JP5208562B2 - Seamless pipe - Google Patents
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- JP5208562B2 JP5208562B2 JP2008097842A JP2008097842A JP5208562B2 JP 5208562 B2 JP5208562 B2 JP 5208562B2 JP 2008097842 A JP2008097842 A JP 2008097842A JP 2008097842 A JP2008097842 A JP 2008097842A JP 5208562 B2 JP5208562 B2 JP 5208562B2
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- 229910000881 Cu alloy Inorganic materials 0.000 claims description 82
- 239000010949 copper Substances 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 description 33
- 238000005452 bending Methods 0.000 description 28
- 238000000034 method Methods 0.000 description 28
- 238000012360 testing method Methods 0.000 description 19
- 238000005728 strengthening Methods 0.000 description 16
- 238000005219 brazing Methods 0.000 description 14
- 239000000956 alloy Substances 0.000 description 13
- 238000012546 transfer Methods 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 11
- 238000001192 hot extrusion Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000003507 refrigerant Substances 0.000 description 9
- 238000005266 casting Methods 0.000 description 7
- 238000005097 cold rolling Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005482 strain hardening Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017888 Cu—P Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910017985 Cu—Zr Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004881 precipitation hardening Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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Description
本発明は、空調機、冷凍機等に用いられる熱交換器用の伝熱管、特に、ヘアピン管、内面溝付管の製造に用いられる継目無管用銅合金及び該銅合金製の継目無管に関する。 TECHNICAL FIELD The present invention relates to a heat transfer tube for a heat exchanger used in an air conditioner, a refrigerator, etc., and more particularly to a seamless pipe copper alloy used for manufacturing a hairpin tube and an inner grooved tube, and a seamless tube made of the copper alloy.
従来より、ルームエアコン、パッケージエアコン等の空調機、冷凍機等に用いられる熱交換器の伝熱管には、継目無管が多く採用されており、強度や加工性、伝熱性等の諸物性、並びに材料及び加工コストにバランスの取れたりん脱酸銅管（ＪＩＳ Ｃ１２２０Ｔ）が使用されてきた。 Conventionally, many heat exchanger tubes used in air conditioners such as room air conditioners and packaged air conditioners, and heat exchangers used in refrigerators, etc. have been adopted seamless pipes, and various physical properties such as strength, workability, and heat transfer properties, In addition, a phosphorus-deoxidized copper pipe (JIS C1220T) having a balanced material and processing cost has been used.
近年、これらの熱交換器では、重量の低減又はコストダウンの要求により、継目無管の薄肉化が必要となってきた。 In recent years, in these heat exchangers, it has become necessary to reduce the thickness of seamless pipes due to demands for weight reduction or cost reduction.
一方、冷媒変更に伴う冷媒圧力の増加や、地球温暖化ガスである冷媒ガスの排出抑制の観点から、配管材料には、高い信頼性が求められるようになってきた。つまり、肉厚が薄くても信頼性が高い配管材料が、要求されている。そして、このような要求を満たすためには、銅合金には、加工性に優れ且つ強度が高いことが求められる。また、該銅合金は、伝熱管や冷却管の原材料となるため、該銅合金には、熱伝導性が高いことも求められる。 On the other hand, piping materials have been required to have high reliability from the viewpoints of an increase in refrigerant pressure accompanying the change of refrigerant and suppression of discharge of refrigerant gas, which is a global warming gas. That is, there is a demand for a piping material with high reliability even if the wall thickness is thin. And in order to satisfy | fill such a request | requirement, it is calculated | required that a copper alloy is excellent in workability and high intensity | strength. In addition, since the copper alloy is a raw material for heat transfer tubes and cooling tubes, the copper alloy is also required to have high thermal conductivity.
しかし、りん脱酸銅では、重量の低減又はコストダウンを目的として薄肉化すると、耐圧強度が低くなり過ぎるため、信頼性が低くなり、薄肉化と高信頼性の要求を両立させることは著しく困難であった。 However, with phosphorous-deoxidized copper, if the thickness is reduced for the purpose of reducing weight or cost, the pressure strength becomes too low, so the reliability is lowered, and it is extremely difficult to achieve both the reduction in thickness and the requirement for high reliability. Met.
ところで、熱交換器用の伝熱管には、ロウ付けによる強度低下が小さいことも要求される。すなわち、熱交換器の種類によっては、組み立てられる際に、配管自体が、８００℃以上の高温に曝されるため、ロウ付けの前後において、強度変化が小さいことが要求される。 By the way, a heat exchanger tube for a heat exchanger is also required to have a small decrease in strength due to brazing. That is, depending on the type of heat exchanger, the pipe itself is exposed to a high temperature of 800 ° C. or higher when assembled, so that it is required that the strength change is small before and after brazing.
しかし、りん脱酸銅は、高温に曝されると、粒成長が起こり、それを起因とする強度及び延性の低下が起こる。この現象は、信頼性を低くする原因となるため、好ましくない。 However, when phosphorus deoxidized copper is exposed to high temperatures, grain growth occurs, resulting in a decrease in strength and ductility. This phenomenon is not preferable because it causes low reliability.
そこで、薄肉化ができ且つ信頼性を高くするため、あるいは、ロウ付けによる強度低下の問題を解決するための対策合金として、析出強化型合金及び固溶強化型合金が提案されている。 Accordingly, precipitation strengthened alloys and solid solution strengthened alloys have been proposed as countermeasure alloys for reducing the thickness and increasing the reliability, or for solving the problem of strength reduction due to brazing.
具体的には、析出強化型合金としては、例えば、特許文献１には、重量％でＣｏ：０．０２〜０．２％、Ｐ：０．０１〜０．０５％を含有し、残りがＣｕ及び不可避不純物からなり、前記不可避不純物として含まれる酸素含有量を５０ｐｐｍ以下に規制した組成の銅合金が、また、特許文献２には、ロウ付け熱交換器に用いられ、再結晶温度が高く、優れた伝導率を有する銅合金において、該合金は、０．１重量％以上且つ０．３重量以下のクロムを含むことを特徴とする銅合金が開示されている。また、特許文献３には、継目無管製造用銅合金におけるＦｅ、Ｚｒ、Ｐ及びＯの含有量を、Ｆｅ：０．００５〜０．８％、Ｐ：０．０１〜０．０２６％、Ｚｒ：０．００５〜０．３％、Ｏ：３〜３０ｐｐｍとし、これ以外の合金成分は実質的に含有しない継目無管用銅合金が開示されている。また、固溶強化型合金としては、特許文献４には、Ｓｎ：０．１乃至１．０質量％、Ｐ：０．００５乃至０．１質量％、Ｏ：０．００５質量％以下及びＨ：０．０００２質量％以下を含有し、残部がＣｕ及び不可避不純物からなる組成を有し、平均結晶粒径が３０μｍ以下である銅合金が開示されている。また、特許文献５には、Ｓｎ：０．１乃至１．０質量％、Ｐ：０．００５乃至０．１質量％、Ｏ：０．００５質量％以下及びＨ：０．０００２質量％以下を含有し、残部がＣｕ及び不可避的不純物からなるビレットを、７８０乃至９００℃に加熱して熱間押出加工をした後、７５０℃以上の温度から冷却することにより、１００℃までの平均冷却速度が１．５℃／秒以上となるように冷却し、その後、加工率９２％以下の圧延加工及び加工率４０％以下の抽伸加工を順次行うことにより得られる熱交換器用銅合金平滑管及び熱交換器用銅合金内面溝付管が開示されている。 Specifically, as a precipitation strengthening type alloy, for example, Patent Document 1 contains Co: 0.02 to 0.2% by weight%, P: 0.01 to 0.05%, and the rest A copper alloy composed of Cu and inevitable impurities and having a composition in which the oxygen content contained as the inevitable impurities is regulated to 50 ppm or less is used in Patent Document 2 for brazing heat exchangers and has a high recrystallization temperature. A copper alloy having excellent conductivity is disclosed, wherein the alloy contains 0.1 wt% or more and 0.3 wt% or less of chromium. Moreover, in patent document 3, content of Fe, Zr, P, and O in the copper alloy for seamless pipe manufacture is made into Fe: 0.005-0.8%, P: 0.01-0.026%, A seamless pipe copper alloy containing Zr: 0.005 to 0.3% and O: 3 to 30 ppm and containing substantially no other alloy components is disclosed. Moreover, as a solid solution strengthening type alloy, in patent document 4, Sn: 0.1 thru | or 1.0 mass%, P: 0.005 thru | or 0.1 mass%, O: 0.005 mass% or less and H : A copper alloy containing 0.0002% by mass or less, the balance being Cu and inevitable impurities, and an average crystal grain size of 30 μm or less is disclosed. Patent Document 5 includes Sn: 0.1 to 1.0 mass%, P: 0.005 to 0.1 mass%, O: 0.005 mass% or less, and H: 0.0002 mass% or less. The billet containing Cu and the inevitable impurities contained therein is heated to 780 to 900 ° C. and subjected to hot extrusion, and then cooled from a temperature of 750 ° C. or higher, so that the average cooling rate up to 100 ° C. Copper alloy smooth tube for heat exchanger and heat exchange obtained by cooling to 1.5 ° C / second or higher, and then performing rolling with a processing rate of 92% or less and drawing with a processing rate of 40% or less A dexterous copper alloy internally grooved tube is disclosed.
