JP2835271B2 - Copper alloy tube with inner protective film for hot and cold water supply and method for producing the same - Google Patents
Copper alloy tube with inner protective film for hot and cold water supply and method for producing the sameInfo
- Publication number
- JP2835271B2 JP2835271B2 JP28988693A JP28988693A JP2835271B2 JP 2835271 B2 JP2835271 B2 JP 2835271B2 JP 28988693 A JP28988693 A JP 28988693A JP 28988693 A JP28988693 A JP 28988693A JP 2835271 B2 JP2835271 B2 JP 2835271B2
- Authority
- JP
- Japan
- Prior art keywords
- copper alloy
- weight
- protective film
- water supply
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000001681 protective effect Effects 0.000 title claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 39
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000010949 copper Substances 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 238000007747 plating Methods 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 229910000765 intermetallic Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011253 protective coating Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 20
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 17
- 229910001431 copper ion Inorganic materials 0.000 description 17
- 238000010828 elution Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910017482 Cu 6 Sn 5 Inorganic materials 0.000 description 2
- 229910017755 Cu-Sn Inorganic materials 0.000 description 2
- 229910017927 Cu—Sn Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101150096674 C20L gene Proteins 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 102220543923 Protocadherin-10_F16L_mutation Human genes 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 101100445889 Vaccinia virus (strain Copenhagen) F16L gene Proteins 0.000 description 1
- 101100445891 Vaccinia virus (strain Western Reserve) VACWR055 gene Proteins 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Rigid Pipes And Flexible Pipes (AREA)
- Chemically Coating (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は給水給湯配管に使用され
る内面をＳｎめっきした給水給湯用内面保護皮膜付き銅
合金管及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper alloy pipe having an inner surface protective film for water / hot water supply, the inner surface of which is used for a water / hot water supply pipe and having an inner surface coated with Sn.
【０００２】[0002]
【従来の技術】従来使用されている給水・給湯用配管材
料としては、銅管、亜鉛めっき鋼管、塩化ビニル管、ス
テンレス鋼管又は塩化ビニルライニング鋼管等がある。
この中でも特に銅管は、施工性及び耐食性が優れ、長尺
物であってもコイル状に巻き上げることができるので運
搬が容易であるという利点がある。そのため、銅管は給
水給湯用配管として広く使用されている。2. Description of the Related Art Conventionally used piping materials for water supply and hot water supply include copper pipes, galvanized steel pipes, vinyl chloride pipes, stainless steel pipes and vinyl chloride-lined steel pipes.
Among them, the copper pipe is particularly advantageous in that it has excellent workability and corrosion resistance, and can be easily transported because it can be rolled up into a coil even if it is long. Therefore, copper pipes are widely used as water supply and hot water supply pipes.
【０００３】しかし、ある種の水質、例えばｐＨが低い
水及び遊離炭酸が多い水等では、管壁から銅イオンが溶
出して、上水中の銅イオン濃度が公的に定められている
上水の水質基準である１ｐｐｍを超える場合がある。ま
た、銅イオン濃度が１ｐｐｍ以下であっても、白布等が
青色に着色されることがあるので、水中への銅イオンの
溶出は少ないことが望ましい。この銅イオン溶出対策と
しては、従来、給水中への薬品投与、銅イオン溶出抑制
合金の開発、又は管内面の被覆等が行われてきた。給水
中への薬品投与及び銅イオン溶出抑制合金の開発は銅イ
オンの溶出防止上、効果はあるものの、製造コストが高
くなり、実用的でない。また、管内面被覆としては、銅
管内面に低融点金属粉とフラックスとを塗布し、加熱に
より被覆するもの（特開昭６０−２００９５４号、特開
昭６０−２００９７５号、特開昭６２−６１７１７号、
特開昭６２−６１７１８号）と、銅管内面にＣｕ−Ｓｎ
合金層を形成したもの（特開昭６１ー２２１３５９号）
と、銅管内面に溶融めっきしたもの（特開昭６２−６１
７１６号）等が公知であるが、これらの方法は管の直径
に対し長さが短い管には適用できるが、管の直径に対し
長さが長い管には適用できなかった。However, in certain water qualities, for example, water having a low pH and water having a large amount of free carbonic acid, copper ions are eluted from the tube wall, and the water concentration in which the copper ion concentration in the water is officially determined. May exceed 1 ppm, which is the standard for water quality. Further, even when the copper ion concentration is 1 ppm or less, the white cloth or the like may be colored blue, so that it is desirable that the copper ions be eluted into the water little. Conventionally, as a countermeasure against the copper ion elution, administration of a chemical into water supply, development of an alloy for suppressing copper ion elution, coating of the inner surface of the pipe, and the like have been conventionally performed. The administration of chemicals into the water supply and the development of copper ion elution control alloys are effective in preventing the elution of copper ions, but they increase the production cost and are not practical. As the coating on the inner surface of the tube, a low-melting metal powder and a flux are applied to the inner surface of a copper tube and coated by heating (Japanese Patent Application Laid-Open Nos. 60-200954, 60-200975, 62-200975). No. 61717,
JP-A-62-61718) and that Cu-Sn
Having an alloy layer (JP-A-61-221359)
And hot-dip plating on the inner surface of a copper tube (Japanese Patent Laid-Open No. 62-61)
No. 716) is known, but these methods can be applied to a tube whose length is shorter than the diameter of the tube, but cannot be applied to a tube whose length is longer than the diameter of the tube.
