることが好ましい。
The copper alloy material of the present embodiment includes Cr in an amount of 0.1 mass% to 1.5 mass%, Zr in an amount of 0.05 mass% to 0.25 mass%, and P in an amount of 0.005 mass% to 0.10 mass%. The balance has a composition of Cu and inevitable impurities.
In the copper alloy material of the present embodiment, if necessary, further contains Co in the range of 0.02 mass% or more and 0.15 mass% or less, and the mass ratio of Co and P [Co]/[P]. May be within a range of 0.5≦[Co]/[P]≦5.0. When Co is contained, the total content of Ti and Hf which are inevitable impurities is preferably 0.10 mass% or less.
そして、本実施形態である銅合金素材においては、CrとZrとPを含むCr−Zr−P化合物が存在し、組織観察においてCr−Zr−P化合物の面積率が0.5%以上5.0%以下の範囲内とされている。また、上述のCr−Zr−P化合物は、針状もしくは粒状の形態をとり、最長となる辺の長さが100μm以下とされている。
さらに、本実施形態である銅合金素材においては、1000℃で30分保持の熱処理を実施した後の平均結晶粒径が200μm以下とされている。
In the copper alloy material of the present embodiment, a Cr-Zr-P compound containing Cr, Zr, and P exists, and the area ratio of the Cr-Zr-P compound is 0.5% or more in the structure observation. It is set within the range of 0% or less. Further, the Cr-Zr-P compound described above has a needle-like or granular form, and the longest side length is set to 100 μm or less.
Further, in the copper alloy material of the present embodiment, the average crystal grain size after the heat treatment of holding at 1000° C. for 30 minutes is 200 μm or less.
以下に、本実施形態である銅合金素材において、成分組成、結晶組織等を上述のように規定した理由について説明する。 Hereinafter, the reasons for defining the component composition, the crystal structure, etc. in the copper alloy material of the present embodiment as described above will be described.
(Cr:0.1mass%以上1.5mass%以下)
Crは、時効処理によって母相の結晶粒内にCr系の析出物を微細に析出させることにより、強度(硬さ)及び導電率を向上させる作用効果を有する元素である。
ここで、Crの含有量が0.1mass%未満の場合には、時効処理において析出量が不十分となり、強度(硬さ)向上の効果を十分に得られないおそれがある。また、Crの含有量が1.5mass%を超える場合には、粗大なCr晶出物が形成され、加工性が低下するおそれがある。
以上のことから、本実施形態では、Crの含有量を0.1mass%以上1.5mass%以下の範囲内に設定している。なお、上述の作用効果を確実に奏功せしめるためには、Crの含有量の下限を0.3mass%以上とすることが好ましく、Crの含有量の上限を1.0mass%以下とすることが好ましい。
(Cr: 0.1 mass% or more and 1.5 mass% or less)
Cr is an element having the effect of improving strength (hardness) and conductivity by finely depositing a Cr-based precipitate in the crystal grains of the mother phase by aging treatment.
Here, when the content of Cr is less than 0.1 mass %, the amount of precipitation becomes insufficient in the aging treatment, and the effect of improving the strength (hardness) may not be sufficiently obtained. Further, if the Cr content exceeds 1.5 mass %, coarse Cr crystallized substances are formed, and the workability may deteriorate.
From the above, in the present embodiment, the Cr content is set within the range of 0.1 mass% or more and 1.5 mass% or less. In order to surely bring out the above-mentioned effects, the lower limit of the Cr content is preferably 0.3 mass% or more, and the upper limit of the Cr content is preferably 1.0 mass% or less. ..
(Zr:0.05mass%以上0.25mass%以下)
Zrは、時効処理によって母相の結晶粒界にZr系の析出物を微細に析出することにより、強度(硬さ)及び導電率を向上させる作用効果を有する元素である。
ここで、Zrの含有量が0.05mass%未満の場合には、時効処理において析出量が不十分となり、強度(硬さ)向上の効果を十分に得られないおそれがある。また、Zrの含有量が0.25mass%を超える場合には、導電率及び熱伝導率が低下してしまうおそれがある。また、Zrを0.25mass%を超えて含有しても、さらなる強度向上の効果が得られないおそれがある。
以上のことから、本実施形態では、Zrの含有量を0.05mass%以上0.25mass%以下の範囲内に設定している。なお、上述の作用効果を確実に奏功せしめるためには、Zrの含有量の下限を0.07mass%以上とすることが好ましく、Zrの含有量の上限を0.15mass%以下とすることが好ましい。
(Zr: 0.05 mass% or more and 0.25 mass% or less)
Zr is an element having the effect of improving the strength (hardness) and the conductivity by finely depositing Zr-based precipitates on the crystal grain boundaries of the mother phase by the aging treatment.