ところが、引用文献１〜５記載の銅合金であっても、加工性及び強度の両方を高くすることは難しく、薄肉化したときの信頼性が不十分であるという問題があった。 However, even with the copper alloys described in the cited references 1 to 5, it is difficult to increase both the workability and the strength, and there is a problem that the reliability when thinned is insufficient.
すなわち、熱交換器用伝熱管においては、析出強化はロウ付け強度低下を少なくする効果はあるが、ロウ付け温度によっては析出元素の再固溶が起こるため、十分な強度を確保できないという問題があり、このような再固溶のために、粒成長が更に促進されるという問題があった。 In other words, in heat exchanger tubes for heat exchangers, precipitation strengthening has the effect of reducing a decrease in brazing strength, but depending on the brazing temperature, there is a problem that sufficient strength cannot be ensured because re-dissolution of the precipitated elements occurs. There is a problem that the grain growth is further promoted due to such re-dissolution.
また、析出強化は、延性を低下させるため、加工性が悪くなるという問題があった。特に、上述の熱交換器用伝熱管は、熱交換性能を向上させるため、管内面に冷間で転造加工を行って、らせん状の溝を形成させることが一般的である。このようならせん溝の形状は、熱交換器の高性能化の要求に従って、難加工性の形状になってきており、このような溝形状を冷間での転造加工で形成させることが難しくなってきている。従って、冷間での転造加工性は、熱交換器用銅合金材料にとって、非常に重要な要素となっている。 Moreover, since precipitation strengthening reduces ductility, there was a problem that workability deteriorated. In particular, in order to improve the heat exchange performance of the heat exchanger tube for heat exchanger described above, it is common to form a helical groove by cold rolling on the inner surface of the tube. The shape of the spiral groove has become difficult to process in accordance with the demand for higher performance of the heat exchanger, and it is difficult to form such a groove shape by cold rolling. It has become to. Therefore, cold rolling processability is a very important factor for the copper alloy material for heat exchangers.
また、熱交換器用伝熱管は、熱交換器に組付けられる際に、ヘアピン曲げと称する強度の曲げ加工が部分的に行われる。このようなヘアピン曲げ加工は、熱交換器のコンパクト化により、その曲げ半径がますます小さくなってきていると共に、銅管の曲げ部の表面しわが発生する等が問題視されてきており、ヘアピン曲げ加工性も、熱交換器用銅合金材料にとって非常に重要な要素となっている（参考文献：特開２００４−３２２１４１号公報「ヘアピン曲げ銅管および銅管のヘアピン曲げ加工方法」）。 Moreover, when the heat exchanger tube for heat exchanger is assembled to the heat exchanger, a bending process with a strength called hairpin bending is partially performed. In such hairpin bending processing, the bend radius is becoming smaller and smaller due to the compact heat exchanger, and surface wrinkling of the bent portion of the copper tube has been regarded as a problem. Bending workability is also a very important factor for copper alloy materials for heat exchangers (reference document: Japanese Patent Application Laid-Open No. 2004-322141 “Hairpin bending copper tube and hairpin bending method of copper tube”).
析出強化元素を添加することは、このような転造加工性やヘアピン曲げ加工性に悪影響を及ぼすので、単純に適用することには問題があった。 The addition of a precipitation strengthening element has an adverse effect on such rolling processability and hairpin bending processability, so that there is a problem in applying it simply.
一方、固溶強化の場合には、十分な強度を維持するためには、析出元素と比較して、多量の添加が必要となり、その結果、熱伝導性が低下するという問題があった。熱伝導性を確保するために更に薄肉化することも考えられるが、十分な強度を確保することが困難であり、実用的ではない。 On the other hand, in the case of solid solution strengthening, in order to maintain sufficient strength, a large amount of addition is required as compared with the precipitated elements, and as a result, there is a problem that the thermal conductivity is lowered. Although it is conceivable to further reduce the thickness in order to ensure thermal conductivity, it is difficult to ensure sufficient strength and is not practical.
すなわち、析出強化又は固溶強化のみでは、近年の熱交換器用伝熱管の高性能化の要求を、十分に満足させることはできなかった。 That is, only the precipitation strengthening or the solid solution strengthening could not sufficiently satisfy the recent demand for higher performance of heat exchanger tubes for heat exchangers.
従って、本発明は、加工性に優れ、強度が高く、ロウ付けによる強度低下が少なく、且つ、熱伝導性が高い継目無管用銅合金及び継目無管を提供することにある。また、本発明は、特に、冷間での難加工性の転造加工性及び強度のヘアピン曲げ加工性に優れ、強度が高く、ロウ付けによる強度低下が少なく、且つ、熱伝導性が高い継目無管用銅合金及び継目無管を提供することにある。 Accordingly, it is an object of the present invention to provide a seamless pipe copper alloy and a seamless pipe that are excellent in workability, high in strength, less in strength reduction due to brazing, and high in thermal conductivity. In addition, the present invention has a seam that is particularly excellent in cold-working rolling processability and strength hairpin bending processability, high in strength, less in strength reduction due to brazing, and high in thermal conductivity. The object is to provide a copper alloy for seamless pipes and a seamless pipe.
