EP3997251A1 - Alliage comprenant des structures eutectiques fines, en particulier nano-eutectiques, et production de celui-ci - Google Patents

Alliage comprenant des structures eutectiques fines, en particulier nano-eutectiques, et production de celui-ci

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Publication number
EP3997251A1
EP3997251A1 EP20735621.3A EP20735621A EP3997251A1 EP 3997251 A1 EP3997251 A1 EP 3997251A1 EP 20735621 A EP20735621 A EP 20735621A EP 3997251 A1 EP3997251 A1 EP 3997251A1
Authority
EP
European Patent Office
Prior art keywords
alloy
eutectic
phase
pseudo
composition
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.)
Pending
Application number
EP20735621.3A
Other languages
German (de)
English (en)
Inventor
Stefan Gneiger
Clemens Simson
Alexander GROSSALBER
Simon Frank
Andreas Betz
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.)
LKR Leichtmetallkompetenzzentrum Ranshofen GmbH
Original Assignee
LKR Leichtmetallkompetenzzentrum Ranshofen GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by LKR Leichtmetallkompetenzzentrum Ranshofen GmbH filed Critical LKR Leichtmetallkompetenzzentrum Ranshofen GmbH
Publication of EP3997251A1 publication Critical patent/EP3997251A1/fr
Pending legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • 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
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium 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
    • C22C21/10—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
    • C22C21/16—Alloys based on aluminium with copper as the next major constituent with 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
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C24/00—Alloys based on an alkali or an alkaline earth metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper 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
    • 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
    • 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
    • C22F1/047—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 magnesium 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
    • C22F1/05—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 of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions
    • 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
    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

Definitions

  • the invention relates to an alloy, in particular a light metal alloy, comprising an alloy composition with at least three components and a
  • eutectic structure which is obtained by cooling the alloy from a liquid state to a solid state.
  • the invention also relates to a method for producing an alloy, in particular a light metal alloy, with a eutectic structure, the alloy having an alloy composition with at least three components and the alloy for forming the eutectic structure starting from a liquid state into a solid state of the alloy is cooled.
  • Application alloys are often binary cast alloys, that is, alloys with two components that have eutectic structures. These are usually characterized by a eutectic point in their phase diagram, at which a liquid phase of the alloy and two solid phases of the alloy are in thermodynamic equilibrium with one another or, when the alloy cools from the liquid phase, a direct transition from a liquid state to a solid state takes place, whereby a eutectic structure is formed.
  • Degree of freedom f 0.
  • the direct transition from the liquid phase to the solid phase often leads to the formation of a fine and lamellar structure.
  • the object of the invention is to specify an alloy with at least three components which has high strength and good formability.
  • Composition of the alloy lies in a region around a pseudo-eutectic point of a phase diagram of the alloy, so that at least 85 mol% or at% eutectic structure are present in the alloy.
  • the invention is based on the knowledge that when an alloy is composed with at least three components or elements, which in the phase diagram of the alloy is at or near a pseudo-eutectic point, a particularly fine-scale or finely structured eutectic structure can be formed, which, in particular, can have a finer eutectic structure than an alloy with a selected composition that is at the “usual” eutectic point in the phase diagram.
  • characteristic structural distances of the eutectic structure in the low micrometer range and in particular nanometer range can be implemented, also referred to as nanoeutectic structure.
  • the eutectic structure formed thereby generally represents an essential or dominant structure and in particular in the vicinity or in an area around, in particular on, a eutectic Point often only a small or negligibly small or no primary solidification phase and / or residual solidification phase occurs.
  • the alloy dominant presence in the alloy enables the alloy to be formed with both high strength, in particular compressive strength, and also pronounced
  • the pseudo-eutectic point is usually abbreviated as “e” or “pE” in representations and the eutectic point is abbreviated as "E”.
  • the liquidus line and solidus line known from the binary phase diagram usually correspond to curved surfaces and binary phase surfaces correspond to phase volumes.
