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WO2025131865A1 - Tube en alliage de cuivre destiné à être utilisé dans un système hvacr - Google Patents

Tube en alliage de cuivre destiné à être utilisé dans un système hvacr Download PDF

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Publication number
WO2025131865A1
WO2025131865A1 PCT/EP2024/085445 EP2024085445W WO2025131865A1 WO 2025131865 A1 WO2025131865 A1 WO 2025131865A1 EP 2024085445 W EP2024085445 W EP 2024085445W WO 2025131865 A1 WO2025131865 A1 WO 2025131865A1
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WO
WIPO (PCT)
Prior art keywords
copper alloy
less
alloy tube
tube
tube according
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.)
Pending
Application number
PCT/EP2024/085445
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English (en)
Inventor
Spyridon CHASKIS
George Hinopoulos
Ioannis BIRIS
Fani TZEVELEKOU
Vasiliki PANTELEAKOU
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.)
Elvalhalcor Hellenic Copper & Aluminium Industry SA
Original Assignee
Elvalhalcor Hellenic Copper & Aluminium Industry SA
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
Application filed by Elvalhalcor Hellenic Copper & Aluminium Industry SA filed Critical Elvalhalcor Hellenic Copper & Aluminium Industry SA
Publication of WO2025131865A1 publication Critical patent/WO2025131865A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C22C9/04—Alloys based on copper with zinc as the next major constituent

