WO2018123731A1 - Tuyau en cuivre résistant à la corrosion en nids de fourmis et procédé d'amélioration de la résistance à la corrosion l'utilisant - Google Patents

Tuyau en cuivre résistant à la corrosion en nids de fourmis et procédé d'amélioration de la résistance à la corrosion l'utilisant Download PDF

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Publication number
WO2018123731A1
WO2018123731A1 PCT/JP2017/045531 JP2017045531W WO2018123731A1 WO 2018123731 A1 WO2018123731 A1 WO 2018123731A1 JP 2017045531 W JP2017045531 W JP 2017045531W WO 2018123731 A1 WO2018123731 A1 WO 2018123731A1
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WIPO (PCT)
Prior art keywords
mass
corrosive
copper tube
corrosion
content
Prior art date
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Ceased
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PCT/JP2017/045531
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English (en)
Japanese (ja)
Inventor
早織 前
博一 玉川
良彦 京
良行 大谷
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.)
UACJ Corp
UACJ Copper Tube Corp
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UACJ Corp
UACJ Copper Tube Corp
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Publication date
Application filed by UACJ Corp, UACJ Copper Tube Corp filed Critical UACJ Corp
Publication of WO2018123731A1 publication Critical patent/WO2018123731A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • 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
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • 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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent

Definitions

  • the present invention relates to the improvement of ant-corrosion resistant copper tube, and in particular, a technology for improving the corrosion resistance to ant-like corrosion of a copper tube suitably used for a heat transfer pipe, a refrigerant pipe and the like in air conditioners and refrigeration equipment. It is about
  • phosphorus (P) exhibits excellent characteristics in corrosion resistance, brazing property, thermal conductivity, bending workability, etc. in pipe materials such as heat transfer pipes of air conditioners and refrigerant piping (in-machine piping) of refrigeration equipment.
  • Deoxidized copper JIS-H3300-C1220T has been mainly used.
  • phosphorus-deoxidized copper pipes which are pipes used for such air conditioners and refrigeration equipment, are abnormal corrosion that progresses in the form of ant nest from the surface of the pipe in the thickness direction of the pipe, so-called ant nest It is recognized that corrosion may occur.
  • This ant's nest corrosion is considered to occur in a wet environment using a lower carboxylic acid such as formic acid or acetic acid as a corrosive medium, and a chlorinated organic solvent such as 1,1,1-trichloroethane or a certain lubricating oil The same occurrence of corrosion has been confirmed even in the presence of formaldehyde and the like.
  • Patent Document 1 WO2014 / 148127
  • P (phosphorus) is contained at a ratio of 0.05 to 1.0% by weight, and the balance is made of Cu (copper) and Cu material which is an unavoidable impurity.
  • a highly corrosion resistant copper tube is proposed, characterized in that it can improve the corrosion resistance to ant-like corrosion. That is, there is practically advantageously obtained a copper tube which can further improve the corrosion resistance to ant-like corrosion in a region where the P content is larger than a conventional tube made of phosphorus-deoxidized copper. The fact that it can be done is pointed out.
  • the present invention has been made on the background of such circumstances, and the problem to be solved is an air conditioner which can exhibit even higher corrosion resistance against nest-like corrosion of ant. And providing a copper pipe having excellent corrosion resistance that can be suitably used as a heat transfer pipe, a refrigerant pipe, etc. in refrigeration equipment, and a method of improving the corrosion resistance using the same, and using such a copper pipe. It also advantageously improves the life of the equipment being
  • the present inventors determined P at a ratio of 0.15 to 0.50 mass%.
  • the present invention has been accomplished by finding out the fact that the corrosion resistance against nest-like corrosion can be further improved.
  • P phosphorus
  • Zn zinc
  • Sn titanium
  • Termite-resistant characterized in that it contains 0.1 to 5.0% by mass in total of at least one element of Ni (nickel), and the balance is Cu and Cu which is an unavoidable impurity.
  • the copper tube excellent in the nest-like corrosion property is the summary.
  • the copper tube excellent in the nest corrosion resistance according to the present invention more preferably, P is contained in a proportion of 0.15 to 0.50 mass%, and Zn, Sn or Ni is contained.
  • the copper pipe is made of Cu material adjusted to have a content of 0.1 to 4.0% by mass to form a copper pipe, whereby a copper pipe having excellent corrosion resistance against ant-like nest corrosion is obtained. It can be advantageously formed.
  • the content of the unavoidable impurities is 0.05 mass% or less.
  • the corrosive medium comprising a lower carboxylic acid, disposed in a wet environment, provides a tube wall thickness direction from the tube surface
  • An ant-resistant corrosive copper tube is provided, characterized in that it is a copper tube that is exposed to the corrosive effect which proceeds in an ant-like manner.
  • the heat transfer pipe and refrigerant piping (in-machine piping) in air conditioners and refrigeration equipment comprising the above-mentioned nest-like corrosive copper pipe as described above are also the gist of the invention. .
  • the lower carboxylic acid generated from the surface is generated in the wet environment as a corrosive medium
  • the copper tube contains P in a proportion of 0.15 to 0.50% by mass and at least one of Zn, Sn, and Ni as a method for improving the corrosion resistance against nest corrosion of ant It is characterized by using a dovetail corrosive-resistant copper tube which contains two elements in a total amount of 0.1 to 5.0% by mass and the balance is Cu and Cu material which is an unavoidable impurity.
  • the method of improving corrosion resistance is also the gist of the invention.
  • a practical copper pipe which can exhibit further excellent corrosion resistance than conventionally known copper pipes in corrosion resistance to ants' nest-like corrosion can be advantageously provided.
  • a highly corrosion-resistant copper tube as a heat transfer pipe, refrigerant piping (in-machine piping), and the like in air conditioners and refrigeration equipment, the life of those equipments can be further effectively enhanced. It will be.
  • the P content in the Cu material constituting it is in the range of 0.15 to 0.50 mass%, and Zn, Sn, Ni
  • a major feature is that at least one of the elements is contained so as to have a ratio of 0.1 to 5.0% by mass in the total content.
  • the P content when the P content is less than 0.15% by mass, a selective corrosion form is caused.
  • the content needs to be 0.15 mass% or more.
  • P content increases and exceeds 0.50% by mass, there is almost no change in the corrosion resistance against ant nest corrosion, but rather, the processability decreases in the production of a copper tube.
  • the upper limit of the P content needs to be limited to 0.50% by mass, since problems such as cracking easily occur.
  • the Zn content when the content of Zn combined with the high P content as described above is less than 0.1% by mass, selective corrosion forms occur in a more severe corrosive environment.
  • the Zn content needs to be 0.1% by mass or more.
  • the Zn content increases and exceeds 5.0% by mass, there is almost no change in the corrosion resistance against ants' nest corrosion, and the brazing temperature is lowered because the melting point of the copper material is lowered by the addition of Zn.
  • the upper limit of the Zn content is 5.0% by mass, preferably 4.0% by mass.
  • the Sn content needs to be 0.1% by mass or more.
  • the upper limit of the Sn content is 5.0% by mass, preferably 4.0% by mass, since problems such as cracking of the material are likely to occur.
  • the content of Ni combined with the high content of P is less than 0.1% by mass, selective corrosion morphology will be triggered under more severe corrosive environment
  • the Ni content needs to be 0.1% by mass or more.
  • the Ni content increases and exceeds 5.0% by mass, there is almost no change in the corrosion resistance to the ant-like corrosion, but rather, plastic working in cold working etc. in the production of copper tubes.
  • the upper limit of the Ni content is 5.0% by mass, preferably 4.0% by mass is adopted, since it is likely that problems such as cracking and grooving can not be caused in roll forming due to a decrease in Be done.
  • the remainder is composed of Cu (copper) and unavoidable impurities in addition to the P content and the content of Zn and / or Sn and / or Ni according to the present invention.
  • Inevitable impurities such as Fe, Pb, Si, S, Bi, etc. are generally composed of 0.05 mass% or less, preferably 0.005 mass% or less, in total. It is adjusted to be as follows.
  • the total content of added Zn and / or Sn and / or Ni in addition to the specified amount of P content is kept within the specified range.
  • the copper tube according to the present invention is disposed in a wet environment utilizing such characteristics, and proceeds from the surface of the tube in the thickness direction of the tube in an ant-like manner by a corrosive medium consisting of lower carboxylic acid. It is advantageously used as a tube exposed to the corrosive effect.
  • the copper pipe according to the present invention as described above can be suitably used as a heat transfer pipe, refrigerant pipe, etc. in an air conditioner, and similarly, it can be used as a heat transfer pipe, refrigerant pipe (in-machine pipe), etc. in refrigeration equipment. It can be suitably used.
  • the balance is Cu and unavoidable impurities in the above-mentioned P content (concentration) and Zn, Sn and / or Ni content (concentration).
  • the method of obtaining the target copper tube through the same process as the conventional one such as casting, homogenization treatment, hot extrusion of the tube, and drawing of the tube.
  • the size such as the outer diameter and the wall thickness (tube wall thickness) is appropriately selected according to the application of the copper tube.
  • the copper tube according to the present invention is used as a heat transfer tube, it is well known that flat inner and outer surfaces which are surface shapes formed by tube extrusion are adopted, It is also effective to form a heat transfer tube which is provided with various forms of inner and outer grooves by being subjected to various kinds of inner and outer surface processing known in the art.
  • each of the various types of rolled blanks obtained above is subjected to a plurality of cold-drawing operations several times, and the outer diameter is 7.8 to 10.0 mm, the bottom thickness is 0.25 to 0.
  • a 30 mm draw tube was obtained.
  • the working ratio in the whole of this cold drawing was 95.1 to 97.0% in terms of reduction in area.
  • the total working ratio in cold rolling and cold drawing ie, the total working ratio in cold working, was 98.9 to 99.3% in terms of reduction in area.
  • one or more intermediate annealings were performed in the above-described drawing process. Then, after final drawing processing, intermediate annealing was performed to manufacture a raw pipe for rolling processing.
  • the various raw pipes thus obtained are subjected to ball rolling in the same manner as in the prior art, and various inner surfaces having a spiral inner groove form and shape as shown in FIGS. 1 and 2.
  • a grooved tube was obtained.
  • the inner grooved tube has an outer diameter of 7.0 mm, a thickness (t) of 0.23 mm, a fin height (h) of 0.22 mm, a fin apex angle ( ⁇ ) of 13 °, and a groove. It was formed so as to have the dimensional specifications of the number of lines: 44 and the lead angle ( ⁇ ): 28 °.
  • Test copper tube No. In the cases of 19, 23 and 27, since a Cu material having a high P content is used, defects such as cracks occur in the pipe making process, and processing can not be performed to the end, and corrosion is caused. It was not possible to obtain a copper tube that could be subjected to the test. Moreover, the test copper pipe No. In the case of No. 24, since a Cu material having a high Sn content is used, a defect such as a crack occurs in the hot step, so that copper can not be processed to the end and can be subjected to a corrosion test. I could not get a tube. Furthermore, the test copper pipe No. In the case of No. 28, since a Cu material having a high Ni content is used, a defect such as a crack occurs in the cold process, and the copper can not be processed to the end and can be subjected to a corrosion test. I could not get a tube.
  • test copper tubes No. 1 to 29 an ant-like corrosion test was carried out using the test apparatus shown in FIG.
  • 2 is a 2 L poly container which can be sealed with a cap 4, and a test copper pipe 10 is passed through the cap 4 so as to penetrate a silicon plug 6 attached.
  • the lower end opening of the test copper tube 10 is closed by a silicon plug 8 while being inserted into the poly container 2 at a predetermined depth.
  • the test copper tube 10 has a length of 18 cm, and the length of the portion exposed in the poly container 2 is 15 cm.
  • 100 ml of a formic acid aqueous solution having a predetermined concentration is accommodated in the poly container 2 in such a form that the formic acid aqueous solution does not come in contact with the test copper tube 10.
  • test copper pipe No. which is a comparative example is. As for 21, 25, and 29, it was recognized that significant ant-like corrosion had occurred because the P content was less than 0.15% by weight. Furthermore, the test copper pipe No. In 18, 20, 22 and 26, although the P content is within the range of the present invention, any of Zn, Sn, Ni, because the concentration of each additive element is outside the specified range, And significant ant-like corrosion occurred.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Metal Extraction Processes (AREA)

