EP0996754B1 - Korrosionsbeständige aluminiumlegierung mit zircon - Google Patents

Korrosionsbeständige aluminiumlegierung mit zircon Download PDF

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Publication number
EP0996754B1
EP0996754B1 EP98942668A EP98942668A EP0996754B1 EP 0996754 B1 EP0996754 B1 EP 0996754B1 EP 98942668 A EP98942668 A EP 98942668A EP 98942668 A EP98942668 A EP 98942668A EP 0996754 B1 EP0996754 B1 EP 0996754B1
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EP
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Prior art keywords
weight
alloy
extrudability
aluminium
corrosion resistance
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.)
Expired - Lifetime
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EP98942668A
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English (en)
French (fr)
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EP0996754A1 (de
Inventor
Lars Auran
Trond Furu
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Norsk Hydro ASA
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Norsk Hydro ASA
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium

Definitions

  • the invention relates to an improved aluminium alloy and more particularly to an aluminium alloy which contains controlled amounts of defined compounds and is characterized by the combination of high extrudability and high corrosion resistance.
  • aluminium alloys are used in a number of applications, especially for tubing because of the extrudability of the alloys combined with relatively high strength and low weight
  • aluminium alloys for use in heat exchangers or air conditioning condensers.
  • the alloy must have a good strength, a sufficient corrosion resistance and good extrudability.
  • a typical alloy used in this application is AA 3102. Typically this alloy contains approximately 0,43% by weight Fe, 0,12% by weight Si and 0,25% by weight Mn.
  • WO97/46726 there is described an aluminium alloy containing up to 0,03% by weight copper, between 0,05 - 0,12% by weight silicon, between 0,1 and 0,5% by weight manganese, between 0,03 and 0,30 % by weight titanium between 0,06 and 1,0% weight zinc, less than 0,01% by weight of magnesium, up to 0,50% by weight iron, less than 0,01 % by weight nickel and up to 0,50% by weight chromium.
  • a number of elements may be present as normal impurities, including Zn, Zr, Ni V and Cr, the maximum amount per element being 0,05 by weight percent
  • Zn, Zr, Ni V and Cr the maximum amount per element being 0,05 by weight percent
  • the alloy according to this document is intended to be used as finstock, and no indication is given about its extrudability. From table 6 it becomes clear (see no. 10,11 and 19) that the corrosion resistance is due to the high amount of Zn present in the alloy, and not as a result of the balanced presence of different elements, as eludicated by the alloys A - E according to the invention.
  • the aluminium alloy according to the present invention includes controlled amounts of iron, silicon, manganese, zirconium, chromium and zinc.
  • the iron content of the alloy according to the invention is between 0,06-0,15 % by weight. In this way the corrosion resistance and the extrudability is optimal, as both characteristics are substantially reduced with high iron content.
  • the zirconium content is preferably between 0,10-0,18 % by weight. In this range the extrudability of the alloy is practically not influenced by any change in the amount of zirconium.
  • the chromium content is between 0,10-0,18 % by weight.
  • An increase in chromium content results in an increased resistance against corrosion, within this range the extrudability is slightly reduced but still within an acceptable range.
  • Zinc will in even small consentration, negatively affect the anodizing properties of AA 6000 alloys.
  • the level of Zn should be kept low to make the alloy more recycleable and save costs in the cast house. Otherwise, zinc has a positive effect on the corrosion resistance up to at least 0,70% by weight, but for the reason given above the amount of zinc is preferable between 0,10 - 0,18 % by weight.
  • copper may be present to up to 0,70 % by weight, it is preferred to have the copper content below 0,01 % by weight in order to have the best possible extrudability. In some circumstances it might be necessary to add copper to the alloy to control the corrosion potential, making the product less electo negative, to avoid galvanic corrosion attack of the product. It has been found that copper increases the corrosion potential with some 100mV for each % of copper added, but at the same time decreases the extrudability substantially.
  • the aluminium product may be obtained by means of extrusion.
  • the alloy will be homogenized by means of an heat treatment at elevated temperatures, e.g. 550-610°C during 3-10 hours. It has been found that by such a heat treatment the extrudability was slightly improved, but the corrosion resistance was negatively influenced.
  • the aluminium product is produced by only one heat treatment of the aluminium alloy after casting preheating immediately before extrusion.
  • Such preheating takes place at lower temperatures than the homogenization step and only takes a few minutes, so that the characteristics of the alloy with respect to extrudability and corrosion resistance are hardly effected.
  • alloys according to the invention have been prepared, which alloys are listed below in table 1 the alloys A - E.
  • table 1 the composition of these alloys has been indicated in % by weight, taking into account that each of these alloys may contain up to 0,02 % by weight of incidental impurities.
