WO2006041518A1 - Feuille de brasage se pretant a une utilisation dans des echangeurs de chaleur et analogues - Google Patents

Feuille de brasage se pretant a une utilisation dans des echangeurs de chaleur et analogues Download PDF

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Publication number
WO2006041518A1
WO2006041518A1 PCT/US2005/009841 US2005009841W WO2006041518A1 WO 2006041518 A1 WO2006041518 A1 WO 2006041518A1 US 2005009841 W US2005009841 W US 2005009841W WO 2006041518 A1 WO2006041518 A1 WO 2006041518A1
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WO
WIPO (PCT)
Prior art keywords
alloy
brazing sheet
max
heat exchanger
liner
Prior art date
Application number
PCT/US2005/009841
Other languages
English (en)
Inventor
Zayna M. Connor
Original Assignee
Pechiney Rolled Products
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 Pechiney Rolled Products filed Critical Pechiney Rolled Products
Priority to PCT/US2005/034707 priority Critical patent/WO2006039304A1/fr
Publication of WO2006041518A1 publication Critical patent/WO2006041518A1/fr
Priority to US11/694,589 priority patent/US20080056931A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/016—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of aluminium or aluminium alloys

Definitions

  • the present invention relates generally to aluminum alloy brazing sheet materials including brazing sheet tube stock, and more particularly to increased strength and erosion/corrosion resistant aluminum alloy brazing sheet materials, as well as, to methods for their manufacture and use.
  • Aluminum brazing sheet is widely used to manufacture various heat exchangers such as radiators, charge air coolers, evaporators and condensers in the automotive industry.
  • One of the much-needed improvements in the automotive industry is the overall weight reduction in order to enhance fuel economy.
  • the goal of weight reduction extends to all components of a vehicle including heat exchangers. Accordingly, research and development efforts are continuing to down gauge the tube stock in automotive radiators, while increasing strength and erosion/corrosion resistance. Long life of heat exchangers from the viewpoint of corrosion is of importance not only to improve their performance, but also towards down gauging of radiator tube stock.
  • the material properties of interest in this regard are 'post-braze' strength, braze flow, and internal (water-side) and external (air-side) corrosion resistance of the brazing sheet.
  • radiator tube material is a composite, with a non-heat treatable core alloy of 3xxx series, which is sandwiched between an inner liner and a 'braze' clad of an Al-Si alloy.
  • the strength is provided by the core alloy, whereas the inner liner improves the coolant-side corrosion resistance.
  • the air-side corrosion resistance is affected by the core alloy and interactions between core and 'braze' clad alloys during the brazing process.
  • Formation of an anodic near-surface layer, known as 'brown band' through diffusion of Si into the core alloy during the brazing process is one of the methods of improving the external corrosion resistance. See, e.g., Marshall, et al., "Development of a Long Life Aluminum Brazing Sheet Alloy with Enhanced Mechanical Performance," SAE paper 940505, (1994). Another way of increasing the air-side corrosion resistance is by adding Ti to the core alloy. See, e.g., Yasuaki, et al., "Development of Corrosion Resistant Brazing Sheet for Drawn Cup Type Evaporators, Part 2: Application to Evaporator," SAE Technical paper No. 930149, (1993).
  • Palmer et al. provide aluminum alloy brazing sheet materials that have an increased yield strength when the materials have been "peak aged.”
  • peak aged refers to the treatment where a brazing alloy is subjected to a brazing cycle and then aged at various temperatures and times to determine its "peak age," i.e., the time and temperature combination where the maximum strength is observed.
  • the peak-aged alloy of the Palmer et al. invention demonstrated yield strength at 175° C.
  • invention comprises in weight percent based on the weight of the core alloy: less than 0.2% Si, less than 0.2% Fe, 1.3-1.7% Mn, 0.4-0.8% Mg, 0.3-0.7% Cu and less than 0.2% Ti and at least one element selected from the group consisting of Cr, Sc, V, Zr, Hf, and Ni, and balance aluminum and unavoidable impurities.
  • AA 3005 has been attempted to be used, AA 3005 has many defects and is not capable of passing the OY water test. Moreover, AA 3005 generally does not have sufficient strength characteristics and corrosion/erosion resistance that is often desired in many applications.
  • a brazing sheet composite comprising an aluminum core alloy wherein the core alloy comprises an aluminum alloy modified with Mg to invoke solute strengthening, and/or to increase erosion/corrosion resistance.
  • a core alloy comprises 3xxx series aluminum alloy wherein Mg is from 0.0 to about 0.35%, along with a dispersoid- forming element such as Mn, Cr, and Zr.
  • a further embodiment of the invention includes liner alloys comprising lxxx series aluminum modified by Zn, Mn 5 Mg, and/or dispersoid forming elements.
  • Still a further embodiment includes a radiator tube core alloy that possesses improved 'post-braze' strength at room temperature and normal radiator operating temperatures.
  • Other embodiments of the invention are core alloys with improved 'post- braze 'strength at elevated temperatures suitable for charge air cooler applications.
  • FIG. 1 Further embodiments of the present invention are inner liner materials developed to improve water-side corrosion resistance of radiator tubes.
  • brazing sheet materials including tube stock and heat exchangers as well as further applications.
  • Figure 1 is a graph showing the effect of Mg, added to a 3xxx series aluminum core alloy, has on strength, measured in MPa.
  • Figure 2 is a graph showing the effect of various dispersoid forming elements, added to a 3xxx series aluminum core alloy, have on strength, measured in MPa.
  • Figure 3 is a graph showing the effect of various dispersoid forming elements, added to either a 3xxx series aluminum core alloy, or liner, have on strength, measured in MPa.
  • Figure 4 is a graph showing the effect of various dispersoid forming elements, added to a 3xxx series aluminum core alloy, without an inner liner present, have on strength, measured in MPa.
  • Figure 5 is a graph showing the effect of various dispersoid forming elements, added to a 3xxx series aluminum core alloy, have on strength measured from 0-350° C.
  • Figure 6 is a graph showing corrosion pit depth data of liners with Zn.
  • Figure 7 is a graph showing the depth from the water-side surface in microns, of liners with Zn.
  • Figure 8 is a graph showing the effect of Mg in a liner composition, measured in terms of surface pit depth.
  • Figure 9 is a graph showing the corrosion potential, in mV, versus depth from water-side surface of Mg containing liners.
  • Figure 10 is a graph showing pit depth data of liners with and without Zn, and, as a core with no liner.
  • Figure 11 is a graph showing corrosion potential, in mV, versus depth from the water-side surface of liners with and without Zn, and, as a core with no liner.
  • heat exchanger tube materials can include, but are not limited to radiators, charge air cooler, condenser, evaporator tubes and the like.
  • heat exchanger tube core alloy development to improve 'post-braze' strength at room temperature and normal heat exchanger tube operating temperatures
  • development of core alloys to improve 'post-braze' strength at elevated temperatures for heat exchanger applications and, inner liner materials developed to improve water-side erosion/corrosion resistance of heat exchanger tubes.
  • the 'post-braze' strength of 3xxx aluminum alloys can be improved to some extent through alloying modifications.
  • the applicable strengthening mechanism is primarily solid solution strengthening.
  • Grain size strengthening is another mechanism, wherein smaller grain size can contribute to an increase in strength at lower temperatures.
  • Mg is an element of interest for solute strengthening.
  • solute strengthening is a metallurgical term, whereby solute atoms are of a size and lattice parameters that they allow for strengthening of the alloy to occur.
  • Precipitation hardening to a small extent is also possible if Mg is present in the core alloy.
  • the mechanism of age hardening involves precipitation of Mg 2 Si during the 'post-braze' aging treatment. The gain in strength through age hardening, however, is not stable at elevated temperatures because of coarsening of precipitate particles.
  • Alloying additions, such as Mn, that result in fine dispersion of intermetallic particles (e.g. MnAl 6 ) may result in some dispersion strengthening.
  • Intermetallic dispersoids being thermally stable, may provide some elevated temperature strengthening, which is of interest to enhance the operating temperature of charge air coolers.
  • Mg is present in an amount from 0.01 to about 0.4 % based on the weight of the alloy, particularly from about 0.10-0.35 weight %.
  • Modifications involving dispersoid-forming elements such as Mn, Cr Ti and Zr are also disclosed.
  • the dispersoid forming elements are preferably present in total in an amount from 0.75 to 2.15%.
  • Mn if present is preferably present in an amount from 0.1-2.0, particularly preferably from 0.7 to 1.7%
  • Cr if present is from 0.01 to 0.5%, particularly from 0.05 to 0.2%
  • Zr if included is preferably included in an amount from 0.01 to 0.35%, particularly from 0.05 to 0.25%
  • Ti, if included is preferably included in an amount advantageously from about 0.01 to 0.25%, particularly from 0.1-0.2%.
  • An inner liner can be present on materials of the present invention. Alternatively, alloys of the present invention can be used unclad, or "bare.” Alternatively, alloys of the present invention can function as liners themselves. Different alloy compositions of 3xxx aluminum alloys are disclosed which improve strength at ambient and elevated temperatures. Modifications of water-side liner compositions with the addition of Mg are also disclosed which enhance the 'post- braze' strength of the brazing sheet.
  • the mechanisms of water-side corrosion such as localized pitting and erosion- corrosion are of interest towards designing alloys for better corrosion resistance.
  • Zn is commonly added to the liners in order to enhance the water-side corrosion resistance.
  • the corrosion potential of Zn being lower (less noble) than Al, alloying with Zn makes the liner alloy more anodic.
  • the Zn containing liner may serve as a sacrificial anode that promotes lateral attack rather than localized pitting.
  • the corrosion response of Zn containing liners in terms of the effects such as the concentration of Zn in the liner is desired towards selecting the optimal composition.
  • Erosion-corrosion means simultaneous mechanical and chemical action.
  • the tubes used in such applications are subject to both mechanical erosion through the high velocity of water or other liquid running therethrough, as well as, outside forces of rocks hitting the tubes when in use.
  • the tubes are subjected to chemical erosion due to environmental forces (salt/sand) as well as other contact with chemicals on their inner sides.
  • the dual interaction, (mechanical/chemical) often leads to more rapid damage of the heat exchange material (such as radiator tubes).
  • the extent of erosion-corrosion in applications such as radiator tubes is affected by variables such as fluid velocity, test temperature and mechanical properties of the material.
  • alloys of the following preferable composition Mg up to 0.35% maximum, Si from 0.4 to 0.9%, Fe from 0.2 to 0.7%, Cu from 0.4 to 0.9%, Mn from 0.7 to 1.7%, Cr from 0.05 to 0.2%, Ti from 0.1 to 0.2%,
  • Mg and dispersoid forming elements were analyzed.
  • a core alloy was exposed to a coolant directly without a liner in order to compare its performance to the performance of the same alloy used as a liner.
  • Coupons of the brazing sheets without fluxing were exposed to a standard brazing cycle in a CAB furnace. It involved a ramp up rate of 20°C/minute from room temperature to 600 0 C, holding at 600 0 C for 3 minutes and then air cooling.
  • OY water test means the instantly defined test using the OY water above.
  • ASTM water test means the instantly defined test using the ASTM water above.
  • FD Focal Difference
  • the corrosion potential profiles from the water ⁇ side surface were of interest to assess various inner liners in terms of their corrosion response.
  • material was removed by electro-machining making use of an electrolyte of sodium chloride solution in water.
  • OY water is more aggressive than ASTM water in all materials within the range of explored parameters. While minor pitting occurred with K3I and K4A liners, through-thickness perforations were observed in 7072 and K4B liners in OY water. Thus the highest pitting resistance is seen in K3I and K4A liners.
  • the corrosion potential measurements indicate an anodic surface layer in all Zn containing liners except K4B where it appears that the Zn in the 'braze' clad did not appreciably diffuse into the core during the braze cycle. Profuse pitting occurred in the case of K4B liner, just as in the case without a liner.
  • the overall internal corrosion test results suggest that the corrosion resistance of various liners decreases in the order of K3I, K4A, 7072 and K4B.
  • K3I and K4A liners were modified with the addition of 0.3% Mg.
  • the results of these liners with Mg are compared with the corresponding ones without Mg ( Figures 8 and 9).
  • the corrosion performance deteriorated by alloying with Mg. While minor pitting was noticed in K3I and K4A, through-thickness perforations resulted on adding Mg under similar test conditions.
  • the corrosion potential profiles were not, however, modified on adding Mg ( Figure 9). Fine precipitates involving Al, Zn and Mg may be the sites of localized and severe pitting because of the differences in the corrosion potentials between the precipitates and matrix alloy.
  • a maximum 'post-braze' tensile strength of 180 MPa at room temperature was obtained with the alloying modifications of the core alloy.
  • a gain of ⁇ 10 MPa in yield strength and ⁇ 20 MPa in tensile strength was observed over a base alloy of
  • the instantly disclosed alloys can also be used as clad layers on any desired core material if desired for any reason.