Here, when the content of Zr is less than 0.05 mass%, the amount of precipitation becomes insufficient in the aging treatment, and the effect of improving the strength (hardness) may not be sufficiently obtained. Moreover, when the content of Zr exceeds 0.25 mass %, the electrical conductivity and the thermal conductivity may decrease. Further, even if Zr is contained in an amount of more than 0.25 mass %, the effect of further improving the strength may not be obtained.
From the above, in the present embodiment, the Zr content is set within the range of 0.05 mass% or more and 0.25 mass% or less. In order to surely bring out the above-described effects, the lower limit of the Zr content is preferably 0.07 mass% or more, and the upper limit of the Zr content is preferably 0.15 mass% or less. ..
(P:0.005mass%以上0.10mass%以下)
Cu−Cr−Zr合金にPを添加することにより、CrとZrとPを含むCr−Zr−P化合物が生成する。このCr−Zr−P化合物は、1000℃といった高温条件でも消失しないことから、高温環境下で使用した場合でも結晶粒界のピン止め効果を発揮し、結晶の粗大化を抑制することが可能となる。
ここで、Pの含有量が0.005mass%未満の場合には、上述のCr−Zr−P化合物を十分に形成することができなくなるおそれがある。一方、Pの含有量が0.10mass%を超える場合には、導電率が低下するとともに、Cr−Zr−P化合物が粗大化し、ピン止め効果が十分に発揮されなくなるおそれがある。
以上のことから、本実施形態では、Pの含有量を0.005mass%以上0.10mass%以下の範囲内に設定している。なお、上述の作用効果を確実に奏功せしめるためには、Pの含有量の下限を0.01mass%以上とすることが好ましく、Pの含有量の上限を0.05mass%以下とすることが好ましい。
(P: 0.005 mass% or more and 0.10 mass% or less)
By adding P to the Cu-Cr-Zr alloy, a Cr-Zr-P compound containing Cr, Zr and P is produced. Since this Cr-Zr-P compound does not disappear even under a high temperature condition of 1000°C, even when used in a high temperature environment, the pinning effect of the crystal grain boundaries is exerted, and the crystal coarsening can be suppressed. Become.
Here, if the content of P is less than 0.005 mass%, the above-mentioned Cr-Zr-P compound may not be sufficiently formed. On the other hand, when the content of P exceeds 0.10 mass %, the conductivity decreases and the Cr—Zr—P compound becomes coarse, and the pinning effect may not be sufficiently exhibited.
From the above, in the present embodiment, the P content is set within the range of 0.005 mass% or more and 0.10 mass% or less. In order to surely bring out the above-mentioned effects, the lower limit of the P content is preferably 0.01 mass% or more, and the upper limit of the P content is preferably 0.05 mass% or less. ..
(Co:0.02mass%以上0.15mass%以下)
Coを添加することにより、CoP化合物及びCo2P化合物が形成され、これらCoP化合物及びCo2P化合物と上述のCr−Zr−P化合物とによって、結晶粒界のピン止め効果が発揮され、高温環境下で使用した場合であっても結晶粒の粗大化を確実に抑制することができる。
ここで、Coの含有量が0.02mass%未満の場合には、CoP化合物及びCo2P化合物を十分に形成することができず、Coを添加したにもかかわらず、さらなるピン止め効果の向上を図ることができないおそれがある。一方、Coの含有量が0.15mass%を超える場合には、CoP化合物及びCo2P化合物が粗大化し、Coを添加したにもかかわらず、さらなるピン止め効果の向上を図ることができないおそれがある。
以上のことから、本実施形態では、Coを添加する場合には、Coの含有量を0.02mass%以上0.15mass%以下の範囲内に設定している。なお、上述の作用効果を確実に奏功せしめるためには、Coの含有量の下限を0.03mass%以上とすることが好ましく、Coの含有量の上限を0.1mass%以下とすることが好ましい。また、Coを意図的に添加しない場合には、Coを不純物として0.02mass%未満含有していてもよい。
(Co: 0.02 mass% or more and 0.15 mass% or less)
By adding Co, is formed CoP compounds and Co 2 P compound, by the these CoP compounds and Co 2 P compounds with the above-mentioned Cr-Zr-P compound, the pinning effect of crystal grain boundary is exhibited, a high temperature Even when used in an environment, it is possible to reliably suppress coarsening of crystal grains.
Here, when the Co content is less than 0.02 mass%, the CoP compound and the Co 2 P compound cannot be sufficiently formed, and the pinning effect is further improved despite the addition of Co. May not be able to On the other hand, when the Co content exceeds 0.15 mass %, the CoP compound and the Co 2 P compound become coarse, and although the Co is added, the pinning effect may not be further improved. is there.