  • table 1 is also shown the composition of the traditional 3102-alloy.
  • All these alloys have been prepared in the traditional way .
  • the extrusion of the billet after preparation of the alloy was preceded by a preheating to temperatures between 460-490°C.
  • Chemical composition of the different alloys Alloy Fe Si Mn Zr Cr Zn A 0,10 0,08 0,07 0,18 0,11 0,00 B 0,12 0,07 0,07 0,12 0,11 0,10 C 0,12 0,07 0,07 0,14 0,14 0,17 D 0,13 0,07 0,07 0,10 0,13 0,19 E 0,11 0,07 0,09 0,07 0,00 0,24 3102 0,43 0,12 0,25 - - -
  • the extrudability is related to the die force and the maximum extrusion force indicated as max force. Those parameters are registered by pressure transducers mounted on the press, giving a direct read out of these values.
  • the test sample was an extruded tube with a wall thickness of 0,4mm. This test was performed according to ASTM-standard G85-85 Annex A3, with alternating 30 minutes spray periods and 90 minutes soak periods at 98% humidity.
  • the electrolyte is artificial sea water acidified with acetic acid to a pH of 2,8 to 3,0 and a composition according to ASTM standard D1141. The temperature is kept at 49°C. The test was run in a Liebisch KTS-2000 salt spray chamber.
  • test as described are in general use with the automotive industry, where an acceptable performance is qualified as being above 20 days.
  • the testing of mechanical properties was carried out on a budget Universal Testing Instrument (Module 167500) and in accordance with the Euronorm standard. In the testing the E-module was fixed to 70000N/mm 2 during the entire testing. The speed of the test was constant and 10 N/mm 2 per second until Rp0,2 was reached, whilst the testing speed from Rp0,2 until fracture was 40% Lo/min, Lo being the initial gauge length.
  • Alloy E which contains no Cr, and alloy A which does not contain Zn give results which are much better than the acceptable limit of 20 days, however, the corrosion resistance is significantly lower than the alloys B, C and D. This clearly shows that both Cr and Zn should be present in a long life alloy in order to optimize the corrosion resistance. In addition, comparing the results from alloy C and D indicate the importance of Zr. Increasing the Zr-content improves the corrosion behaviour in a significant way.
  • the extrudability is affected by small additions of the different alloying elements. By introducing Cr and Zr it is seen that the die force and the maximum force increases (i.e. the extrudability is reduced). Zinc, on the other hand, does not affect the extrudability in any significant way which as such is well known.
  • the mechanical properties in terms of ultimate tensile strength and yield strength are seen to be significantly improved when Cr is added. In that case the new alloys match the 3102 alloy properties.
  • the corrosion test have been performed on samples taken at different location of the coil. About 10 samples were taken from the very start of the coil (from the front of the billet), 10 samples from the middle part of the coil (middle part of the billet) and 10 samples from the end of the coil (end of the billet). Each sample was about 50 cm long. The results were very consistent which means that there is no effects on the corrosion resistance related to extrusion speed and material flow during the exterusion of one billet, for the extrusion parameters used.
  • the x-axis represents the content of the alloying agent expressed in % by weight
  • the y-axis is a relative representation of the different properties
  • the square dots being used to represent the ultimate tensile strength in MPa
  • the black triangular dots being used to represent the entrudability expressed in ktons and using the die force as representative measurement
  • the white triangular dots being used to represent the SWAAT-test results expressed in days.
  • the corrosion resistance is reduced in a significant way with higher Fe-contents (keeping Si-content at the same level of 0,08 % by weight). This effect especially occurs at Fe-contents in the range of 0,2 - 0,3 % by weight.
  • the extrudability is significantly reduced with higher Fe-contents. It should be noted that a reduction of 2-3% of the extrudability (expressed as 2-3% increase of the break through pressure) is an unacceptable increase for an extrusion plant. Otherwise an increase of the Fe-content results in an increase of the tensile strength. As becomes clear for Fig.
  • Fig.6 there is shown a diagram showing the influence of the Cu-content on the extrudability and on the corrosion potential.
  • the amount of Cu in % by weight On the X-axis is shown the amount of Cu in % by weight, whereas the left Y-axis is the extrusion force expressed in kN and the right Y-axis is the corrosion potential expressed in mV according to ASTM G69.
  • the upper line in the graph is the evolution of the corrosion potential, whereas the lower line is the evolution of the extrusion force.
  • the extruded product such as a heat exchanger tube
  • another product such as a header with a clad containing no Zinc
  • Cu additions modify the corrosion potential of the extruded product in such a way that the tube becomes more noble (less negative) than the header material. This will curb any attacks of the tube due to galvanic corrosion.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Of Metal (AREA)
  • Cookers (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Springs (AREA)
  • Powder Metallurgy (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Crushing And Grinding (AREA)
  • Glass Compositions (AREA)

