EP2471967B2 - Procédé pour obtenir des propriétés mécaniques améliorées dans des moulages d'aluminium recyclés dépourvus de phases bêta en forme de plaquettes - Google Patents

Procédé pour obtenir des propriétés mécaniques améliorées dans des moulages d'aluminium recyclés dépourvus de phases bêta en forme de plaquettes

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Publication number
EP2471967B2
EP2471967B2 EP10382360.5A EP10382360A EP2471967B2 EP 2471967 B2 EP2471967 B2 EP 2471967B2 EP 10382360 A EP10382360 A EP 10382360A EP 2471967 B2 EP2471967 B2 EP 2471967B2
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EP
European Patent Office
Prior art keywords
casting
aluminium alloy
iron
aluminium
mpa
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.)
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Application number
EP10382360.5A
Other languages
German (de)
English (en)
Other versions
EP2471967A1 (fr
EP2471967B1 (fr
Inventor
Ana Isabel Fernández Calvo
Andrea Niklas
Ignacio Alfaro Abreu
Iñigo Anza Ortiz de Apodaca
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Befesa Aluminio SL
Casa Maristas Azterlan
Original Assignee
Befesa Aluminio SL
Casa Maristas Azterlan
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Application filed by Befesa Aluminio SL, Casa Maristas Azterlan filed Critical Befesa Aluminio SL
Priority to ES10382360T priority Critical patent/ES2507865T5/es
Priority to EP10382360.5A priority patent/EP2471967B2/fr
Priority to PCT/ES2011/070911 priority patent/WO2012089886A2/fr
Publication of EP2471967A1 publication Critical patent/EP2471967A1/fr
Publication of EP2471967B1 publication Critical patent/EP2471967B1/fr
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Classifications

    • 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
    • C22C21/04—Modified aluminium-silicon alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/026—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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
    • C22F1/043—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 silicon as the next major constituent