【０００４】そこで、管内面被覆法におけるこれらの欠
点を解決するために、銅管内面に無電解錫めっきを施こ
す管内面被覆法が提案された（特開平４−４５２８２
号、特開平４−９９１８０号）。Therefore, in order to solve these drawbacks in the tube inner surface coating method, a tube inner surface coating method in which electroless tin plating is applied to the inner surface of a copper tube has been proposed (Japanese Patent Laid-Open No. 4-45282).
No., JP-A-4-99180).
【０００５】この銅管内面に無電解錫めっきを施こす管
内面被覆法は、製造コストが低いと共に、管の直径に対
し長さが長い管にも適用でき、特に銅管がコイル状のま
までも被覆できるという利点があるため、極めて有用な
技術である。また、この技術は、従前のＳｎ被覆銅管で
問題となっていた孔食に対しても耐食性を有するという
利点がある。[0005] This tube inner surface coating method in which the inner surface of a copper tube is subjected to electroless tin plating has a low manufacturing cost and can be applied to a tube whose length is longer than the diameter of the tube. However, it is an extremely useful technique because it has the advantage that it can be coated. In addition, this technique has an advantage that it has corrosion resistance to pitting corrosion, which has been a problem in conventional Sn-coated copper tubes.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、この従
来の無電解錫めっきを施した銅管は、給水・給湯用配管
としての使用に伴ってしだいに表面の自然電位が上昇
し、ついには母材の自然電位を上回って、孔食の危険性
が高くなるという問題点があった。However, the conventional electroless tin-plated copper pipe gradually increases its natural potential on its surface as it is used as a water supply / hot water supply pipe, and eventually the base metal is used. And the risk of pitting corrosion increases.
【０００７】この原因としては以下のように考えられ
る。使用当初においては、表面にＳｎが存在するため、
母材よりも高い電位を示すことはないが、時間の経過と
共に、Ｓｎめっき層と管本体のＣｕとの間で拡散反応が
進行し、Ｃｕ−Ｓｎ金属間化合物であるε相（Ｃｕ3Ｓ
ｎ相）が成長し、このε相が表面にまで達する。このε
相は母材の自然電位より貴な酸化皮膜を形成するため、
ε相に欠落部（ピンホール又は擦過傷等）があると、母
材が孔食を受ける危険性が高まる。この現象は使用環境
が高温であるほど顕著となり、１００℃に近い湯を扱う
給湯環境においては、早期に発生する虞がある。The cause is considered as follows. At the beginning of use, since Sn exists on the surface,
Although it does not show a potential higher than that of the base material, the diffusion reaction proceeds between the Sn plating layer and Cu of the tube body with the passage of time, and the ε phase (Cu 3 S) which is a Cu—Sn intermetallic compound is formed.
n phase) and the ε phase reaches the surface. This ε
Since the phase forms an oxide film that is more noble than the natural potential of the base material,
If there is a missing portion (such as a pinhole or abrasion) in the ε phase, the risk of pitting of the base material increases. This phenomenon becomes more remarkable as the use environment becomes hotter, and may occur early in a hot water supply environment where hot water close to 100 ° C. is used.
【０００８】本発明はかかる問題点に鑑みてなされたも
のであって、保護皮膜の表面に孔食の発生原因となるε
相が生成することを抑制することにより、銅イオンの溶
出を防止して耐孔食性を高めた給水給湯用内面保護皮膜
付き銅合金管及びその製造方法を提供することを目的と
する。[0008] The present invention has been made in view of the above problems, and ε, which causes pitting corrosion on the surface of the protective film, has been developed.
An object of the present invention is to provide a copper alloy tube with an inner surface protective film for water supply and hot water supply, which suppresses generation of a phase to prevent elution of copper ions and enhances pitting corrosion resistance, and a method for producing the same.
【０００９】[0009]
【課題を解決するための手段】本発明に係る給水給湯用
内面保護皮膜付き銅合金管は、Ｚｎ及びＭｎの少なくと
も１種を総量で０．０２重量％以上含有し、Ｚｎ含有量
を５重量％以下、Ｍｎ含有量を３重量％以下に規制し、
残部が銅及び不可避的不純物である銅合金からなる管本
体と、この銅合金管本体の内面に設けられＳｎ及び不可
避的不純物からなる保護皮膜と、を有することを特徴と
する。Means for Solving the Problems A copper alloy tube with an inner protective film for hot and cold water supply according to the present invention contains at least one of Zn and Mn in a total amount of 0.02% by weight or more, and has a Zn content of 5% by weight. % Or less, the Mn content is restricted to 3% by weight or less,
The balance is characterized by having a tube main body made of copper and a copper alloy which is an unavoidable impurity, and a protective film provided on the inner surface of the copper alloy tube main body and made of Sn and an unavoidable impurity.