  • the intersection lines of liquidus surfaces in the ternary phase diagram usually form eutectic grooves, also referred to as liquidus boundary lines or monovariant lines, which open into a ternary eutectic point of the phase diagram.
  • the pseudo-eutectic point represents a point on the liquidus boundary line, which forms a saddle point, i.e. a local extreme along the liquidus boundary line and a minimum perpendicular to it - in relation to the delimiting single-phase regions.
  • pseudo-eutectic point is characterized in that its existence requires an addition or presence of at least a third component or a third element.
  • the pseudo-eutectic point pE in the ternary alloy system represents a local extremum along the liquidus boundary line which, compared to the ternary eutectic E, has a number of
  • Degrees of freedom and compared to a single-phase solidification MK has a number of degrees of freedom reduced by 1.
  • Gibbs' phase rule f N - P +1 with a number of thermodynamic degrees of freedom f, a number of components N and a number of equilibrium phases P this corresponds to:
  • the liquidus boundary line corresponds accordingly to a two-dimensional surface and the pseudo-eutectic point to a pseudo-eutectic line.
  • the dimensionality of the corresponding increases
  • pseudoeutectic point should therefore be understood in particular as a generic term, which includes both a pseudoeutectic point in a phase diagram of a ternary alloy and a corresponding pseudoeutectic line in a phase diagram of an alloy with four components or a corresponding pseudoeutectic line multidimensional area in one
  • Phase diagram of an alloy with more than four components Phase diagram of an alloy with more than four components.
  • pseudo-eutectic point and pseudo-eutectic area are used synonymously in particular. It goes without saying that a pseudo-eutectic point of a ternary alloy system represents a special variant.
  • the pseudo-eutectic point of the phase diagram of the alloy with at least three components N is thus characterized in particular by the fact that, according to Gibbs' phase rule, the number of degrees of freedom f lies between 0 and N-1.
  • the formability of the alloy is sufficient if the alloy composition is close to or in an area around the, in particular at, the pseudo-eutectic point or the saddle point represented by this, so that in the alloy at least 85 mol% or at% ( given in mol percent or atomic percent) eutectic structure is present. It is preferred if at least 90 mol% or at%, particularly preferably at least 95 mol% or at%, eutectic structure is present in the alloy. As a result, the advantageous properties of high strength combined with good formability can be particularly pronounced.
  • the eutectic structure usually forms during a liquid-solid phase transition or when the alloy solidifies.
  • High strength and pronounced formability of the alloy can be achieved both when the alloy is a ternary alloy and when the alloy has four components or at least five components.
  • the alloy can have a large number of components, depending on the application objective, for example in the form of further added components for solid solution hardening and / or precipitation hardening.
  • the alloy with high strength and formability can be formed particularly simply and practically if the alloy is ternary
  • a particularly pronounced strength and formability can be achieved if the average distance is less than 2 pm, in particular less than 1 pm. This can be achieved, for example, if the alloy composition of the alloy is selected in closer proximity to the stoichiometric composition of the pseudo-eutectic point. Particularly high strengths can be achieved if the average distance is less than
  • the average spacing of the phase components can be influenced by varying a cooling rate of the alloy when the alloy solidifies.
  • the alloy has a residual solidification with a proportion of at most 5 mol% or at%, preferably at most 3 mol% or at%, particularly preferably at most 2 mol% or at%. -%, having.
  • the proportion of residual solidification can be adjusted by choosing the alloy composition closer to the stoichiometric composition of the pseudo-eutectic point.
  • Residual solidification usually denotes that part of the structure in which a residual part of the liquid phase solidifies after the formation of the eutectic structure in the form of a no longer eutectic structure or at the end of the eutectic solidification the number or type of the forming phase changes.