From the above, in the present embodiment, when Co is added, the Co content is set within the range of 0.02 mass% or more and 0.15 mass% or less. In order to surely achieve the above-mentioned effects, the lower limit of the Co content is preferably 0.03 mass% or more, and the upper limit of the Co content is preferably 0.1 mass% or less. .. Moreover, when Co is not intentionally added, Co may be contained as an impurity in an amount of less than 0.02 mass %.
(CoとPの質量比〔Co〕/〔P〕:0.5以上5.0以下)
また、Coを添加する場合には、CoとPの質量比〔Co〕/〔P〕が、0.5≦〔Co〕/〔P〕≦5.0の範囲内とする。このようにCoとPの質量比〔Co〕/〔P〕を規定することにより、CoP化合物及びCo2P化合物の形成に寄与しない余剰のCoやPが母相中に固溶して導電率が低下することを抑制できる。なお、上述の作用効果を確実に奏功せしめるためには、CoとPの質量比〔Co〕/〔P〕の下限を1.0以上とすることが好ましく、CoとPの質量比〔Co〕/〔P〕の上限を3.0以下とすることが好ましい。
( Mass ratio of Co and P [Co]/[P]: 0.5 or more and 5.0 or less)
When Co is added, the mass ratio [Co]/[P] of Co and P is in the range of 0.5≦[Co]/[P]≦5.0. By defining the mass ratio [Co]/[P] of Co and P in this way, excess Co and P that do not contribute to the formation of the CoP compound and the Co 2 P compound are solid-dissolved in the matrix and the conductivity is increased. Can be suppressed. In order to surely bring out the above effects, the lower limit of the mass ratio [Co]/[P] of Co and P is preferably 1.0 or more, and the mass ratio [Co] of Co and P [Co]. The upper limit of /[P] is preferably 3.0 or less.
(Ti.Hfの合計:0.10mass%以下)
さらに、Coを添加する場合には、不可避不純物であるTi、Hfの含有量の合計が0.10mass%以下とすることが好ましい。これらTi、Hfといった元素は、Coとの化合物を生成しやすいことから、CoP化合物及びCo2P化合物を十分に形成することができなくなるおそれがある。よって、不可避不純物であるTi、Hfの含有量の合計を上述のように規定することで、CoP化合物及びCo2P化合物を確実に形成し、ピン止め効果を発揮させることができる。なお、上述の作用効果を確実に奏功せしめるためには、不可避不純物であるTi、Hfの含有量の合計量を0.03mass%以下とすることが好ましい。
(Total of Ti.Hf: 0.10 mass% or less)
Furthermore, when Co is added, it is preferable that the total content of Ti and Hf which are inevitable impurities is 0.10 mass% or less. Since these elements such as Ti and Hf easily form a compound with Co, there is a possibility that a CoP compound and a Co 2 P compound cannot be sufficiently formed. Therefore, by defining the total content of Ti and Hf which are unavoidable impurities as described above, the CoP compound and the Co 2 P compound can be reliably formed and the pinning effect can be exhibited. In order to surely bring out the above-mentioned effects, it is preferable that the total content of Ti and Hf which are unavoidable impurities is 0.03 mass% or less.
(その他の不可避不純物:0.05mass%以下)
なお、上述したCr,Zr,P,Co,Ti,Hf以外のその他の不可避的不純物としては、B、Al,Fe,Sn,Zn,Si,Mg,Ag,Ca,Te,Mn,Ni,Sr,Ba,Sc,Y,V,Nb,Ta,Mo,W,Re,Ru,Os,Se,Rh,Ir,Pd,Pt,Au,Cd,Ga,In,Li,Ge,As,Sb,Tl,Pb,Be,N,H,Hg,Tc,Na,K,Rb,Cs,Po,Bi,ランタノイド、O,S,C等が挙げられる。これらの不可避不純物は、導電率及び熱伝導率を低下させるおそれがあるため、総量で0.05mass%以下とすることが好ましい。
(Other unavoidable impurities: 0.05 mass% or less)
Other unavoidable impurities other than the above-mentioned Cr, Zr, P, Co, Ti, and Hf include B, Al, Fe, Sn, Zn, Si, Mg, Ag, Ca, Te, Mn, Ni, and Sr. , Ba, Sc, Y, V, Nb, Ta, Mo, W, Re, Ru, Os, Se, Rh, Ir, Pd, Pt, Au, Cd, Ga, In, Li, Ge, As, Sb, Tl , Pb, Be, N, H, Hg, Tc, Na, K, Rb, Cs, Po, Bi, lanthanoid, O, S, C and the like. Since these unavoidable impurities may reduce the electrical conductivity and the thermal conductivity, the total amount is preferably 0.05 mass% or less.