Definitions

  • the present invention relates to a copper alloy tube for use in a HVACR (Heating, Ventilation, Air Conditioning, Refrigeration) system.
  • HVACR Heating, Ventilation, Air Conditioning, Refrigeration
  • Copper alloys are not only used in tubes of HVACR systems, but also in other technical fields. See JP H09 31570 A and EP 0 908 526 Al as examples of this.
  • JP H09 31570 A discloses a copper alloy for use as a building material, the copper alloy having a chemical composition comprising, by mass, 0.1 - 15 % Zn, 0.05 - 2 % Sn, more than 0.01 to 0.04 % P, and the balance Cu and unavoidable impurities.
  • EP 0 908 526 Al discloses a copper alloy for electrical applications, the copper alloy having a chemical composition comprising, by mass, 1.0 - 15 % Zn, 0.1 - 1.5 % Sn, 0.01 - 0.8 % Fe, 0.01 - 0.35 % P, and the balance Cu and unavoidable impurities.
  • copper alloy tubes are widely used because of their excellent thermal conductivity, which allows for efficient heat exchange. Copper alloy tubes are also resistant to corrosion, which ensures long-term durability and reduces the risk of leaks. Additionally, copper is a malleable material, making it easy to bend and shape the copper alloy tubes during installation. Examples of the use of copper alloy tubes in a heat exchanger can be found in US 4 935 076 A, EP 1 630 240 Al, JP 2003 268467 A, and EP 2 055 795 A2.
  • US 4 935 076 A discloses a copper alloy for use as the material of a heat exchanger, the copper alloy having a chemical composition comprising, by mass, 1 - 4.5 % Zn, 1.1 - 2.5 % Sn, 0.005 - 0.05 % P, and the balance Cu and unavoidable impurities.
  • EP 1 630 240 Al discloses a copper alloy for use as a heat exchanger tube, the copper alloy having a chemical composition comprising, by mass, 0.01 - 0.40 % Zn, 0.02 - 0.25 % Sn, 0.15 - 0.33 % Co, 0.041 - 0.089 % P, and the balance Cu and unavoidable impurities.
  • JP 2003 268467 A discloses a copper alloy tube for a heat exchanger, the copper alloy tube having a chemical composition comprising, by mass, 0.01 - 1.0 % Zn, 0.1 - 1.0 % Sn, 0.005 - 0.1 % P, 0.005 % or less O, 0.005 % or less H, and the balance Cu and unavoidable impurities.
  • EP 2 055 795 A2 discloses a copper alloy tube for a heat exchanger, the copper alloy tube having a chemical composition comprising, by mass, 0.1 - 2.0 % Sn, 0.005 - 0.1 % P, 0.005 % or less S, 0.005 % or less O, 0.0002 % or less H, and the balance Cu and unavoidable impurities.
  • CO2 carbon dioxide
  • ODP ozone depletion potential
  • GWP minimal global warming potential
  • CO2 operates at a much higher pressure compared to conventional refrigerants that typically operate at a pressure below 45 bar.
  • the critical point of CO2 is around 31°C and 73.8 bar, which means that transcritical CO2 systems operate above this pressure to maintain refrigeration temperature.
  • Subcritical CO2 systems operate between 45 bar and 73 bar.
  • WO 2011/066345 Al discloses a copper alloy tube for heat exchangers in high pressure applications with cooling media such as CO2, the copper alloy tube having a chemical composition comprising, by mass, 0.07 - 1.0 % Sn, 0.02 - 0.2 % Fe, optionally 0.01 - 0.07 % P, and the balance Cu and unavoidable impurities.
  • US 2009/0301701 Al discloses a copper alloy tube for use in a refrigerator or heat pump operating with CO2, the copper alloy tube having a chemical composition comprising, by mass, 0.05 - 3 % Fe, 0.01 - 0.15 % P, and optionally 0.05 - 0.2 % Zn, 0.02 - 0.05 % Sn, and the balance Cu and unavoidable impurities.
  • JP 2008 240128 A discloses a copper alloy tube for a heat exchanger using CO2, the copper alloy tube having a chemical composition comprising, by mass, 0.03 - 0.15 % Co, 0.1 - 1.0 % Zn, 0.1 - 1.0 % Sn, 0.004 - 0.08 % P, 0.005 % or less S, 0.005 % or less O, 0.0002 % or less H, and the balance Cu and unavoidable impurities.
  • JP 2011 042825 A discloses a copper alloy tube for a heat exchanger using CO2, the copper alloy tube having a chemical composition comprising, by mass, 0.70 % Sn, 0.03 % P, 1.000 % Zn, and the balance Cu with unavoidable impurities.
  • Formicary corrosion is a localized corrosion phenomenon that occurs in the presence of organic acids, such as formic acid, acetic acid, or other volatile organic compounds. These acids can be generated by the degradation of certain materials, including insulation, adhesives, and cleaning agents used in HVACR systems.
  • Formicary corrosion typically manifests as tiny, thread-like channels or tunnels on the inner and outer surfaces of the copper alloy tubes. These channels can penetrate the tube walls, leading to leaks and system inefficiencies.