  • the proportion of residual solidification usually represents a factor which adversely affects the properties brought about by the eutectic structure formed, which is why it is advantageous if the residual solidification is kept as small as possible. It is particularly favorable for this if the residual solidification is not configured in the manner of a network or in the form of a network structure, but rather, if present, in the form of islands or units that are separated from one another.
  • the residual solidification is formed in a proportion of at least 1 mol% or at%, but can preferably also be less.
  • Alloy has a primary solidification with a proportion of less than 10 mol% or at%, in particular less than 5 mol% or at%, preferably less than 3 mol% or at%. This enables a very dominant formation of the eutectic structure or a formation of the eutectic structure with a high proportion of the structure advantageous to achieve the aforementioned properties.
  • the primary solidification which describes that part of the solidified microstructure which does not solidify in the form of a eutectic structure immediately before the formation of the eutectic structure, is less relevant than the aforementioned residual solidification with regard to an impairment of the properties to be achieved with the formation of the eutectic structure, but should are also preferably kept as small as possible.
  • the primary solidification is formed with a proportion of at least 1 mol% or at%, but can preferably also be less.
  • the primary solidification is formed with or from a mixed crystal phase and in particular not with or not from an intermetallic phase. This appears to be an advantageous criterion for all alloy systems in order to achieve particularly user-friendly strength and formability properties.
  • the proportion of the aforementioned residual solidification and / or primary solidification can be in
  • Scheil-Gulliver can be checked or predetermined in the usual way with a thermodynamic calculation according to Scheil-Gulliver.
  • the Scheil-Gulliver calculation or equation sometimes just called Scheil calculation or equation, describes one
  • the alloy has a density of less than 8.0 g / cm 3 , in particular less than 7.5 g / cm 3 , preferably less than 6 g / cm 3 .
  • the alloy can have a particularly advantageous strength-to-weight ratio in relation to an application, in particular as a structural component. It is particularly advantageous if the alloy is designed as a light metal alloy. This makes it possible to achieve a particularly high level of application suitability for the alloy. It is advantageous if the alloy for this purpose has less than 5.0 g / cm 3 , in particular less than 3.0 g / cm 3 . For practical use as application material, it is beneficial if the
  • Lithium-based alloy or titanium-based alloy is.
  • the alloy is a cast alloy. This enables a particularly practicable production, in particular of structural components with in particular the aforementioned properties.
  • the alloy is an Al-Mg alloy.
  • the alloy can have additional alloy components. In this way, application components are particularly relevant in practice, in particular
  • the alloy is an Al-Mg-Si alloy.
  • the alloy can also advantageously contain zinc (Zn), in particular with a proportion of more than 0.01% by weight, usually more than 1% by weight. This allows a compressive strength of the alloy to be optimized.
  • the alloy usually has less than 15% by weight, in particular less than 10% by weight, preferably between 1.0% by weight and 5.0% by weight, particularly preferably about 3.0% by weight , Zinc on.
  • the alloy is an Al-Cu-Li alloy, Al-Cu-Mg alloy, Mg-Li-Al alloy, Mg-Cu -Zn alloy, Al-Cu-Mg-Zn alloy or Al-Mg-Si-Zn alloy.
  • Structural component which shows particularly high strength and formability, can be achieved if the alloy is a magnesium-based alloy, having, in particular consisting of, (in at .-%)
  • Such a Mg-Li-Al alloy has an alloy composition in an area around or in the vicinity of an alloy composition pseudoeutectic point in the Mg-Li-Al phase diagram, so that a
  • finely structured or microscale eutectic microstructure can be achieved.
  • the fine-scale microstructure is associated with high strength, in particular high compressive strength, while at the same time good formability of the
  • Magnesium alloy is given with the corresponding aforementioned proportions of lithium in the magnesium alloy.
  • the orientation line in the phase diagram is in particular a ratio of aluminum to magnesium (in atomic percent, abbreviated to atomic%) of approx. 3: 6, as this ratio results in a particularly homogeneous fine-scale or homogeneous fine lamellar microstructure or morphology .
