EP2451604B1 - Alliage de cuivre pour tube d'échangeur de chaleur - Google Patents

Alliage de cuivre pour tube d'échangeur de chaleur Download PDF

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Publication number
EP2451604B1
EP2451604B1 EP10797826.4A EP10797826A EP2451604B1 EP 2451604 B1 EP2451604 B1 EP 2451604B1 EP 10797826 A EP10797826 A EP 10797826A EP 2451604 B1 EP2451604 B1 EP 2451604B1
Authority
EP
European Patent Office
Prior art keywords
alloy
tube
copper
weight
inch
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.)
Not-in-force
Application number
EP10797826.4A
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German (de)
English (en)
Other versions
EP2451604A1 (fr
EP2451604A4 (fr
Inventor
Parker M. Finney
Larz Ignberg
Anders Kamf
Tim Goebel
Eric Gong
Ed Rottman
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.)
Virtus Precision Tube LLC
Original Assignee
Luvata Franklin Inc
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Filing date
Publication date
Application filed by Luvata Franklin Inc filed Critical Luvata Franklin Inc
Publication of EP2451604A1 publication Critical patent/EP2451604A1/fr
Publication of EP2451604A4 publication Critical patent/EP2451604A4/fr
Application granted granted Critical
Publication of EP2451604B1 publication Critical patent/EP2451604B1/fr
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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
    • 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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/085—Heat exchange elements made from metals or metal alloys from copper or copper alloys