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Abstract

Matière en feuille de brasage en alliage d'aluminium se prêtant particulièrement à une utilisation dans un tube d'échangeur de chaleur, et ses procédés de fabrication et d'utilisation.
PCT/US2005/009841 2004-10-01 2005-03-23 Feuille de brasage se pretant a une utilisation dans des echangeurs de chaleur et analogues WO2006041518A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2005/034707 WO2006039304A1 (fr) 2004-10-01 2005-09-28 Feuilles de brasage d'aluminium modifiees
US11/694,589 US20080056931A1 (en) 2004-10-01 2007-03-30 Aluminum Alloy And Brazing Sheet Manufactured Therefrom

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
US61448904P 2004-10-01 2004-10-01
US61448304P 2004-10-01 2004-10-01
US61449004P 2004-10-01 2004-10-01
US60/614,483 2004-10-01
US60/614,489 2004-10-01
US60/614,490 2004-10-01
US61716104P 2004-10-12 2004-10-12
US60/617,161 2004-10-12
US64698505P 2005-01-27 2005-01-27
US60/646,985 2005-01-27

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/694,589 Continuation-In-Part US20080056931A1 (en) 2004-10-01 2007-03-30 Aluminum Alloy And Brazing Sheet Manufactured Therefrom

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WO2006041518A1 true WO2006041518A1 (fr) 2006-04-20

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PCT/US2005/034707 WO2006039304A1 (fr) 2004-10-01 2005-09-28 Feuilles de brasage d'aluminium modifiees

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2039790A1 (fr) 2007-09-18 2009-03-25 Hydro Aluminium Deutschland GmbH Couche anti-corrosion
US9546829B2 (en) 2013-03-13 2017-01-17 Novelis Inc. Brazing sheet core alloy for heat exchanger
US9545777B2 (en) 2013-03-13 2017-01-17 Novelis Inc. Corrosion-resistant brazing sheet package
EP3269485A1 (fr) 2016-07-14 2018-01-17 Modine Manufacturing Company Brasure cab pauvre en fondant pour des échangeurs de chaleur

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105397430A (zh) * 2015-12-24 2016-03-16 常熟市欧迪管业有限公司 列管式换热器用钛管
CN105648280A (zh) * 2016-01-22 2016-06-08 济南大学 一种铝单板用铸态合金材料及其制备方法
CN115418533A (zh) * 2016-05-27 2022-12-02 诺维尔里斯公司 用于hvac&r系统的高强度和耐腐蚀合金

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4673551A (en) * 1984-05-25 1987-06-16 Sumitomo Light Metal Industries, Ltd. Fin stock material for use in plate fin heat exchanger adapted for superhigh pressure service
US5976278A (en) * 1997-10-03 1999-11-02 Reynolds Metals Company Corrosion resistant, drawable and bendable aluminum alloy, process of making aluminum alloy article and article
US6800244B2 (en) * 1999-11-17 2004-10-05 Corus L.P. Aluminum brazing alloy

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2232747T3 (es) * 2001-03-02 2005-06-01 Pechiney Rhenalu Chapa de aleacion de aluminio para soldadura a alta temperatura y metodo de fabricacion y usos de la misma.
FR2862894B1 (fr) * 2003-11-28 2007-02-16 Pechiney Rhenalu Bande en alliage d'alluminium pour brasage

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4673551A (en) * 1984-05-25 1987-06-16 Sumitomo Light Metal Industries, Ltd. Fin stock material for use in plate fin heat exchanger adapted for superhigh pressure service
US5976278A (en) * 1997-10-03 1999-11-02 Reynolds Metals Company Corrosion resistant, drawable and bendable aluminum alloy, process of making aluminum alloy article and article
US6800244B2 (en) * 1999-11-17 2004-10-05 Corus L.P. Aluminum brazing alloy

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2039790A1 (fr) 2007-09-18 2009-03-25 Hydro Aluminium Deutschland GmbH Couche anti-corrosion
WO2009037263A1 (fr) * 2007-09-18 2009-03-26 Hydro Aluminium Deutschland Gmbh Revêtement anti-corrosion
US9546829B2 (en) 2013-03-13 2017-01-17 Novelis Inc. Brazing sheet core alloy for heat exchanger
US9545777B2 (en) 2013-03-13 2017-01-17 Novelis Inc. Corrosion-resistant brazing sheet package
EP3269485A1 (fr) 2016-07-14 2018-01-17 Modine Manufacturing Company Brasure cab pauvre en fondant pour des échangeurs de chaleur

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WO2006039304B1 (fr) 2006-11-02
WO2006039304A1 (fr) 2006-04-13

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