(Cr−Zr−P化合物の面積率:0.5%以上5.0%以下)
上述のCr−Zr−P化合物の面積率が0.5%未満の場合には、Cr−Zr−P化合物による結晶粒界のピン止め効果が不十分となり、結晶粒の粗大化を抑制できなくなるおそれがある。一方、Cr−Zr−P化合物の面積率が5.0%を超えると、加工性が低下するおそれがある。
以上のことから、本実施形態では、Cr−Zr−P化合物の面積率を0.5%以上5.0%以下に規定している。なお、Cr−Zr−P化合物の面積率の下限は1.0%以上とすることが好ましく、Cr−Zr−P化合物の面積率の上限は3.0%以下とすることが好ましい。
(Area ratio of Cr-Zr-P compound: 0.5% or more and 5.0% or less)
When the area ratio of the Cr-Zr-P compound is less than 0.5%, the pinning effect of the crystal grain boundaries by the Cr-Zr-P compound becomes insufficient, and it becomes impossible to suppress the coarsening of the crystal grains. There is a risk. On the other hand, if the area ratio of the Cr-Zr-P compound exceeds 5.0%, the workability may decrease.
From the above, in the present embodiment, the area ratio of the Cr-Zr-P compound is specified to be 0.5% or more and 5.0% or less. The lower limit of the area ratio of the Cr-Zr-P compound is preferably 1.0% or more, and the upper limit of the area ratio of the Cr-Zr-P compound is preferably 3.0% or less.
(針状、粒状のCr−Zr−P化合物の最長の辺となる長さ:100μm以下)
針状、粒状の形態をなすCr−Zr−P化合物の最長の辺となる長さが100μmを超える場合には、上述のピン止め効果が十分に発揮されないおそれがある。
以上のことから、本実施形態では、Cr−Zr−P化合物の最長の辺となる長さを100μm以下に規定している。なお、Cr−Zr−P化合物の最長の辺となる長さの上限は80μm以下とすることが好ましい。
(Length of the longest side of the acicular or granular Cr-Zr-P compound: 100 μm or less)
When the length of the longest side of the needle-like or granular Cr-Zr-P compound exceeds 100 μm, the pinning effect described above may not be sufficiently exhibited.
From the above, in the present embodiment, the length of the longest side of the Cr-Zr-P compound is specified to be 100 μm or less. The upper limit of the length of the longest side of the Cr-Zr-P compound is preferably 80 μm or less.
(1000℃で30分保持の熱処理を実施した後の平均結晶粒径:200μm以下)
1000℃で30分保持の熱処理後の平均結晶粒径が200μm以下とされることにより、例えば500℃以上の高温環境下で使用した際の結晶粒の粗大化が確実に抑制され、強度等の特性が安定することになる。
以上のことから、本実施形態では、1000℃で30分保持の熱処理を実施した後の平均結晶粒径を200μm以下としている。
(Average crystal grain size after heat treatment of holding at 1000° C. for 30 minutes: 200 μm or less)
By setting the average crystal grain size after heat treatment of holding at 1000° C. for 30 minutes to 200 μm or less, coarsening of crystal grains when used in a high temperature environment of, for example, 500° C. or more is reliably suppressed, and The characteristics will be stable.
From the above, in the present embodiment, the average crystal grain size after the heat treatment of holding at 1000° C. for 30 minutes is set to 200 μm or less.
次に、本発明の一実施形態に係る銅合金素材の製造方法を、図1のフロー図を参照して説明する。 Next, a method for manufacturing a copper alloy material according to an embodiment of the present invention will be described with reference to the flowchart of FIG.
(溶解・鋳造工程S01)
まず、銅の純度が99.99mass%以上の無酸素銅からなる銅原料を、カーボンるつぼに装入し、真空溶解炉を用いて溶解し、銅溶湯を得る。次いで、得られた溶湯に、所定の濃度となるように前述の添加元素を添加して、成分調製を行い、銅合金溶湯を得る。
ここで、添加元素であるCr、Zr、Pの原料としては、純度の高いものを使用し、例えばCrの原料は純度99.99mass%以上のものを使用し、Zrの原料は純度99.95mass%以上、Pの原料は純度99.99mass%以上のものを使用する。また、Coを必要に応じて添加する。なお、Cr、Zr、Co,Pの原料として、Cuとの母合金を用いてもよい。
そして、成分調製された銅合金溶湯を鋳型に注湯して鋳塊を得る。
(Melting/casting process S01)
First, a copper raw material made of oxygen-free copper having a copper purity of 99.99 mass% or more is charged into a carbon crucible and melted using a vacuum melting furnace to obtain a molten copper. Next, the above-mentioned additional elements are added to the obtained molten metal so as to have a predetermined concentration, the components are prepared, and a molten copper alloy is obtained.
Here, as a raw material of Cr, Zr, and P which are additive elements, a high purity one is used, for example, a Cr raw material having a purity of 99.99 mass% or more is used, and a Zr raw material has a purity of 99.95 mass%. % Or more, and the raw material of P has a purity of 99.99 mass% or more. Moreover, Co is added as needed. A mother alloy with Cu may be used as a raw material for Cr, Zr, Co, and P.