Definitions

  • the present invention pertains generally to copper alloys and use of the copper alloys in tubes for heat exchangers. Specifically, the invention pertains to a high strength copper alloy tube that has desirable pressure fracture strength and processability properties.
  • the alloy is suitable to reduce thickness, and therefore, conserves material, for existing air conditioning and refrigeration (ACR) heat exchangers, and is suitable for use in a heat exchanger using a cooling medium such as CO 2 .
  • Heat exchangers for air conditioners may be constructed of a U-shaped copper tube bent like a hairpin and fins made from aluminum or aluminum alloy plate.
  • a copper tube used for the above type heat exchanger requires suitable conductivity, formability, and brazing properties.
  • HCFC hydro-chlorofluorocarbon
  • HCFC hydro-chlorofluorocarbon
  • Green refrigerants for example, CO 2 , which is a natural cooling medium, have been used for heat exchangers.
  • the condensing pressure during operation needs to be increased to use CO 2 as a cooling media to maintain the same heat transfer performance as HCFC-based fluorocarbons.
  • pressures at which these cooling media are used pressure of a fluid that flows in the heat exchanger tube
  • R22 gas cooler in CO 2
  • R22 a HCFC-based fluorocarbon
  • the CO 2 cooling medium needs to have a condensing pressure of about 7 to 10 MPa (supercritical state). Therefore, the operating pressures of the new cooling media are increased as compared with the operating pressure of the conventional cooling medium R22.
  • JP52145327 , JP1316431 , JP52145328 , JP4006234 , and JP6094390 disclose various copper alloys comprising nickel and/or tin in wide ranges, wherein the alloys are suitable for use in e.g. tubes used in heat exchangers.
  • the present invention provides a copper alloy, for use in heat exchanger tubes, having, for example, high tensile strength, excellent processability and good thermal conductivity.
  • the invention is defined in the claims.
  • the present invention provides tubes for ACR applications as defined in the claims comprising a copper alloy composition consisting of Cu, Ni, Sn, P and naturally occurring impurities.
  • the present invention provides a high strength alloy which can, for example, reduce the wall thickness and therefore reduce the cost associated with existing ACR tubing and/or provide ACR tubing capable of withstanding the increased pressures associated with cooling media such as CO 2 .
  • high strength it is meant that the alloy and/or tube made from the alloy has at least the levels of tensile strength and/or burst pressure and/or cycle fatigue failure set out herein.
  • the copper alloy can provide savings in material, costs, environmental impact and energy consumption.
  • the selected alloy should have appropriate material properties and perform well with regard to processability.
  • Important material properties include properties such as, for example, burst pressure/strength, ductility, conductivity, and cycle fatigue. The characteristics of the alloy and/or tube described herein are desirable so they can withstand ACR operating environments.
  • High tensile strength and high burst pressure are desirable tube properties because they define what operating pressure a tube can withstand before failing. For example, the higher the burst pressure, the more robust the tube design or for a given burst pressure minimum the present alloy allows for a thinner wall tube.
  • the alloy and/or tube comprising the alloy has, for example, a material tensile strength of a minimum of 262 MPa (38 ksi, kilo-pound per square inch).
  • the material tensile strength can be measured by methods known in the art such as, for example, the ASTM E-8 testing protocol.
  • the alloy and/or tube comprising the alloy has a material tensile strength of 269, 276, 283 or 290 MPa (39, 40, 41 or 42 ksi).
  • Ductility of the alloy and/or a tube made from the alloy is a desirable property because, in one embodiment, tubes need to be bent 180 degrees into hairpins without fracturing or wrinkling for use in the coil.
  • Elongation is an indicator of material ductility.
  • the alloy and/or tube comprising the alloy has, for example, an elongation of a minimum of 40 %. The elongation can be measured by methods known in the art such as, for example, the ASTM E-8 testing protocol.
  • the alloy and/or tube comprising the alloy has a minimum elongation of 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50%.
  • Conductivity is a desirable property because it relates to heat transfer capability and therefore, it is a component of the efficiency of an ACR coil. Also, conductivity can be important for tube formation.
  • the alloy and/or tube comprising the alloy has, for example, a conductivity of a minimum of 35% IACS. The conductivity can be measured by methods known in the art such as, for example, the ASTM E-1004 testing protocol. In various embodiments, the alloy and/or tube comprising the alloy has a minimum conductivity of 36, 37, 38, 39, 40, 45, 50, 55, 60 or 65% (IACS).
  • the alloy and/or tube has, for example, at least equal resistance to cycle fatigue failure as the current alloy in use, e.g., C122 as shown in Table 2. Further, it is desirable that the alloy and/or tube has, for example, at least equivalent resistance against one or more types of corrosion (e.g., galvanic corrosion and formicary corrosion) as the current alloy in use, e.g., C122.
  • corrosion e.g., galvanic corrosion and formicary corrosion
  • a tube comprising an alloy of the present invention has improved softening resistance (which can be important for brazing) and/or increased fatigue strength relative to a standard copper tube, e.g., a tube made from C122.
  • a tube depicted in Figures 3(a) - (c) with reduced wall thickness t (relative to a tube comprising a conventional alloy, e.g., C122) comprising the present alloy has equal or improved burst pressure and/or cycle fatigue relative to tube comprising a conventional alloy, e.g., C122.
  • the tube wall thickness of a tube of the present invention is minimized relative to a standard tube, e.g. a C122 tube, which reduces total material cost, and both tubes exhibit the same burst pressure.
  • the tube wall thickness is at least 10, 15 or 20% less than a C122 tube, where both tubes have the same burst pressure.
  • the burst pressure can be measured by methods known in the art such as, for example, CSA-C22.2 No. 140.3 Clause 6.1 Strength Test - UL 207 Clause 13.
  • the cycle fatigue can be measured by methods known in the art such as, for example, CSA-C22.2 No. 140.3 Clause 6.4 Fatigue Test - UL 207 Clause 14.
  • the alloy of the present invention can be fabricated according to methods known in the art. During the alloy fabrication process and/or tube formation process, it can be important to control the temperature. Control of temperature can be important in keeping the elements in solution (preventing precipitation) and controlling grain size. For example, conductivity can increase and formability can suffer if processed incorrectly.
  • heat treatment in the production process will occur over a short time such that the temperature of the alloy and/or tube will be between 400-600 °C with a rapid (e.g., 10 to 500 °C/second) upward and downward ramping of the temperature.
  • the tube made from the alloy has a desired grain size, being from 1 micron to 50 microns, including all integers between 1 micron and 50 microns. In another embodiment, the grain size is from 10 microns to 25 microns. In yet another embodiment, the grain size is from 10 microns to 15 microns. The grain size can be measured by methods known in the art such as, for example, the ASTM E-112 testing protocol.
  • the alloy compositions of the present invention include the following where relative amounts of the components in the alloy are given as percentages by weight.
  • the ranges of percentage by weight include all fractions of a percent (including, but not limited to, tenths and hundredths of a percent) within the stated ranges.
  • the composition consists of copper, nickel, tin, phosphorus, and impurities.
  • the nickel is present in the range of 0.3% to 0.7%; tin in the range of 0.3% to 0.7%; phosphorus in the range of 0.01% to 0,07%; and its remainder is copper and impurities.
  • the composition of the alloy is CuNi(0.5)Sn(0.5)P(0.020).
  • the impurities can be, for example, naturally-occurring or occur as a result of processing.
  • impurities include, for example, zinc, iron and lead.
  • the impurities can be a maximum of 0.6 %. In various other embodiments, the impurities can be a maximum of 0.5, 0.45, 0.3, 0.2 or 0.1%.
  • Phosphorus is present in the range of 0.01% to 0.07%, and more specifically in the range of 0.015% to 0.030%, or at 0.02%. Without intending to be bound by any particular theory, it is considered that inclusion of an appropriate amount of phosphorus in the alloy increases the weldability of the alloy by effecting the flow characteristics and oxygen content of the metal, while addition of too much phosphorus leads to poor grain structure and unwanted precipitates.
  • composition of the alloy consists of Cu, Ni, Sn, P and impurities in the aforementioned ranges.
  • the alloy of the present invention may be produced for use by various processes such as cast and roll, extrusion or roll and weld.
  • the processing requirement includes, for example, brazeability. Brazing occurs when the tubes are connected as described below.
  • the alloy in the roll and weld process the alloy is cast into bars, roll reduced to thin gauge, heat treated, slit to size, embossed, formed into tube, welded, annealed, and packaged.
  • the alloy in the cast and roll process the alloy is cast into "mother" tube, drawn to size, annealed, machined to produce inner grooves, sized, annealed, and packaged.
  • the alloy in the extrusion process, the alloy is cast into a solid billet, reheated, extrusion pressed, drawn and grooved to final dimensions, annealed and packaged.
  • the present invention provides tubes as defined in the claims which are from 2.5 mm (0.100 inch) to 25 mm (1 inch) in outer diameter, including all fractions of an inch between 2.5 mm (0.100 inch) and 25 mm (1 inch), and have a wall thickness of from 0.10 mm (0.0004 inch) to 1.0 mm (0.040 inch) including all fractions of an inch between 0.10 mm (0.0004 inch) to 1.0 mm (0.040 inch).
  • tubes as defined in the claims which are from 2.5 mm (0.100 inch) to 25 mm (1 inch) in outer diameter, including all fractions of an inch between 2.5 mm (0.100 inch) and 25 mm (1 inch), and have a wall thickness of from 0.10 mm (0.0004 inch) to 1.0 mm (0.040 inch) including all fractions of an inch between 0.10 mm (0.0004 inch) to 1.0 mm (0.040 inch).
  • the tubes are used in ACR applications. It is desirable that the tubes have sufficient conductivity (e.g., so that the tubes can be joined by welding) and formability (e.g., ability to be shaped, e.g., bent, after formation of the tube). Also, it is desirable that the tubes have properties such that the tube can have internal groove enhancement.
  • One example of a process suited for the alloy of the present invention is a heat exchanger coil having tubes formed with a roll and weld process.
  • the copper alloy of the present invention is cast into slabs followed by hot and cold rolling into flat strips.
  • the cold rolled strips are soft annealed.
  • the soft annealed copper alloy strips are then formed into heat exchanger tubes by means of a continuous roll forming and weld process.
  • the tubes may be provided with internal enhancements such as grooves or ribs on the inside wall of the tube as will be evident to those of ordinary skill in the art.
  • the tubes are formed in a continuous roll and weld process and the output may be wound into a large coil. The large coil may then be moved to another area where the coil is cut into smaller sections and formed into the U or hairpin shape.
  • the hairpin is threaded into through-holes of aluminum fins and a jig is inserted into the U-shaped copper tube to expand the tube, thereby closely attaching the copper tube and the aluminum fin to each other. Then the open end of the U-shaped copper tube is expanded and a shorter hairpin similarly bent into a U-shape is inserted into the expanded end. The bent copper tube is brazed to the expanded open end using a brazing alloy thereby being connected to an adjacent hairpin to make a heat exchanger.
  • Material of a composition of Alloy B of 0.5 % Ni 0.5 % Sn and 0.020% P, denoted as CuNi(0.5)Sn(0.5) was produced in full production scale and formed to tubes using the roll and weld method.
  • the tubes were produced both in standard wall thickness (e.g., 0.300 mm (0.0118 inches)) and with 13 % lower wall thickness.
  • Mechanical properties of the tubes were tested using ASTM and UL (e.g., UL testing protocols and compared with tubes made of "present use" copper alloy C12200 with standard wall thickness. The results are shown in Table 2.
  • the alloy of the invention CuNi(0.5)Sn(0.5) has higher strength and higher burst pressure in standard wall thickness.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
  • Conductive Materials (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Claims (6)