  • EP 1 769 211 Al discloses a formicary corrosion resistant heat transfer tube constructed of a tin brass alloy comprising, by mass, 86.0 - 90.0 % Cu, 0.8 - 1.4 % Sn, no more than 0.05 % Pb, no more than 0.05 % Fe, no more than 0.35 % P, and the balance Zn.
  • the copper alloy tubes of WO 2011/066345 Al and US 2009/0301701 Al offer high strength and improved resistance to stress corrosion cracking. However, their high strength results in a lack of formability during tube production and in a spring- back effect. In addition, the copper alloy tubes are not resistant to formicary corrosion.
  • the brass alloy tube of EP 1 769 211 Al also suffers under a lack of formability during tube production and has a poor thermal conductivity.
  • the object of the present invention is to provide a copper alloy tube, which is suitable for use in a HVACR. system, especially in a system operating with CO2 as a refrigerant, and which has high thermal conductivity, high tensile strength and high formability during tube production as well as excellent corrosion resistance to formicary corrosion (ant-nest corrosion).
  • the copper alloy tube of the present invention has a chemical composition comprising, by mass, 0.80 - 0.95 % Zn (zinc), 0.50 - 0.65 % Sn (tin), 0.020 - 0.027 % P (phosphorus), and the balance Cu (copper) and unavoidable impurities.
  • the copper alloy tube achieves a good balance between thermal conductivity, tensile strength and formability as well as excellent corrosion resistance to formicary corrosion.
  • Zn is preferably 0.90 % or less, more preferably 0.85 % or less.
  • Sn is preferably 0.60 % or less, more preferably 0.55 % or less.
  • P is preferably 0.025 % or less, more preferably 0.023 % or less.
  • the copper alloy tube has a microstructure including submicron P2Zn 3 particles. During solidification of the molten cooper alloy, the P2Zn 3 particles precipitate in the melt and act as nucleation points for a solid Cu phase. The copper alloy tube therefore has a fine-grained homogeneous microstructure. As explained in the detailed description below, the P 3 Zn 3 particles also play an important role in suppressing formicary corrosion.
  • the resistance to formicary corrosion can be assessed using the formicary corrosion test specified in the detailed description below.
  • the copper alloy tube is sufficiently resistant to formicary corrosion if the average depth of the ten deepest pits in a sample subjected to the formicary corrosion test is less than 150 pm after 14 days of exposure.
  • the average depth of the ten deepest pits is more preferably less than 100 pm after 14 days of exposure and even more preferably less than 100 pm after 21 days of exposure.
  • the copper alloy tube preferably has a grain size between 5 and 30 pm.
  • the copper alloy tube preferably has a tensile strength of at least 270 MPa, preferably of at least 290 MPa, as measured in accordance with ISO 6892-1 :2019.
  • the total content of the unavoidable impurities is preferably 0.10 % or less, more preferably 0.05 % or less.
  • the respective content of all unavoidable impurities other than Fe may be less than 0.010 % and the content of Fe may be less than 0.050 %.
  • the respective content of all unavoidable impurities other than Fe, Pb, S and Sb may be even less than 0.0010 %.
  • the copper alloy tube of the present invention is suitable for use in a HVACR system.
  • the copper alloy tube is particularly suitable for use in a HVACR. system operating with CO2, including a system operating above the critical point of CO2 which is around 31°C and 73.8 bar.
  • Fig. 1 shows a phase diagram calculated by the inventors for a CuZnSnP alloy having different contents of Zn and fixed contents of 0.65 % by mass Sn and 0.025 % by mass P.
  • Fig. 2 shows a precipitation volume fraction diagram derived from the phase diagram shown in Fig. 1.
  • Fig. 4 shows a precipitation volume fraction diagram derived from the phase diagram shown in Fig. 3.
  • Fig. 5 shows the microstructure of a plain copper alloy tube according to a first embodiment of the present invention.
  • Fig. 6 shows the microstructure of an inner-grooved copper alloy tube according to a second embodiment of the present invention.
  • Fig. 7 shows the corrosion morphology of a copper alloy tube according to the first embodiment of the present invention and a DHP copper tube after 14 days of exposure.
  • Fig. 8 shows the corrosion morphology of a copper alloy tube according to the first embodiment of the present invention and a DHP copper tube after 21 days of exposure.
  • Fig. 9 shows the corrosion morphology of a copper alloy tube according to the second embodiment of the present invention and a DHP copper tube after 14 days of exposure.
  • Fig. 10 shows the corrosion morphology of a copper alloy tube according to the second embodiment of the present invention and a DHP copper tube after 21 days of exposure.