【００１０】この保護皮膜は、Ｓｎ、ＳｎとＣｕとの金
属間化合物及び不可避的不純物からなるものであっても
よく、この場合は、この保護皮膜の表面にＣｕ3Ｓｎが
実質的に存在しないことが必要である。This protective film may be composed of Sn, an intermetallic compound of Sn and Cu, and unavoidable impurities. In this case, Cu 3 Sn does not substantially exist on the surface of the protective film. It is necessary.
【００１１】また、保護皮膜は、ＳｎとＣｕとの金属間
化合物及び不可避的不純物からなるものであってもよ
い。この場合も、この保護皮膜の表面にＣｕ3Ｓｎが実
質的に存在しないことが必要である。The protective film may be made of an intermetallic compound of Sn and Cu and unavoidable impurities. Also in this case, it is necessary that Cu 3 Sn does not substantially exist on the surface of the protective film.
【００１２】更に、前記銅合金管本体は、Ｐ、Ｂ、Ｍｇ
及びＳｉからなる群から選択された少なくとも１種の元
素を総量で０．２０重量％以下含有していてもよい。Further, the copper alloy pipe main body is made of P, B, Mg.
And at least one element selected from the group consisting of Si and Si in a total amount of 0.20% by weight or less.
【００１３】更にまた、前記銅合金管本体は、Ａｌ、Ｓ
ｎ及びＮｉからなる群から選択された少なくとも１種の
元素を総量で２重量％以下含有していてもよい。Furthermore, the copper alloy tube main body is made of Al, S
At least one element selected from the group consisting of n and Ni may be contained in a total amount of 2% by weight or less.
【００１４】更にまた、前記保護皮膜の管周方向の平均
厚さは０．２乃至４μｍであることが好ましい。Further, it is preferable that the average thickness of the protective film in the circumferential direction of the tube is 0.2 to 4 μm.
【００１５】本発明に係る給水給湯用内面保護皮膜付き
銅合金管の製造方法は、Ｚｎ及びＭｎの少なくとも１種
を総量で０．０２重量％以上含有し、Ｚｎ含有量を５重
量％以下、Ｍｎ含有量を３重量％以下に規制し、残部が
銅及び不可避的不純物である銅合金からなる管本体の内
面に、Ｓｎめっき層を形成することを特徴とする。The method for producing a copper alloy tube with an inner protective film for hot and cold water supply according to the present invention contains at least one of Zn and Mn in a total amount of 0.02% by weight or more, and has a Zn content of 5% by weight or less. The Mn content is regulated to 3% by weight or less, and the Sn plating layer is formed on the inner surface of the tube main body whose balance is made of copper and a copper alloy which is an unavoidable impurity.
【００１６】なお、Ｃｕ3Ｓｎはε相、Ｃｕ6Ｓｎ5はη
相である。Note that Cu 3 Sn is an ε phase, and Cu 6 Sn 5 is an η phase.
Phase.
【００１７】[0017]
【作用】本発明者らは種々研究を行った結果、内面に錫
めっきを施した銅管において、仮にη相がＳｎめっき層
の表面（銅管内面）に生成しても、ε相が表面に生成さ
れなければ孔食の危険性がないことを見出した。また、
このε相の生成を抑制するためには、ＣｕがＳｎめっき
層中をその表面に向けて拡散することを防止すればよ
く、このＣｕの拡散を防止するために、銅合金母材中に
Ｚｎ又はＭｎを添加すればよいことを見いだした。これ
により、使用中に温度上昇がある給湯環境においても、
孔食の危険性が解消される。本発明はこのような知見に
基いて完成されたものである。銅合金管の内面にＳｎを
無電解めっき法などによりめっきすると、経時的には、
このＳｎめっき保護皮膜と、銅合金管本体との界面で、
ＣｕとＳｎとの金属間化合物が生成する。従って、銅合
金管本体の内面にＳｎをめっきして形成した保護皮膜
は、Ｓｎのみの状態から、Ｓｎと、Ｃｕ3Ｓｎ（ε相）
及びＣｕ6Ｓｎ5（η相）とが混在した状態となる。この
ように、保護皮膜がＳｎ単層の場合に限らず、Ｓｎのほ
かにε相及びη相が混在した状態でも、孔食の防止効果
は奏される。しかし、前述のごとく、ε相が保護皮膜の
表面に生成すると、孔食が発生するため、このε相が保
護皮膜の表面に生成しないようにすることが必要であ
る。The present inventors have conducted various studies. As a result, even if an η phase is formed on the surface of the Sn plating layer (the inner surface of the copper tube), a ε phase is formed on the surface of the Sn-plated copper tube. Found that there is no danger of pitting if not produced. Also,
In order to suppress the generation of the ε phase, it is only necessary to prevent Cu from diffusing in the Sn plating layer toward its surface. In order to prevent the diffusion of Cu, Zn is contained in the copper alloy base material. Alternatively, it has been found that Mn may be added. As a result, even in a hot water supply environment where the temperature rises during use,
The risk of pitting is eliminated. The present invention has been completed based on such findings. When Sn is plated on the inner surface of the copper alloy tube by an electroless plating method or the like,
At the interface between the Sn plating protective film and the copper alloy tube main body,
An intermetallic compound of Cu and Sn is generated. Therefore, the protective film formed by plating Sn on the inner surface of the copper alloy tube main body is changed from the state of only Sn to Sn and Cu 3 Sn (ε phase).