なお、特許文献６には、Ｆｅ、Ｃｒ、Ｍｎ、Ｎｉ、Ａｇ、Ｚｎ、Ｓｎ、Ａｌ、Ｓｉ、Ｐｂ、Ｍｇ、Ｔｅ、Ｚｒ、Ｂ及びＴｉから選ばれる１種又は２種以上の元素を合わせて０．０１〜０．５重量％含み、残部Ｃｕ及び不可避不純物からなる銅合金が開示されている。しかし、特許文献６に記載されている銅合金は、溶接管用の銅合金である。また、固溶強化元素及び析出強化元素を合わせて添加することを含むものではあるが、上述した高性能の熱交換器用伝熱管に要求される導電率及び加工性をバランス良く合わせ持った銅合金材料を実現することはできない。 In Patent Document 6, one or more elements selected from Fe, Cr, Mn, Ni, Ag, Zn, Sn, Al, Si, Pb, Mg, Te, Zr, B, and Ti are combined. In other words, a copper alloy containing 0.01 to 0.5% by weight, the balance being Cu and inevitable impurities is disclosed. However, the copper alloy described in Patent Document 6 is a copper alloy for welded pipes. In addition, a copper alloy that includes a solid solution strengthening element and a precipitation strengthening element in combination, but has a well-balanced conductivity and workability required for the above-described high performance heat exchanger tubes. Material cannot be realized.
本発明者らは、上記従来技術における課題を解決すべく、鋭意研究を重ねた結果、銅合金に、特定の元素を特定の含有量で含有させることにより、加工性、特に、冷間での転造加工性及びヘアピン曲げ加工性に優れ、強度が高く、ロウ付けによる強度低下が少なく、且つ、熱伝導性が高い銅合金が得られることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above-described problems in the prior art, the present inventors have made a copper alloy contain a specific element at a specific content, thereby improving workability, particularly in cold conditions. It has been found that a copper alloy having excellent rolling processability and hairpin bending processability, high strength, little strength decrease due to brazing, and high thermal conductivity can be obtained, and the present invention has been completed.
すなわち、本発明は、銅合金を加工して得られる銅合金製の継目無管であり、
該銅合金は、Ｓｎと、０〜０．１質量％のＺｎと、０．０１〜０．０６質量％のＺｒと、０．００４〜０．０４質量％のＰと、を含有し、残部Ｃｕ及び不可避不純物からなり、
該銅合金中のＳｎ、Ｚｎ及びＺｒの含有量が、下記式（１）、（２）及び（３）：
（１）Ａ＋Ｂ≦０．６０
（２）０．４≦Ａ＋Ｂ＋２Ｃ≦０．７
（３）０．４１≦Ａ＋Ｂ
（式中、ＡはＳｎの含有量（質量％）を示し、ＢはＺｎの含有量（質量％）を示し、ＣはＺｒの含有量（質量％）を示す。）
のいずれも満たすこと、
を特徴とする継目無管を提供するものである。
That is, the present invention is a copper alloy seamless pipe obtained by processing a copper alloy,
The copper alloy contains Sn, 0 to 0.1% by mass of Zn, 0.01 to 0.06 % by mass of Zr, and 0.004 to 0.04% by mass of P, and the balance Consisting of Cu and inevitable impurities,
The contents of Sn, Zn and Zr in the copper alloy are the following formulas (1) , (2) and (3) :
(1) A + B ≦ 0.60
(2) 0.4 ≦ A + B + 2C ≦ 0.7
(3) 0.41 ≦ A + B
(In the formula, A represents the Sn content (mass%), B represents the Zn content (mass%), and C represents the Zr content (mass%).)
Meeting any of the
A seamless tube characterized by the above is provided.
本発明によれば、加工性に優れ、強度が高く、ロウ付けによる強度低下が少なく、且つ、熱伝導性が高い継目無管用銅合金及び継目無管を提供することができうる。また、本発明によれば、特に、冷間での難加工性の転造加工性及び強度のヘアピン曲げ加工性に優れ、強度が高く、ロウ付けによる強度低下が少なく、且つ、熱伝導性が高い継目無管用銅合金及び継目無管を提供することができる。 According to the present invention, it is possible to provide a seamless pipe copper alloy and a seamless pipe that are excellent in workability, high in strength, little in strength reduction due to brazing, and high in thermal conductivity. Further, according to the present invention, in particular, it is excellent in cold-working rolling processability and strength hairpin bending processability, high in strength, less in strength reduction due to brazing, and has high thermal conductivity. High seamless copper alloys and seamless pipes can be provided.
本発明の継目無管は、銅合金を加工して得られる銅合金製の継目無管であり、
該銅合金は、Ｓｎと、０〜０．１質量％のＺｎと、０．０１〜０．１質量％のＺｒと、を含有し、残部Ｃｕ及び不可避不純物からなり、
該銅合金中のＳｎ、Ｚｎ及びＺｒの含有量が、下記式（１）及び（２）：
（１）Ａ＋Ｂ≦０．６０
（２）０．４≦Ａ＋Ｂ＋２Ｃ≦０．７
（式中、ＡはＳｎの含有量（質量％）を示し、ＢはＺｎの含有量（質量％）を示し、ＣはＺｒの含有量（質量％）を示す。）
のいずれも満たす継目無管である。
The seamless pipe of the present invention is a copper alloy seamless pipe obtained by processing a copper alloy,
The copper alloy contains Sn, 0 to 0.1% by mass of Zn, and 0.01 to 0.1% by mass of Zr, and consists of the balance Cu and inevitable impurities,
The contents of Sn, Zn and Zr in the copper alloy are the following formulas (1) and (2):
(1) A + B ≦ 0.60
(2) 0.4 ≦ A + B + 2C ≦ 0.7
(In the formula, A represents the Sn content (mass%), B represents the Zn content (mass%), and C represents the Zr content (mass%).)
Both are seamless pipes.
本発明の継目無管に係る該銅合金は、Ｓｎと、０〜０．１質量％のＺｎと、０．０１〜０．１質量％のＺｒと、を含有し、残部Ｃｕ及び不可避不純物からなる銅合金であり、
該銅合金中のＳｎ、Ｚｎ及びＺｒの含有量が、下記式（１）及び（２）：
（１）Ａ＋Ｂ≦０．６０
（２）０．４≦Ａ＋Ｂ＋２Ｃ≦０．７
（式中、ＡはＳｎの含有量（質量％）を示し、ＢはＺｎの含有量（質量％）を示し、ＣはＺｒの含有量（質量％）を示す。）
のいずれもを満たす継目無管用の銅合金である。
そして、本発明の継目無管に係る該銅合金は、好ましくは、更に下記式（３）：
（３）０．４０≦Ａ＋Ｂ
（式中、Ａ、Ｂ及びＣは、前記と同義である。）
を満たし、且つ、Ｚｒの含有量が０．０６質量％以下である継目無管用の銅合金である。
The copper alloy according to the seamless pipe of the present invention contains Sn, 0 to 0.1% by mass of Zn, and 0.01 to 0.1% by mass of Zr, from the remaining Cu and inevitable impurities. Copper alloy
The contents of Sn, Zn and Zr in the copper alloy are the following formulas (1) and (2):
(1) A + B ≦ 0.60
(2) 0.4 ≦ A + B + 2C ≦ 0.7
(In the formula, A represents the Sn content (mass%), B represents the Zn content (mass%), and C represents the Zr content (mass%).)
It is a copper alloy for seamless pipes that satisfies any of the above.
The copper alloy according to the seamless pipe of the present invention is preferably further represented by the following formula (3):
(3) 0.40 ≦ A + B
(In the formula, A, B, and C are as defined above.)
And the Zr content is 0.06% by mass or less and is a copper alloy for seamless pipes.
本発明の継目無管に係る該銅合金は、Ｓｎ及びＺｒを必須元素として含有し、Ｚｎを任意元素として含有し、残部Ｃｕ及び不可避不純物からなる銅合金である。 The copper alloy according to the seamless pipe of the present invention is a copper alloy containing Sn and Zr as essential elements, Zn as an optional element, and the balance being Cu and inevitable impurities.
