EP3670691A1 - Alliage de magnesium et son procédé de fabrication - Google Patents

Alliage de magnesium et son procédé de fabrication Download PDF

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Publication number
EP3670691A1
EP3670691A1 EP19212085.5A EP19212085A EP3670691A1 EP 3670691 A1 EP3670691 A1 EP 3670691A1 EP 19212085 A EP19212085 A EP 19212085A EP 3670691 A1 EP3670691 A1 EP 3670691A1
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EP
European Patent Office
Prior art keywords
phase
magnesium
based alloy
aluminum
alloy
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EP19212085.5A
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German (de)
English (en)
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EP3670691B1 (fr
Inventor
Stefan Gneiger
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LKR Leichtmetallkompetenzzentrum Ranshofen GmbH
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LKR Leichtmetallkompetenzzentrum Ranshofen GmbH
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002—Castings of light metals
    • B22D21/007—Castings of light metals with low melting point, e.g. Al 659 degrees C, Mg 650 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/04—Casting aluminium or magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal 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
    • C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Definitions

  • the invention relates to a magnesium-based alloy.
  • the invention relates to a method for producing the magnesium-based alloy.
  • Mg-Al alloys are frequently used casting alloys and are particularly widely used in the automotive industry. Especially for die casting processes, additive manufacturing processes or thixomolding processes, Mg-Al alloys have proven themselves, because in addition to good mechanical properties at room temperature, they are particularly suitable for castability through the formation of a eutectic or a eutectic phase at around 437 ° C exhibit.
  • the eutectic is formed with an intermetallic Mg 17 Al 12 phase ( ⁇ (Mg) + Mg 17 Al 12 ), which increases the strength of the alloy, but at the same time reduces the ductility of the alloy.
  • Mg-Al alloys with an Al content between 2% by weight and 9% by weight are customary.
  • Known alloys are, for example, AZ61 (Mg-Al6% -Zn1%) or AZ91 (Mg-Al9% -Zn1%), designated according to the technical short name according to the ASTM standard, the proportions each being given in% by weight.
  • the usual Al content of Mg-Al alloys between 2% and 9% by weight can be explained by the fact that with a higher Al content a higher proportion of the Mg 17 Al 12 phase is formed and thus an extensibility of the Alloy is steadily reduced.
  • Applicable Mg-Al alloys therefore generally have an Al content of less than 10.0% by weight.
  • the object of the invention is to provide a magnesium-based alloy which has both great strength and great ductility and is particularly suitable for die casting processes or additive manufacturing processes.
  • Another object of the invention is to provide a method for producing such a magnesium-based alloy.
  • a magnesium-based alloy comprising (in% by weight) in a first part magnesium, in a second proportion more than 10.0% aluminum, a third portion of one or more elements, which forms at least a first phase with aluminum, optionally more than 0.0 to 2.0% tin, Balance magnesium and production-related impurities, wherein the magnesium base alloy contains a Mg 17 Al 12 phase and a formation temperature of the first phase is higher than a formation temperature of the Mg 17 Al 12 phase.
  • the invention is based on the idea of using the strength-increasing effect of aluminum in a magnesium-based alloy, that is to say providing comparatively high Al fractions in the magnesium-based alloy, but at the same time reducing a fraction of the intermetallic Mg 17 Al 12 phase in order to avoid a possible one Reduction in stretchability of the magnesium-based alloy.
  • the proportion of Mg 17 Al 12 phase or eutectic phase formed, which is formed with Mg 17 Al 12 phase, is reduced, as a result of which a negative influence of the Mg 17 Al 12 phase on the ductility is reduced.
  • the first phase which is formed with aluminum, contributes to the strength of the magnesium-based alloy. It is advantageous if the first phase has a favorable morphology in terms of its mechanical properties, in particular high strength or extensibility.
  • the first phase is in the form of a non-contiguous structure, preferably in the form of predominantly isolated islands, and / or precipitates of the first phase are as small as possible and / or Precipitates of the first phase have a round or block shape, as explained in detail below.
  • the magnesium-based alloy has both great strength and great ductility.
  • the proportion of Al expediently represents the highest proportion of an element in the magnesium-based alloy after magnesium.
  • the formation temperature of the Mg 17 Al 12 phase or of the eutectic with the Mg 17 Al 12 phase is generally in a range of approximately 437 ° C, as shown in a binary phase diagram of Mg-Al, shown in Fig. 1 , can be removed.
