WO1994010352A1 - Conduite d'eau froide et d'eau chaude en alliage de cuivre resistant a la corrosion par piqures - Google Patents

Conduite d'eau froide et d'eau chaude en alliage de cuivre resistant a la corrosion par piqures Download PDF

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Publication number
WO1994010352A1
WO1994010352A1 PCT/JP1993/001541 JP9301541W WO9410352A1 WO 1994010352 A1 WO1994010352 A1 WO 1994010352A1 JP 9301541 W JP9301541 W JP 9301541W WO 9410352 A1 WO9410352 A1 WO 9410352A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper alloy
addition
pitting
pitting corrosion
water supply
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.)
Ceased
Application number
PCT/JP1993/001541
Other languages
English (en)
Japanese (ja)
Inventor
Toshiyuki Cho
Yoshimasa Shiraishi
Tsutomu Takahashi
Masato Watanabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Materials Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP35576292A external-priority patent/JPH06184669A/ja
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Priority to DE4395519T priority Critical patent/DE4395519T1/de
Priority to DE4395519A priority patent/DE4395519C2/de
Priority to JP51088494A priority patent/JP3374398B2/ja
Publication of WO1994010352A1 publication Critical patent/WO1994010352A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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

Definitions

  • the present invention relates to a copper alloy pipe for hot water supply having excellent pitting corrosion resistance.
  • phosphorus oxidizing pipes have been widely used as pitting resistant pipes for hot and cold water supply in hotels, hospitals, condominiums, and the like. This is because the phosphoric acid-deoxidized copper pipe is excellent in corrosion resistance, workability, ie property, etc., and is excellent as a pitting corrosion-resistant pipe for hot and cold water supply.
  • Type I mainly occurs in the cold water of hard water in Europe, and in Japan, Typel I is located below ⁇ of Ito. Pitting has occurred.
  • Type II pitting corrosion is formed on the inner surface of copper alloy piping when the anion ratio in the water quality is [S ⁇ 4 2 —] Z [HC ⁇ 3 -] ⁇ 1 and the residual chlorine is high.
  • C 10 2 "are concentrated, C 10 2" at the bottom of the Cu 2 0 coating acts as a strong oxidizing agent, by himself oxidizes C u with bear is reduced force source one de reaction It forms Cu0, and at the same time, produces a corrosive anion C-factory, which is the starting point of pitting.
  • the C ⁇ ion concentrates with the passage of time, and with the concentration of the C 1 "ion, H 'also concentrates to cause a decrease in pH, and pitting of Type II proceeds.
  • the present inventors conducted a study to develop a copper alloy pipe having more excellent pitting corrosion resistance than the conventional copper alloy pipe, as described above, and as a result, the following research results were obtained. Was obtained.
  • Y 0.005 to 1% and Zr: 0.005 to: Contains one or two of L%, the remainder consisting of a copper alloy of Ito Makoto consisting of Cu and unavoidable impurities Pitting corrosion-resistant copper alloy piping for hot and cold water supply,
  • a pitting corrosion-resistant copper alloy for hot and cold water supply which contains one or two of Sn and Ag in a content of 0.05 to 5% by weight and a balance of Cu and unavoidable impurities.
  • one or two of Sn and Ag contain 0.05 to 5% by Igfi,
  • a pitting-resistant pitting corrosion-resistant copper alloy containing one or two elements selected from Ti and R containing 0.005 to 1% by weight and a balance of Cu and unavoidable impurities.
  • one or two i: elements selected from Ti and R contain 0.005 to 1% by
  • W 0.001% to 1%, the balance being Cu and a copper alloy of 15% of yarn composed of ⁇ ⁇ ⁇ evading impurities.
  • Y from 0.005 to 1% and Z r: 1 kind of 0.005 to 1% or comprise two or,
  • W 0.001% to 1%, the balance being a copper alloy having a composition composed of Cu and o ⁇ I impurities, a pitting-resistant corrosion-resistant copper alloy pipe for hot and cold water supply,
  • Y 0.005 to 1%
  • Zr One or two of 0.005 to 1%
  • one or two elements selected from Ti and R are contained by 0.005 to 1% by weight, and the rest is Cu and ⁇ ! Thread made of impurities! Pitting corrosion-resistant copper alloy piping for water supply and hot water supply consisting of ⁇ alloy
  • Y from 0.005 to 1% and Z r: 1 kind of 0.005 to 1% or comprise two or,
  • J elements selected from Ti and R are contained in 0.005 to 1% by ⁇ *,
  • pitting corrosion-resistant copper alloy piping for hot water supply which contains 0.0005 to 1% of W: balance of copper and copper
  • W 0.001% to 1%, the balance being a copper alloy having a composition of Cu and contaminating impurities, a pitting-resistant copper alloy pipe for hot and cold water supply,
  • ⁇ is an active metal that, when added to Cu, lowers the potential and concentrates on the surface to form a stable oxide, thereby suppressing the occurrence of pitting and its growth.
  • the content is less than 0.05% by weight, the effect of lowering the potential of the copper alloy pipe is not sufficient, and the formation of a stable oxide film is not sufficient, and the effect of suppressing pitting corrosion is satisfactory.
  • Y is set to 0.05 to l fi *%. A preferred range is from 0.03 to 0.3fi *%.
  • Y When oxidized by the corrosion reaction, Y concentrates between the cuprous oxide formed on the copper alloy pipe surface and the copper alloy pipe surface, protecting the copper alloy pipe surface and protecting the copper alloy pipe surface. In addition, it has the function of improving the stability of cuprous oxide, suppressing the oxidation of cuprous oxide by cupric oxide by an oxidizing agent such as residual chlorine, and preventing pitting corrosion. In addition, even if the pitting corrosion is strong, Cu dissolves at the tip of the pit, and a stable oxide film is formed on the alloy surface by Y, and the progress of pitting is remarkably suppressed. .
  • Zr is also an active metal like Y.
  • it lowers the potential and concentrates on the surface to form stable oxides M, thereby suppressing the occurrence of pitting corrosion and its growth.
  • the content is less than 0.05 M »%, the effect of lowering the potential of the copper alloy pipe is not sufficient, and the formation of a stable oxide film is not sufficient and the pitting is satisfactory.
  • the content is too large, the effect of improving the pitting corrosion resistance will be saturated, and the workability will be drastically reduced, leading to a decrease in the ⁇ property. Therefore, it was determined to be : 0.05 to 1% by weight. A preferred range is from 0.03 to 0.3%.