  • the copper alloy tube of the present invention has a chemical composition comprising 0.80 - 0.95 % Zn, 0.50 - 0.65 % Sn, 0.020 - 0.027 % P, and the balance Cu and unavoidable impurities.
  • phase diagrams in Figs. 1 and 3 show that, during solidification of the molten copper alloy, a solid Cu phase including P2Zn 3 particles is initially formed, and then an intermetallic Cu 3 Sn phase is formed.
  • the volume fraction of intermetallic Cu 3 Sn increases for a content of Zn in the range 0.1 % or more as the content of Zn increases.
  • Zn is preferably 0.90 % or less, more preferably 0.85 % or less.
  • intermetallic Cu 3 Sn forms at a content of Sn in the range of 0.5 % or more.
  • the volume fraction of intermetallic Cu 3 Sn is related to tensile strength and formability during tube production.
  • Sn is less than 0.50 %, it is difficult to achieve a tensile strength of at least 270 MPa that is needed for high- pressure applications.
  • Sn is more than 0.65 %, formability becomes a problem. Since Sn has a lower thermal conductivity than Cu, thermal conductivity also suffers.
  • Sn is preferably 0.60 % or less, more preferably 0.55 % or less.
  • the volume fraction of P2Zn 3 particles is substantially constant at different contents of Zn and Sn for a fixed content of 0.025% P. In other words, the content of P determines the volume fraction of P 3 Zn 3 particles.
  • the thin passive layer of CU2O formed on the surface of a copper alloy tube is rapidly dissolved in the presence of organic acids, and local discontinuity of the CU2O layer allows dissolution of metallic copper and the onset of formicary corrosion (ant-nest corrosion).
  • the presence of P on the surface of the copper alloy tube causes release of H2PO4, which leads to a widening of the pit mouth at an early stage and to a corrosion morphology of both formicary corrosion and wide shallow pit corrosion.
  • the amount of H2PO4 increases to such an extent that it has an impact on oxygen consumption and suppresses the development of CU2O, leading to a corrosion morphology of micro pitting corrosion.
  • the inventors believe that a preferential dissolution of Zn and Sn occurs in the copper alloy tube of the present invention and results in the development of Sn oxides that suppress the development of CU2O at a much lower content of P and much lower levels of H2PO4 than expected by the prevailing opinion.
  • P is preferably 0.025 % or less, more preferably 0.023 % or less.
  • Elements other than Cu, Zn, Sn, and P are considered impurities that should be avoided as they could have an undesirable effect on thermal conductivity, tensile strength, formability during tube production, and corrosion morphology.
  • the total content of unavoidable impurities is preferably 0.10 % or less, more preferably 0.05 % or less.
  • the unavoidable impurities include elements such as Pb (lead), Fe (iron), Ni (nickel), Al (aluminum), Si (silicon), Mn (manganese), S (sulfur), Cd (cadmium), Bi (bismuth), Cr (chromium), Sb (antimony), Mg (magnesium), As (arsenic), Se (selenium), Te (tellurium), Ag (silver), Co (cobalt), and Zr (zirconium).
  • elements such as Pb (lead), Fe (iron), Ni (nickel), Al (aluminum), Si (silicon), Mn (manganese), S (sulfur), Cd (cadmium), Bi (bismuth), Cr (chromium), Sb (antimony), Mg (magnesium), As (arsenic), Se (selenium), Te (tellurium), Ag (silver), Co (cobalt), and Zr (zirconium).
  • the content of Fe is typically less than 0.050 % and preferably less than 0.020 %.
  • the respective content of all unavoidable impurities other than Fe is typically less than 0.010 % and preferably less than 0.005 %.
  • the respective content of all unavoidable impurities other than Fe, Pb, S and Sb may be even less than 0.0010 %.
  • the copper alloy tube of the present invention may have a grain size between 5 and 30 pm. When the grain size exceeds 30 pm, fatigue strength can be a problem. It is noted that good fatigue strength is crucial for HVACR. components.
  • the copper alloy tube of the present invention preferably has a tensile strength of at least 270 MPa as measured in accordance with ISO 6892-1 :2019, more preferably of at least 290 MPa.
  • the copper alloy tube of the present invention may have a yield strength R.pO.2 of at least 60 MPa and an elongation of at least 40 %.
  • the copper alloy tube of the present invention may have an outer diameter in a range of 3 - 16 mm and a wall thickness in a range of 0.15 - 1 mm.
  • the necessary wall thickness is 0.66 mm.
  • a material saving of 21 % is achieved.
  • the copper alloy tube of the present invention may be seamless produced by hot extrusion and cold drawing.
  • the copper alloy tube is a plain tube having an inner surface without grooves as shown in Fig. 5.