  • the Mg 17 Al 12 phase and its formation temperature relate in particular to those Mg 17 Al 12 phase which, in the course of forming a eutectic ( ⁇ (Mg) + Mg 17 Al 12 ), when the Mg-Al alloy cools is formed.
  • ⁇ (Mg) + Mg 17 Al 12 eutectic
  • Mg-Al alloy in a real solidification process of a Mg-Al alloy, particularly due to a low diffusion rate of aluminum in magnesium, small amounts of Mg 17 Al 12 already at higher temperatures, for example even at a solidus temperature of the Mg-Al alloy. Alloy that can be excreted. Understandably, according to the invention, such fractions do not fall under the term Mg 17 Al 12 phase used and accordingly do not represent a limitation for the magnesium-based alloy according to the invention.
  • the third portion forms several different first phases with aluminum, the formation temperatures of which are greater than the formation temperature of the Mg 17 Al 12 phase.
  • This enables a differentiated setting of the desired strength and ductility of the magnesium-based alloy.
  • different elements can be used to form the first phase or a plurality of first phases.
  • rare earth metals (RE) and / or calcium (Ca) have proven to be favorable for the formation of the first phase.
  • the third portion forms the at least first phase with at least a portion of aluminum which in the second portion exceeds 10% by weight of aluminum.
  • the third part thus forms with at least the second portion of aluminum minus 10.0% by weight aluminum, the at least one first phase.
  • a maximum of 10.0% by weight of aluminum is then available for the formation of a Mg 17 Al 12 phase, since the remaining portion of aluminum is bound in the at least first phase.
  • the negative influence of the Mg 17 Al 12 phase on the ductility is reduced to a practical level.
  • the third portion of one or more elements can in principle be formed with all elements, apart from magnesium and aluminum, which together with aluminum form a first phase, the formation temperature of which is higher than that of the Mg 17 Al 12 phase, by a portion of the Mg 17 Al 12 phase or the eutectic with the Mg 17 Al 12 phase.
  • the minimum addition factor defines a minimum proportion of a respective element for binding 1.0 at.% Aluminum by the respective element in the at least first phase.
  • a preferably provided portion of an element of the third portion is thus obtained by multiplying the portion of aluminum to be bound by the element in the first phase by the minimum addition factor of the element.
  • the first phase can be formed with one of the aforementioned elements, in particular in accordance with the minimum addition factor of the element, or with several of the aforementioned elements, the proportion of aluminum to be bound in the first phase then divided in particular among the several elements according to their respective minimum addition factors.
  • the first phase and / or the Mg 17 Al 12 phase are each formed as a non-contiguous structure.
  • a non-contiguous structure means a formation in the form of predominantly isolated islands, in contrast to a formation of a network-like structure, as is often the case in conventional alloys.
  • more than 50% by weight of the first phase or Mg 17 Al 12 phase is formed in the form of isolated islands.
  • a high strength can be achieved if more than 70% by weight, preferably more than 90% by weight, of the first phase or Mg 17 Al 12 phase in Form of isolated islands are formed. It is expedient if excretions of the first phase and / or excretions of the Mg 17 Al 12 phase are as small as possible.
  • a structure of the first phase and / or Mg 17 Al 12 phase or a size of its precipitations can be set practically when the starting materials of the magnesium-based alloy are cooled, starting from a liquid phase, by appropriately selecting a cooling rate.
  • the cause is in particular a slow diffusion rate of aluminum in magnesium.
  • a size of the precipitations can be kept small with such a cooling rate. Due to the slow diffusion rate of aluminum in magnesium, a portion of the Mg 17 Al 12 phase is further reduced.
  • cooling rate of more than 20 K / s is used, particularly small and homogeneously distributed, non-contiguous precipitations of the first phase and / or Mg 17 Al 12 phase can be achieved, as a result of which particularly great strength and great ductility can be achieved.
  • strength is increased further by pronounced solid solution strengthening and corrosion resistance is improved.
  • Such cooling rates are generally used in a die casting process or an arc process or a plasma process, which is why these processes and processes are particularly suitable for use or production of the magnesium-based alloy according to the invention in accordance with the aforementioned effects.
  • a further improvement in the mechanical properties can be achieved if precipitations in the first phase and / or precipitations in the Mg 17 Al 12 phase have a round or block-like shape. This can be achieved by a coordinated choice of the elements of the third component and often also by choosing a suitable cooling rate during production.
  • a marked reduction in a proportion of the Mg 17 Al 12 phase is achieved if the third proportion is formed with rare earth metals, preferably with a proportion of more than 0.0 to 4.0% by weight. This results in a pronounced strength and great elasticity.
