WO2006039303A1 - Composite d'aluminium - Google Patents

Composite d'aluminium Download PDF

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Publication number
WO2006039303A1
WO2006039303A1 PCT/US2005/034706 US2005034706W WO2006039303A1 WO 2006039303 A1 WO2006039303 A1 WO 2006039303A1 US 2005034706 W US2005034706 W US 2005034706W WO 2006039303 A1 WO2006039303 A1 WO 2006039303A1
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WO
WIPO (PCT)
Prior art keywords
alloy
aluminum
braze
aluminum composite
core
Prior art date
Application number
PCT/US2005/034706
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English (en)
Other versions
WO2006039303B1 (fr
Inventor
Zayna Connor
Scott H. Goodrich
Terri J. Burdoff
Timothy S. Jackson
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
Publication of WO2006039303A1 publication Critical patent/WO2006039303A1/fr
Publication of WO2006039303B1 publication Critical patent/WO2006039303B1/fr
Priority to US11/694,589 priority Critical 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
    • 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
    • F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
    • 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
    • F28F21/089—Coatings, claddings or bonding layers made from metals or metal alloys

Definitions

  • the invention is directed to a composite of at least two aluminum alloys.
  • the aluminum composite can be used for material applications such as use in heat exchangers or evaporator tubes.
  • Aluminum brazing sheet typically includes a core alloy of 3xxx and a lower melting braze clad of 4xxx series.
  • 3xxx and 4xxx are designations set forth by The Aluminum Association.
  • solid solution strengthening is one method of enhancing as-brazed strength.
  • Charge air coolers are exposed to extreme temperature fluctuations and elevations in use, and thus, provides challenges in materials design.
  • the materials must be able to exhibit sufficient strength after long-term exposure to temperatures greater than about 170° C.
  • Standard 3xxx series alloy e.g., 3003 allots have been used in the past in some heat exchanger applications since they are easily formed into sheet, fins and tubes. However, they have relatively low strength and generally cannot be used in high temperature applications.
  • Some manufacturers have turned to copper and brass charge air coolers, however, these materials are much heavier and costlier than aluminum. There remains an increasing demand on aluminum alloy manufacturers to obtain a material that has good formability and acceptable strength over the complete temperature profile that is required for operating a charge air cooler.
  • U.S. Patent No. 6,756,133 describes a core alloy for an aluminum brazing sheet that includes from 0.4 wt% to 0.7 wt%.
  • the core alloy is then brazed with a cladding that includes typically silicon.
  • a Mg 2 Si precipitate is formed by virtue of the Si from the clad migrating to the Mg of the core.
  • the formation of these precipitates often have a negative impact on the strength of the as-brazed sheet as well as relatively poor stability if exposed to high temperatures, e.g., over 177° C, over an extended period, e.g., from 10 to 2500 hours.
  • 6,403,232 describes aluminum brazing sheet that restricts Mg content in the core alloy to less than 0.3 wt% and Fe to not more than 0.2 wt%.
  • the core alloy has additional compositional limitations for Cu, Si and Mn.
  • the brazing sheet includes an inner liner alloy on a surface of the core alloy.
  • the inner liner alloy comprises less than 0.2 wt% Si and from 2.0 wt% to 3.5 wt% Mg.
  • Post-braze strength enhancement of braze sheet for folded tube applications also has important commercial applications for heat exchangers, e.g., car and truck radiators.
  • the folded tube material includes a modified 3xxx core, and a modified 7xxx inner liner, with a post-braze tensile strength of ⁇ 140 MPa.
  • materials with a tensile strength of about 170 MPa or more would provide considerable design advantages.
  • Aluminum brazing sheet is a composite structure and typically includes a core alloy with an inner liner alloy on one side of the core alloy. Aluminum brazing sheet can also include brazing clad on an opposite side of the core alloy.
  • the invention is related to an aluminum composite comprising a 3xxx aluminum core alloy or an element alloy modification thereof.
  • the 3xxx aluminum core alloy or the element alloy modification thereof comprises from 0.05 wt% to 0.4 wt% Mg.
  • In contact with the aluminum core alloy is a 7xxx inner liner alloy or an element alloy modification thereof.
  • the 7xxx liner alloy or the element alloy modification thereof comprises from 0.002 wt% to 1.5 wt% Mg.
  • 3xxx alloy and the term “7xxx” alloy are known to those of ordinary skill in the aluminum art, and have a defined alloying element compositional range recognized by "The Aluminum Association”.
  • a 3xxx aluminum alloy will have a compositional range of at least the following alloying elements: less than 1.8 wt% Si; less than 1.0 wt% Fe; less than 0.9 wt% Cu; 0.05 wt% to 1.8 wt% Mn; and less than 0.35 wt% Ti.
  • a 7xxx aluminum alloy will have a compositional range of at least the following alloying elements: less than 0.5 wt% Si; less than 1.4 wt% Fe; less than 2.6 wt% Cu; less than 0.8 wt% Mn; and less than 0.2 wt% Ti. Limiting the proportion of magnesium in the aluminum core alloy to within the compositional range of from 0.05 wt% to 0.4 wt% is believed to limit the degree OfMg 2 Si that forms during brazing.
  • the amount of Mg in the aluminum core alloy is from 0.05 wt% to 0.13 wt%, from 0.13 wt% to 0.16 wt%, from 0.16 wt% to 0.19 wt%, from 0.19 wt% to 0.2.3 wt%, from 0.23 wt% to 0.26 wt%, from 0.26 wt% to 0.29 wt%, from 0.29 wt% to 0.32 wt%, from 0.32 wt% to 0.36 wt%, from 0.36 wt% to 0.4 wt%.
  • the aluminum composite includes an aluminum core alloy comprising from 0.2 wt% to 0.35 wt% Mg. In another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.05 wt% Mg to less than 0.02 wt% Mg. In another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.1 wt% to 0.2 wt% Cr.
  • the aluminum core alloys can also contain one or more elements selected from Cr and Zr. These elements along with aluminum and silicon precipitate during homogenization to form small particles (e.g., from 0.05-0.5 ⁇ m in diameter). The formation of such precipitates is well known in the art.
  • the Zr is present from 0.1 wt% to 0.3 wt%, or from 0.13 wt% to 0.27 wt%.
  • the Cr is included in the alloy, the Cr is present is from 0.1 wt% to 0.3 wt%, or from 0.1 wt% to 0.2 wt%.
  • both Zr and Cr are present in the core alloy.
  • the inclusion of both Zr and Cr elements is believed to provide a synergistic effect in terms of the increase in tensile strength and/or yield strength.
  • the composite aluminum alloy can be used in heat exchanger applications as well as evaporator tubes, and is formed by laminating an inner liner alloy on one surface of a core alloy, and optionally, a brazing clad alloy on the opposite surface of the core alloy.
  • the alloy compositions for each of the alloy materials is described in greater detail below.
  • Core Alloy Beginning from 3xxx series alloy or an elemental modification thereof, one or more alloying elements can be present in the core alloy as follows.
  • Mg Less Than 0.4 wt %.
  • Mg is an effective element for improving the strength of the core alloy. IfMg is present at 0.4 wt % or greater, the brazing property of the aluminum composite is diminished. This is particularly true if the Nocolok Flux Brazing method is used to form the aluminum composite. In many of the core alloys, the Mg content is 0.3 wt % or less.
  • the aluminum composite includes an aluminum core alloy comprising from 0.2 wt % to 0.3 wt % Mg. In another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.05 wt % to 0.2 wt %
  • Cu Greater Than 0.2 wt % and Less Than 1.0 wt %.
  • Cu is typically used to improve the strength of the core alloy. If the Cu content is greater than 1.0 wt %, the workability of the alloy is diminished. If the Cu content is less than 0.2 wt %, there is little, if any, improvement in the strength of the core alloy. In one embodiment, the Cu content is from 0.3 wt % to 0.7 wt%.
  • the aluminum composite includes an aluminum core alloy comprising from 0.05 wt% to 0.5 wt % Si. In another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.05 wt % to 0.2 wt % Si.
  • Mn From 0.5 to 1.7 wt %. Mn is typically used to enhance the corrosion resistance and the strength of the core material. If the Mn content is less than 0.5 wt %, there is little, if any, improvement in the strength of the core alloy. If the Mn content is greater than 1.7 wt %, castability of the alloy is diminished.
  • the aluminum composite includes an aluminum core alloy comprising from 0.8 wt% to 1.4 wt % Mn.
  • the aluminum composite includes an aluminum core alloy comprising from 1.2 wt % to 1.7 wt % Mn.
  • Fe Not More Than 0.4 wt %. If the Fe content is greater than 0.4 wt %, workability is diminished.
  • the aluminum composite includes an aluminum core alloy comprising from 0.0 wt% to 0.2 wt % Fe. In another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.1 wt % to 0.3 wt % Fe.
  • the aluminum composite includes an aluminum core alloy comprising from 0.0 wt% to 0.2 wt % Cr. In another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.1 wt% to 0.2 wt% Cr. In still another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.01 wt % to 0.1 wt % Cr.
  • the aluminum composite includes an aluminum core alloy comprising from 0.0 wt % to 0.2 wt % Zr. In another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.13 wt % to 0.27 wt % Zr. In still another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.01 wt % to 0.1 wt % Zr.
  • both Zr and Cr are present in the core alloy.
  • the inclusion of both Zr and Cr elements is believed to provide a synergistic effect in terms of the increase in tensile strength (yield strength).
  • the total content of (Zr + Cr) is 0.4 wt % or less.
  • Ti Not More Than 0.3 wt %. Ti is useful as a dispersoid. Ti is typically used to improve the corrosion resistance of the core alloy, however, the addition of Ti beyond 0.3 wt % provides little, if any, further improvement in the corrosion resistance. Also, the workability is degraded beyond 0.3 wt % Ti.
  • the aluminum composite includes an aluminum core alloy comprising from 0.0 wt% to 0.2 wt % Ti. In another embodiment, the aluminum composite includes an aluminum core alloy comprising from 0.01 wt % to 0.1 wt % Ti.
  • the tensile strength of the aluminum composite can be enhanced by modifying the composition of the inner liner. For example, adding Mg or Zr to a 7xxx liner alloy or modification thereof increases the tensile strength of the aluminum composite. Again, the amount of Mg or Zr added to the 7xxx liner alloy or modification thereof must be within a well defined compositional range.
  • any type of inner liner alloy known to those of ordinary skill in the aluminum art can be used to form an aluminum composite.
  • the most common aluminum alloy used for an inner liner, particularly for heat exchanger applications, is a 7xxx series type alloy, e.g., 7072 alloy.
  • Zn is typically added to improve the corrosion resistance of the inner liner alloy.
  • the inner liner alloy will have the following alloying elements with the specified compositional range as follows.
  • the aluminum composite includes an aluminum inner liner comprising from 0.0 wt% to 0.5 wt % Mg. In another embodiment, the aluminum composite includes an aluminum inner liner comprising from 0.005 wt % to 0.25 wt % Mg. In still another embodiment, the aluminum composite includes an aluminum inner liner comprising from 0.005 wt % to 0.1 wt % Mg. In still another embodiment, the aluminum composite includes an aluminum inner liner comprising from 0.005 wt % to 0.05 wt % Mg.
  • Zn Not Less Than 0.5 wt % and Less Than 3.0 wt %.
  • Zn is an element for lowering the electric potential of the cladding material serving as a sacrificial anode and improving the corrosion resistance of the inner face. If the Zn content is less than 0.5 wt %, improvement effect for the strength is little, and the corrosion resistance is degraded. Meanwhile, if Zn is added to more than 3.0 wt %, the formability of the cladding material is degraded, which is not preferable. Thus, the additive amount of Zn is defined as not less than 0.5 wt % and less than 3.0 wt %.
  • the aluminum composite includes an aluminum inner liner comprising from 0.8 wt % to 1.5 wt % Mg, and from 1.1 wt % to 1.7 wt % Zn. In another embodiment, the aluminum composite includes an aluminum inner liner comprising from 1.0 wt % to 1.2 wt % Mg, and from 1.3 wt % to 1.5 wt % Zn. In still another embodiment, the aluminum composite includes an aluminum inner liner comprising from 0.005 wt % to 0.1 wt % Mg, and from 1.3 wt % to 1.5 wt % Zn. In still another embodiment, the aluminum composite includes an aluminum inner liner comprising from 1.0 wt % to 1.2 wt % Mg, and from 1.3 wt % to 1.5 wt % Zn.
  • the aluminum composite includes a liner alloy comprising from 0.2 wt% to 0.4 wt% Mg.
  • the composite aluminum alloy will include a liner alloy comprising from 0.1 wt% to 0.3 wt% Zr.
  • An alternative embodiment includes a liner alloy comprising both Mg and Zr. In one particular instance the total Mg + Zr concentration does not exceed 0.5 wt%.
  • brazing clad alloy any type of brazing clad alloy known to those of ordinary skill in the aluminum art can be combined with the aluminum composite to form an aluminum brazing sheet.
  • the aluminum composite will have a hardness ratio defined as (inner liner alloy hardness):(core alloy hardness) of not more than 1.5.
  • the hardness ratio has some relationship to the amount of warping and spring back following or during the material processing of the composite alloy.
  • the hardness ratio can be adjusted by properly setting the final annealing condition.
  • the final annealing temperature can be set from between about 330° C to about 550° C followed by cooling to room temperature at a cooling rate of from about 2° C/hr to 20° C/hr. Examples 1-4, 6, 7, 9 and 10
  • brazing sheets Modified 3xxx aluminum alloys were prepared to yield cast ingots of the core alloy compositions shown in Table 1. The cast ingots were machined suitably for clad application. Brazing sheets of braze clad (4045), core alloy and inner liner were assembled according to the desired clad layer thicknesses according to methods well known in the art. The brazing sheets of Examples 1-4, and 7-9 were prepared with a 7xxx aluminum alloy inner liner and the brazing sheet of Example 6 was prepared with another modified 7xxx alloy in which 0.342 wt% actual Mg was added. The brazing sheet of Example 10 was prepared from a modified 7xxx alloy in which 0.166 actual Zr was added.
  • the brazing sheets were roll-bonded by hot rolling to 0.110" gauge.
  • the hot band of 0.110" gauge was processed by the following steps.
  • Step # 1 Anneal hot band at 710° F for 2 hrs with a heat up rate of 50° F/hr and then air cool (O-temper).
  • Step # 2. Cold rolled to 0.014" gauge.
  • Step # 3. Anneal at 710° F for 2 hrs with a heat up rate of 50 °F/hr and then air cooled (O-temper).
  • the composites with inner liner can be compared to CAl 3 which has AA 4343 (10%) as blaze clad, K328 as core and AA7072 (10%) as liner.
  • K328 is a 3xxx aluminum alloy comprising by weight %: 0.07 Si, 0.17 Fe, 0.50 Cu, 1.45 Mn, 0.09 Mg, 0.03 Ti and the balance aluminum and inevitable impurities.
  • the composites with, inner liner may also be compared to CA55 which has AA 4343 as blaze clad, K328 as core and AA 4343 (10%) as liner.
  • the brazing sheets of CA13 and CA55 were prepared substantially according to the process described for Examples 1-4, 6-7 and 9-10.
  • Post-braze tensile tests were performed according to the procedures of ASTM:B557-94. Tensile specimens were machined from brazed coupons of 2-1/2" width and 8" length. Pre- and post-braze tensile properties of various materials are listed in Table 2. The addition of Mg to the core alloy exhibits improved tensile strength. The addition of Cr alone is shown not to be very effective in improving alloy strength.
  • Core erosion (%) [1 - (T c /T co )] x 100, wherein T c is core thickness in the post-braze sheet, and T co is the original core thickness in the pre-braze material.
  • Example 1-4, 6-7 and 9-10 The pre- and post-braze microstructures of Example 1-4, 6-7 and 9-10 are illustrated in Figures 1-8.
  • the post-braze grain structures of Examples 9 and 10 are shown in Figures 9(a) and 9(b), respectively.
  • the post-braze grain size ⁇ values shown in Table 3 suggest a relative by coarse grain.
  • Post-braze grain structure of materials #9 and #10 are shown in Figure 9.
  • Post braze microstructure of bent samples of materials #9 and #10 are shown, in Figures 10 and 11, respectively.
  • the temper is H14.
  • Post-braze grain structure of bent samples of materials #9 and #10 are shown in Figures 12 and 13, respectively.
  • Corrosion damage according to the SWAAT standard for materials #9 and #10 are shown in Figures 14 and 15, respectively.
  • Post-braze microstructures of bent composite aluminum alloys of Examples 1- 4 and 6-7 are shown in Figures 16-21.
  • Post-braze grain structures of Examples 1-4, 6 and 7 are shown in Figures 22(a)-22(f).
  • Post-braze grain structures of bent composite aluminum alloys of Examples 1-4 and 6-7 are shown in Figures 23-28.
  • Brazed drip strips were corrosion tested according to SWAAT, ASTM G85- A3.
  • the corrosion damage in the SWAAT tests was evaluated by preparing failed SWAAT coupons and examining them metallographically.
  • the SWAAT life of various coupons was in the range of 140 hrs to 344 hrs. All of the SWAAT coupons appear to exhibit lateral mode of corrosive attack, but their SWAAT life is lower than 345 hrs.
  • the sag amount for alloys 1-4, 6-7, and 9-10 is in the range of 2.39 to 7.55 mm (See Table 4). Good braze flow (> 50 %) is noted in the Example alloys.
  • Charts 7 and 8 The effects of adding Mg, Cr and Zr to the core alloy on braze clad side and water side are shown in Charts 7 and 8, respectively.
  • Charts 11 and 12 show the corrosion potential of Examples 9 and 10 from the braze clad side and the inner liner side, respectively.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)

Abstract

L'invention concerne des composites d'alliages d'aluminium dotés d'une enveloppe de brasure et d'une garniture interne. Les composites présentent une résistance et une résistance à la corrosion améliorées. Ces composites peuvent être utilisés notamment pour des échangeurs thermiques et des tubes d'évaporation.
PCT/US2005/034706 2004-10-01 2005-09-28 Composite d'aluminium WO2006039303A1 (fr)

Priority Applications (1)

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

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US61449604P 2004-10-01 2004-10-01
US60/614,496 2004-10-01
US61766604P 2004-10-13 2004-10-13
US60/617,666 2004-10-13
US62708504P 2004-11-12 2004-11-12
US60/627,085 2004-11-12

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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WO2006039303A1 true WO2006039303A1 (fr) 2006-04-13
WO2006039303B1 WO2006039303B1 (fr) 2006-06-22

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013170192A3 (fr) * 2012-05-10 2014-01-16 Alcoa Inc. Produit de feuille d'alliage d'aluminium multi-couches, produit de feuille pour tubes pour échangeurs thermiques et procédés de fabrication

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020037426A1 (en) * 2000-08-10 2002-03-28 Noriyuki Yamada Aluminum alloy brazing sheet for a heat exchanger
US6627330B1 (en) * 1999-06-23 2003-09-30 Sumitomo Light Metal Industries, Ltd. Aluminum alloy brazing sheet for vacuum brazing exhibiting excellent corrosion resistance, and heat exchanger using the brazing sheet

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6627330B1 (en) * 1999-06-23 2003-09-30 Sumitomo Light Metal Industries, Ltd. Aluminum alloy brazing sheet for vacuum brazing exhibiting excellent corrosion resistance, and heat exchanger using the brazing sheet
US20020037426A1 (en) * 2000-08-10 2002-03-28 Noriyuki Yamada Aluminum alloy brazing sheet for a heat exchanger

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013170192A3 (fr) * 2012-05-10 2014-01-16 Alcoa Inc. Produit de feuille d'alliage d'aluminium multi-couches, produit de feuille pour tubes pour échangeurs thermiques et procédés de fabrication
US9964364B2 (en) 2012-05-10 2018-05-08 Arconic Inc. Multi-layer aluminum alloy sheet product for tubes for heat exchangers

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