And Cu 6 Sn 5 (η phase) are mixed. As described above, the effect of preventing pitting corrosion is exhibited not only when the protective film is a single Sn layer but also when ε phase and η phase are mixed in addition to Sn. However, as described above, when the ε phase is formed on the surface of the protective film, pitting occurs. Therefore, it is necessary to prevent the ε phase from being generated on the surface of the protective film.
【００１８】以下、本発明にて規定した各構成要件の限
定理由について説明する。Hereinafter, the reasons for limiting each of the constituent elements specified in the present invention will be described.
【００１９】管本体を構成する銅合金母材中のＺｎ，Ｍ
ｎ合金成分 銅合金中に、Ｚｎ及びＭｎを単独で、又はその双方を、
総量で０．０２重量％以上含有することが必要である。
これにより、ε相の成長が抑制される。この場合に、ε
相の成長抑制効果を得るためには、Ｚｎ及び／又はＭｎ
は、総量で０．０２重量％以上添加する必要があり、よ
り効果的にするためには０．０５重量％以上が望まし
い。 Zn, M in the copper alloy base material constituting the pipe body
In the n-alloy component copper alloy, Zn and Mn alone or both,
It is necessary that the total content be 0.02% by weight or more.
Thereby, the growth of the ε phase is suppressed. In this case, ε
In order to obtain a phase growth suppressing effect, Zn and / or Mn
Must be added in a total amount of 0.02% by weight or more, and more preferably 0.05% by weight or more in order to be more effective.
【００２０】一方、Ｚｎ含有量が５重量％を超えると、
応力腐食割れの危険性が高くなる。また、Ｍｎ含有量が
３重量％を超えると、配管材として使用する際に、曲げ
加工性が低下して実用に供し得なくなる。このため、Ｚ
ｎ含有量は５重量％以下、Ｍｎ含有量は３重量％以下と
する。On the other hand, when the Zn content exceeds 5% by weight,
Increased risk of stress corrosion cracking. On the other hand, when the Mn content exceeds 3% by weight, when used as a piping material, the bending workability is reduced, and the material cannot be put to practical use. For this reason, Z
The n content is 5% by weight or less, and the Mn content is 3% by weight or less.
【００２１】銅合金母材中に、Ｐ、Ｂ、Ｍｇ及びＳｉか
らなる群から選択された少なくとも１種の元素を総量で
０．２０重量％以下含有すること Ｐ、Ｂ、Ｍｇ及びＳｉはいずれも脱酸材として、又は強
度を向上させる元素として添加してもよい。しかし、こ
れらの成分が総量で０．２０重量％を超えると熱間加工
性が低下する。従って、これらの各成分を添加する場合
は、その添加量は総量で０．２０重量％以下とする。In the copper alloy base material, P, B, Mg and Si
At least one element selected from the group consisting of
P, B, Mg, and Si that are contained at 0.20% by weight or less may be added as a deoxidizing agent or as an element for improving strength. However, when the total amount of these components exceeds 0.20% by weight, the hot workability decreases. Therefore, when each of these components is added, the amount of addition should be 0.20% by weight or less in total.
【００２２】銅合金母材中に、Ａｌ、Ｓｎ及びＮｉから
なる群から選択された少なくとも１種の元素を総量で
２．０重量％以下含有すること Ａｌ、Ｓｎ及びＮｉは銅管の強度、耐熱性及び耐食性を
向上させるために添加してもよい。しかし、これらの効
果は、これらの元素を総量で２．０重量％を超えて含有
しても飽和するため、無駄であり、また製造コストの上
昇をもたらす。従って、これらの各成分を添加する場合
は、その添加量は総量で２．０重量％以下とする。[0022]Al, Sn and Ni in copper alloy base metal
At least one element selected from the group consisting of
2.0% by weight or less Al, Sn and Ni improve the strength, heat resistance and corrosion resistance of copper tubes.
You may add in order to improve. However, these effects
Fruit contains over 2.0% by weight of these elements in total
Even if it is saturated, it is wasteful and increases production costs.
Bring ascension. Therefore, when adding each of these components
Is added in a total amount of 2.0% by weight or less.
【００２３】ε相が保護皮膜の表面に生成されないこと ε相が表面に出ると給水給湯中の溶存酸素により酸化さ
れ、母材に対して自然電位が著しく貴となって孔食の危
険性が高くなる。このため、ε相が保護皮膜の表面に生
成されないことが必要である。The fact that the ε-phase is not formed on the surface of the protective film When the ε-phase comes out on the surface, it is oxidized by dissolved oxygen in the hot and cold water supply, the natural potential becomes significantly noble with respect to the base material, and the danger of pitting corrosion Get higher. For this reason, it is necessary that the ε phase is not generated on the surface of the protective film.