  • the third portion is formed with calcium, preferably with a portion of more than 0.0 to 4.0% by weight.
  • the third portion with rare earth metals preferably with a portion of more than 0.0 to 4.0 wt .-%, and with calcium, preferably with a portion of more than 0, 0 to 4.0 wt .-% is formed.
  • This enables a particularly pronounced reduction in a proportion of the Mg 17 Al 12 phase and, as a result, great strength and great elasticity.
  • the rare earth metals are provided in a proportion of more than 0.0 to 4.0% by weight and calcium in a proportion of more than 0.0 to 4.0% by weight.
  • mixed metal or cerium mixed metal has proven to be particularly suitable for achieving the effects provided according to the invention. It is correspondingly favorable if the third portion is formed with mixed metal, in particular with a portion of more than 0.0 to 4.0% by weight. Particularly in combination with calcium, preferably in accordance with the aforementioned proportions, there is a particularly pronounced strength and great elasticity.
  • the third portion is formed with more than 0.0 to 0.5% by weight, preferably about 0.3% by weight, of manganese. In addition to an increase in strength, this also improves corrosion resistance.
  • the third portion is formed with rare earth metals, calcium and manganese, expediently in accordance with the aforementioned respective portions. This provides great strength, great elasticity and excellent corrosion resistance. It is further advantageous for this if the third portion is also formed with strontium, preferably with a portion between 0.1% by weight and 0.8% by weight.
  • magnesium-based alloy is formed with more than 0.0 to 1.0% by weight, preferably about 0.5% by weight, of zinc. This further increases strength.
  • the magnesium-based alloy has more than 10.0% by weight to about 30.0% by weight of aluminum. It has been shown that the effects provided according to the invention can be achieved particularly practically with regard to conventional production processes with high cooling rates if the Magnesium-based alloy has more than 10.0% by weight to 15.0% by weight, preferably between 10.2% by weight to 12.5% by weight, of aluminum.
  • the further object of the invention is achieved by a method for producing a magnesium-based alloy according to the invention, starting materials of the magnesium-based alloy being cooled starting from a liquid phase or a melt in order to form the first phase and then the Mg 17 Al 12 phase.
  • a corresponding magnesium-based alloy can advantageously be produced with the method. Since the first phase has a formation temperature which is higher than the formation temperature of the Mg 17 Al 12 phase, a proportion of the aluminum is bound in the first phase and, to the extent bound, is no longer responsible for the formation of the Mg 17 Al 12 phase Available.
  • a composition of the liquid phase or melt corresponds to the general composition explained above or, if appropriate, to one of the special compositions also explained.
  • the starting materials are cooled at a cooling rate of more than 10 K / s, preferably more than 20 K / s.
  • a cooling rate of more than 20 K / s is used, particularly small and homogeneously distributed, non-contiguous precipitations of the first phase and / or Mg 17 Al 12 phase can be achieved, as a result of which particularly great strength and great ductility can be achieved.
  • cooling takes place in such a way that such a cooling rate is given continuously at least during a cooling from the formation temperature of the Mg 17 Al 12 phase to approximately 150 ° C. below the formation temperature of the Mg 17 Al 12 phase. This is especially true if the cooling takes place in such a way that such a cooling rate is continuous during a cooling from a liquid phase of the starting materials to a temperature 150 ° C. below the formation temperature of the Mg 17 Al 12 phase.
  • wire arc additive manufacturing In particular has proven to be particularly suitable.
  • An arc welding process is used to build up a component in layers.
  • the high cooling rates used in wire-arc additive manufacturing lead to homogeneous and finely divided precipitates of both the first phase and the Mg 17 Al 12 phase, which means that great strength and ductility can be achieved. This enables the production of complex components with the magnesium-based alloy according to the invention, which are particularly robust.
  • a starting material, semi-finished product or component is advantageously produced with a magnesium-based alloy according to the invention or according to a method according to the invention.
  • a primary material, semi-finished product or component formed with the magnesium-based alloy also has an advantageously high strength and great ductility.
  • Fig. 1 shows a phase diagram known from the prior art for an alloy composition of Mg and aluminum, shown up to a proportion of 60 wt .-% aluminum.
  • a conventional alloy with Mg-Al9% (in% by weight) known from the prior art is drawn in with a vertical, dashed line in the phase diagram.