Then, the ingot is obtained by pouring the copper alloy molten metal whose components are prepared into a mold.
(均質化処理工程S02)
次に、得られた鋳塊の均質化のために熱処理を行う。
具体的には、鋳塊を大気雰囲気にて、950℃以上1050℃以下、1時間以上の条件で均質化処理を行う。
(Homogenization process step S02)
Next, heat treatment is performed to homogenize the obtained ingot.
Specifically, the ingot is subjected to a homogenization treatment in an air atmosphere under the conditions of 950° C. or higher and 1050° C. or lower for 1 hour or longer.
(熱間加工工程S03)
次いで、鋳塊に対して900℃以上1000℃以下の温度範囲で、加工率50%以上99%以下の熱間圧延を行い、圧延材を得る。なお、熱間加工の方法は、熱間鍛造であっても良い。この熱間加工後、直ちに水冷によって冷却する。
(Hot working step S03)
Then, the ingot is hot-rolled at a working rate of 50% to 99% within a temperature range of 900°C to 1000°C to obtain a rolled material. The hot working method may be hot forging. Immediately after this hot working, it is cooled by water cooling.
(溶体化処理工程S04)
次いで、熱間加工工程S03で得られた圧延材を、920℃以上1050℃以下、0.5時間以上5時間以下の条件で加熱処理を施し、溶体化処理を行う。加熱処理は、例えば大気または不活性ガス雰囲気で行い、加熱後の冷却は、水冷によって行う。
(Solution treatment step S04)
Next, the rolled material obtained in the hot working step S03 is subjected to heat treatment under the conditions of 920° C. or higher and 1050° C. or lower for 0.5 hours or longer and 5 hours or shorter, and solution treatment is performed. The heat treatment is performed, for example, in the atmosphere or an inert gas atmosphere, and the cooling after the heating is performed by water cooling.
なお、インライン溶体化処理を行うことにより、熱間加工工程S03と溶体化処理工程S04を同時に行ってもよい。
具体的には、鋳塊に対して900℃以上1000℃以下の温度範囲で、加工率50%以上99%以下の熱間圧延を行うとともに、920℃以上1050℃以下の温度から直ちに水冷によって冷却することにより、溶体化処理を行う。
The hot working step S03 and the solution treatment step S04 may be performed simultaneously by performing the in-line solution treatment.
Specifically, the ingot is hot-rolled at a working rate of 50% to 99% in a temperature range of 900°C to 1000°C, and immediately cooled by water cooling from a temperature of 920°C to 1050°C. By doing so, solution treatment is performed.
(時効処理工程S05)
次に、溶体化処理工程S04の後に、時効処理を実施し、Cr系析出物及びZr系析出物などの析出物を微細に析出させ、時効処理材を得る。
ここで、時効処理は、例えば400℃以上530℃以下、0.5時間以上5時間以下の条件で行う。
なお、時効処理時の熱処理方法は、特に限定しないが、不活性ガス雰囲気で行うことが好ましい。また、加熱処理後の冷却方法は、特に限定しないが、水冷で行うことが好ましい。
このような工程により、本実施形態である銅合金素材が製造される。
(Aging treatment step S05)
Next, after the solution treatment step S04, an aging treatment is carried out to finely precipitate Cr-based precipitates and Zr-based precipitates to obtain an aging-treated material.
Here, the aging treatment is performed, for example, under the conditions of 400° C. or higher and 530° C. or lower and 0.5 hours or longer and 5 hours or shorter.
The heat treatment method during the aging treatment is not particularly limited, but it is preferably performed in an inert gas atmosphere. The cooling method after the heat treatment is not particularly limited, but water cooling is preferable.
Through such steps, the copper alloy material of this embodiment is manufactured.
以上のような構成とされた本実施形態に係る銅合金素材によれば、Crを0.1mass%以上1.5mass%以下、Zrを0.05mass%以上0.25mass%以下、Pを0.005mass%以上0.10mass%以下、含み、残部がCu及び不可避不純物からなる組成とされているので、時効処理によって微細な析出物を析出させることにより、強度(硬さ)及び導電率を向上させることができる。 According to the copper alloy material according to the present embodiment configured as described above, Cr is 0.1 mass% or more and 1.5 mass% or less, Zr is 0.05 mass% or more and 0.25 mass% or less, and P is 0. Since it has a composition of 005 mass% or more and 0.10 mass% or less and the balance of Cu and unavoidable impurities, it improves strength (hardness) and conductivity by precipitating fine precipitates by aging treatment. be able to.