Definitions

  • the present invention relates to a process for the preparation of aluminium alloy castings from recycled aluminium alloys in order to obtain recycled aluminium casting free of platelet-shaped beta-phases.
  • the present invention also relates to aluminium alloy castings obtainable by said process, more particularly, it relates to aluminium alloy castings suitable as components for instance for vehicles, machines and electric applications which are required to have high strength and high elongation values among other properties
  • Aluminium alloys are widely used in diverse applications for instance as components in the automotive, aerospace, industrial machines, electric applications etc., because of their excellent mechanical properties as well as other technological properties such as corrosion resistance and reduced hot cracking tendency.
  • the primary production which is of minerals rich in aluminium (bauxite)
  • aluminium recycling secondary alloy whose raw material is dross and other residues rich in aluminium.
  • the primary alloy production consists basically in reducing the oxide present in bauxite enhancing the purity of aluminium by electrolysis.
  • the most important drawback of this method is the high quantity of energy (from 14 to 15 Kwh/kg) which is necessary to produce aluminium whereas in the aluminium recycling method the costs are about 0,5-0,75 Kwh/kg, that is lower than 5% of the primary production.
  • AlSiMg alloys are nowadays one of the most common aluminium castings alloys for high safety parts, such as automotive or aerospace components, which require high mechanical properties. This alloy presents also high ductility due to the low content in impurities and to the addition of elements such as Ti or Sr which refine and modify the microstructure, respectively. AlSiMg alloys are broadly used for castings produced in sand, permanent and investment moulds.
  • the high content in impurities, especially the high iron content, in secondary alloys (recycled aluminium) is considered as the main disadvantage.
  • the iron content increases in recycled aluminium after each subsequent melting; its elimination or reduction is technically very complex and rather expensive, not being economically feasible.
  • the microstructure of AlSiMg alloys presents alpha aluminium dendrites and Al-Si eutectic and other intermetallic phases among which the iron-rich ones can be highlighted.
  • Iron is well known for being the most common and detrimental impurity in aluminium alloys for mechanical properties, promoting the appearance of hard and brittle intermetallic iron-rich phases during solidification.
  • the platelet-shaped beta phase (Al 5 FeSi) is the most prejudicial since it is well known that ductility and toughness are significantly decreased. Therefore, there has been recently an increasing interest in developing methods for producing improved recycled aluminium alloys in which the formation of the beta phase is reduced and the mechanical properties are thus improved.
  • the strategy was based on the inhibition of the platelet morphology by promoting the precipitation of the Al 15 Fe 3 Si 2 -type phase with the addition of a neutralizing element (Mn, Cr, Co and Be) and in some case controlling the condition of crystallization.
  • a neutralizing element Mn, Cr, Co and Be
  • the patent WO 97/13882 discloses a method for producing iron-containing AlSi-alloys in particular Al-Si-Mn-Fe- alloys.
  • the mechanical properties of aforementioned Al-alloys with iron contents between 0,4 and 2.0 wt.% can be improved by controlling the morphology of the iron containing intermetallic precipitates.
  • the precipitation of platelet-shaped beta phase ( ⁇ -Al 5 FeSi) has been found to be suppressed by a primary precipitation of the hexagonal Al 8 Fe 2 Si-type phase which is in turn less harmful one.
  • the method comprises further controlling the condition of the crystallization by the addition of one or more elements such as Ti, Zr, Sr, Na and Ba.
  • the present invention which is given in the claims refers to a process for the preparation of an iron containing aluminium alloy casting, hereinafter referred to as the alloy casting of the invention, which is free from primary platelet-shaped beta-phase of the Al 5 FeSi-type in the solidified structure presenting the following compositions (amounts expressed in weight percentage, wt.% in respect to the total weight of the alloy): Si 6.00 - 9.50 Fe 0.15 - 0.60 Mn 0.04 - 0.60 Mg 0.20 - 0.70 Cr 0.01 - 0.60 Ti 0.05 - 0.30 Sr and/or Na 0.001 - 0.25 V 0.00 - 0.60 Cu 0.01 - 0.25 Ni 0.01 - 0.1 Zn 0.01 - 0.1
  • the iron-containing aluminium alloy casting of the invention presents a composition characterized in that the amount of Mn plus Cr in weight percentage is equal or larger than 50 % of Fe amount.
  • the iron-containing aluminium alloy casting of the invention presents a composition characterized in that the amount of Mn plus Cr plus V in weight percentage is equal or larger than 50 % of Fe amount.
  • the iron-containing aluminium alloy casting of the invention presents a Fe content between 0.15 - 0.40% in weight percentage and an amount of Mn plus Cr plus V comprised between 0.15 - 0.40 wt.%.
  • the process for the preparation of the aluminium alloy casting of the invention comprises the following steps:
  • the process of the invention comprises the degassing process according to already known methods such as treating the molten alloy with dry nitrogen or dry argon until the hydrogen content dissolved in the melt is low enough.
  • the process comprises the addition of alloying elements added as pure elements or as master alloys.
  • the present invention resides in the addition of alloying elements: Mn+Cr or Mn+Cr+V, to the base composition of a secondary AlSi7Mg ingot of second fusion (or recycled aluminium).
  • the process comprises the addition of grain refiner and eutectic modification agents by means of master alloys additions.
  • the modifier agent Na or Sr are the most common ones and are added to achieve the modification of the eutectic Al-Si structure, which precipitates during solidification, showing a rounded morphology instead of needle structure, typical when such a modifying agent is not added. It is well known that the presence of such needle structures reduces the mechanical properties (ductility, strength) of the alloys, promoting the appearance of cracks.
