US20030165397A1 - Corrosion resistant aluminum alloy - Google Patents

Corrosion resistant aluminum alloy Download PDF

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Publication number
US20030165397A1
US20030165397A1 US10/296,335 US29633503A US2003165397A1 US 20030165397 A1 US20030165397 A1 US 20030165397A1 US 29633503 A US29633503 A US 29633503A US 2003165397 A1 US2003165397 A1 US 2003165397A1
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Prior art keywords
weight
alloy
content ranges
recryst
aluminium
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US10/296,335
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Lars Auran
Trond Furu
Ole Daaland
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Norsk Hydro ASA
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Assigned to NORSK HYDRO, A.S. reassignment NORSK HYDRO, A.S. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AURAN, LARS
Assigned to NORSK HYDRO, A.S. reassignment NORSK HYDRO, A.S. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FURU, TROND
Assigned to NORSK HYDRO, A.S. reassignment NORSK HYDRO, A.S. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAALAND, OLE
Publication of US20030165397A1 publication Critical patent/US20030165397A1/en
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    • 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
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • 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
    • 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
    • C22C21/02—Alloys based on aluminium with silicon 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
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent

Definitions

  • the present invention is directed to a group of corrosion resistant and extrudable aluminium alloys with improved elevated temperature strenght, especially to a AA3000 series type aluminium alloy including controlled amounts of titanium, vanadium and zirconium for improved extrudability and/or drawability.
  • AA1000 series alloys have been replaced with more highly alloyed materials such as the AA3000 series types aluminium alloys.
  • AA3102 and AA3003 are examples of higher strength aluminium alloys having good corrosion resistance.
  • Aluminium alloys of the AA3000 series type have found extensive use in the automotive industry due to their good combination of strength, light weight, corrosion resistance and extrudability. These alloys are often made into tubing for use in heat exchanger or air conditioning condenser applications.
  • U.S. Pat. No. 5,286,316 discloses an aluminium alloy with both high extrudability and high corrosion resistance.
  • This alloy consists essentially of about 0.1-0.5% by weight of manganese, about 0.05-0.12% by weight of silicon, about 0.10-0.20% by weight of titanium, about 0.15-0.25% by weight of iron, with the balance aluminium and incidental impurities.
  • the alloy preferably is essentially copper free, with copper being limited to not more than 0.01%.
  • a still further object of the present invention is to provide an aluminium alloy which has good both hot- and cold-formability and corrosion resistance.
  • the present invention provides a corrosion resistant aluminium alloy consisting essentially of, in weight percent, 0.05-1.00% of iron, 0.05-0.60% of silicon, less than 0.50% of copper, up to 1.20% of manganese, 0.02-0.20% of zirconium, up to 0.50% of chromium, 0.02 to 1.00% of zinc, 0.02-0.20% of titanium, 0.02-0.20% of vanadium, up to 2.00% of magnesium, up to 0.10% of antimony, up to 0.02% of incidental impurities and the balance aluminium.
  • iron preferably is between 0.05-0.55%, more preferably, between 0.05-0.25%. Reducing the Fe content improves the corrosion resistance. Silicon is preferably between 0.05 and 0.20%, more preferably, not more than 0.15%. Copper is below 0.50%, as this elements normally negatively influences the extrusion speed and the corrosion resistance. But in some circumstances some copper might be needed to adjust the electro-potential of the allay. Preferablly the Cu-content is below 0.05% by weight. Zirconium is preferably between 0.02 and 0.18%.
  • Zn should always be present in at least 0.02% by weight in order to improve the general level of corrosion resistance and preferably zinc content is between 0.10 and 0.50%, more preferably between 0.10 and 0.25%.
  • Ttitanium is preferably between 0.02 and 0.15%, and vanadium is preferably between 0.02 and 0.12%.
  • the preferred amount of manganese is highly dependent on the intended use of the article because manganese impacts extrudability, especially with thin sections.
  • manganese is preferably present in amounts between 0.05-0.30% by weight.
  • Fe is preferably present in amounts between 0.05-0.25% by weight.
  • chromium is between 0.02 and 0.25%.
  • the magnesium amount is preferably below 0.03%.
  • Zn is preferably present in amounts between 0.10-0.5% by weight.
  • the alloy When the alloy is intended to be used in applications, in which after extrusion further deformation processes will be used in order to obtain a final product, such as cold deforming as e.g. drawing and/or bending, and where higher strength is required, it is preferred to have the amount of manganese between 0.50 and 0.80% by weight.
  • chromium is preferably between 0.02 and 0.18% by weight and magnesium below 0.30% by weight, for brazeability reasons.
  • the Fe content should be kept low for improved corrosion resistance.
  • 0.10-0.5% Zn is added.
  • controlled additions of V, Zr and Ti each not more than 0.2% by weight are made to further improve corrosion resistance.
  • the alloy is to be used in high temperature applications the role of V, Ti and especially Zr becomes important.
  • the amounts added of each of these elements will depend on the functional requirements, however, the amount of zirconium is preferably between 0.10 and 0.18% by weight.
  • post heat treatment of the cast alloy in that it is heated to a temperature of between 450 and 550° C. with a heating rate of less than 150° C./hour, and maintain the alloy at that temperature for between 2 and 10 hours.
  • the final product may also for certain applications and especially after cold working, require a “back annealing” treatment consisting of heating the work piece to temperatures between 150 and 350 degrees Centigrade and keep at temperature for between 10 and 10000 min.
  • Zr and Ti in solid solution are used separately to improve corrosion resistance in low alloy highly extrudable alloys e.g. for use in extruded tubes for automotive A/C systems.
  • the useful maximum additions of Zr and Ti when added separately is less than 0.2% by weight. Above this level primary compounds are formed that reduces the level of these elements in solid solution.
  • the primary compounds from Zr and Ti Al3Zr, Al3Ti
  • Both Zr and Ti will upon solidification go through a peritectic reaction.
  • the product of this reaction is revealed as a highly concentrated region of the elements in the centre of the grain (large positive partition ratio). These regions or zones will upon rolling or extrusion form a lamellae structure parallel to the surface of the work piece and slow down the corrosion in the through thickness direction.
  • V is an element with much the same behaviour and effect as Zr and Ti, but has up to now not been used much in these type of alloys. V will improve the mechanical properties in the same way as Zr and Ti, but do not have the same effect on corrosion unless the Zr-content is higher than the V-content.
  • the transition elements such as Zr, Ti, and V are known to improve formability by increasing the work hardening coefficient (“n”).
  • n increases with increased amount of the transition elements almost linearly up to some 0.5%.
  • Zr, Ti and V up to 0.45% of the transition elements may be added without the formation of deleterious primary particles of the type Al3Zr, as opposed to below 0.2% if only one of the elements is added. But it has found otherwise that above a total level of 0.3% by weight some characteristics are negatively influenced.
  • Zr, Ti and V, and in particular Zr are known to impede the tendency of recrystalization, provided optimum heat treatment before high temperature processing.
  • the ability to retard recrystalization is related to the number and size of small coherent semi-coherent precipitates that are stable at temperature up to 300-400 degrees Centigrade for prolonged times.
  • the fine polygenized structure that will result from back annealing at temperatures in the 150 to 350 degrees Centigrade range will have higher mechanical strength than the corresponding recrystalized structure resulting in the absence of such transition elements.
  • Billets with different content of Zr, V and Ti were cast using the laboratory casting equipment at Sunndals ⁇ ra. For each alloy, four billets with a diameter of 95 mm and a length of 1.1 m were produced. At the beginning of the casting the casting speed was 115 mm/min, increasing to 240 mm/min after 15 cm cast billet. The temperature in the launder was set to be 705° C. and the temperature was recorded during casting. Grain refiner (Ti 5 B-wire) were added in the furnace before the casting.
  • each billet were cut, producing three samples for extrusion and two samples for spectrographic analysis (first one sample for spectrographic analysis, then two samples for extrusion, then the second sample for spectrographic analysis (i.e. ⁇ in the middle of the billet) and finally the third sample for extrusion).
  • Samples from the as-cast material ( ⁇ middle of the billet) was etched to reveal feathery crystals, in addition samples were prepared to show grain structure and particle structure. Hardness and conductivity measurements were carried out for each alloy on specimens (2 cm ⁇ 2 cm ⁇ 1 cm) that were grinded to a grit size of 2000.
  • FIG. 1 a diagram showing for the alloys 1-11 in the Y-axis the electrical conductivity (in MS/m) in function of the total amount of Ti, V and Zr (wt % in X-axis),
  • FIG. 2 a diagram showing for the alloys 1-11 in the Y-axis the main extrusion force (in kN) in function of the total amount of Ti, V and Zr (wt % in X-axis),
  • FIG. 3 a diagram showing for the alloys 1-11 in the Y-axis the yield strength (round dots) and the ultimate tensile strength (square dots) in function of the total amount of Ti, V and Zr (wt % in X-axis).
  • FIG. 4 a diagram showing for the alloys 41-56 in the Y-axis the electrical conductivity (in MS/m) in function of the total amount of Ti, V and Zr (wt % in X-axis),
  • FIG. 5 a diagram showing for the alloys 41-56 in the Y-axis the break through pressure (in kN) of the alloy as cast in function of the total amount of Ti, V and ZR (wt % in X-axis),
  • FIG. 6 a diagram showing for the alloys 41-56 in the Y-axis the breakthrough pressure (in kN) of the alloy after homogenizing at 470° C. for 1 hour in function of the total amount of Ti, V and Zr (wt % in X-axis),
  • FIG. 7 a diagram showing for the alloys 41-56 in the Y-axis the yield strenght (in MPa) of the alloy after extrusion in function of the total amount of Ti, V and ZR (wt % in X-axis),
  • FIG. 8 a diagram showing for the alloys 41-56 in the Y-axis the ultimate tensile strenght (in MPa) of the alloy after extrusion in function of the total amount of Ti, V and ZR (wt % in X-axis),
  • FIG. 9 a diagram showing for the alloys 41-56 in the Y-axis yield strenght (in MPa) of the alloy after extrusion and subsequently homogenizing at 470° C. for 1 hour in function of the total amount of Ti, V and ZR (wt % in X-axis),
  • FIG. 10 a diagram showing for the alloys 41-56 in the Y-axis the ultimate tensile strenght (in MPa) of the alloy after extrusion and subsequently homogenizing at 470° C. for 1 hour in function of the total amount of Ti, V and ZR (wt % in X-axis),
  • FIG. 11 a diagram showing for the alloys 41-56 in the Y-axis the ultimate tensile strenght (in MPa) of the alloy after homogenizing at 470° C. for 1 hour and subsequently extrusion in function of the total amount of Ti, V and ZR (wt % in X-axis),
  • the as-cast material represents the starting point for the extrusion process and the following mechanical and corrosion testing. An investigation of the starting material has been carried out, and the results are shown in the following. Samples from the as-cast material were investigated to find the actual chemical composition and to reveal the microstructure (grain structure and particle structure) in the various alloys. The chemical composition of the material was obtained by spectrographic analysis, and the results are listed in Table 1 (alloys 1-11), Table 2 (alloys 20-35) and Table 3 (alloys 41-56).
  • FIGS. 3, 4 The results from the tension testing of the extruded tubes are shown in FIGS. 3, 4. As can be seen from the table and the figure, the variations in stress with changing alloy are small. The stress at max load is seen to increase slightly with increasing content of alloying elements, while the effect on the yield stress is not clear. This qualitative evalutation of the results were confirmed by a statistical analysis.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Extrusion Of Metal (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
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US10/296,335 2000-05-22 2001-05-21 Corrosion resistant aluminum alloy Abandoned US20030165397A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP00201808A EP1158063A1 (fr) 2000-05-22 2000-05-22 Alliage d'aluminium présentant une grande résistance à la corrosion
EP00201808.3 2000-05-22