そして、本実施形態においては、CrとZrとPを含むCr−Zr−P化合物が存在し、組織観察においてCr−Zr−P化合物の面積率が0.5%以上5.0%以下の範囲内とされているので、高温環境下で使用した場合でもCr−Zr−P化合物が消失せず、このCr−Zr−P化合物のピン止め効果によって、結晶粒の粗大化を抑制することができる。 And in this embodiment, the Cr-Zr-P compound containing Cr, Zr, and P exists, and the area ratio of the Cr-Zr-P compound is 0.5% or more and 5.0% or less in the structure observation. Therefore, even when used in a high temperature environment, the Cr—Zr—P compound does not disappear, and the pinning effect of this Cr—Zr—P compound can suppress the coarsening of crystal grains. ..
また、本実施形態においては、Cr−Zr−P化合物が、針状もしくは粒状の形態をとり、最長となる辺の長さが100μm以下とされているので、上述のピン止め効果を確実に奏功せしめることが可能となる。
さらに、本実施形態においては、1000℃で30分保持の熱処理を実施した後の平均結晶粒径が200μm以下とされているので、500℃以上の高温環境下で使用された場合であっても、結晶粒が粗大化せず、機械的特性や導電率が安定している。
In addition, in the present embodiment, the Cr-Zr-P compound has a needle-like or granular form, and the longest side length is 100 μm or less, so that the pinning effect described above is reliably achieved. It is possible to blame.
Further, in the present embodiment, the average crystal grain size after the heat treatment of holding at 1000° C. for 30 minutes is set to 200 μm or less, so that even when used in a high temperature environment of 500° C. or more. , The crystal grains do not become coarse, and the mechanical properties and conductivity are stable.
また、本実施形態において、さらにCoを0.02mass%以上0.15mass%以下の範囲内で含み、CoとPの質量比〔Co〕/〔P〕が、0.5≦〔Co〕/〔P〕≦5.0の範囲内とされている場合には、CoP化合物及びCo2P化合物が形成され、上述のCr−Zr−P化合物とともに、結晶粒界のピン止め効果を発揮することができ、高温環境下で使用した場合であっても結晶粒の粗大化を確実に抑制することが可能となる。また、CoとPの質量比〔Co〕/〔P〕が、0.5≦〔Co〕/〔P〕≦5.0の範囲内とされているので、余剰のCo、Pが母相中に固溶することを抑制でき、導電率の低下を抑制することができる。
さらに、Coを含有する場合には、不可避不純物であるTi、Hfの含有量の合計が0.10mass%以下とすることにより、CoP化合物及びCo2P化合物を確実に形成することができ、結晶粒界のピン止め効果を効果的に発揮させ、結晶粒の粗大化を抑制することが可能となる。
Further, in the present embodiment, Co is further included in the range of 0.02 mass% or more and 0.15 mass% or less, and the mass ratio [Co]/[P] of Co and P is 0.5≦[Co]/[ P]≦5.0, a CoP compound and a Co 2 P compound are formed and, together with the above-mentioned Cr—Zr—P compound, a pinning effect of crystal grain boundaries may be exhibited. This makes it possible to reliably suppress coarsening of crystal grains even when used in a high temperature environment. Further, since the mass ratio [Co]/[P] of Co and P is within the range of 0.5≦[Co]/[P]≦5.0, surplus Co and P are in the parent phase. The solid solution can be suppressed, and the decrease in conductivity can be suppressed.
Further, when Co is contained, the total content of Ti and Hf which are inevitable impurities is 0.10 mass% or less, whereby the CoP compound and the Co 2 P compound can be reliably formed, and the crystal is formed. It becomes possible to effectively exert the pinning effect of the grain boundaries and suppress the coarsening of the crystal grains.
以上、本発明の実施形態について説明したが、本発明はこれに限定されることはなく、その発明の技術的思想を逸脱しない範囲で適宜変更可能である。 Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be appropriately modified without departing from the technical idea of the invention.
以下に、本発明の効果を確認すべく行った確認実験の結果について説明する。
純度99.99mass%以上の無酸素銅からなる銅原料を準備し、これをカーボンるつぼに装入し、真空溶解炉(真空度10−2Pa以下)で溶解し、銅溶湯を得た。得られた銅溶湯内に、各種添加元素を添加して表1に示す成分組成に調製し、5分間保持した後、銅合金溶湯を鋳鉄製の鋳型に注湯して鋳塊を得た。鋳塊の大きさは、幅約80mm、厚さ約50mm、長さ約130mmとした。
なお、添加元素であるCrの原料は純度99.99mass%以上、Zrの原料は純度99.95mass%以上のものを使用した。
The results of confirmation experiments conducted to confirm the effects of the present invention will be described below.
A copper raw material made of oxygen-free copper having a purity of 99.99 mass% or more was prepared, charged into a carbon crucible, and melted in a vacuum melting furnace (vacuum degree 10 −2 Pa or less) to obtain a copper melt. Various additive elements were added to the obtained molten copper to prepare the component composition shown in Table 1, which was held for 5 minutes, and then the molten copper alloy was poured into a cast iron mold to obtain an ingot. The ingot had a width of about 80 mm, a thickness of about 50 mm, and a length of about 130 mm.