本発明の継目無管において、Ｓｎ及びＺｎには、固溶強化により銅合金の強度を向上させる効果及び常温での延性を向上させる効果がある。また、これらの元素の場合、比較的低温で合金化できるので、製造上有利である。 In the seamless pipe of the present invention, Sn and Zn have the effect of improving the strength of the copper alloy by solid solution strengthening and the effect of improving the ductility at room temperature. In addition, these elements are advantageous in production because they can be alloyed at a relatively low temperature.
本発明の継目無管において、Ｚｒには、析出強化により銅合金の強度を向上させる効果がある。また、Ｚｒには、ロウ付け温度が過剰に高くならない前提では、Ｚｒ析出物が残存し、結晶粒の粗大化を抑制することにより、強度低下を小さくする効果がある。 In the seamless pipe of the present invention, Zr has the effect of improving the strength of the copper alloy by precipitation strengthening. Further, in Zr, on the premise that the brazing temperature does not become excessively high, Zr precipitates remain, and there is an effect of reducing the strength reduction by suppressing the coarsening of crystal grains.
本発明の継目無管に係る該銅合金中、Ｚｒの含有量は、０．０１〜０．１質量％である。銅合金中のＺｒの含有量が、０．０１質量％未満だと、結晶粒粗大化を抑制する効果が小さく、ロウ付けによる強度低下が大きくなり、また、Ｓｎ及びＺｎによる固溶強化とＺｒによる析出強化を合わせても銅合金の強化が不十分となる。一方、銅合金中のＺｒの含有量が、０．１質量％を超えると、過剰な析出硬化が起こり、加工性を低下させる原因となる。特に、冷間での転造加工性が悪くなる。その結果、管内面のらせん溝形状の転写が不十分となり、Ｃ１２２０で得られたような伝熱性能が得られ難くなる。 In the copper alloy according to the seamless pipe of the present invention, the content of Zr is 0.01 to 0.1% by mass. When the content of Zr in the copper alloy is less than 0.01% by mass, the effect of suppressing the coarsening of crystal grains is small, the strength decrease due to brazing becomes large, and the solid solution strengthening by Sn and Zn and Zr Even if precipitation strengthening due to is combined, strengthening of the copper alloy becomes insufficient. On the other hand, if the content of Zr in the copper alloy exceeds 0.1% by mass, excessive precipitation hardening occurs, causing workability to deteriorate. In particular, the rolling processability in the cold is deteriorated. As a result, the transfer of the spiral groove shape on the inner surface of the tube becomes insufficient, making it difficult to obtain the heat transfer performance obtained with C1220.
本発明の継目無管に係る該銅合金中のＺｎは、Ｓｎに比べて、延性を向上させる効果が小さく、また、過剰なＺｎは応力腐食感受性を高めるため、本発明の継目無管に係る該銅合金では、Ｓｎを主として、Ｚｎの含有量は０．１質量％以下とする。銅合金中のＺｎの含有量が０．１質量％を超えると、応力腐食感受性が高くなり過ぎるので好ましくない。また、本発明の継目無管に係る該銅合金では、Ｓｎは必須元素であるが、Ｚｎは任意元素なので、本発明の継目無管に係る該銅合金中のＺｎの含有量は、０〜０．１質量％である。また、本発明の継目無管に係る該銅合金は、他の不可避的不純物の含有量の一般的な上限である０．０１質量％より、多い量のＺｎを含有してもよいので、溶解原料としてＣｕ−Ｚｎ系銅合金のスクラップを使用することができる。 Zn in the copper alloy according to the seamless pipe of the present invention has a smaller effect of improving ductility than Sn, and excess Zn increases the stress corrosion susceptibility, so that it relates to the seamless pipe of the present invention. In the copper alloy, the Sn content is mainly 0.1% by mass or less. If the Zn content in the copper alloy exceeds 0.1% by mass, the stress corrosion sensitivity becomes too high, which is not preferable. Further, in the copper alloy according to the seamless pipe of the present invention, Sn is an essential element, but Zn is an optional element, so the content of Zn in the copper alloy according to the seamless pipe of the present invention is from 0.1% by mass. In addition, the copper alloy according to the seamless pipe of the present invention may contain a larger amount of Zn than 0.01% by mass, which is a general upper limit of the content of other inevitable impurities. Cu-Zn copper alloy scrap can be used as a raw material.
本発明の継目無管に係る該銅合金中のＳｎの含有量をＡ（質量％）、Ｚｎの含有量をＢ（質量％）、Ｚｒの含有量をＣ（質量％）とすると、本発明の継目無管に係る該銅合金では、Ａ＋Ｂは０．６０以下であること、すなわち、下記式（１）：
（１）Ａ＋Ｂ≦０．６０
を満たし、
好ましくはＡ＋Ｂは０．５５以下であること、すなわち、下記式（１ａ）：
（１ａ）Ａ＋Ｂ≦０．５５
を満たす。Ａ＋Ｂが上記範囲内にあることより、熱伝導率が高くなる。一方、Ａ＋Ｂが、０．６０を超えると、熱伝導性が低くなり、熱交換器用伝熱管として適用できなくなる。
In the copper alloy according to the present invention, the Sn content is A (mass%), the Zn content is B (mass%), and the Zr content is C (mass%). In the copper alloy according to the seamless pipe, A + B is 0.60 or less, that is, the following formula (1):
(1) A + B ≦ 0.60
The filling,
A + B is preferably 0.55 or less, that is, the following formula (1a):
(1a) A + B ≦ 0.55
Meet. Since A + B is within the above range, the thermal conductivity is increased. On the other hand, when A + B exceeds 0.60, the thermal conductivity becomes low, and it cannot be applied as a heat exchanger tube for a heat exchanger.
本発明の継目無管に係る該銅合金では、好ましくは更にＡ＋Ｂが０．４０以上であること、すなわち、下記式（３）：
（３）０．４０≦Ａ＋Ｂ
を満たし、且つ、Ｚｒの含有量が０．０６質量％以下であり、
特に好ましくは更にＡ＋Ｂが０．４３以上であること、すなわち、下記式（３ａ）：
（３ａ）０．４３≦Ａ＋Ｂ
を満たし、且つ、Ｚｒの含有量が０．０６質量％以下である。本発明の継目無管に係る該銅合金のように、Ｚｒ等の析出強化元素を含む銅合金の場合、時効析出によって強度が向上する一方、延性低下を引き起こす。本発明の継目無管に係る該銅合金では、延性の低下による加工性の阻害を抑えるべく、Ｚｒの含有量の上限を０．１質量％としてはいるが、厳しい加工性が必要となる場合、例えば、厳しい曲げ条件によるヘアピン曲げ加工や、高性能化の要求により難加工の内面溝形状を転造加工によって作製する場合などにおいては、十分な加工性を維持するために、ＳｎやＺｎを積極的に添加することが望ましい。Ｓｎ及びＺｎは、前記のように、常温での延性を向上させる効果があり、Ｚｒの含有量が０．０１〜０．０６質量％の場合、Ｚｒの含有量を０．０６質量％以下とし、且つ、Ｓｎ及びＺｎの合計量を０．４０質量％以上とすることにより、加工性改善効果を奏する。
In the copper alloy according to the seamless pipe of the present invention, preferably, A + B is 0.40 or more, that is, the following formula (3):
(3) 0.40 ≦ A + B
And the Zr content is 0.06% by mass or less,
Particularly preferably, A + B is 0.43 or more, that is, the following formula (3a):
(3a) 0.43 ≦ A + B
And the Zr content is 0.06% by mass or less. In the case of a copper alloy containing a precipitation strengthening element such as Zr like the copper alloy according to the seamless pipe of the present invention, the strength is improved by aging precipitation, but the ductility is lowered. In the copper alloy according to the seamless pipe of the present invention, the upper limit of the content of Zr is set to 0.1% by mass in order to suppress inhibition of workability due to a decrease in ductility, but severe workability is required. For example, in the case of hairpin bending processing under severe bending conditions, or in the case where a difficult-to-process inner surface groove shape is formed by rolling processing due to a demand for high performance, Sn or Zn is used in order to maintain sufficient workability. It is desirable to add it positively. As described above, Sn and Zn have an effect of improving ductility at normal temperature. When the content of Zr is 0.01 to 0.06% by mass, the content of Zr is set to 0.06% by mass or less. And the workability improvement effect is produced by making the total amount of Sn and Zn 0.40 mass% or more.