Claims (7)

  1. Legierung auf der Basis von Aluminium, bestehend aus:
    0,06 - 0,25 Gew.-% Eisen,
    0,05 - 0,15 Gew.-% Silicium,
    bis zu 0,70 Gew.-% Kupfer,
    0,03 bis 0,10 Gew.-% Mangan,
    0,02 bis 0,20 Gew.-% Zirconium,
    bis zu 0,18 Gew.-% Chrom,
    bis zu 0,70 Gew.-% Zink,
    0,005 bis 0,02 Gew.-% Titan (als Kornverfeinerungsmittel),
    bis zu 0,02 Gew.-% zufälligen Verunreinigungen,
    wobei der Rest aus Aluminium besteht, wobei die Legierung auf der Basis von Aluminium eine hohe Korrosionsbeständigkeit und Strangpressfähigkeit aufweist.
  2. Legierung nach Anspruch 1, wobei der Eisengehalt im Bereich von 0,06 - 0,15 Gew.-% liegt.
  3. Legierung nach Anspruch 2, wobei der Mangangehalt im Bereich von 0,03 - 0,08 Gew.-% liegt.
  4. Legierung nach Anspruch 3, wobei der Zirconiumgehalt im Bereich von 0,10 - 0,18 Gew.-% liegt.
  5. Legierung nach Anspruch 4, wobei der Chromgehalt im Bereich von 0,10 - 0,18 Gew.-% liegt.
  6. Legierung nach Anspruch 5, wobei der Zinkgehalt im Bereich von 0,10 - 0,18 Gew.-% liegt.
  7. Legierung nach einem der vorhergehenden Ansprüche, wobei der Kupfergehalt im Bereich unter 0,01 Gew.-% liegt.
EP98942668A 1997-07-17 1998-07-10 Korrosionsbeständige aluminiumlegierung mit zircon Expired - Lifetime EP0996754B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98942668A EP0996754B1 (de) 1997-07-17 1998-07-10 Korrosionsbeständige aluminiumlegierung mit zircon

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP97202233 1997-07-17
EP97202233A EP0893512A1 (de) 1997-07-17 1997-07-17 Hochextrudierbare, korrosionsbeständige Aluminiumlegierung
PCT/EP1998/004956 WO1999004050A1 (en) 1997-07-17 1998-07-10 High corrosion resistant aluminium alloy containing zirconium
EP98942668A EP0996754B1 (de) 1997-07-17 1998-07-10 Korrosionsbeständige aluminiumlegierung mit zircon

Publications (2)

Publication Number Publication Date
EP0996754A1 EP0996754A1 (de) 2000-05-03
EP0996754B1 true EP0996754B1 (de) 2004-04-21

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP97202233A Withdrawn EP0893512A1 (de) 1997-07-17 1997-07-17 Hochextrudierbare, korrosionsbeständige Aluminiumlegierung
EP98942668A Expired - Lifetime EP0996754B1 (de) 1997-07-17 1998-07-10 Korrosionsbeständige aluminiumlegierung mit zircon

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP97202233A Withdrawn EP0893512A1 (de) 1997-07-17 1997-07-17 Hochextrudierbare, korrosionsbeständige Aluminiumlegierung

Country Status (13)