The raw material of Cr, which is an additional element, had a purity of 99.99 mass% or more, and the raw material of Zr had a purity of 99.95 mass% or more.
次に、大気雰囲気において1000℃で1時間の条件で均質化処理を行った後、熱間圧延を実施した。熱間圧延時の圧下率を80%とし、幅約100mm×厚さ約10mm×長さ約520mmの熱間圧延材を得た。
なお、本実施例においては、熱間圧延終了時に表1に示す冷却速度で冷却することで溶体化処理を兼ねており、いわゆるインライン溶体化を実施した。
次に、500(±15)℃で3時間の条件で時効処理を実施した。これにより、銅合金素材を得た。
Next, a homogenizing treatment was performed in the atmosphere at 1000° C. for 1 hour, and then hot rolling was performed. The rolling reduction during hot rolling was set to 80% to obtain a hot rolled material having a width of about 100 mm×a thickness of about 10 mm×a length of about 520 mm.
In the present example, the so-called in-line solution treatment was performed by cooling at the cooling rate shown in Table 1 at the end of hot rolling, which also serves as solution treatment.
Next, an aging treatment was carried out under the condition of 500 (±15)° C. for 3 hours. Thereby, a copper alloy material was obtained.
得られた銅合金素材について、時効処理後の銅合金素材の組織観察を行い、Cr−Zr−P化合物について評価した。また、時効処理後の銅合金素材の導電率及び引張強度を測定した。
さらに、時効処理後の銅合金素材に対して、1000℃で30分保持後の熱処理を実施し、その後水冷した銅合金素材について、平均結晶粒径及び引張強度を評価した。
With respect to the obtained copper alloy material, the structure of the copper alloy material after the aging treatment was observed, and the Cr-Zr-P compound was evaluated. Further, the electrical conductivity and the tensile strength of the copper alloy material after the aging treatment were measured.
Furthermore, the copper alloy material after the aging treatment was subjected to a heat treatment after holding at 1000° C. for 30 minutes, and then the water-cooled copper alloy material was evaluated for the average crystal grain size and the tensile strength.
(組成分析)
得られた銅合金素材の成分組成は、ICP−MS分析によって測定した。測定結果を表1に示す。
(Composition analysis)
The component composition of the obtained copper alloy material was measured by ICP-MS analysis. The measurement results are shown in Table 1.
(Cr−Zr−P化合物)
得られた銅合金素材の板厚で板幅中心部から10mm×15mmの試料を切り出し、圧延方向(RD方向)の面を研磨後、ミクロエッチングを行った。
この試料をSEM観察し、SEM−EPMA画像(250μm×250μmの視野)において、母相よりもCr,Zr,P濃度が高い領域を「Cr−Zr−P化合物」であると判断し、最長となる辺の長さを測定した。そして、Cu−Zr−P化合物の面積率を以下の式で求めた。
面積率=(Cr−Zr−P化合物が占める面積)/(250μm×250μm)
図4に本発明例2のSEM−EPMA画像を、図5に比較例1のSEM−EPMA画像を示す。また、Cu−Zr−P化合物の面積率を算出する際のSEM−EPMA画像(250μm×250μmの視野)の一例を図6に示す。
(Cr-Zr-P compound)
A sample having a thickness of the obtained copper alloy material and having a thickness of 10 mm×15 mm was cut out from the center of the plate width, and the surface in the rolling direction (RD direction) was polished and then microetched.
This sample was observed by SEM, and in the SEM-EPMA image (field of view of 250 μm×250 μm), the region having a higher Cr, Zr, P concentration than the parent phase was judged to be the “Cr-Zr-P compound”, and it was determined as the longest The length of the side was measured. Then, the area ratio of the Cu-Zr-P compound was determined by the following formula.
Area ratio=(area occupied by Cr-Zr-P compound)/(250 μm×250 μm)
FIG. 4 shows the SEM-EPMA image of Inventive Example 2, and FIG. 5 shows the SEM-EPMA image of Comparative Example 1. Moreover, an example of the SEM-EPMA image (the visual field of 250 μm×250 μm) when calculating the area ratio of the Cu—Zr—P compound is shown in FIG.
(平均結晶粒径)
銅合金素材の板厚で板幅中心部から10mm×15mmの試料を切り出し、圧延方向(RD方向)の面を研磨後、ミクロエッチングを行った。
この試料を観察し、JIS H 0501に規定された切断法により、平均結晶粒径を測定した。
(Average grain size)
A sample having a thickness of the copper alloy material and having a thickness of 10 mm×15 mm was cut out from the center of the plate width, the surface in the rolling direction (RD direction) was polished, and then microetching was performed.