本発明の継目無管に係る該銅合金では、Ａ＋Ｂ＋２Ｃは０．４〜０．７であること、すなわち、下記式（２）：
（１）０．４≦Ａ＋Ｂ＋２Ｃ≦０．７
を満たす。
銅合金中のＺｒの含有量が０．１質量％以下であっても、Ｓｎ及びＺｎの含有量が多過ぎると、加工硬化が著しくなり、加工性、特に、冷間での引き抜き加工性が悪くなり、焼き鈍し工程の追加等のコスト増大を招く要因となるので、Ａ＋Ｂ＋２Ｃを０．７以下とする必要がある。
また、Ａ＋Ｂ＋２Ｃを０．４以上とし、且つ、Ｚｒの含有量を０．０１質量％以上とすることにより、厳しい加工性が必要となる場合でも、継目無管の強度を最低限維持することができる。一方、Ａ＋Ｂ＋２Ｃが０．４未満だと、継目無管の強度が不足する。
In the copper alloy according to the seamless pipe of the present invention, A + B + 2C is 0.4 to 0.7, that is, the following formula (2):
(1) 0.4 ≦ A + B + 2C ≦ 0.7
Meet.
Even if the content of Zr in the copper alloy is 0.1% by mass or less, if the content of Sn and Zn is too large, the work hardening becomes remarkable, and the workability, in particular, the cold drawability is improved. It becomes worse and causes an increase in cost such as the addition of an annealing process, so A + B + 2C needs to be 0.7 or less.
Further, by setting A + B + 2C to be 0.4 or more and the Zr content to be 0.01% by mass or more, even when severe workability is required, the strength of the seamless pipe can be kept to a minimum. it can. On the other hand, if A + B + 2C is less than 0.4, the strength of the seamless pipe is insufficient.
本発明の継目無管に係る該銅合金中のＰの含有量は、０．００４〜０．０４０質量％であることが好ましく、０．０１５〜０．０３０質量％であることが特に好ましい。銅合金が、Ｐ元素を０．００４質量％以上含有することにより、材料中の脱酸が十分であることが示される。そして、銅合金中のＰの含有量が、多すぎると、銅合金の熱伝導性が低くなるので、銅合金中のＰの含有量は、０．０４０質量％以下が好ましい。 The content of P in the copper alloy according to the seamless pipe of the present invention is preferably 0.004 to 0.040% by mass, and particularly preferably 0.015 to 0.030% by mass. It is shown that the deoxidation in the material is sufficient when the copper alloy contains 0.004% by mass or more of the P element. And if there is too much content of P in a copper alloy, since the heat conductivity of a copper alloy will become low, 0.040 mass% or less is preferable as content of P in a copper alloy.
本発明の継目無管に係る該銅合金は、冷間での加工性に優れ、強度が高く、且つ、熱伝導性が高いので、管内面に溝が形成される熱交換器用伝熱管の製造用に好適に用いられる。そのため、該銅合金を加工して得られる本発明の継目無管は、冷間での転造加工に優れている。 The copper alloy according to the seamless pipe of the present invention is excellent in cold workability, has high strength, and has high thermal conductivity, and therefore, manufacture of a heat exchanger tube for a heat exchanger in which a groove is formed on the inner surface of the pipe. It is suitably used for. Therefore, the seamless pipe of the present invention obtained by processing the copper alloy is excellent in cold rolling.
本発明の継目無管は、管内面に溝が形成されている内面溝付管であり、熱交換器用の伝熱管として用いられる。 The seamless tube of the present invention is an internally grooved tube having a groove formed on the tube inner surface, and is used as a heat transfer tube for a heat exchanger.
本発明の継目無管は、常法に従って、溶解、鋳造し、所定の元素が所定の含有量で配合されているビレットを得る鋳造工程を行い、次いで、造塊されたビレットを均質化する均質化処理→熱間押出加工→圧延加工又は引抜加工等の冷間加工の順に行い、次いで、冷間で転造加工を行い、管内面にらせん状の溝を形成させ、次いで、時効処理することにより製造される。また、必要に応じて、上記工程内に、中間焼鈍、溶体化処理又は焼入れ処理を加えることもできる。 The seamless pipe of the present invention is subjected to a casting process to obtain a billet in which a predetermined element is blended in a predetermined content by melting and casting in accordance with a conventional method, and then homogenizing the agglomerated billet. Processing → hot extrusion → cold processing such as rolling or drawing, then cold rolling to form a spiral groove on the inner surface of the tube, then aging treatment Manufactured by. Moreover, an intermediate annealing, solution treatment, or a quenching process can also be added in the said process as needed.
該鋳造工程では、例えば、銅の地金及び本発明の継目無管用銅合金の含有元素の地金又は該含有元素と銅の合金を、本発明の継目無管用銅合金中の含有量が、所定の含有量となるように配合して、成分調整を行い、次いで、高周波溶解炉等を用いて、ビレットを鋳造する。 In the casting process, for example, the content of the copper ingot and the alloy of the seamless element copper alloy of the present invention or the alloy of the element and copper in the seamless pipe copper alloy of the present invention, It mix | blends so that it may become predetermined | prescribed content, a component adjustment is performed, and then a billet is cast using a high frequency melting furnace etc. FIG.
Ｚｒは活性な金属なので、溶解時の酸化ロスが多くなるため、成分調整においては、Ｚｒの溶解時の酸化ロスを考慮した配合が必要である。 Since Zr is an active metal, the oxidation loss at the time of dissolution increases. Therefore, in adjusting the components, it is necessary to blend in consideration of the oxidation loss at the time of dissolution of Zr.
また、該鋳造工程では、Ｐを配合することにより、溶湯の流動性が高くなるので、鋳造性が高くなり、ガス孔等の鋳造欠陥の発生が抑制され、また、脱酸効果が得られるので、上記Ｚｒの溶解時の酸化ロスを少なくすることができる。そして、Ｐの配合量が多くなりすぎると、銅合金中のＰ元素の含有量が多くなりすぎるため、熱伝導性が低くなる。そのため、該鋳造工程では、銅合金中のＰ含有量が、０．００４〜０．０４０質量％となるようにＰを配合することが好ましく、０．０１５〜０．０３０質量％となるようにＰを配合することが特に好ましい。 Further, in the casting process, by adding P, the fluidity of the molten metal is increased, so that the castability is improved, the occurrence of casting defects such as gas holes is suppressed, and the deoxidation effect is obtained. The oxidation loss during the dissolution of Zr can be reduced. And when the compounding quantity of P increases too much, since content of P element in a copper alloy will increase too much, thermal conductivity will become low. Therefore, in this casting process, it is preferable to mix | blend P so that P content in a copper alloy may be 0.004-0.040 mass%, and it may become 0.015-0.030 mass%. It is particularly preferable to blend P.
該鋳造工程で得られたビレットを、所定の温度で均質化処理した後、熱間押出加工を行う。また、該熱間押出加工前に、ビレットを加熱するが、この熱間押出加工前の加熱に、均質化処理を兼ねさせることもできる。該熱間押出加工は、マンドレル押出によって行われる。すなわち、加熱前に、冷間で予め穿孔したビレット、あるいは、押出前に熱間で穿孔したビレットに、マンドレルを挿入した状態で、熱間押出を行なって、継目無熱間押出素管を得る。 The billet obtained in the casting process is homogenized at a predetermined temperature and then subjected to hot extrusion. Moreover, although a billet is heated before this hot extrusion process, the heating before this hot extrusion process can also be made to serve as a homogenization process. The hot extrusion process is performed by mandrel extrusion. That is, hot extruding is performed with a mandrel inserted into a billet that has been previously perforated cold before heating, or a billet that has been perforated hot before extrusion to obtain a seamless hot extruded element tube. .
該熱間押出加工により得られた該継目無熱間押出素管を、冷却した後、圧延加工や引き抜き加工等の冷間加工を行い、管の外径及び肉厚を減じていく。 After the seamless hot-extrusion element tube obtained by the hot extrusion process is cooled, cold processing such as rolling or drawing is performed to reduce the outer diameter and thickness of the pipe.
該時効処理は、該冷間での転造加工を施した銅管を、４００〜７００℃で加熱し、冷却することにより行なわれる。 The aging treatment is performed by heating and cooling the cold-rolled copper tube at 400 to 700 ° C.
該転造加工は、引抜加工後の内面平滑素管内に、外面にらせん状の溝加工を施した転造プラグを配置して、高速回転する複数の転造ボールによって、管の外側から押圧して、管の内面に転造プラグの溝を転写することにより行われる（特開２００３−１９１００６号公報参照）。 In the rolling process, a rolling plug with a spiral groove formed on the outer surface is placed in the smooth inner pipe after drawing, and pressed from the outside of the pipe by a plurality of rolling balls rotating at high speed. This is done by transferring the groove of the rolled plug to the inner surface of the tube (see Japanese Patent Application Laid-Open No. 2003-191006).
近年、管内面のらせん溝の形状については、伝熱管の高性能化の要求のもと、らせん角度を大きくしたり、フィンの高さを高くしたり、フィンの幅を小さくしたり、各種の方策が講じられている（特開２００１−３３１８５号公報参照）。このような加工は、転造加工性を低下させることになるので、転造加工性が悪い銅合金だと、転造速度を遅くすることが必要となったり、正常な溝の形成自体が困難となったりする。また、最近では、地球温暖化防止等の見地から、従来のフロン系冷媒から炭酸ガス冷媒に転換が図られてきている。このような炭酸ガス冷媒用の内面溝付管においては、冷媒の運転圧力が高いので、従来より厚肉化することが必要なため、転造加工による内面溝の形成がより難しくなってきている。 In recent years, with regard to the shape of the spiral groove on the inner surface of the tube, various demands for higher performance of heat transfer tubes have been made, such as increasing the helix angle, increasing the height of the fin, reducing the width of the fin, Measures have been taken (see JP 2001-33185 A). Such a process reduces the rolling processability, so if the copper alloy has poor rolling processability, it is necessary to slow the rolling speed or it is difficult to form a normal groove itself. It becomes. Recently, from the viewpoint of prevention of global warming and the like, conversion from a conventional chlorofluorocarbon refrigerant to a carbon dioxide refrigerant has been attempted. In such an inner grooved tube for carbon dioxide refrigerant, since the operating pressure of the refrigerant is high, it is necessary to increase the thickness of the refrigerant, and therefore it is more difficult to form the inner groove by rolling. .
本発明の銅合金は、上述した組成を有するので、優れた転造加工性を有している。また、本発明の銅合金は、該冷間での転造加工で、内面溝のらせん角度を大きくしたり、フィンの高さを高くしたり、フィンの幅を小さくしたり、あるいは、厚肉化したりしても、転造加工性が良好であり、本発明の継目無管には正常なフィンが形成されている。 Since the copper alloy of the present invention has the above-described composition, it has excellent rolling processability. In addition, the copper alloy of the present invention can be formed by increasing the helical angle of the inner surface groove, increasing the height of the fin, reducing the width of the fin, Even if it is made into a roll, the rolling processability is good, and normal fins are formed in the seamless pipe of the present invention.
このようにして作製された本発明の継目無管は、熱交換器用の伝熱管としてコイル形状に巻き取られ、熱交換器（クロスフィンチューブ型熱交換器）作製工程に供される。 The seamless tube of the present invention thus manufactured is wound up in a coil shape as a heat transfer tube for a heat exchanger, and used for a heat exchanger (cross fin tube heat exchanger) manufacturing process.
該クロスフィンチューブ型熱交換器は、空気側のアルミニウムフィンと冷媒側の伝熱管が一体に組付けられて構成されているものである。 The cross fin tube type heat exchanger is constructed by integrally assembling an air-side aluminum fin and a refrigerant-side heat transfer tube.
該クロスフィンチューブ型熱交換器作製工程では、先ず、プレス加工等により、所定の組付け孔が複数形成されたアルミニウムプレートフィンを作製する。 In the cross fin tube type heat exchanger manufacturing step, first, an aluminum plate fin in which a plurality of predetermined assembly holes are formed is manufactured by pressing or the like.
次いで、得られたアルミニウムプレートフィンを積層した後、前記組付け孔の内部に、伝熱管を挿通する。該伝熱管は、該冷間での転造加工によって内面に溝が形成された本発明の継目無管を、定尺切断及びヘアピン曲げ加工して作製される。 Next, after stacking the obtained aluminum plate fins, a heat transfer tube is inserted into the assembly hole. The heat transfer tube is produced by subjecting the seamless tube of the present invention in which a groove is formed on the inner surface by the cold rolling process to a regular cut and a hairpin bending process.
次いで、該伝熱管を、該アルミニウムプレートフィンに拡管固着し、ヘアピン曲げ加工を施した側とは反対側の伝熱管端部に、Ｕベンド管をロウ付けして、熱交換器を作製する。 Next, the heat transfer tube is expanded and fixed to the aluminum plate fin, and a U-bend tube is brazed to the end of the heat transfer tube opposite to the side subjected to the hairpin bending process, thereby producing a heat exchanger.
このような工程中で、本発明の継目無管は、ヘアピン曲げ加工という強加工が施される。該ヘアピン曲げ加工は、継目無管に中子を挿入した上で、管をＵ字状に曲げ加工するような加工である。 In such a process, the seamless pipe of the present invention is subjected to strong processing called hairpin bending. The hairpin bending process is a process of bending a tube into a U-shape after inserting a core into a seamless tube.
また、本発明の継目無管は、高強度の内面溝付ヒートパイプ用としても適用可能である。 The seamless pipe of the present invention can also be applied to a high-strength internally grooved heat pipe.
次に、実施例を挙げて本発明を更に具体的に説明するが、これは単に例示であって、本発明を制限するものではない。
（実施例）
（銅合金の製造）
Ｃｕ、Ｓｎ及びＺｎの地金又はスクラップ、並びにＣｕ−Ｚｒ母合金及びＣｕ−Ｐ母合金を用いて、表２に示す成分に配合し、高周波溶解炉を用いてφ２５４ｍｍの鋳塊を製造後、熱間押出を行い、φ８１ｍｍ×ｔ１．５ｍｍ管（押出素管）とした。そして、該押出素管を、熱間押出後直ちに水槽へ投入して冷却した。次いで、φ８１ｍｍ×ｔ１．５ｍｍ管を、冷間で圧延加工し、さらに冷間で引抜加工及び適宜中間焼鈍を行って、転造加工用の原管（引き抜き加工素管）を作製した。
EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.