  • Fig. 5 shows an example of the microstructure of the plain tube in a longitudinal cross-section.
  • the copper alloy tube is an inner- grooved tube having grooves on the inner surface as shown in Fig. 6.
  • the grooves enhance heat transfer performance.
  • Fig. 6 shows an example of the microstructure of the inner-grooved tube in a transversal cross-section.
  • the formicary corrosion test used for evaluating the resistance to formicary corrosion is as follows.
  • Specimens are cut to a desired length. Specimen length is selected based on the available total sample dimensions, but should not be lower than 50 mm. Three specimens are tested from each sample category, in each interval. Prior to exposure, the exposed area of each specimen is calculated, and specimen weight and macroscopic and stereoscopic appearance are recorded. In case of inner- grooved samples, the inner groove is included in the calculated area.
  • the specimens are suspended in a formic acid solution having a concentration of 1000 ppm, in glass jars, with 45° inclination, using PTFE threads or a similar material able to resist the exposure conditions.
  • the number of specimens placed in each glass jar should allow for uniform exposure of each specimen.
  • the specimens should not come in contact with adjacent specimens or with the wall of the glass jar.
  • the volume of the formic acid solution to the exposed area ratio is 0.03 ml/mm 2 .
  • 125 ml formic acid solution are placed in a glass jar.
  • the rubber band inserts of each glass jar are covered with PTFE tape.
  • the glass jars are placed in an environmental chamber that performs daily thermal cycles 16 h: 40°C and 8 h: 25°C. The samples are examined and evaluated at different exposure periods.
  • Max pit Deepest single value per sample category
  • AVE-10 Average depth of the ten deepest pits per sample category
  • Pitting Factor deepest penetration/average penetration
  • CAI is a comparative assessment of tube failure tendency and not of absolute corrosion evolution. CAI ranges from 0: no attack to 100: tube failure.
  • the material of the copper alloy tube according to the first embodiment of the present invention (in the following referred to as "invention alloy” or "CuZnSnP alloy”) had a chemical composition comprising 0.9 % Zn, 0.6 % Sn, 0.025 % P, and the balance Cu and unavoidable impurities.
  • the material of the DHP copper tube had a chemical composition comprising 0.02 % P, and the balance Cu and unavoidable impurities.
  • Fig. 7 shows the corrosion morphology of the samples after 14 days of exposure
  • Fig. 8 shows the corrosion morphology of the samples after 21 days of exposure.
  • Figs. 7 and 8 show X-ray diffraction (XRD) images of the samples at different magnifications.
  • the DHP copper tube shows significantly more formicary corrosion than the invention alloy tube.
  • a copper alloy tube according to the second embodiment of the present invention i.e., an inner-grooved CuZnSnP alloy tube
  • an inner-grooved DHP copper tube in terms of resistance to formicary corrosion.
  • the chemical compositions of the tubes were the same as in the first comparative test.
  • Figs. 9 and 10 are XRD images of the samples at different magnifications, showing the corrosion morphology of the samples after 14 days of exposure and 21 days of exposure, respectively.
  • the DHP copper tube shows significantly more formicary corrosion than the CuZnSnP alloy tube. This is particularly evident from the criterion Ave-10, i.e. the average depth of the ten deepest pits per sample category. The average depth of the ten deepest pits for the CuZnSnP alloy tube is significantly lower than for the DHP copper tube.
  • Ave-10 i.e. the average depth of the ten deepest pits per sample category.
  • the average depth of the ten deepest pits for the CuZnSnP alloy tube is significantly lower than for the DHP copper tube.
  • a sample is assessed as having insufficient resistance to formicary corrosion if the average depth of the ten deepest pits in the sample is 150 pm or more after 14 days of exposure.
  • the sample is assessed as sufficiently resistant to formicary corrosion if the average depth of the ten deepest pits in the sample is less than 150 pm after 14 days of exposure.
  • the sample is assessed as having good resistance to formicary corrosion if the average depth of the ten deepest pits is 100 pm after 14 days of exposure.
  • the sample is assessed as having excellent resistance to formicary corrosion if the average depth of the ten deepest pits is less than 100 pm after 21 days of exposure. Based on this classification, the DHP copper tube is assessed as having insufficient resistance to formicary corrosion, whereas the CuZnSnP alloy tube is assessed as having excellent resistance to formicary corrosion.

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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)

Abstract

L'invention concerne un tube en alliage de cuivre dont la composition chimique comprend, en masse, 0,80 à 0,95% de Zn, 0,50 à 0,65% de Sn, 0 020 à 0 027% de P, et le reste étant du Cu et des impuretés inévitables. Le tube en alliage de cuivre permet d'obtenir un bon équilibre entre la conductivité thermique, la résistance à la traction et la formabilité pendant la production de tube, ainsi qu'une excellente résistance à la corrosion notamment à la corrosion formicaire.
PCT/EP2024/085445 2023-12-22 2024-12-10 Tube en alliage de cuivre destiné à être utilisé dans un système hvacr Pending WO2025131865A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23219698 2023-12-22
EP23219698.0 2023-12-22

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WO2025131865A1 true WO2025131865A1 (fr) 2025-06-26

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PCT/EP2024/085443 Pending WO2025131864A1 (fr) 2023-12-22 2024-12-10 Tube en alliage de cuivre destiné à être utilisé dans un système hvacr
PCT/EP2024/085445 Pending WO2025131865A1 (fr) 2023-12-22 2024-12-10 Tube en alliage de cuivre destiné à être utilisé dans un système hvacr

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4935076A (en) 1988-05-11 1990-06-19 Mitsui Mining & Smelting Co., Ltd. Copper alloy for use as material of heat exchanger
JPH0931570A (ja) 1995-07-14 1997-02-04 Mitsui Mining & Smelting Co Ltd 耐食性に優れた外装用建材
EP0908526A1 (fr) 1997-09-16 1999-04-14 Waterbury Rolling Mills, Inc. Alliage de cuivre et procédé pour sa production
JP2003268467A (ja) 2002-03-18 2003-09-25 Kobe Steel Ltd 熱交換器用銅合金管
EP1630240A1 (fr) 2003-03-03 2006-03-01 Sambo Copper Alloy Co., Ltd Materiaux en alliage de cuivre resistant a chaud
EP1769211A1 (fr) 2004-05-05 2007-04-04 Luvata Oy Tube de transfert thermique constitue d'un alliage etain-laiton
JP2008240128A (ja) 2007-03-29 2008-10-09 Kobelco & Materials Copper Tube Inc 銅合金管
EP2055795A2 (fr) 2007-11-05 2009-05-06 Kobelco & Materials Copper Tube, Ltd. Tube d'alliage en cuivre pour échangeurs thermiques
US20090301701A1 (en) 2006-03-23 2009-12-10 Andreas Beutler Use of a Heat Exchanger Tube
JP2011042825A (ja) 2009-08-20 2011-03-03 Kobe Steel Ltd 加工性に優れた熱交換器用銅合金管
WO2011066345A1 (fr) 2009-11-25 2011-06-03 Luvata Espoo Oy Alliages de cuivre et tubes échangeurs de chaleur

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4935076A (en) 1988-05-11 1990-06-19 Mitsui Mining & Smelting Co., Ltd. Copper alloy for use as material of heat exchanger
JPH0931570A (ja) 1995-07-14 1997-02-04 Mitsui Mining & Smelting Co Ltd 耐食性に優れた外装用建材
EP0908526A1 (fr) 1997-09-16 1999-04-14 Waterbury Rolling Mills, Inc. Alliage de cuivre et procédé pour sa production
JP2003268467A (ja) 2002-03-18 2003-09-25 Kobe Steel Ltd 熱交換器用銅合金管
EP1630240A1 (fr) 2003-03-03 2006-03-01 Sambo Copper Alloy Co., Ltd Materiaux en alliage de cuivre resistant a chaud
EP1769211A1 (fr) 2004-05-05 2007-04-04 Luvata Oy Tube de transfert thermique constitue d'un alliage etain-laiton
US20090301701A1 (en) 2006-03-23 2009-12-10 Andreas Beutler Use of a Heat Exchanger Tube
JP2008240128A (ja) 2007-03-29 2008-10-09 Kobelco & Materials Copper Tube Inc 銅合金管
EP2055795A2 (fr) 2007-11-05 2009-05-06 Kobelco & Materials Copper Tube, Ltd. Tube d'alliage en cuivre pour échangeurs thermiques
JP2011042825A (ja) 2009-08-20 2011-03-03 Kobe Steel Ltd 加工性に優れた熱交換器用銅合金管
WO2011066345A1 (fr) 2009-11-25 2011-06-03 Luvata Espoo Oy Alliages de cuivre et tubes échangeurs de chaleur

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KOZO KAWANO ET AL.: "Influence of P concentration on Ant's Nest Corrosion in Copper Tubes", MATERIALS SCIENCE, 2018
TAMBANG MANIK ET AL.: "Effect of phosphorus on the ant nest corrosion mechanism", MATERIALS TODAY COMMUNICATIONS, vol. 36, 2023, pages 106560

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