【００２４】保護皮膜の厚さが０．２〜４μｍであるこ
と 保護皮膜の厚さが０．２μｍ未満になると、銅イオンの
溶出量が急激に増大するのに加え、保護皮膜が物理的剥
離作用を受けたときにこれに耐え得なくなる。また、保
護皮膜の厚さが４μｍを超えると、保護皮膜の形成コス
トが高くなる。このため、保護皮膜の厚さは０．２から
４μｍであることが好ましい。 The thickness of the protective film is 0.2 to 4 μm.
When the thickness of the protective film is less than 0.2 μm, the amount of copper ions eluted rapidly increases, and when the protective film is subjected to a physical peeling action, it cannot withstand this. When the thickness of the protective film exceeds 4 μm, the cost of forming the protective film increases. For this reason, the thickness of the protective film is preferably from 0.2 to 4 μm.
【００２５】[0025]
【実施例】次に、本発明の実施例について説明する。下
記表１に示すめっき液並びに下記表２及び表３に示す組
成の管材を用い、銅イオン溶出試験、ε相の成長促進試
験、腐食試験、熱間加工性、曲げ加工性、及び応力腐食
割れ性の各試験を行なった。各特性の評価方法を以下に
示す。Next, an embodiment of the present invention will be described. Using a plating solution shown in the following Table 1 and a tube material having a composition shown in the following Tables 2 and 3, a copper ion elution test, an ε-phase growth promotion test, a corrosion test, hot workability, bending workability, and stress corrosion cracking were performed. Each sex test was performed. The evaluation method of each characteristic is shown below.
【００２６】熱間加工性 各合金鋳塊から直径が１５ｍｍ、長さが１５ｍｍの落槌
試験用試料をサンプリングし、８５０℃で変形率が５０
％の落槌試験を行ない、割れの有無を調べた。 Hot workability A sample of a hammer test having a diameter of 15 mm and a length of 15 mm was sampled from each of the alloy ingots, and the deformation rate was 850 ° C. and 50%.
A drop hammer test was conducted to check for cracks.
【００２７】曲げ加工性 各合金管（外径１５．８８ｍｍ、肉厚０．７１ｍｍ）を
曲げピッチが５０ｍｍの曲げ試験し、曲げ部のしわ及び
破断の有無を調べた。The bending workability each alloy tube (outside diameter 15.88 mm, thickness 0.71 mm) pitch bend is bending test of 50 mm, was investigated wrinkles and presence or absence of breakage of the bent portion.
【００２８】応力腐食割れ性 各合金管（外径１５．８８ｍｍ、肉厚０．７１ｍｍ、長
さ１００ｍｍ）について耐力の８割の応力を印加し、１
２％のアンモニア水を入れたデシケーターに液面から５
０ｍｍ離して入れ、常温で２時間アンモニア雰囲気中に
暴露した後、割れの有無を調べた。 Stress Corrosion Cracking Resistance 80% of the proof stress was applied to each alloy tube (outer diameter 15.88 mm, wall thickness 0.71 mm, length 100 mm),
5% from the liquid level in a desiccator containing 2% ammonia water
After putting in a 0 mm space and exposing it to an ammonia atmosphere at room temperature for 2 hours, the presence or absence of cracks was examined.
【００２９】ε相の成長抑制 各合金管（外径１５．８８ｍｍ、肉厚０．７１ｍｍ、長
さ１００ｍｍ）に下記表１に示すめっき液を通流させ
て、厚さが１．５μｍのめっきを施した後、１００℃に
９００時間加熱してε相成長の促進試験を行ない、走査
型電子顕微鏡で断面を観察してε相の厚さを測定した。The plating solution shown in the following Table 1 is passed through each alloy tube (outer diameter 15.88 mm, wall thickness 0.71 mm, length 100 mm) to suppress the growth of the ε phase, and the thickness of the plating is 1.5 μm. After heating at 100 ° C. for 900 hours, a test for accelerating the growth of the ε phase was performed, and the cross section was observed with a scanning electron microscope to measure the thickness of the ε phase.
【００３０】腐食試験、銅イオン溶出試験 各合金管（外径１５．８８ｍｍ、肉厚０．７１ｍｍ、長
さ５００ｍｍ）に下記表１に示すめっき液を通流させて
めっきを施した後、熱処理を行い、保護皮膜の制御を行
った後、水道水を充填して２４時間経過後における銅イ
オンの溶出量を原子吸光法により測定した。その後、そ
の管を使用して水道水を１年間通水（４００リットル／日）
して孔食の有無を調べた。 Corrosion test, copper ion elution test A plating solution shown in the following Table 1 was passed through each alloy tube (outer diameter 15.88 mm, wall thickness 0.71 mm, length 500 mm), followed by heat treatment. After controlling the protective film, tap water was filled and the elution amount of copper ions after 24 hours was measured by an atomic absorption method. After that, tap water is passed through the pipe for one year (400 liters / day).