  • TiB master alloys are used to obtain a microstructures which shows a fine grain size and thus improving the final mechanical properties and also, reducing the porosity tendency.
  • the properties of the recycled alloy castings obtained according to the process of the present invention show mechanical properties comparable to those obtained in primary alloys.
  • the aluminium alloys used in high responsibility castings need to fulfil certain mechanical and technological properties. For this reason, these parts are generally submitted to a T6 heat treatment.
  • the process of the present invention for making an aluminium alloy casting also comprises submitting the solidified casting as described above to a T6 heat treatment (step h).
  • a T6 treatment comprises a first step of solution heat treatment, heating the castings at a temperature between 500 to 600°C for 2 to 6 hours, followed by quenching.
  • the second step will consist in an artificial aging at a temperature between 150 to 180°C for 2 to 8 hours.
  • the aluminium alloy casting obtainable by the above defined process presents a tensile strength between 250-300 MPa, a yield strength between 190-230 MPa and elongation values between 4.5-9%.
  • the aluminium alloy casting of the invention can be used as a component for transport components such as wheels, suspension parts, brake parts, and energetic industry components.
  • a further aspect of the invention relates to a component made from recycled aluminium alloy castings such as steering knuckle, master cylinder and brake calliper.
  • tensile test specimen are poured in sand mould and permanent moulds from the aluminium alloy of the invention with additions of Mn, Cr and V.
  • the mechanical properties were determined with tensile test specimen according to norm (UNE UNE-EN_1706), (see fig 2 ).
  • the aluminium alloys present a tensile strength of at least 250 MPa, a yield strength of at least 190 MPa and an elongation of at least 4.5 %.
  • the test pieces according to the invention were submitted to microstructural analysis. The inventors found that the addition of controlled amounts of Mn, Cr and V according to the present invention eliminates the platelet-shape beta-phases (Al 5 FeSi).
  • the aluminium alloys have been produced by using secondary AlSi7Mg ingots, obtained from scrap, recycled aluminium dross and other metal residues rich in aluminium.
  • the following table shows the chemical compositions of recycled ingots used in the examples, with iron contents between 0.28 and 0.34 wt.%.
  • Three recycled ingots (ref. I, II and III) have been used in the experimental tests (Base Composition) are shown, the rest being Al: Ingot Secondary AlSi7 Mg alloy Chemical Composition (wt.%) Si Fe Cu Mn Mg Cr Ni Zn Ti Sr V Ref. I 7.11 0.34 0.06 0.09 0.27 0.017 0.01 0.07 0.07 0.005 ⁇ 0.01 Ref. II 6.94 0.28 0.04 0.04 0.28 0.004 0.00 0.04 0.14 ⁇ 0.003 ⁇ 0.01 Ref. III 6.92 0.28 0.04 0.04 0.25 ⁇ 0.01 0.01 0.04 0.16 ⁇ 0.003 ⁇ 0.01 Aluminium in balance
  • the recycled ingots were melted in an electric furnace (capacity of 50 kg of molten aluminium) at 710-750oC. The melt was then alloyed and liquid treated according to the predetermined following schedule:
  • the melt was held for 10 minutes between consecutive additions for chemical homogenization.
  • medals were cast and analysed thereafter by means of spark emission spectrometry.
  • the melt was subjected to degassing by using N 2 during approximately 20 minutes.
  • the effectiveness of degassing was checked by means of Reduced Pressure or Straube-Pfeiffer Test where samples for alloy density evaluation were taken after degassing. In all cases, a minimum density of 2.65 gr/cm 3 was obtained in samples solidified in vacuum.
  • the metal liquid was poured into chemically bonded sand moulds, at temperatures between 710 y 740 °C, in order to obtain tensile test specimens (norm UNE-EN-ISO 6892-1).
  • the tensile test specimens ( Figure 2 ) were subjected to a T6 heat treatment in a laboratory furnace with a temperature control of ⁇ 2 oC.
  • the sequences of this thermal process were the following:
  • microstructures of the cast alloys were examined using optical and scanning electron microscopy: grain size, modification rate, iron rich phases and porosity have been evaluated in the tensile casting, see example in Figure 3 .
  • the Figure 4 shows different morphologies of iron phases observed in recycled aluminium alloys by using optical microscopy. Iron is known to be the most common and at the same time most detrimental impurity in aluminium alloys since it causes hard and brittle iron-rich intermetallic phases to precipitate during solidification. The most detrimental phase in the microstructure is the beta-phase of the Al 5 FeSi- type because of its platelet-shape, see Figure 4a ). This figure shows a typical ⁇ -A 5 FeSi phase with a monoclinic crystal structure and plate like morphology. Such platelets may have an extension of several millimetres and appear as needles in micrographic sections.
  • aluminium alloys with Mn, Cr and V additions do not present interactions with TiB master alloys (grain refiner agent) and Sr additions (modification of Si eutectic phases), obtaining good levels of grain refinement, Si modification and hydrogen degassing.
  • the Figure 5 shows micrographs which correspond to aluminium alloys: a) without alloying additions (Mn, Cr, V) and b) with the additions of Mn + Cr and c) with the addition of Mn, Cr and V. From results it can be seen that in b) and c) no platelet-shape phases (beta-phases) were found when performing the aforementioned additions in the conditions previously described in opposition to a) where these platelet-shape phases can be clearly observed (see arrows pointing thereto).
  • beta phase morphology (platelet-shape) is modified with the additions of Mn plus Cr or Mn plus Cr plus V, obtaining phases with a globular/chinese script morphology less harmful to mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Continuous Casting (AREA)