(Example)
(Manufacture of copper alloys)
Using Cu, Sn and Zn ingots or scraps, and Cu-Zr master alloy and Cu-P master alloy, blended with the components shown in Table 2, after producing a 254 mm ingot using a high frequency melting furnace, Hot extrusion was performed to obtain a φ81 mm × t1.5 mm tube (extrusion tube). And this extrusion element pipe was thrown into the water tank immediately after hot extrusion, and was cooled. Next, a φ81 mm × t1.5 mm tube was cold-rolled, and further cold-drawn and appropriately subjected to intermediate annealing, thereby producing a raw tube for rolling (drawing-processed raw tube).
（加工性評価）
１．転造加工性評価
＜転造加工試験＞
上記で得た引抜加工素管の転造加工を行い、図１及び表１に示す形状の内面溝付継目無管を作製した。なお、図１は、転造加工試験の溝形状を示す図である。
比較的転造加工性の容易な溝形状として、溝形状１を選択した。また、高性能化を目的として、フィン高さを高く、フィン頂角を小さく、らせん角を大きくした難加工性の溝形状として、溝形状２を選択した。
(Processability evaluation)
1. Rolling processability evaluation <Rolling process test>
The drawn blank pipe obtained above was rolled to produce seamless pipes with inner grooves having the shapes shown in FIG. 1 and Table 1. In addition, FIG. 1 is a figure which shows the groove shape of a rolling process test.
The groove shape 1 was selected as a groove shape that is relatively easy to roll. Further, for the purpose of improving the performance, the groove shape 2 was selected as a difficult-to-work groove shape having a high fin height, a small fin apex angle, and a large helix angle.
＊フィン幅ｗ：フィンの高さ方向の真ん中の位置のフィン幅である。
＊フィンピッチＰｆ：フィンの根本の位置でのフィン同士の間隔である。
* Fin width w: Fin width at the center position in the height direction of the fin.
* Fin pitch Pf: The distance between fins at the base position of the fins.
＜評価方法＞
正常なフィン形状が得られたものを「○」と、正常なフィン形状が得られなかったものを「×」とした。その結果を表３に示す。
なお、正常なフィン形状が得られたかったものとは、転造加工時に、転造プラグの溝にメタルが十分に充満しない部分が生じたものである。
<Evaluation method>
The case where a normal fin shape was obtained was indicated as “◯”, and the case where a normal fin shape was not obtained was indicated as “x”. The results are shown in Table 3.
In addition, what the normal fin shape was not obtained means that a portion where the metal is not sufficiently filled in the groove of the rolled plug occurred during the rolling process.
（機械的性質評価）
上記転造加工試験により得た溝形状の継目無管を、表４に示す時効処理温度にて時効処理を行った後、ＪＩＳ Ｚ ２２４１に準じ、０．２％耐力、引張強さを測定した。その結果を表４に示す。
なお、時効処理を、Ｚｒの含有量によって、４３０℃、５２０℃又は６５０℃のいずれかの温度にて行った。表２及び表３中の試験Ｎｏ．７については、５２０℃と、６５０℃と、の２種類の温度で時効処理を行った。
（導電率評価）
上記転造加工試験により得た溝形状の継目無管を、表４に示す時効処理温度にて時効処理を行った後、四端子法にて導電率を測定した。その結果を表４に示す。
(Mechanical property evaluation)
The groove-shaped seamless pipe obtained by the rolling test was subjected to aging treatment at the aging treatment temperature shown in Table 4, and then 0.2% proof stress and tensile strength were measured according to JIS Z2241. . The results are shown in Table 4.
The aging treatment was performed at a temperature of 430 ° C., 520 ° C., or 650 ° C. depending on the Zr content. Test No. in Table 2 and Table 3 For No. 7, aging treatment was performed at two temperatures of 520 ° C. and 650 ° C.
(Conductivity evaluation)
The groove-shaped seamless pipe obtained by the rolling process test was subjected to aging treatment at the aging treatment temperature shown in Table 4, and then the conductivity was measured by the four-terminal method. The results are shown in Table 4.
（加工性評価）
２．ヘアピン曲げ加工性評価
＜ヘアピン曲げ加工試験＞
上記転造加工試験により得た溝形状１の継目無管を、表４に示す時効処理温度にて時効処理を行った後、管内に心金を挿入し、ベンダーで曲げ加工を行う公知のヘアピン曲げ加工方法により、図２に示す形状のヘアピン曲げ管を作製した。なお、曲げピッチＰ＝１６ｍｍとした。
＜評価方法＞
曲げ部（図２中、矢印１０で示す部分）にしわの発生がなかったものを合格とした。その結果を表４に示す。
(Processability evaluation)
2. Hairpin bending processability evaluation <Hairpin bending process test>
A known hairpin in which a seamless pipe having a groove shape 1 obtained by the rolling process test is subjected to aging treatment at the aging treatment temperature shown in Table 4, and then a mandrel is inserted into the pipe and bent by a bender. A hairpin bending tube having the shape shown in FIG. 2 was produced by a bending method. The bending pitch P was 16 mm.
<Evaluation method>
A bent portion (portion indicated by an
なお、表中には、性能評価の指標とするために、りん脱酸銅Ｃ１２２０についても測定した結果を記載した。 In addition, in the table | surface, in order to use as a parameter | index of performance evaluation, the result measured also about the phosphorus deoxidation copper C1220 was described.
＊表２中の数値は、「質量％」である。 * Numerical values in Table 2 are “% by mass”.
１）Ｃ１２２０：りん脱酸銅Ｃ１２２０ 1) C1220: Phosphorus deoxidized copper C1220
１）Ｃ１２２０：りん脱酸銅Ｃ１２２０ 1) C1220: Phosphorus deoxidized copper C1220
＜試験Ｎｏ．１〜２４＞
Ｎｏ．１〜２４のいずれも、耐力、引張強さ、導電率のいずれについても良好であり、また、溝形状１の転造加工試験に合格し、加工性は良好であった。このことから、Ｎｏ．１〜２４は、いずれも、加工性に優れ、強度が高く、且つ、熱伝導性が高く、総合的に性能のバランスが良い継目無管であった。
特に、Ｎｏ．１〜１０、２１及び２２は、難加工性の溝形状２の転造加工試験及びヘアピン曲げ加工試験も合格し、冷間での加工性に関し顕著な加工性を示した。
Ｎｏ．２１は、Ｐ含有量が高いため、Ｎｏ．９と比較して、導電率が若干低くなり、熱伝導率が若干劣る。
Ｎｏ．２２は、Ｐ含有量が低いため、Ｎｏ．９と比較して、脱酸が十分ではなく、熱交換器組み立て工程中の、炉中ろう付けをする際に、雰囲気（水素ガス）の影響によって、水素脆化を生じるものが見られた。
<Test No. 1-24>
No. All of Nos. 1 to 24 were good in terms of proof stress, tensile strength, and electrical conductivity, passed the rolling process test of the groove shape 1, and had good workability. From this, No. Each of Nos. 1 to 24 was a seamless tube having excellent workability, high strength, high thermal conductivity, and a good overall balance of performance.