Then, the presence or absence of pitting corrosion was examined.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】[0035]
【表５】 [Table 5]
【００３６】[0036]
【表６】 [Table 6]
【００３７】これらの各試験の結果を上記表４に示す。
表４において熱間加工性欄の「○」は良好、「×」は割
れが発生した場合であり、曲げ加工性欄の「○」は良
好、「△」はしわが発生した場合、「×」は破断した場
合である。また、応力腐食割れ性欄の「○」は良好、
「×」は割れが発生した場合である。更に、表５におい
て、めっき種類欄の符号は表１に示すめっき液に対応す
る。The results of each of these tests are shown in Table 4 above.
In Table 4, “○” in the hot workability column indicates good, “X” indicates that cracks occurred, “B” in the bendability column indicates good, and “△” indicates that wrinkles occurred. "" Indicates the case where the fracture occurred. In addition, "○" in the field of stress corrosion cracking is good,
“X” indicates the case where cracks occurred. Further, in Table 5, reference numerals in the plating type column correspond to the plating solutions shown in Table 1.
【００３８】表４から明らかなように、Ｚｎ及び／又は
Ｍｎを所定量含有した本実施例合金Ｎｏ．１〜２０は、
ε相の成長が確実に抑制されている。また、Ｐ等及びＡ
ｌ等の元素を所定量含有した本実施例合金Ｎｏ．１〜２
０は、これらの元素を含有しないものに比べて、ε相成
長抑制効果は同等であり、熱間加工性、曲げ加工性及び
応力腐食割れ性も良好であり、実用上支障は認められな
い。As is clear from Table 4, the alloy of the present example containing a predetermined amount of Zn and / or Mn. 1 to 20,
The growth of the ε-phase is reliably suppressed. Also, P etc. and A
The alloy No. 1 of the present example containing a predetermined amount of an element such as 1-2
A value of 0 is equivalent to the effect of suppressing ε-phase growth, good in hot workability, bending workability, and stress corrosion cracking, as compared with those not containing these elements, and does not cause any practical problems.
【００３９】一方、比較例合金Ｎｏ．２１，２２，２
３，２４，２５，２６は、Ｚｎ及び／又はＭｎの含有量
が少ないか、又は含有していないため、ε相の成長が抑
制されていない。また、Ｐ等の元素を総量で０．２重量
％を超えて含有している比較例合金Ｎｏ．２４，２７，
３２は熱間加工性が不良となっており、Ｍｎ含有量が３
重量％を超えている比較例合金Ｎｏ．２９，３０，３
１，３２は曲げ不良が発生している。更に、Ｚｎ含有量
が５重量％を超えている比較例合金Ｎｏ．２７，２８，
３１，３２では応力腐食割れが発生しているため、実用
に適さない。On the other hand, in Comparative Example Alloy No. 21, 22, 2
3, 24, 25, and 26 do not contain Zn and / or Mn in a small amount or contain no Zn, and therefore, the growth of the ε phase is not suppressed. The alloy of Comparative Example No. P containing elements such as P in excess of 0.2% by weight in total amount. 24, 27,
No. 32 has poor hot workability and a Mn content of 3
% Of the comparative alloy No. 29, 30, 3
Nos. 1 and 32 have bending defects. Further, the alloy of Comparative Example No. 5 having a Zn content exceeding 5% by weight. 27, 28,
In Nos. 31 and 32, since stress corrosion cracking has occurred, they are not suitable for practical use.
【００４０】また、表５は表２に示す組成を有する合金
について、表１に示すめっき液を使用してＳｎ層を形成
し、表５の熱処理欄に記載の条件で熱処理した場合の保
護膜を構成する相の種類及び保護膜の厚さを示す。ま
た、表６は、その試料に対して、腐食試験及び銅イオン
溶出試験をした結果、この腐食試験により得られた最大
腐食深さ及び銅イオン溶出量を示す。Table 5 shows a protective film when an alloy having the composition shown in Table 2 was formed using a plating solution shown in Table 1 to form a Sn layer and heat-treated under the conditions described in the heat treatment column of Table 5. Are shown and the thickness of the protective film is shown. Table 6 shows the maximum corrosion depth and the copper ion elution amount obtained by the corrosion test and the copper ion elution test on the sample.
【００４１】表６から明らかなように、表層部にε相が
出ているものには孔食が発生し、保護皮膜厚さが０．２
μｍ以下のものは銅イオン溶出量の増大が認められ、実
用に供し得ない。As is apparent from Table 6, pitting occurred on the surface layer having the ε phase, and the thickness of the protective film was 0.2%.
When the particle size is less than μm, the amount of copper ions eluted is increased and cannot be put to practical use.