  • Mg-Al9% alloy cools off from a liquid phase L, only a solid solution phase ⁇ (Mg) solidifies first.
  • a eutectic or a eutectic phase formed with an Mg 17 Al 12 phase is finally excreted, as can be seen from the phase diagram.
  • This brittle intermetallic Mg 17 Al 12 phase usually leads to an increase in the strength of a Mg-Al alloy, in particular also the Mg-Al 9% alloy shown, but at the same time reduces its ductility.
  • an Al content of both the alloy AEX11-1 and the alloy AEX11-2 was selected in a range slightly above 10.0% by weight in order to have advantageous effects of the two alloys in comparison with conventional Mg
  • Al alloys which usually have Al proportions of up to about 9.0 wt .-%.
  • Fig. 2 shows a comparison of the AEX11-1 alloy with that of a conventional AZ91 alloy, showing different phase fractions of the two alloys, which were calculated with the simulation software Thermocalc.
  • Phase components of the AEX11-1 alloy are shown as solid lines, phase components of the AZ91 alloy as dashed lines.
  • the proportions of the liquid phase L, the ⁇ (Mg) and the Mg 17 Al 12 phase are shown both for the AEX11-1 alloy and for the AZ91 alloy.
  • an Al 11 RE 3 phase of the alloy AEX11-1 is also shown.
  • RE stands for abbreviation for rare earth metals.
  • the formation temperature of the Mg 17 Al 12 phase is between 360 ° C and 370 ° C in both AEX11-1 and AZ91.
  • the formation temperature of the Al 11 RE 3 phase of the AEX11-1 alloy is around 560 ° C.
  • the formation temperature of the Al 11 RE 3 phase is significantly higher than the formation temperature of the Mg 17 Al 12 phase
  • cooling of a starting composition of the AEX11-1 alloy starting from the liquid phase results in formation of the Al 11 RE 3 Phase bound an Al portion, so that when the formation temperature of the Mg 17 Al 12 phase is reached, only a reduced Al portion is available to form the Mg 17 Al 12 phase.
  • the Al 11 RE 3 phase contributes to the high strength of the AEX11-1 alloy, the reduced proportion of the Mg 17 Al 12 phase leads to a high ductility of the AEX11-1 alloy.
  • Other phases of the AEX11-1 alloy, such as an Al-Mn phase are shown in Fig. 2 not shown since this have negligibly small proportions compared to the Al 11 RE 3 phase.
  • the AEX11-2 alloy shows a behavior analogous to that of the AEX11-1 alloy.
  • the alloy samples for AEX11-1 and AEX11-2 were cast into bolts using gravity casting and further processed into wires using an extrusion process. Finally, sample parts made of the AEX11-1 alloy or the AEX11-2 alloy were produced from the wires using an arc welding process using wire arc additive manufacturing.
  • Fig. 3 shows a representative microstructure image of an AEX11-1 sample part.
  • a relatively fine, homogeneous structure can be seen, which shows acicular Al-RE excretion phases (in dark gray) and Mg 17 Al 12 excretion phases (in light gray).
  • the phases shown are each advantageously designed as a non-coherent structure, in particular as insulated islands, as a result of which a particularly pronounced strength can be achieved.
  • the AEX11-2 sample parts show analog microstructure images.
  • Fig. 4 shows a scanning electron microscope image of the AEX11-1 alloy. Needle-shaped precipitates of the AI-RE phase (in light gray) and precipitates of the Mg 17 Al 12 phase (in dark gray) are clearly visible.
  • the Mg 17 Al 12 phase or the eutectic phase formed therewith is advantageously dissolvable by a heat treatment and subsequently excreted if necessary to increase the strength.
  • Fig. 5 shows a stress-strain diagram as a result of dilatometer tensile tests of the sample parts before and after a heat treatment.
  • Stress-strain curves for an AEX11-1 sample part before its heat treatment, shown in, are shown Fig. 5 with reference numeral 1, and after its heat treatment, marked with reference symbol 2, and stress-strain curves for an AEX11-2 sample part before its heat treatment, marked with reference symbol 3, and after its heat treatment, marked with reference symbol 4.
  • a comparison is a stress-strain curve, for a standard AZ61 alloy sample, characterized in Fig. 5 represented with reference number 5, which is produced using a process corresponding to the production process of the two AEX11 sample parts.
  • the AEX11-1 sample part and AEX11-2 sample part have very high yield strengths, which are higher than a yield strength of the AZ61 alloy sample. Elongations of the AEX11-1 sample part and AEX11-2 sample part before the heat treatment of the sample parts are lower than that of the AZ61 alloy sample. After the heat treatment has been carried out, both the AEX11-1 sample part and the AEX11-2 sample part have great strengths and great elasticity. Heat treatment thus enables the strength and extensibility to be adjusted. In the case of a conventional AZ61 alloy, however, heat treatment does not lead to an improvement in strength or ductility. This is when considering a microstructure image of the AZ61 alloy sample shown in Fig. 6 , also understandable.
  • a magnesium-based alloy according to the invention thus advantageously has both great strength and great ductility and in particular offers the possibility of adjusting strength and ductility by heat treatment.

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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)
  • Continuous Casting (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP19212085.5A 2018-12-18 2019-11-28 Alliage de magnesium et son procédé de fabrication Active EP3670691B1 (fr)

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ATA51127/2018A AT522003B1 (de) 2018-12-18 2018-12-18 Magnesiumbasislegierung und Verfahren zur Herstellung derselben

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EP3670691A1 true EP3670691A1 (fr) 2020-06-24
EP3670691B1 EP3670691B1 (fr) 2023-01-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3899076B1 (fr) * 2018-12-18 2024-02-28 LKR Leichtmetallkompetenzzentrum Ranshofen GmbH Procédé permettant d'augmenter la résistance à la corrosion galvanique d'une pièce formée d'un alliage à base de magnésium, ainsi que pièce résistante à la corrosion pouvant être ainsi obtenue

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2692884A1 (fr) * 2011-03-29 2014-02-05 Advanced Technologies, Inc. Alliage de magnésium
WO2018116940A1 (fr) * 2016-12-21 2018-06-28 住友電気工業株式会社 Alliage de magnésium
DE112017001307T5 (de) * 2016-07-15 2018-11-29 National University Corporation University Of Toyama Magnesiumlegierung

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
JP2001247926A (ja) * 2000-03-03 2001-09-14 Japan Steel Works Ltd:The 流動性に優れたマグネシウム合金およびマグネシウム合金材
KR101127113B1 (ko) * 2004-01-09 2012-03-26 켄지 히가시 다이캐스트용 마그네슘 합금 및 이것을 사용한 마그네슘다이캐스트 제품
DE102005033835A1 (de) * 2005-07-20 2007-01-25 Gkss-Forschungszentrum Geesthacht Gmbh Magnesiumsekundärlegierung
JP4539572B2 (ja) * 2006-01-27 2010-09-08 株式会社豊田中央研究所 鋳造用マグネシウム合金および鋳物
TWI427158B (zh) * 2009-06-26 2014-02-21 Foxconn Tech Co Ltd 鎂合金及其製備方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2692884A1 (fr) * 2011-03-29 2014-02-05 Advanced Technologies, Inc. Alliage de magnésium
DE112017001307T5 (de) * 2016-07-15 2018-11-29 National University Corporation University Of Toyama Magnesiumlegierung
WO2018116940A1 (fr) * 2016-12-21 2018-06-28 住友電気工業株式会社 Alliage de magnésium

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3899076B1 (fr) * 2018-12-18 2024-02-28 LKR Leichtmetallkompetenzzentrum Ranshofen GmbH Procédé permettant d'augmenter la résistance à la corrosion galvanique d'une pièce formée d'un alliage à base de magnésium, ainsi que pièce résistante à la corrosion pouvant être ainsi obtenue

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EP3670691B1 (fr) 2023-01-25
AT522003A3 (de) 2021-07-15
AT522003B1 (de) 2021-10-15

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