In particular, no. 1 to 10, 21 and 22 passed the rolling process test and the hairpin bending process test of the difficult-to-process groove shape 2, and showed remarkable processability with respect to the processability in the cold.
No. No. 21 has a high P content. Compared to 9, the conductivity is slightly lower and the thermal conductivity is slightly inferior.
No. No. 22 has a low P content. Compared to 9, deoxidation was not sufficient, and when the furnace was brazed during the heat exchanger assembly process, hydrogen embrittlement was observed due to the influence of the atmosphere (hydrogen gas).
＜Ｎｏ．３１及び３３＞
Ｚｒ含有量が低いため、耐力、引張強さが不十分であった。
＜Ｎｏ．３９、４０及び４１＞
Ａ＋Ｂ＋２Ｃの値が低過ぎるため、耐力、引張強さが不十分であった。
＜Ｎｏ．３４、３５及び３６＞
Ａ＋Ｂ＋２Ｃの値が高過ぎるため、加工性が悪く、溝形状１の転造加工試験が不合格であった。そのため、溝形状２の転造加工試験及びヘアピン曲げ加工試験を行わなかった。
＜Ｎｏ．３７及び３８＞
Ｚｒ含有量が多過ぎるため、加工性が悪く、溝形状１の転造加工試験が不合格であった。そのため、溝形状２の転造加工試験及びヘアピン曲げ加工試験を行わなかった。
＜Ｎｏ．３２＞
Ａ＋Ｂの値が高過ぎるため、導電率が低過ぎる結果となった。そのため、熱伝導率が低過ぎて、熱交換器用としての使用に適さない。
＜Ｎｏ．４２＞
強度、導電率、加工性とも良好な結果であったが、Ｚｎ含有量が多過ぎるため、応力腐食割れ感受性が高くなり、熱交換器用としての使用に適さない。
<No. 31 and 33>
Since the Zr content is low, the yield strength and tensile strength were insufficient.
<No. 39, 40 and 41>
Since the value of A + B + 2C was too low, the yield strength and tensile strength were insufficient.
<No. 34, 35 and 36>
Since the value of A + B + 2C was too high, the workability was poor, and the rolling process test for the groove shape 1 was rejected. Therefore, the rolling process test of the groove shape 2 and the hairpin bending process test were not performed.
<No. 37 and 38>
Since there was too much Zr content, workability was bad and the rolling process test of the groove shape 1 was disqualified. Therefore, the rolling process test of the groove shape 2 and the hairpin bending process test were not performed.
<No. 32>
Since the value of A + B was too high, the conductivity was too low. For this reason, the thermal conductivity is too low to be suitable for use as a heat exchanger.
<No. 42>
Although strength, electrical conductivity, and workability were good results, since the Zn content is too high, the stress corrosion cracking susceptibility becomes high and is not suitable for use as a heat exchanger.
本発明によれば、加工性、特に、冷間での転造加工性及びヘアピン曲げ加工性に優れ、強度が高く、ロウ付けによる強度低下が少なく、且つ、熱伝導性が高い継目無管を提供することができるので、高性能な熱交換器又は冷媒として二酸化炭素を用いる熱交換器を製造できる。また、該継目無管は、この他、高強度の内面溝付ヒートパイプとして適用することも可能である。 According to the present invention, a seamless tube having excellent workability, in particular, cold-rolling workability and hairpin bending workability, high strength, little strength reduction due to brazing, and high thermal conductivity. Therefore, a high-performance heat exchanger or a heat exchanger using carbon dioxide as a refrigerant can be manufactured. In addition, the seamless pipe can also be applied as a heat pipe with a high strength inner surface groove.
１０ 曲げ部
Ｄ 外径
ｔ 肉厚
ｈ フィン高さ
α フィン頂角
ｗ フィン幅
Ｐｆ フィンピッチ
Ｐ 曲げピッチ
10 Bending part D Outer diameter t Thickness h Fin height α Fin apex angle w Fin width Pf Fin pitch P Bending pitch
Claims (2)
該銅合金は、Ｓｎと、０〜０．１質量％のＺｎと、０．０１〜０．０６質量％のＺｒと、０．００４〜０．０４質量％のＰと、を含有し、残部Ｃｕ及び不可避不純物からなり、
該銅合金中のＳｎ、Ｚｎ及びＺｒの含有量が、下記式（１）、（２）及び（３）：
（１）Ａ＋Ｂ≦０．６０
（２）０．４≦Ａ＋Ｂ＋２Ｃ≦０．７
（３）０．４１≦Ａ＋Ｂ
（式中、ＡはＳｎの含有量（質量％）を示し、ＢはＺｎの含有量（質量％）を示し、ＣはＺｒの含有量（質量％）を示す。）
のいずれも満たすこと、
を特徴とする継目無管。 It is a seamless pipe made of copper alloy obtained by processing copper alloy,
The copper alloy contains Sn, 0 to 0.1% by mass of Zn, 0.01 to 0.06 % by mass of Zr, and 0.004 to 0.04% by mass of P, and the balance Consisting of Cu and inevitable impurities,
The contents of Sn, Zn and Zr in the copper alloy are the following formulas (1) , (2) and (3) :
(1) A + B ≦ 0.60
(2) 0.4 ≦ A + B + 2C ≦ 0.7
(3) 0.41 ≦ A + B
(In the formula, A represents the Sn content (mass%), B represents the Zn content (mass%), and C represents the Zr content (mass%).)
Meeting any of the
Seamless tube characterized by
（３ａ）０．４３≦Ａ＋Ｂ
（式中、Ａ、Ｂ及びＣは、前記と同義である。）
を満たすことを特徴とする請求項１記載の継目無管。 The contents of Sn, Zn and Zr in the copper alloy are further represented by the following formula (3a):
(3 a ) 0.4 3 ≦ A + B
(In the formula, A, B, and C are as defined above.)
The seamless pipe according to claim 1, wherein:
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| JP2008097842A JP5208562B2 (en) | 2008-04-04 | 2008-04-04 | Seamless pipe |
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|---|---|---|---|
| JP2008097842A JP5208562B2 (en) | 2008-04-04 | 2008-04-04 | Seamless pipe |
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| JPS5461026A (en) * | 1977-10-24 | 1979-05-17 | Sumitomo Electric Ind Ltd | Copper alloy for lead of semiconductor device |
| JP2758536B2 (en) * | 1992-08-11 | 1998-05-28 | 三菱伸銅株式会社 | Welded copper alloy pipe with inner groove |
| JPH06184669A (en) * | 1992-12-18 | 1994-07-05 | Mitsubishi Materials Corp | Pitting corrosion resistant copper alloy piping for feeding water and hot water |
| WO1994010352A1 (en) * | 1992-10-27 | 1994-05-11 | Mitsubishi Materials Corporation | Pitting-resistant copper alloy pipe for water and hot-water supply |
| JP4387027B2 (en) * | 2000-03-07 | 2009-12-16 | 三菱伸銅株式会社 | Pitting corrosion resistant copper base alloy tubing |
| JP5138170B2 (en) * | 2006-02-12 | 2013-02-06 | 三菱伸銅株式会社 | Copper alloy plastic working material and method for producing the same |
| JP4694527B2 (en) * | 2007-03-30 | 2011-06-08 | 株式会社コベルコ マテリアル銅管 | Copper alloy tube for heat-resistant and high-strength heat exchanger and method for producing the same |
| JP5260109B2 (en) * | 2007-03-31 | 2013-08-14 | 株式会社コベルコ マテリアル銅管 | Copper alloy member and heat exchanger |
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