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US (1) US20030165397A1 (fr)
EP (2) EP1158063A1 (fr)
JP (1) JP2003534455A (fr)
KR (1) KR20030013427A (fr)
CN (1) CN1443249A (fr)
AU (1) AU2001274064A1 (fr)
BR (1) BR0111053A (fr)
CA (1) CA2409870A1 (fr)
IS (1) IS6629A (fr)
NO (1) NO20025562L (fr)
RU (1) RU2002134484A (fr)
WO (1) WO2001090430A1 (fr)

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US20060088438A1 (en) * 2004-10-21 2006-04-27 Visteon Global Technologies, Inc. Aluminum-based alloy composition and method of making extruded components from aluminum-based alloy compositions
US20080050269A1 (en) * 2006-08-24 2008-02-28 Furukawa-Sky Aluminum Corp. Aluminum piping material for automobile heat exchanger
WO2008034604A2 (fr) * 2006-09-19 2008-03-27 Behr Gmbh & Co. Kg Échangeur thermique destiné à un moteur à combustion interne
US20080196923A1 (en) * 2005-02-08 2008-08-21 The Furukawa Electric Co., Ltd. Aluminum conducting wire
CN100445406C (zh) * 2006-12-13 2008-12-24 中国铝业股份有限公司 3104铝合金扁锭熔炼配料方法
US20130292012A1 (en) * 2011-01-20 2013-11-07 Nippon Light Metal Company, Ltd. Aluminum alloy for small-bore hollow shape use excellent in extrudability and intergranular corrosion resistance and method of production of same
CN103397228A (zh) * 2013-07-26 2013-11-20 广西德骏门窗幕墙有限公司 可挤压、可拉伸、耐腐蚀铝合金
US20140262182A1 (en) * 2011-10-18 2014-09-18 Carrier Corporation Micro channel heat exchanger alloy system
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US20200283875A1 (en) * 2015-10-14 2020-09-10 NanoAL LLC Aluminum-iron-zirconium alloys
US20220267884A1 (en) * 2021-02-17 2022-08-25 Northwestern University Ultra-strong aluminum alloys for ambient and high-temperature applications
US11466346B2 (en) 2017-03-27 2022-10-11 Furukawa Electric Co., Ltd. Aluminum alloy material, and conductive member, conductive component, spring member, spring component, semiconductor module member, semiconductor module component, structural member and structural component including the aluminum alloy material
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US20090266530A1 (en) 2008-04-24 2009-10-29 Nicholas Charles Parson Aluminum Alloy For Extrusion And Drawing Processes
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US11255002B2 (en) 2016-04-29 2022-02-22 Rio Tinto Alcan International Limited Corrosion resistant alloy for extruded and brazed products
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Cited By (18)

* Cited by examiner, † Cited by third party
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AU2001274064A1 (en) 2001-12-03
EP1158063A1 (fr) 2001-11-28
NO20025562L (no) 2002-12-20
CN1443249A (zh) 2003-09-17
EP1287175A1 (fr) 2003-03-05
JP2003534455A (ja) 2003-11-18
BR0111053A (pt) 2003-04-15
WO2001090430A1 (fr) 2001-11-29
IS6629A (is) 2002-11-19
CA2409870A1 (fr) 2001-11-29

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