【００４２】[0042]
【発明の効果】以上説明したように、本発明に係る給水
給湯用保護皮膜付き銅合金管は、銅イオン溶出抑制効果
が優れていると共に、給湯環境においても孔食が発生す
る虞れがなく、その信頼性と寿命を著しく増大すること
ができるので、建築用配管等に使用される銅合金管とし
て極めて有用である。As described above, the copper alloy tube with a protective coating for hot and cold water supply according to the present invention has an excellent effect of suppressing copper ion elution and has no risk of pitting occurring even in a hot water supply environment. It is extremely useful as a copper alloy pipe used for architectural piping and the like because its reliability and life can be significantly increased.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平７−83595（ＪＰ，Ａ) 特開 平７−118865（ＪＰ，Ａ) 特開 平６−192773（ＪＰ，Ａ) 特開 平５−104253（ＪＰ，Ａ) 特開 平５−1386（ＪＰ，Ａ) 特開 平４−131384（ＪＰ，Ａ) 特開 平４−99180（ＪＰ，Ａ) 特開 平４−45282（ＪＰ，Ａ) 特開 昭61−231131（ＪＰ，Ａ) 特開 昭61−221359（ＪＰ，Ａ) 特開 昭58−6966（ＪＰ，Ａ) 特開 昭63−293129（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C23C 24/00 - 30/00 C22C 9/00 F16L 9/02 C23C 18/00 - 20/08────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-83595 (JP, A) JP-A-7-118865 (JP, A) JP-A-6-192773 (JP, A) JP-A-5-185 104253 (JP, A) JP-A-5-1386 (JP, A) JP-A-4-131384 (JP, A) JP-A-4-99180 (JP, A) JP-A-4-45282 (JP, A) JP-A-61-231131 (JP, A) JP-A-61-221359 (JP, A) JP-A-58-6966 (JP, A) JP-A-63-293129 (JP, A) (58) (Int.Cl. 6 , DB name) C23C 24/00-30/00 C22C 9/00 F16L 9/02 C23C 18/00-20/08
Claims (7)
０．０２重量％以上含有し、Ｚｎ含有量を５重量％以
下、Ｍｎ含有量を３重量％以下に規制し、残部が銅及び
不可避的不純物である銅合金からなる管本体と、この銅
合金管本体の内面に設けられＳｎ及び不可避的不純物か
らなる保護皮膜と、を有することを特徴とする給水給湯
用内面保護皮膜付き銅合金管。1. At least one of Zn and Mn is contained in a total amount of 0.02% by weight or more, the Zn content is restricted to 5% by weight or less, the Mn content is restricted to 3% by weight or less, and the balance is copper and inevitable. Alloy tube having a pipe main body made of a copper alloy that is a natural impurity, and a protective film provided on the inner surface of the copper alloy pipe main body and made of Sn and unavoidable impurities, provided with an inner protective film for water supply and hot water supply. .
０．０２重量％以上含有し、Ｚｎ含有量を５重量％以
下、Ｍｎ含有量を３重量％以下に規制し、残部が銅及び
不可避的不純物である銅合金からなる管本体と、この銅
合金管本体の内面に設けられＳｎ、ＳｎとＣｕとの金属
間化合物及び不可避的不純物からなる保護皮膜と、を有
し、この保護皮膜の表面にＣｕ3Ｓｎが実質的に存在し
ないことを特徴とする給水給湯用内面保護皮膜付き銅合
金管。2. At least one of Zn and Mn is contained in a total amount of 0.02% by weight or more, the Zn content is regulated to 5% by weight or less, the Mn content is regulated to 3% by weight or less, and the balance is copper and inevitable. A pipe body made of a copper alloy that is a potential impurity, and a protective film made of Sn, an intermetallic compound of Sn and Cu, and an unavoidable impurity provided on the inner surface of the copper alloy pipe body. A copper alloy tube with an inner protective film for hot and cold water supply, characterized in that Cu 3 Sn is substantially absent on the surface.
０．０２重量％以上含有し、Ｚｎ含有量を５重量％以
下、Ｍｎ含有量を３重量％以下に規制し、残部が銅及び
不可避的不純物である銅合金からなる管本体と、この銅
合金管本体の内面に設けられＳｎとＣｕとの金属間化合
物及び不可避的不純物からなる保護皮膜と、を有し、こ
の保護皮膜の表面にＣｕ3Ｓｎが実質的に存在しないこ
とを特徴とする給水給湯用内面保護皮膜付き銅合金管。3. At least one of Zn and Mn is contained in a total amount of 0.02% by weight or more, the Zn content is regulated to 5% by weight or less, the Mn content is regulated to 3% by weight or less, and the balance is copper and inevitable. Tube body made of a copper alloy that is a natural impurity, and a protective film made of an intermetallic compound of Sn and Cu and an unavoidable impurity provided on the inner surface of the copper alloy tube body. A copper alloy tube with an inner surface protective film for hot and cold water, wherein Cu 3 Sn is substantially absent.
Ｓｉからなる群から選択された少なくとも１種の元素を
総量で０．２０重量％以下含有することを特徴とする請
求項１乃至３のいずれか１項に記載の給水給湯用内面保
護皮膜付き銅合金管。4. The copper alloy tube main body contains at least one element selected from the group consisting of P, B, Mg and Si in a total amount of 0.20% by weight or less. 4. The copper alloy pipe with an inner surface protective film for hot and cold water supply according to any one of claims 3 to 3.
ｉからなる群から選択された少なくとも１種の元素を総
量で２重量％以下含有することを特徴とする請求項１乃
至４のいずれか１項に記載の給水給湯用内面保護皮膜付
き銅合金管。5. The copper alloy tube body is made of Al, Sn and N.