Claims (6)

  1. Procédé de préparation d'une pièce moulée en alliage d'aluminium contenant du fer et exempte d'une phase bêta en forme de plaquette primaire de type Al5FeSi dans la structure solidifiée, présentant la composition suivante (quantités exprimées en % en poids par rapport au poids total de l'alliage) : Si 6,00 à 9,50 Fe 0,15 à 0,60 Mn 0,04 à 0,60 Mg 0,20 à 0,70 Cr 0,01 à 0,60 Ti 0,05 à 0,30 Sr et/ou Na 0,001 à 0,25 V 0,00 à 0,60 Cu 0,01 à 0,25 Ni 0,01 à 0,1 Zn 0,01 à 0,1
    le reste étant de l'Al et les impuretés inévitables,
    dans lequel la pièce moulée en alliage d'aluminium contenant du fer présente une composition caractérisée en ce que la quantité totale de Mn et de Cr en pourcentage en poids (% en poids) est supérieure ou égale à 50 % de la quantité de Fe, ou
    dans lequel la pièce moulée en alliage d'aluminium contenant du fer présente une composition caractérisée en ce que la quantité totale de Mn, de Cr et de V en pourcentage en poids (% en poids) est supérieure ou égale à 50 % de la quantité de Fe,
    comprenant :
    a) la fonte d'un lingot d'AlSi7Mg d'une seconde fusion,
    b) l'ajout de Mn et de Cr, ou de Mn et de Cr et de V, à la composition de base du lingot secondaire d'AlSi7Mg d'une seconde fusion,
    c) l'ajout d'un agent d'affinage de grain et d'un agent de modification de silicium eutectique,
    d) la soumission de l'alliage fondu obtenu dans l'étape c) à un procédé de dégazage,
    e) l'introduction de l'alliage fondu dégazé dans un moule,
    f) la solidification d'une pièce moulée à l'intérieur du moule,
    g) l'extraction de la pièce moulée du moule, et
    la soumission de la pièce moulée solidifiée de l'étape g) à un traitement thermique T6 h)
    dans lequel la pièce moulée obtenue dans l'étape h) présente une résistance à la traction située entre 250 MPa et 300 MPa, une limite d'élasticité située entre 190 MPa et 230 MPa et des valeurs d'allongement situées entre 4,5 % et 9 %.
  2. Procédé selon la revendication 1, dans lequel l'alliage d'aluminium contenant du fer présente une composition caractérisée en ce que la teneur en Fe est de 0,15 % à 0,40 % en poids et que la quantité de Mn, de Cr et de V pris ensemble est comprise entre 0,15 % et 0,40 % en poids.
  3. Procédé selon la revendication 1, dans lequel les éléments d'alliage sont ajoutés sous la forme d'éléments purs ou sous la forme d'alliages mères.
  4. Pièce moulée en alliage d'aluminium, présentant la composition telle que définie dans l'une quelconque des revendications 1 à 3 et présentant une résistance à la traction située entre 250 MPa et 300 MPa, une limite d'élasticité située entre 190 MPa et 230 MPa et des valeurs d'allongement situées entre 4,5 % et 9 %, et qui peut être obtenue par le procédé de l'une quelconque des revendications 1 à 3.
  5. Utilisation de la pièce moulée en alliage d'aluminium de la revendication 4, comme composant destiné à des composants de transport choisis parmi les roues, les pièces des suspensions et les pièces des freins.
  6. Composant fabriqué à partir de la pièce moulée en alliage d'aluminium de la revendication 4, choisi parmi un porte-fusée de direction, un maître-cylindre et un étrier de frein.
EP10382360.5A 2010-12-28 2010-12-28 Procédé pour obtenir des propriétés mécaniques améliorées dans des moulages d'aluminium recyclés dépourvus de phases bêta en forme de plaquettes Active EP2471967B2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
ES10382360T ES2507865T5 (en) 2010-12-28 2010-12-28 Method for obtaining improved mechanical properties in recycled aluminium castings free of platelet-shaped beta-phases
EP10382360.5A EP2471967B2 (fr) 2010-12-28 2010-12-28 Procédé pour obtenir des propriétés mécaniques améliorées dans des moulages d'aluminium recyclés dépourvus de phases bêta en forme de plaquettes
PCT/ES2011/070911 WO2012089886A2 (fr) 2010-12-28 2011-12-28 Procédé d'obtention de propriétés mécaniques améliorées dans des coulées d'aluminium recyclé exemptes de phases bêta, sous forme de lamelle

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP10382360.5A EP2471967B2 (fr) 2010-12-28 2010-12-28 Procédé pour obtenir des propriétés mécaniques améliorées dans des moulages d'aluminium recyclés dépourvus de phases bêta en forme de plaquettes

Publications (3)

Publication Number Publication Date
EP2471967A1 EP2471967A1 (fr) 2012-07-04
EP2471967B1 EP2471967B1 (fr) 2014-07-09
EP2471967B2 true EP2471967B2 (fr) 2025-07-30

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Country Status (3)

Country Link
EP (1) EP2471967B2 (fr)
ES (1) ES2507865T5 (fr)
WO (1) WO2012089886A2 (fr)

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EP2471967A1 (fr) 2012-07-04
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EP2471967B1 (fr) 2014-07-09
WO2012089886A3 (fr) 2012-12-13
WO2012089886A2 (fr) 2012-07-05

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