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EP (2) EP0893512A1 (de)
JP (1) JP4107632B2 (de)
KR (1) KR100549389B1 (de)
CN (1) CN1090245C (de)
AT (1) ATE264927T1 (de)
AU (1) AU9071798A (de)
BR (1) BR9810877A (de)
CA (1) CA2297116A1 (de)
DE (1) DE69823356T2 (de)
ES (1) ES2221193T3 (de)
IL (1) IL134037A (de)
TR (1) TR199902872T2 (de)
WO (1) WO1999004050A1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6602363B2 (en) * 1999-12-23 2003-08-05 Alcoa Inc. Aluminum alloy with intergranular corrosion resistance and methods of making and use
US6503446B1 (en) 2000-07-13 2003-01-07 Reynolds Metals Company Corrosion and grain growth resistant aluminum alloy
US6458224B1 (en) 1999-12-23 2002-10-01 Reynolds Metals Company Aluminum alloys with optimum combinations of formability, corrosion resistance, and hot workability, and methods of use
EP1576332B1 (de) 2002-12-23 2016-03-16 Alcan International Limited Aus alulegierung bestehende rohr und rippen vorrichtung für wärmetauschern mit verbessertem korrosionschutz nach dem löten
JP5878235B2 (ja) * 2012-04-05 2016-03-08 日本軽金属株式会社 押出性と耐粒界腐食性に優れた微細孔中空形材用アルミニウム合金およびその製造方法
KR101465389B1 (ko) * 2013-09-27 2014-11-25 성균관대학교산학협력단 알루미늄 합금 조성물, 이를 포함하는 관통저항성이 향상된 알루미늄 압출 튜브와 핀 재 및 이로 구성된 열교환기
CN105568063A (zh) * 2014-10-13 2016-05-11 焦作市圣昊铝业有限公司 一种高强度耐腐蚀的铝合金
CN107299264B (zh) * 2017-05-26 2018-07-13 广东伟业铝厂集团有限公司 汽车底盘用高性能铝合金型材
CN108754246A (zh) * 2018-06-19 2018-11-06 江苏亨通电力特种导线有限公司 汽车冷凝管用铝合金材料及其制备方法
CN111647774A (zh) * 2020-02-17 2020-09-11 海德鲁挤压解决方案股份有限公司 生产耐腐蚀和耐高温材料的方法
WO2021165266A1 (en) 2020-02-17 2021-08-26 Hydro Extruded Solutions As Method for producing a corrosion and high temperature resistant aluminium alloy extrusion material

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH622031A5 (en) * 1976-09-02 1981-03-13 Alusuisse Use of pure aluminium for aluminium cans
JPS6022278B2 (ja) * 1980-10-01 1985-05-31 株式会社デンソー アルミニウム合金製熱交換器の製造方法
JPS57203743A (en) * 1981-06-08 1982-12-14 Mitsubishi Alum Co Ltd Al alloy with superior thermal deformation resistance and heat conductivity
AU582139B2 (en) * 1984-03-06 1989-03-16 Furukawa Aluminum Co., Ltd. Aluminum and aluminum alloy for fin and heat exchanger using same
WO1991014794A1 (en) * 1990-03-27 1991-10-03 Alcan International Limited Improved aluminum alloy
JPH05125472A (ja) * 1991-11-06 1993-05-21 Furukawa Alum Co Ltd アルミニウムクラツドフイン材
US5286316A (en) * 1992-04-03 1994-02-15 Reynolds Metals Company High extrudability, high corrosion resistant aluminum-manganese-titanium type aluminum alloy and process for producing same
JPH09137245A (ja) * 1995-11-09 1997-05-27 Denso Corp 熱交換器用アルミニウム管体および該アルミニウム管体を使用したアルミニウム製熱交換器

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Publication number Publication date
WO1999004050A1 (en) 1999-01-28
IL134037A (en) 2004-03-28
CN1264431A (zh) 2000-08-23
AU9071798A (en) 1999-02-10
DE69823356D1 (de) 2004-05-27
DE69823356T2 (de) 2005-05-04
BR9810877A (pt) 2000-08-08
KR100549389B1 (ko) 2006-02-08
EP0893512A1 (de) 1999-01-27
CN1090245C (zh) 2002-09-04
ATE264927T1 (de) 2004-05-15
TR199902872T2 (xx) 2000-05-22
ES2221193T3 (es) 2004-12-16
IL134037A0 (en) 2001-04-30
CA2297116A1 (en) 1999-01-28
JP2001510239A (ja) 2001-07-31
EP0996754A1 (de) 2000-05-03
KR20010013860A (ko) 2001-02-26
JP4107632B2 (ja) 2008-06-25

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