EP2451604A1 - Alliage de cuivre pour tube d'échangeur de chaleur - Google Patents

Alliage de cuivre pour tube d'échangeur de chaleur

Info

Publication number
EP2451604A1
EP2451604A1 EP10797826A EP10797826A EP2451604A1 EP 2451604 A1 EP2451604 A1 EP 2451604A1 EP 10797826 A EP10797826 A EP 10797826A EP 10797826 A EP10797826 A EP 10797826A EP 2451604 A1 EP2451604 A1 EP 2451604A1
Authority
EP
European Patent Office
Prior art keywords
alloy
tube
weight
present
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.)
Granted
Application number
EP10797826A
Other languages
German (de)
English (en)
Other versions
EP2451604A4 (fr
EP2451604B1 (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 Espoo Oy
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 Luvata Espoo Oy filed Critical Luvata Espoo Oy
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
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
  • CO2 which is a natural cooling medium
  • 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 present invention is a copper alloy composition, which includes the following where the percentages are by weight.
  • the composition comprises copper (Cu), nickel (Ni) and tin (Sn).
  • the alloy has a composition of 99% copper by weight, 0.5% nickel by weight and 0.5% tin by weight, represented as
  • nickel is present in the range of 0.2% to 1.0%, tin in the range of 0.2% to 1.0%, and the remainder includes Cu and impurities.
  • the composition optionally comprises phosphorus in the range of 0.01% to 0.07%.
  • the present invention provides tubes for ACR applications comprising the copper alloy composition.
  • the alloy composition is formed into tubes for ACR applications.
  • Figure 1 Graphical representation of relative metal value per feet vs. copper price for a presently used alloy, C122, at standard wall thickness compared with an alloy of the present invention CuNi(0.5)Sn(0.5) at reduced wall thickness.
  • Figure 2. Graphical representation of tensile strength and conductivity for tested alloys as a function of Ni and Sn contents. Sn has a greater influence on both strength and conductivity.
  • Figure (a) is a perspective view
  • Figure (b) is a cross-section of the tube of (a) as viewed along a longitudinal axis
  • Figure (c) is a cross-section of the tube of (a) and (b) as viewed along an axis normal to the longitudinal axis.
  • 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 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 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., C 122.
  • 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., C 122) comprising the present alloy has equal or improved burst pressure and/or cycle fatigue relative to tube comprising a conventional alloy, e.g., C 122.
  • 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 C 122 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 0 C with a rapid (e.g., 10 to 500 °C/second) upward and downward ramping of the temperature.
  • the grain size is 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 comprises copper, nickel, tin, and, optionally, phosphorus.
  • the nickel is present in the range of 0.2% to 1.0%, and more specifically in the range of 0.3% to 0.7%; tin in the range of 0.2% to 1.0%, and more specifically in the range of 0.3% to 0.7%; and its remainder includes copper and impurities.
  • the composition of the alloy is CuNi(0.5)Sn(0.5). In another
  • 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, optionally, 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.
  • the composition consists essentially of Cu, Ni and Sn in the aforementioned ranges. In another embodiment the composition consists essentially of Cu, Ni, Sn and P in the aforementioned ranges. In various embodiments, addition of components other than copper, nickel, tin (and phosphorus in the case of the second embodiment) does not result in an adverse change of greater than 5, 4, 3, 2 or 1% in properties of the alloys of the present invention such as, for example, burst pressure/strength, ductility, conductivity, and cycle fatigue.
  • the composition of the alloy consists of Cu, Ni, Sn and P in the aforementioned ranges. In another embodiment, the composition of the alloy consists of Cu, Ni, Sn and P 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 comprising a copper-nickel- tin alloy (described herein).
  • the tubes are from 0.100 inch to 1 inch in outer diameter, including all fractions of an inch between 0.100 inch and 1 inch, and have a wall thickness of from 0.004 inch to 0.040 inch, including all fractions of an inch between 0.004 and 0.040 inch.
  • One advantage of the present invention is that thinner walled tubes can be used in ACR applications. This leads to reduced materials costs (see Figure 1).
  • the tubes comprising the copper-nickel-tin alloy are from 0.100 inch to 1 inch in outer diameter, including all fractions of an inch between 0.100 inch and 1 inch, and have a wall thickness of from 0.004 inch to 0.040 inch, including all fractions of an inch between 0.004 and 0.040 inch.
  • 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. In an initial step, 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 Before the roll forming and welding 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 0.5 % Ni and 0.5 % Sn (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., 0.0118 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 C 12200 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. For tubes produced with reduced wall thickness the burst pressure for an alloy of the present invention (CuNi(0.5) Sn(0.5)) is still higher compared with C122 at 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)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (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)

Abstract

L'invention porte sur un alliage comprenant du cuivre, du nickel, de l'étain et, facultativement, du phosphore, lequel alliage peut être utilisé dans, par exemple, un tube d'alliage de cuivre pour échangeurs de chaleur. Cet alliage assure une excellente résistance à la rupture et une excellente aptitude au traitement, ce qui permet de réduire le poids du tube et permet son utilisation dans des applications à haute pression, avec des fluides de refroidissement tels que du dioxyde de carbone.
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 true EP2451604A1 (fr) 2012-05-16
EP2451604A4 EP2451604A4 (fr) 2013-04-10
EP2451604B1 EP2451604B1 (fr) 2017-08-30

Family

ID=43426607

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10797826.4A Not-in-force EP2451604B1 (fr) 2009-07-10 2010-07-08 Alliage de cuivre pour tube d'échangeur de chaleur

Country Status (11)

Country Link
US (2) US20110005739A1 (fr)
EP (1) EP2451604B1 (fr)
JP (2) JP2012532990A (fr)
CN (2) CN107739880A (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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CN109706343A (zh) * 2018-12-10 2019-05-03 上海海亮铜业有限公司 一种镍掺杂c12200紫铜合金
EP3797891B1 (fr) * 2019-09-30 2023-08-02 Nexans Procédé de fabrication en continu de profilés creux, ondulés par sections, minces, de petit diamètre en metal non ferreux
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EP2451604A4 (fr) 2013-04-10
CA2767242C (fr) 2016-09-27
WO2011005926A1 (fr) 2011-01-13
ES2649557T3 (es) 2018-01-12
MX340861B (es) 2016-07-28
BR112012000607A2 (fr) 2017-09-05
BR112012000607B1 (pt) 2019-03-06
US20160363397A1 (en) 2016-12-15
MY173128A (en) 2019-12-30
HK1251625A1 (zh) 2019-02-01
BR112012000607A8 (pt) 2018-02-06
JP2015178679A (ja) 2015-10-08
CN102470471A (zh) 2012-05-23
CA2767242A1 (fr) 2011-01-13
CN107739880A (zh) 2018-02-27
JP2012532990A (ja) 2012-12-20
EP2451604B1 (fr) 2017-08-30
JP6087982B2 (ja) 2017-03-01
US20110005739A1 (en) 2011-01-13

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