  1. Tube ACR à utiliser dans un échangeur de chaleur pour réfrigération et conditionnement d'air (ACR), dans lequel le tube comprend un alliage de cuivre constitué de :
    a) nickel compris entre 0,3 % et 0,7% en poids ;
    b) étain compris entre 0,3% et 0,7% en poids ; et
    c) phosphore compris entre 0,01% et 0,07% en poids,
    dans lequel le reste de l'alliage est du cuivre et des impuretés apparaissant naturellement sont présentes en un maximum de 0,6% en poids ;
    l'alliage ayant une granulométrie comprise entre 1 micron et 50 microns ; et
    le tube ayant une épaisseur de paroi comprise entre 0,10 mm (0,004 pouce) et 1,0 mm (0,040 pouce).
  2. Tube ACR suivant la revendication 1, dans lequel le tube comprend un alliage de cuivre constitué de :
    a) nickel compris entre 0,3% et 0,7% en poids ;
    b) étain compris entre 0,3% et 0,7% en poids ; et
    c) phosphore compris entre 0,01% et 0,07% en poids,
    dans lequel le reste de l'alliage est du cuivre ;
    l'alliage ayant une granulométrie comprise entre 1 micron et 50 microns ; et
    le tube ayant une épaisseur de paroi comprise entre 0,10 mm (0,004 pouce) et 1,0 mm (0,040 pouce).
  3. Tube ACR suivant la revendication 1 ou 2, dans lequel le nickel est présent en une teneur de 0,5% en poids, et dans lequel l'étain est présent en une teneur de 0,5% en poids.
  4. Tube ACR suivant la revendication 1 ou 2, dans lequel le phosphore est présent dans l'alliage à 0,020% en poids.
  5. Tube ACR suivant la revendication 1 ou 2, dans lequel l'alliage a une granulométrie comprise entre 10 microns et 25 microns.
  6. Tube ACR suivant la revendication 1 ou 2, dans lequel le tube a un diamètre extérieur compris entre 2,5 mm (0,100 pouce) et 25 mm (1 pouce).
EP10797826.4A 2009-07-10 2010-07-08 Alliage de cuivre pour tube d'échangeur de chaleur Not-in-force EP2451604B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US22467109P 2009-07-10 2009-07-10
PCT/US2010/041313 WO2011005926A1 (fr) 2009-07-10 2010-07-08 Alliage de cuivre pour tube d'échangeur de chaleur