The copper alloy tube with an inner protective film for hot and cold water supply according to any one of claims 1 to 4, wherein at least one element selected from the group consisting of i is contained in a total amount of 2% by weight or less. .
が０．２乃至４μｍであることを特徴とする請求項１乃
至５のいずれか１項に記載の給水給湯用内面保護皮膜付
き銅合金管。6. The inner protective film for hot and cold water supply according to claim 1, wherein the protective coating has an average thickness in a circumferential direction of the pipe of 0.2 to 4 μm. Copper alloy tube.
０．０２重量％以上含有し、Ｚｎ含有量を５重量％以
下、Ｍｎ含有量を３重量％以下に規制し、残部が銅及び
不可避的不純物である銅合金からなる管本体の内面に、
Ｓｎめっき層を形成することを特徴とする給水給湯用内
面保護皮膜付き銅合金管の製造方法。7. At least one of Zn and Mn is contained in a total amount of 0.02% by weight or more, the Zn content is regulated to 5% by weight or less, the Mn content is regulated to 3% by weight or less, and the balance is copper and inevitable. On the inner surface of the pipe body made of copper alloy
A method for producing a copper alloy tube with an inner protective film for water / hot water supply, comprising forming an Sn plating layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28988693A JP2835271B2 (en) | 1993-10-25 | 1993-10-25 | Copper alloy tube with inner protective film for hot and cold water supply and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28988693A JP2835271B2 (en) | 1993-10-25 | 1993-10-25 | Copper alloy tube with inner protective film for hot and cold water supply and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07118873A JPH07118873A (en) | 1995-05-09 |
| JP2835271B2 true JP2835271B2 (en) | 1998-12-14 |
Family
ID=17749049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28988693A Expired - Fee Related JP2835271B2 (en) | 1993-10-25 | 1993-10-25 | Copper alloy tube with inner protective film for hot and cold water supply and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2835271B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3331589B2 (en) * | 1998-02-16 | 2002-10-07 | 三菱マテリアル株式会社 | Manufacturing method of copper tube coated with inner plating |
| JP5544591B2 (en) * | 2011-01-20 | 2014-07-09 | 株式会社神戸製鋼所 | Copper alloy tube |
| JP6913489B2 (en) * | 2017-03-21 | 2021-08-04 | 東京瓦斯株式会社 | Piping, water supply system and water supply method |
-
1993
- 1993-10-25 JP JP28988693A patent/JP2835271B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07118873A (en) | 1995-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP4163413B1 (en) | Plated steel material | |
| JP2002121630A (en) | Ni-based alloy product and method of manufacturing the same | |
| JP4387027B2 (en) | Pitting corrosion resistant copper base alloy tubing | |
| US4417929A (en) | Special brass with dezincification corrosion resistance | |
| JP2835271B2 (en) | Copper alloy tube with inner protective film for hot and cold water supply and method for producing the same | |
| JPH05247567A (en) | Zirconium-bismuth-niobium alloy for bulkhead for nuclear fuel cladding | |
| WO1996028686A1 (en) | Copper alloy pipe for water/hot water supply equipped with protective film on its inner surface, production thereof, and heat-exchanger for hot water supply | |
| JPH07118865A (en) | Copper alloy pipe with protected film on inner surface for supplying cold water and hot water and its manufacture | |
| JPH06184669A (en) | Pitting corrosion resistant copper alloy piping for feeding water and hot water | |
| JP3205410B2 (en) | High strength and high corrosion resistance aluminum alloy brazing sheet for heat exchanger | |
| JP3374398B2 (en) | Pitting corrosion resistant copper alloy piping for hot and cold water supply | |
| JP2011001611A (en) | Steel sheet excellent in delayed fracture resistance, and method for producing the same | |
| JPS6017055A (en) | Cr steel with superior weather resistance | |
| JPH06184673A (en) | Pitting corrosion resistant copper alloy piping for feeding water and hot water | |
| JPS61231131A (en) | Corrosion resistant copper alloy pipe | |
| JPH11140572A (en) | High strength aluminum alloy brazing sheet for heat exchanger excellent in intergranular corrosion resistance | |
| Kim et al. | Dealloying behavior of unleaded brasses containing bismuth in potable water | |
| JP3341242B2 (en) | Corrosion resistant copper tube and its manufacturing method | |
| JPH06184670A (en) | Pitting corrosion resistant copper alloy piping for feeding water and hot water | |
| JPH08176742A (en) | Duplex stainless steel with excellent corrosion resistance in hydrogen sulfide environment | |
| JPH04325644A (en) | High strength al alloy tube stock for al heat exchanger excellent in pitting corrosion resistance | |
| JP4469055B2 (en) | Hot-dip Zn-Mg-Al alloy plating method | |
| JP3154341B2 (en) | Method of forming synthetic hemimorphite corrosion resistant film | |
| JPS61136648A (en) | Corrosion resistant copper alloy pipe | |
| JPH06184672A (en) | Pitting corrosion resistant copper alloy piping for feeding water and hot water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |