EP1753885B1 - Verfahren zur herstellung eines aluminiumlegierungslötblechs und aluminiumlegierungslötblech - Google Patents

Verfahren zur herstellung eines aluminiumlegierungslötblechs und aluminiumlegierungslötblech Download PDF

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Publication number
EP1753885B1
EP1753885B1 EP05746552.8A EP05746552A EP1753885B1 EP 1753885 B1 EP1753885 B1 EP 1753885B1 EP 05746552 A EP05746552 A EP 05746552A EP 1753885 B1 EP1753885 B1 EP 1753885B1
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Prior art keywords
alloy
sheet
brazing
core
process according
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French (fr)
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EP1753885B2 (de
EP1753885A1 (de
Inventor
Scott William Haller
Job Anthonius Van Der Hoeven
Klaus Vieregge
Achim BÜRGER
Sampath Desikan
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Novelis Koblenz GmbH
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Aleris Rolled Products Germany GmbH
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Classifications

    • 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
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc 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
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/14—Alloys based on aluminium with copper as the next major constituent with silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/16—Alloys based on aluminium with copper as the next major constituent with magnesium

Definitions

  • the invention relates to a process for producing an Al-Mn alloy sheet with improved liquid film migration resistance when used as core alloy in brazing sheet materials.
  • the invention further relates to an Al-Mn alloy sheet produced according to said process and to the use of said alloy sheet.
  • LFM Liquid Film Migration'
  • a core alloy of a brazing sheet product requires a good combination of strength and formability.
  • the susceptibility to LFM has to be at a sufficiently low level to ensure adequate corrosion resistance and brazeability.
  • Higher strength can be obtained by alloying with elements such as silicon, manganese, chromium, zirconium or vanadium.
  • these alloying elements also increase the susceptibility to LFM.
  • the use of a non O-temper, such as H14-temper or H24-temper has also been suggested to reduce the susceptibility to LFM.
  • H14-temper or H24-temper has also been suggested to reduce the susceptibility to LFM.
  • Other alternative processes such light cold deforming process such as tension levelling, or the use of a non-recrystallised surface layer are difficult to control in mass-production practice and therefore may compromise reproducibility and/or formability.
  • EP1291165 discloses a brazing sheet with a two-layer structure or a three-layer structure, having a core sheet made of an aluminium alloy core material and on one side or both sides thereof a brazing layer of an aluminium alloy containing silicon as main alloying element, wherein the aluminium alloy of the core sheet composition consists of (in weight %): Mn 0.5-1.5, Cu 0.5-2.0, Si 0.3-1.5, Mg ⁇ 0.05, Fe ⁇ 0.4, Ti ⁇ 0.15, Cr ⁇ 0.35, Zr and/ or V ⁇ 0.35 in total Zn ⁇ 0.25 balance aluminium and unavoidable impurities, and wherein said brazing sheet has a post-braze 0.2% yield strength of at least 50 MPa and a corrosion life of more than 12 days in a SWAAT test without perforations in accordance with ASTM G-85.
  • one or more of the objects is reached with a process for producing an Al-Mn alloy sheet with improved liquid film migration resistance when used as core alloy in brazing sheet, comprising the steps of:
  • Casting takes place using regular production techniques such as DC casting or continuous casting.
  • the process according to the invention enables production of an Al-Mn alloy which, when used as core alloy in brazing sheet couples a good strength/formability combination to a sufficiently low susceptibility to LFM and an adequate corrosion resistance.
  • the inventors surprisingly found that, although chromium is reported to have an adverse effect on the susceptibility to LFM because of the retarding effect it has on the recrystallisation of the alloy, the combination of the chemistry of the alloy and the process parameters, particularly the homogenisation and preheat process results in a product with a sufficiently low susceptibility to LFM and hence adequate corrosion resistance.
  • the Cr-containing and/or Zr-containing precipitates which are formed in the alloy as a result of the combination of composition and processing conditions, reduce the susceptibility to LFM. Also the chromium strengthens the alloy, whereas the recrystallisation of the alloy results in adequate formability.
  • the Cr and/or Zr content is at least 0.08%.
  • the inventors found that when using a chromium content of at least 0.08% or a zirconium content of at least 0.08% or the combination thereof in combination with the described process conditions resulted in a higher strength in combination with adequate LFM-resistance.
  • the maximum magnesium content is 0.1%, preferably the maximum magnesium content is 0.05%.
  • the magnesium content should be as low as possible to avoid the deleterious effect of magnesium on the flux that is used during Controlled Atmosphere Brazing.
  • the copper content is from 0.7 to 1.2 %.
  • the manganese content is from 0.7 to 1.4 %. If the manganese content exceeds 1.4% difficulties in fabrication increase and below 0.7% the strength of the alloy is insufficient.
  • the maximum zinc content is preferably 0.4% to prevent the core alloy being excessively anodic in certain applications.
  • the iron content is preferably below 0.35% to prevent the formation of undesirable large iron containing intermetallics during industrial casting practices.
  • the homogenisation temperature is between 530 °C and 620°C, preferably between 530 and 595 °C, preferably for between 1 to 25 hours, more preferably for between 10 to 16 hours, and wherein the pre-heat temperature is between 400 °C and 530°C, preferably between 420 and 510 °C, preferably for between 1 to 25 hours, more preferably for between 1 and 10 hours.
  • the alloys according to the invention it appears that the best compromise between the strength, formability, susceptibility to LFM and corrosion resistance was found when the homogenisation temperature and time and the pre-heat temperature and time was chosen within the given boundaries and that a particularly interesting compromise was obtained when processing the alloy according to the abovementioned preferred temperatures and times.
  • the process according to the invention also comprises recrystallisation annealing after cold rolling at an annealing temperature-annealing time combination sufficient for promoting essentially full recrystallisation of the Al-Mn alloy. In this condition the highest formability is reached.
  • the maximum silicon content of the Al-Mn alloy is 0.3 % in weight. In a preferable embodiment of the invention the maximum silicon content of the Al-Mn alloy is 0.15 % in weight. Silicon is known to increase the susceptibility to LFM. Consequently, the silicon content is to be chosen as low as possible. However, the inventors found that when using a silicon content of up to 0.3 % but preferably of up to 0.15 % that an adequate combination of susceptibility to LFM and strength was obtained.
  • Cr ⁇ 0.18% preferably at least 0.06%, more preferably 0.08% ⁇ Cr ⁇ 0.15%, even more preferably 0.08% ⁇ Cr ⁇ 0.12%.
  • the Cr-level exceeds 0.18%, casting of the Al-Mn alloy becomes very difficult as a result of the formation of large intermetallics. Casting the Al-Mn with Cr-contents of below 0.15% or below 0.12 causes no problems.
  • the effect thereof on the susceptibility to LFM in combination with the described process conditions results in an adequate combination of susceptibility to LFM and strength.
  • the process also comprises cladding the Al-Mn alloy on at least one side with an AA4000-series or Al-Si brazing alloy optionally comprising up to 2.0 % Zn.
  • Cladding may for instance be performed by roll-bonding or any other known technique such as spray cladding or cast cladding.
  • the invention is also embodied in a sheet produced according to the process as described hereinabove, wherein the pre-braze elongation is at least 18%, preferably at least 19 %, more preferably at least 21% and/or a pre-braze n-value of at least 0.270, and/or a post-brazing tensile strength of at least 140 MPa, preferably of at least 150 MPa.
  • the elongation is measured over a gauge length of 80 mm, also denoted as A80.
  • the post-braze coupon SWAAT lifetime measured in terms of time to perforation in days and, when tested according to ASTM G85 A3, is at least 15 days, preferably at least 20 days without perforation.
  • the low susceptibility to LFM is reflected in an improved resistance against corrosion in a formed heat exchanger component after brazing.
  • the sheet as described hereinabove is applied as a core in brazing sheet with or without a non-brazing liner or waterside liner alloy such as an AA7072, an AA1145 or an AA 3005 or Al-Mn type alloys containing Zn in the range 0.5-5.0%, preferably in the range 0.5-2.5%, in folded tubes or for applications which are used under similar conditions.
  • a non-brazing liner or waterside liner alloy such as an AA7072, an AA1145 or an AA 3005 or Al-Mn type alloys containing Zn in the range 0.5-5.0%, preferably in the range 0.5-2.5%
  • the requirements as to strength, formability, LFM susceptibility and corrosion resistance are particularly relevant for the application of the sheet as a core in a brazing sheet, for instance for application in heat exchangers utilising folded tubes.
  • the sheet materials produced according to the process described hereinabove are particularly suitable for use as a core alloy in brazing sheet materials intended for manufacturing of components of tube-fin type heat exchangers such as radiators, heater cores and condensers, or for manufacturing of components of plate-fin type heat exchanger such as evaporator or oil cooler core plates or tanks of radiators or heater cores as a core alloy in brazing fin stock materials intended for manufacturing of components for heat exchangers.
  • Table 1 Examples of alloys produced according to the invention. Alloy Cu Fe Si Mn Mg Ti Cr Zr 1 (reference) 0.76 0.18 0.10 1.14 0.03 0.13 ⁇ 0.01 ⁇ 0.01 2 0.80 0.21 0.09 1.15 0.05 0.13 0.05 0.05 3 0.78 0.21 0.09 1.20 0.03 0.13 0.11 ⁇ 0.01 4 0.78 0.20 0.08 1.16 0.02 0.12 0.15 ⁇ 0.01 5 0.72 0.20 0.07 1.21 0.01 0.14 0.08 ⁇ 0.01 6 0.76 0.15 0.08 1.19 0.01 0.12 0.06 ⁇ 0.01 standard 0.5-0.7 ⁇ 0.5 ⁇ 0.3 0.65-1.0 ⁇ 0.02 0.08-0.10 - - other elements ⁇ 0.05 each and total ⁇ 0.20, balance Al.
  • alloys 1-4 were subjected to a homogenisation treatment at various temperatures for various times. Subsequently the alloys were clad on both sides with AA4045, 10% of the thickness on each side, followed by a preheat prior to hot rolling at various temperatures for various times, hot-rolling to 6.5 mm followed by an inter anneal at 350 °C for 3 hours, a first cold rolling to 2.3 mm, again followed by an inter anneal at 350 °C for 3 hours and a second cold rolling to a final gauge of 0.5 mm. The alloy was subjected to a recrystallisation annealing treatment to promote essentially full recrystallisation. To test the LFM behaviour, the materials were stretched between 2 and 10%. The stretch level that showed the deepest penetration was used for the LFM data in Table 2.
  • Alloy 5 and 6 were clad on both sides with AA4045, 10% of the thickness on each side, followed by a preheat prior to hot rolling, and subsequently hot rolled to 3.5 mm and cold-rolled to 0.41 mm without inter annealing. After cold-rolling the material was subjected to a recrystallisation annealing treatment to promote essentially full recrystallisation. The LFM behaviour was tested as described above. The results are presented in Table 2.
  • the alloy designated 'standard' is an alloy which is used for LFM-critical applications. In Table 2:
  • the n-value can be used as an alternative indicator of formability.
  • An n-value of at least 0.270 indicates a good formability in view of the minimum strength requirement of at least 140 MPa.
  • the alloys according to the invention such as alloy 2-6 in Table 2
  • Another particular alloy which can be produced using the method according to the invention has the following compositional ranges, in wt.%:

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Details Of Heat-Exchange And Heat-Transfer (AREA)
  • Continuous Casting (AREA)

Claims (15)

  1. Verfahren zur Herstellung eines Blechs aus Al-Mn-Legierung mit einer verbesserten Flüssigkeitsfilm-Migrationsbeständigkeit, wenn es als Kernlegierung in einem Hartlötblech verwendet wird, das die folgenden Schritte aufweist:
    • Guss einer Zusammensetzung bestehend in Gewichtsprozent aus
    ∘ 0,5 <Mn ≤ 1,7
    ∘ 0,06 < Cu ≤ 1,5
    ∘ Si ≤ 0,15
    ∘ Mg ≤ 0,25
    ∘ Ti < 0,2
    ∘ Zu ≤ 2,0
    ∘ Fe ≤ 0,5
    ∘ mindestens einem der Elemente der Gruppe von Elementen, die besteht aus 0,05 < Zr ≤ 0,25 und 0,05 < Cr ≤ 0,25,
    ∘ anderen Elementen von je < 0,05 und insgesamt < 0,20, Rest Al,
    • Homogenisierung und Vorwärmen
    • Warmwalzen
    • Kaltwalzen und optional Zwischenglühen,
    wobei die Homogenisierungstemperatur mindestens 450°C für eine Dauer von mindestens 1 Stunde beträgt, gefolgt von einer Luftkühlung mit einer Geschwindigkeit von mindestens 20°C/h, und wobei die Vorwärmtemperatur mindestens 400°C für mindestens 0,5 Stunden beträgt.
  2. Verfahren nach Anspruch 1, wobei die Homogenisierungstemperatur zwischen 530°C und 620°C für zwischen 1 und 25 Stunden liegt, und wobei die Vorwärmtemperatur zwischen 400°C und 530°C für zwischen 1 und 25 Stunden liegt.
  3. Verfahren nach Anspruch 1 oder 2, wobei Mn zwischen 0,7 und 1,4% liegt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei Cr ≤ 0,18, vorzugsweise 0,08 < Cr ≤ 0,15, bevorzugter 0,08 < Cr ≤ 0,12.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei Mg ≤ 0,15%, bevorzugter Mg ≤ 0,05%.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei Zn ≤ 0,4%.
  7. Verfahren nach einem der Ansprüche 1 bis 6, das weiter das Plattieren der Al-Mn-Legierung auf mindestens einer Seite mit einer Al-Si-Hartlötlegierung aufweist, die optional bis zu 2,0% Zn aufweist.
  8. Verfahren nach einem der Ansprüche 1 bis 7, das weiter das Plattieren der Al-Mn-Legierung auf mindestens einer Seite mit einer Al-Si-Hartlötlegierung aufweist, die optional bis zu 2,0% Zn aufweist, und die eine nicht-lötende Auskleidungslegierung vom Typ AA7072 oder AA1145 oder AA3005 oder Legierungen des Typs Al-Mn hat, die Zn im Bereich von 0,5-5,0%, vorzugsweise im Bereich von 0,5-2,5% enthalten.
  9. Blech, das nach einem der Ansprüche 1 bis 8 hergestellt wird, wobei die Dehnung vor dem Hartlöten mindestens 18%, vorzugsweise 19%, beträgt.
  10. Blech nach Anspruch 9, wobei die Zugfestigkeit nach dem Hartlöten mindestens 140 MPa, vorzugsweise mindestens 150 MPa beträgt.
  11. Blech nach Anspruch 9 oder 10, wobei der n-Wert vor dem Hartlöten mindestens 0,270 beträgt.
  12. Blech nach einem der Ansprüche 9 bis 11, wobei die Lebensdauer des SWAAT-Probestücks nach dem Hartlöten, wenn es gemäß ASTM G85 A3 getestet wird, mindestens 15 Tage ohne Perforierung beträgt.
  13. Verwendung eines gemäß einem der Ansprüche 1 bis 8 erzeugten Blechs oder des Blechs gemäß einem der Ansprüche 9 bis 12 als eine Kernlegierung in einem Lötblech, das zur Herstellung von Bauteilen der Art Rippenrohr-Wärmetauscher wie Kühler, Heizkerne und Kondensatoren bestimmt ist.
  14. Verwendung eines gemäß einem der Ansprüche 1 bis 8 erzeugten Blechs oder des Blechs gemäß einem der Ansprüche 9 bis 12 als Kernlegierung in einem Lötblech, das zur Herstellung von Bauteilen der Art Plattenrohr-Wärmetauscher wie Verdampfer- oder Ölkühler-Kernplatten oder Behältern von Kühlern oder Heizkernen bestimmt ist.
  15. Verwendung eines gemäß einem der Ansprüche 1 bis 8 erzeugten Blechs oder des Blechs gemäß einem der Ansprüche 9 bis 12 als Kernlegierung beim Hartlöten von Rippen-Lagermaterialien zur Herstellung von Bauteilen für Wärmetauscher.
EP05746552.8A 2004-05-26 2005-05-25 Verfahren zur herstellung eines aluminiumlegierungslötblechs und aluminiumlegierungslötblech Active EP1753885B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05746552.8A EP1753885B2 (de) 2004-05-26 2005-05-25 Verfahren zur herstellung eines aluminiumlegierungslötblechs und aluminiumlegierungslötblech

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP04076545 2004-05-26
EP04076785 2004-06-18
EP04077623 2004-09-23
EP05746552.8A EP1753885B2 (de) 2004-05-26 2005-05-25 Verfahren zur herstellung eines aluminiumlegierungslötblechs und aluminiumlegierungslötblech
PCT/EP2005/005751 WO2005118899A1 (en) 2004-05-26 2005-05-25 Process for producing an aluminium alloy brazing sheet, aluminium alloy brazing sheet

Publications (3)

Publication Number Publication Date
EP1753885A1 EP1753885A1 (de) 2007-02-21
EP1753885B1 true EP1753885B1 (de) 2016-12-28
EP1753885B2 EP1753885B2 (de) 2022-08-24

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EP (1) EP1753885B2 (de)
JP (1) JP5326123B2 (de)
KR (1) KR101216246B1 (de)
CN (1) CN1973056B (de)
CA (1) CA2565978C (de)
HU (1) HUE032303T2 (de)
MX (1) MXPA06013571A (de)
WO (1) WO2005118899A1 (de)

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WO2019245570A1 (en) 2018-06-21 2019-12-26 Arconic Inc. Corrosion resistant high strength brazing street
US11685973B2 (en) 2018-06-21 2023-06-27 Arconic Technologies Llc Corrosion resistant high strength brazing sheet

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HUE032303T2 (en) 2017-09-28
WO2005118899A1 (en) 2005-12-15
JP2008500453A (ja) 2008-01-10
EP1753885B2 (de) 2022-08-24
JP5326123B2 (ja) 2013-10-30
CN1973056A (zh) 2007-05-30
CN1973056B (zh) 2010-11-24
CA2565978C (en) 2013-03-26
CA2565978A1 (en) 2005-12-15
MXPA06013571A (es) 2007-03-15
KR101216246B1 (ko) 2012-12-28
EP1753885A1 (de) 2007-02-21
KR20070058383A (ko) 2007-06-08

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