  • Zr forms a copper suboxide coating formed on the surface of the copper alloy pipe and copper Concentrates between the alloy pipe surface and the copper alloy pipe surface, protects the copper alloy pipe surface, improves the stability of nitrous oxide in the cuprous oxide, and oxidizes it with an oxidizing agent such as residual chlorine. It has the function of preventing copper from being oxidized secondarily and preventing pitting. Furthermore, even if pitting-like corrosion occurs, the pits: ⁇ Fe-like dissolution occurs at the edge, and stable oxidation due to Zr along with Y is formed on the alloy surface, and pitting progresses Is severely restricted.
  • Sn and Ag both form stable oxides and have the effect of suppressing the occurrence and growth of pitting corrosion, and at the same time, once pitting-like corrosion occurs, Copper preferentially dissolves and these elements concentrate on the surface, lowering the potential and increasing the stability of oxidation due to these elements, etc., and suppressing pitting corrosion by suppressing the cathode reaction. It has the effect of blocking and suppressing growth. Therefore, the addition of Sn and Ag significantly increases the corrosion pattern of copper alloy piping from pitting corrosion to general corrosion, and increases corrosion in the surface direction as opposed to corrosion in the depth direction. However, the corroded part becomes shallow and wide.
  • the contents of Sn and Ag were set at 0.05 to 5% by weight.
  • the preferred range is 0.2 to 2% by weight.
  • Ti and R enhance the effect of suppressing pitting corrosion of Y, that is, by being together with Y, contribute to lowering the potential of the copper alloy and concentrate on the alloy surface to further enhance the stability of surface wake-up Although it has the effect of suppressing the occurrence of pitting corrosion, if its content is less than 0.05% by weight, it does not contribute sufficiently to the increase in stability of the surface treatment. On the other hand, the content exceeding 1% As a result, the pitting corrosion resistance effect of J3 ⁇ 4 ⁇ is not recognized, and conversely, the addition property is decreased, which is not preferable. Therefore, the contents of T i and R were determined to be 0.05 to 1% by their ⁇ S. The preferred range is from 0.03 to 0.3% by weight.
  • W W enhances the pitting corrosion-inhibiting effect, that is, together with Y and Zr, contributes to the lowering of the potential of the alloy and concentrates on the surface of the copper alloy to further enhance the stability of the surface coating.
  • the content is less than 0.005
  • the contribution to the increase in the stability of m ⁇ is not sufficient.
  • the content is more than 1, it is not preferable because the pitting corrosion resistance of JLh is not remarkable, and conversely, dissolution or remarkably high results in deterioration of the properties. Therefore, the content of W is set at 0.005 to lfig%. The preferred range is from 0.01 to 0.
  • P Since P has a deoxidizing effect, its addition makes the production of a sound alloy ingot more effective.In addition, pitting corrosion is often caused by surface defects such as entrapment of oxides in the alloy. The addition has the effect of indirectly suppressing the occurrence of pitting corrosion and its growth, but if its content is less than 0.005%, there is no sufficient removal of the pits and defects due to oxide entrapment in the alloy ingot However, since pitting corrosion occurs starting there, sufficient pitting corrosion inhibiting effect cannot be obtained.On the other hand, when 0.5 is contained in a large amount, phosphide is formed, workability is remarkably reduced, and pitting corrosion resistance is reduced. No further results can be obtained. Therefore, the content of P was set to 0.005 to 0.5 fi *%. A preferred range is 0.005 to 0.04% by weight.
  • the pitting corrosion-resistant copper alloy piping for hot and cold water supply of the present invention contains Pb, Bi, As, Fe, Se, A1, S, Sb and the like as unavoidable impurities at a level of several ppm or less, respectively. Even if oxygen is contained at 5 Opm, it does not affect the pitting corrosion resistance at all.
  • Pitting corrosion resistant copper alloy for hot and cold water supply which is made of the copper alloy shown in Tables 1 to 13 and has an outer diameter of 15.88 mm, a wall thickness of 1.02 dragons, and a length of 1000.
  • Piping hereinafter referred to as copper alloy piping of the present invention
  • comparative copper alloy piping pitting corrosion resistant copper alloy piping for specific water supply
  • conventional pitting corrosion resistant alloy piping for hot water supply hereinafter referred to as fine alloy pipes
  • Each of the comparative copper alloy pipes 1 to 18 is a thread of any construction! ⁇ Deviates from the scope of the present invention (yarns deviating from the scope of the present invention are marked with an asterisk and are shown in Tables 12 to 13).
  • the above copper alloy pipes of the present invention 1 to 10; comparative copper alloy pipes 1 to 18;
  • the test was conducted by flowing 60 ° C & K at a flow rate of 1 m / s for 1 year at a water quality of pH: 7 for 1 year. It was investigated by measuring the number of pits generated per unit of water, and the results are shown in Tables 1 to 1o.
  • the ⁇ test has Type II pitting corrosion; considering ⁇ , it is more reliable and reproducible in pitting corrosion generation than the S7K test in which chlorine for residual chlorine is added at the same time as the STK test is started. This is a trial method. That is, if the test water is set to a high residual chlorine from the beginning of the test, there is a danger that the overall corrosion force will proceed rather than the pitting corrosion, and the pitting corrosion resistance of the copper alloy piping cannot be accurately achieved.
  • the copper alloy pipes 1 to 110 of the present invention which are made of a copper alloy containing single or composite additions, have better pitting corrosion resistance than the conventional copper alloy pipes 1 and 2.
  • the force tested in the water quality under which Type II pitting corrosion occurs is excellent.
  • the copper alloy piping of the present invention is also excellent in water quality under which Type I pitting corrosion occurs. Pitting corrosion resistance.
  • the copper alloy piping of the present invention is more excellent in pitting corrosion resistance than before, and when used as a pitting corrosion resistant piping for hot and cold water supply in hotels, hospitals, condominiums, etc., the reliability against pitting corrosion is high. It is more improved than before and has excellent effects.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Domestic Plumbing Installations (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

L'invention concerne une conduite d'eau froide et d'eau chaude, résistant à la corrosion par piqûre, réalisée en un alliage de cuivre comprenant 0,005-1 % en poids de Y et/ou 0,005-1 % en poids de Zr, éventuellement au moins un élément choisi dans le groupe constitué de: (a) Sn et/ou Ag, en une quantité totale de 0,05-5 % en poids, (b) Ti et/ou R (un élément des terres rare à l'exception de Y) en une quantité totale de 0,005-1 % en poids, et (c) 0,005-1 % en poids de W, avec, éventuellement, 0,005-05 % en poids de P, le reste étant constitué de Cu et des impuretés inévitables.
PCT/JP1993/001541 1992-10-27 1993-10-26 Conduite d'eau froide et d'eau chaude en alliage de cuivre resistant a la corrosion par piqures Ceased WO1994010352A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE4395519T DE4395519T1 (de) 1992-10-27 1993-10-26 Gegen Lochkorrosion beständige Kupferlegierungsrohre für die Zufuhr von Kalt- und Heißwasser
DE4395519A DE4395519C2 (de) 1992-10-27 1993-10-26 Gegen Lochkorrosion beständige Kupferlegierungsrohre für die Zufuhr von Kalt- und Heißwasser
JP51088494A JP3374398B2 (ja) 1992-10-27 1993-10-26 給水給湯用耐孔食性銅合金配管

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP31133392 1992-10-27
JP4/311333 1992-10-27
JP4/355762 1992-12-18
JP35576292A JPH06184669A (ja) 1992-12-18 1992-12-18 給水給湯用耐孔食性銅合金配管
JP4/357641 1992-12-24
JP35764192 1992-12-24

Publications (1)

Publication Number Publication Date
WO1994010352A1 true WO1994010352A1 (fr) 1994-05-11

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Application Number Title Priority Date Filing Date
PCT/JP1993/001541 Ceased WO1994010352A1 (fr) 1992-10-27 1993-10-26 Conduite d'eau froide et d'eau chaude en alliage de cuivre resistant a la corrosion par piqures

Country Status (3)

Country Link
JP (1) JP3374398B2 (fr)
DE (2) DE4395519C2 (fr)
WO (1) WO1994010352A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006016631A1 (fr) * 2004-08-10 2006-02-16 Sanbo Shindo Kogyo Kabushiki Kaisha ALLIAGE DE CUIVRE CONTENANT DU Sn ET MÉTHODE DE PRODUCTION RELATIVE
JP2009249675A (ja) * 2008-04-04 2009-10-29 Sumitomo Light Metal Ind Ltd 継目無管
US9303300B2 (en) 2005-09-30 2016-04-05 Mitsubishi Shindoh Co., Ltd. Melt-solidified substance, copper alloy for melt-solidification and method of manufacturing the same
CN107083500A (zh) * 2017-03-27 2017-08-22 东莞市精研粉体科技有限公司 一种导电胶或电磁屏蔽用抗氧化铜合金粉及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5854180B2 (ja) * 1981-04-09 1983-12-03 三井金属鉱業株式会社 高力高導電性銅合金
JPS6059033A (ja) * 1983-09-13 1985-04-05 Sumitomo Light Metal Ind Ltd ヒ−トパイプ用管材料
JPS62218534A (ja) * 1986-03-19 1987-09-25 Furukawa Electric Co Ltd:The 耐孔食性給湯用銅合金管
JPS63293129A (ja) * 1987-05-26 1988-11-30 Furukawa Electric Co Ltd:The 耐孔食性給湯用銅合金管

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1237078A (en) * 1967-11-17 1971-06-30 Imp Metal Ind Kynoch Ltd Copper-base alloy foil heat exchanger elements
EP3124523B1 (fr) 2014-03-28 2020-08-12 Toray Industries, Inc. Film de polypropylène bi-orienté

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5854180B2 (ja) * 1981-04-09 1983-12-03 三井金属鉱業株式会社 高力高導電性銅合金
JPS6059033A (ja) * 1983-09-13 1985-04-05 Sumitomo Light Metal Ind Ltd ヒ−トパイプ用管材料
JPS62218534A (ja) * 1986-03-19 1987-09-25 Furukawa Electric Co Ltd:The 耐孔食性給湯用銅合金管
JPS63293129A (ja) * 1987-05-26 1988-11-30 Furukawa Electric Co Ltd:The 耐孔食性給湯用銅合金管

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006016631A1 (fr) * 2004-08-10 2006-02-16 Sanbo Shindo Kogyo Kabushiki Kaisha ALLIAGE DE CUIVRE CONTENANT DU Sn ET MÉTHODE DE PRODUCTION RELATIVE
CN100535144C (zh) * 2004-08-10 2009-09-02 三菱伸铜株式会社 含锡铜合金及其制造方法
US9328401B2 (en) 2004-08-10 2016-05-03 Mitsubishi Shindoh Co., Ltd. Copper alloy casting having excellent machinability, strength, wear resistance and corrosion resistance and method of casting the same
US10017841B2 (en) 2004-08-10 2018-07-10 Mitsubishi Shindoh Co., Ltd. Copper alloy casting and method of casting the same
US10570483B2 (en) 2004-08-10 2020-02-25 Mitsubishi Shindoh Co., Ltd. Copper-based alloy casting in which grains are refined
US9303300B2 (en) 2005-09-30 2016-04-05 Mitsubishi Shindoh Co., Ltd. Melt-solidified substance, copper alloy for melt-solidification and method of manufacturing the same
JP2009249675A (ja) * 2008-04-04 2009-10-29 Sumitomo Light Metal Ind Ltd 継目無管
CN107083500A (zh) * 2017-03-27 2017-08-22 东莞市精研粉体科技有限公司 一种导电胶或电磁屏蔽用抗氧化铜合金粉及其制备方法

Also Published As

Publication number Publication date
DE4395519T1 (de) 1995-01-26
DE4395519C2 (de) 1997-04-30
JP3374398B2 (ja) 2003-02-04

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