Publications (3)

Publication Number Publication Date
EP2451604A1 EP2451604A1 (fr) 2012-05-16
EP2451604A4 EP2451604A4 (fr) 2013-04-10
EP2451604B1 true EP2451604B1 (fr) 2017-08-30

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US (2) US20110005739A1 (fr)
EP (1) EP2451604B1 (fr)
JP (2) JP2012532990A (fr)
CN (2) CN102470471A (fr)
BR (1) BR112012000607B1 (fr)
CA (1) CA2767242C (fr)
ES (1) ES2649557T3 (fr)
HK (1) HK1251625A1 (fr)
MX (1) MX340861B (fr)
MY (1) MY173128A (fr)
WO (1) WO2011005926A1 (fr)

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WO1998045490A1 (fr) * 1997-04-08 1998-10-15 Kitz Corporation Alliage cuivreux de bonne tenue a la fissuration par corrosion sous contrainte, resistant a la corrosion, se pretant au travail a chaud, et procede de production
JP4257668B2 (ja) * 1998-10-15 2009-04-22 Ｄｏｗａホールディングス株式会社 エッチング加工性に優れたリードフレーム用銅合金とその製造方法
JP2000129377A (ja) * 1998-10-28 2000-05-09 Sumitomo Metal Mining Co Ltd 端子用銅基合金
JP2001241445A (ja) * 2000-02-28 2001-09-07 Daido Metal Co Ltd 銅系摺動材料、その製造方法およびすべり軸受
JP4660735B2 (ja) * 2004-07-01 2011-03-30 Ｄｏｗａメタルテック株式会社 銅基合金板材の製造方法
CA2563094C (fr) * 2004-08-10 2012-03-27 Sanbo Shindo Kogyo Kabushiki Kaisha Moulage d'alliage de cuivre ayant subi un affinage du grain
KR100992281B1 (ko) * 2005-06-08 2010-11-05 가부시키가이샤 고베 세이코쇼 구리 합금, 구리 합금판 및 그의 제조 방법
JP4630323B2 (ja) * 2007-10-23 2011-02-09 株式会社コベルコ マテリアル銅管 破壊強度に優れた熱交換器用銅合金管

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EP2451604A1 (fr) 2012-05-16
CA2767242C (fr) 2016-09-27
WO2011005926A1 (fr) 2011-01-13
JP2015178679A (ja) 2015-10-08
MY173128A (en) 2019-12-30
BR112012000607B1 (pt) 2019-03-06
HK1251625A1 (zh) 2019-02-01
CN102470471A (zh) 2012-05-23
BR112012000607A2 (fr) 2017-09-05
CA2767242A1 (fr) 2011-01-13
CN107739880A (zh) 2018-02-27
US20160363397A1 (en) 2016-12-15
MX340861B (es) 2016-07-28
MX2012000544A (es) 2012-07-20
US20110005739A1 (en) 2011-01-13
ES2649557T3 (es) 2018-01-12
BR112012000607A8 (pt) 2018-02-06
EP2451604A4 (fr) 2013-04-10
JP6087982B2 (ja) 2017-03-01
JP2012532990A (ja) 2012-12-20

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