Abstract

L'invention concerne un tuyau en cuivre doté d'excellentes propriétés anti-corrosion qui est capable de manifester des propriétés anti-corrosion supérieures en termes de corrosion dite "en nids de fourmis" et qui peut être avantageusement utilisé pour des tuyaux de transfert de chaleur, tuyaux à réfrigérant, et autres, de climatiseurs et équipements de réfrigération. Le tuyau en cuivre résistant à la corrosion en nids de fourmis est formé à partir d'un matériau de Cu qui contient du P (phosphore) en une proportion de 0,15 à 0,50 % en poids et au moins un des éléments suivants : Zn (zinc), Sn (étain) et Ni (nickel) en une quantité totale de 0,1 à 5,0 % en poids, le reste étant du Cu et des impuretés inévitables.
PCT/JP2017/045531 2016-12-27 2017-12-19 Tuyau en cuivre résistant à la corrosion en nids de fourmis et procédé d'amélioration de la résistance à la corrosion l'utilisant Ceased WO2018123731A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016252649A JP2018104767A (ja) 2016-12-27 2016-12-27 耐蟻の巣状腐食性銅管
JP2016-252649 2016-12-27

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Publication Number Publication Date
WO2018123731A1 true WO2018123731A1 (fr) 2018-07-05

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PCT/JP2017/045531 Ceased WO2018123731A1 (fr) 2016-12-27 2017-12-19 Tuyau en cuivre résistant à la corrosion en nids de fourmis et procédé d'amélioration de la résistance à la corrosion l'utilisant

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WO (1) WO2018123731A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022152750A (ja) * 2021-03-29 2022-10-12 株式会社富士通ゼネラル 空気調和機
JP7716286B2 (ja) * 2021-09-15 2025-07-31 Ｎｊｔ銅管株式会社 内面溝付管及びその製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235428A (ja) * 2008-03-25 2009-10-15 Kobelco & Materials Copper Tube Inc 銅合金部材及び熱交換器
WO2014148127A1 (fr) * 2013-03-19 2014-09-25 株式会社Uacj Tuyau en cuivre hautement résistant à la corrosion
WO2015122423A1 (fr) * 2014-02-12 2015-08-20 株式会社Uacj Matériau d'alliage de cuivre, et tube en alliage de cuivre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235428A (ja) * 2008-03-25 2009-10-15 Kobelco & Materials Copper Tube Inc 銅合金部材及び熱交換器
WO2014148127A1 (fr) * 2013-03-19 2014-09-25 株式会社Uacj Tuyau en cuivre hautement résistant à la corrosion
WO2015122423A1 (fr) * 2014-02-12 2015-08-20 株式会社Uacj Matériau d'alliage de cuivre, et tube en alliage de cuivre

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