  • a ratio of aluminum to magnesium (in at .-%) of 1: 6 to 4: 6 the fine, especially fine lamellar, microstructure or morphology continues to be found with varying degrees which usually corresponds to different characteristics of a level of strength, in particular a level of a
  • the Mg-Al-Li alloy (in at .-%) 30.0% to 60.0%, in particular 40% to 50%, preferably 45% to 50%, particularly preferably 45% to 48%, lithium. It is also advantageous if the Mg-Al-Li alloy (in at.%) Has more than 0.05%, in particular more than 0.1%, generally more than 1% aluminum.
  • the Mg-Al-Li alloy can be formed with a, in particular lamellar, microstructure with high fineness if the ratio of aluminum to magnesium (in at.%) Is 1.2: 6 to 4: 6 , in particular 1, 4: 6 to 4: 6, preferably 1, 5: 6 to 4: 6. It is beneficial for a pronounced fineness or fine, especially lamellar, microstructure if the ratio of aluminum to magnesium (in At .-%) from 1.8: 6 to 3.5: 6, in particular 2: 6 to 3.5: 6, preferably 2.5: 6 to 3.5: 6. A particularly high strength, in particular compressive strength, can thereby be achieved. This applies particularly to a ratio of aluminum to magnesium (in at.%) Of 2.8: 6 to 3.3: 6, preferably about 3: 6, at which a very homogeneous fine
  • the magnesium alloy (in at.%) Is 30.0% to 60.0% lithium and a ratio of aluminum to magnesium (in at.%) Of 2.5: 6 to 3.5: 6, in particular 2.8: 6 to 3.3: 6, preferably about 3: 6.
  • FIG. 1 of the aforementioned application documents in which a corresponding arrangement is shown schematically in a Mg-Li-Al phase diagram, and the disclosure and the associated description are likewise to be regarded as part of this document.
  • a particularly pronounced homogeneity can also be achieved if the magnesium alloy (in at.%) Has 40.0% to 60.0% lithium.
  • the properties of the Mg-Al-Li alloy can be further optimized if, in addition, proportions of calcium, rare earth metals, in particular yttrium, zinc and / or silicon according to the aforementioned applications with corresponding The salary ranges specified in the aforementioned registrations are available.
  • such an alloy can be used as Mg-20% Li-15% Al-1% Ca-0.5% Y (in% by weight) or Mg-20% Li-24% Al-1% Ca-0.5 % Y (in% by weight).
  • the further aim of the invention is achieved by a method of the type mentioned at the beginning with the proviso that the composition is provided lying in an area around a pseudo-eutectic point of a phase diagram of the alloy, so that when it cools into the solid phase or when it solidifies Alloy forms the eutectic structure with a proportion of at least 85 mol% or at%.
  • the alloy can thereby be formed with high strength and pronounced formability.
  • Alloy composition in an area around the pseudo-eutectic point occurs when the alloy cools from the liquid to the solid state or during the liquid-solid transition, a eutectic phase reaction or phase transformation takes place, which the eutectic microstructure with particularly high fineness or fine structuring as an essential structural component of the Alloy forms.
  • alloy according to the invention in particular described above, can be formed.
  • the same also applies to the alloy according to the invention with regard to a method according to the invention.
  • a starting material, semi-finished product or component is advantageously implemented with, in particular made of, an alloy according to the invention or obtainable by a method according to the invention for producing an alloy according to the invention.
  • Alloy or an alloy produced using a method according to the invention also has a pre-material, semi-finished product or component formed with an alloy, advantageously high strength and good formability.