This sample was observed, and the average crystal grain size was measured by the cutting method specified in JIS H0501.
(導電率)
日本フェルスター社製SIGMA TEST D2.068(プローブ径φ6mm)を用いて、10×15mmのサンプルの断面中心部を3回測定し、その平均値を求めた。
(conductivity)
Using SIGMA TEST D2.068 (probe diameter φ6 mm) manufactured by Nippon Forster Co., the center of the cross section of a 10×15 mm sample was measured three times, and the average value was obtained.
(引張強度)
圧延方向を引張方向としてJIS Z 2241 2号試験片を採取し、100kN引張試験機を用いて試験に供した。
(Tensile strength)
JIS Z 2241 No. 2 test pieces were sampled using the rolling direction as the tensile direction and subjected to the test using a 100 kN tensile tester.
Pを添加していない比較例1においては、針状、粒状のCr−Zr−P化合物が生成しないため、1000℃30分の熱処理後に引張強度が大きく低下した。
針状、粒状のCr―Zr−P化合物の面積率が本発明の範囲を超えた比較例2においては、1000℃30分の熱処理後に引張強度が大きく低下した。
Zrの含有量が本発明の範囲を超えた比較例3においては、導電率が低く、1000℃30分の熱処理後に引張強度が大きく低下した。
Coの含有量が本発明の範囲を超えた比較例4においては、導電率が低くかった。
針状、粒状のCr―Zr−P化合物の面積率が本発明の範囲よりも少ない比較例5においては、1000℃30分の熱処理後に引張強度が大きく低下した。
In Comparative Example 1 in which P was not added, a needle-like or granular Cr-Zr-P compound was not formed, so that the tensile strength was significantly reduced after the heat treatment at 1000°C for 30 minutes.
In Comparative Example 2 in which the area ratio of the acicular or granular Cr-Zr-P compound exceeded the range of the present invention, the tensile strength greatly decreased after the heat treatment at 1000°C for 30 minutes.
In Comparative Example 3 in which the Zr content exceeded the range of the present invention, the conductivity was low, and the tensile strength was significantly reduced after the heat treatment at 1000° C. for 30 minutes.
In Comparative Example 4 in which the Co content exceeded the range of the present invention, the conductivity was low.
In Comparative Example 5 in which the area ratio of the acicular or granular Cr—Zr—P compound was less than the range of the present invention, the tensile strength was significantly reduced after the heat treatment at 1000° C. for 30 minutes.
これに対して、本発明例2,5,6においては、導電率が高く、かつ、1000℃30分の熱処理後においても引張強度が大きく低下することがなかった。また、1000℃30分の熱処理後の結晶粒径が200μm以下とされた本発明例5,6においては、さらに、1000℃30分の熱処理後の引張強度の低下が抑えられていた。 On the other hand, in Inventive Examples 2 , 5 , and 6 , the electrical conductivity was high, and the tensile strength was not significantly reduced even after the heat treatment at 1000° C. for 30 minutes. Further, in Examples 5 and 6 of the present invention in which the crystal grain size after the heat treatment at 1000° C. for 30 minutes was 200 μm or less, the decrease in the tensile strength after the heat treatment at 1000° C. for 30 minutes was further suppressed.
以上のことから、本発明例によれば、500℃以上の高温環境下で使用された場合であっても、結晶粒の粗大化を抑制でき、特性が安定し、かつ、使用寿命に優れた銅合金素材を提供可能であることが確認された。 From the above, according to the example of the present invention, even when used in a high temperature environment of 500° C. or higher, coarsening of crystal grains can be suppressed, the characteristics are stable, and the service life is excellent. It was confirmed that a copper alloy material could be provided.
Claims (3)
CrとZrとPを含むCr−Zr−P化合物が存在し、組織観察において前記Cr−Zr−P化合物の面積率が0.5%以上5.0%以下の範囲内とされており、
前記Cr−Zr−P化合物は、針状もしくは粒状の形態をとり、最長となる辺の長さが100μm以下とされていることを特徴とする銅合金素材。 Cr 0.1 mass% or more and 1.5 mass% or less, Zr 0.05 mass% or more and 0.25 mass% or less, P 0.005 mass% or more and 0.10 mass% or less, Co 0.02 mass% or more and 0.15 mass% It has a composition in which the balance is Cu and unavoidable impurities, and the mass ratio [Co]/[P] of Co and P is 0.5≦[Co]/[P]≦5.0. Is within the range of
There is a Cr-Zr-P compound containing Cr, Zr, and P, and the area ratio of the Cr-Zr-P compound is determined to be within the range of 0.5% or more and 5.0% or less in the structure observation.
The Cr-Zr-P compound has a needle-like or granular form, and has a longest side length of 100 μm or less, which is a copper alloy material.
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