  • 1 and 2 are phase diagram representations of an Al-Mg-Si system in which alloy compositions of alloy examples are given;
  • FIGS. 3 to 12 are optical microscopic photographs of alloy examples from FIGS. 1 and 2, respectively;
  • FIGS. 13 to 20 flow stress diagrams of alloy examples of FIGS. 1 to 12;
  • 21 shows a phase diagram representation of an Al-Cu-Mg system with the alloy composition of an alloy example drawn in;
  • Fig. 22 is optical microscopic photographs of the alloy example of Fig. 21;
  • 23 is a yield stress diagram of the alloy example of FIGS. 21 and 22, respectively; 24 is a phase diagram representation of a Mg-Al-Li system in which
  • 25 and 27 are optical microscopic photographs of alloy examples of FIG. 24; 28 and 29 flow stress diagrams of alloy examples of FIGS. 24 to 27; 30 shows a phase diagram representation of an Mg-Cu-Zn system with the alloy composition of an alloy example drawn in;
  • 31 and 32 are optical microscopic photographs of the alloy example of FIG. 30; 33 is a yield stress diagram of the alloy example of FIGS. 30 to 32; Fig. 34 is an electron microscope photograph showing an alloy example of an Al-Cu-Mg-Zn system;
  • Fig. 35 is a yield stress diagram of the alloy example of Fig. 34;
  • Fig. 36 is a phase fraction diagram of an alloy example of an Al-Mg-Si-Zn system
  • FIGS. 1 and 2 show representations of a ternary phase diagram of an Al-Mg-Si system, FIG. 2 being a detail representation of the phase diagram in order to show the relevant alloy composition range in detail.
  • Alloy examples of the Al-Mg-Si system produced and investigated.
  • the alloy compositions of the alloy examples of the Al-Mg-Si system are given in Table 1 as alloy example 1 to alloy example 10, in each case in weight percent and atomic percent and correspond to the reference numerals 1 to 10, which in particular in the phase diagram of FIGS. 1 and 2 the respective
  • Table 1 Ten alloy examples from the Al-Mg-Si alloy system.
  • the alloy examples 8 to 10 each have compositions which, in an area around one
  • pseudoeutectic point pE are arranged, the alloy examples 8 and 9 very close to the pseudo-eutectic point and the alloy example 10 are positioned at a somewhat greater distance from the pseudo-eutectic point pE.
  • Alloy composition of alloy example 9 is practically at the pseudo-eutectic point pE.
  • the pseudoeutectic point pE is illustrated in FIG. 2 with a drawn reference line, the pseudoeutectic point pE being at the intersection of the monovariant line in the direction of AhMg2 and the reference line. It can also be seen in FIG. 2 that the alloy examples 3 to 5 are arranged in an area around a eutectic point E of the phase diagram. Alloy Examples 6 and 7 are also provided as comparisons, their
  • compositions are located at a great distance from the pseudo-eutectic point pE, as can be seen in FIG. 2, as well as the alloy examples 1 and 2, which are positioned in the immediate vicinity of a liquidus boundary line, but at a greater distance from both the pseudo-eutectic point pE and the eutectic point E. in Fig. 1.
  • FIGS. 3 to 12 optical microscope images of the alloy examples 1 to 10 are shown in order to illustrate a respective microstructure.
  • flow stress diagrams are shown as the results of dilatometric test series of the Al-Mg-Si alloy examples, which were carried out at room temperature, about 20 ° C. Yield stress curves are shown, with a yield stress, in MPa, being shown as a function of the degree of deformation.
  • Yield stress diagrams show several yield stress curves of alloy samples with an alloy composition corresponding to the alloy composition of one of alloy examples 1 to 10. Each flow stress diagram therefore represents an alloy composition of one of alloy examples 1 to 10.
  • Alloy examples 8 to 10 which have alloy compositions in the vicinity or an area around the pseudo-eutectic point pE, a dominant, finely structured or finely-scaled eutectic structure.
  • FIGS. 6 and 7 microscopic photographs of alloy examples 4 and 5, which have an alloy composition in the vicinity of the eutectic point E, can be observed. These show an expression of a eutectic structure, which in comparison to the structure of the alloy examples 8 and 9 is coarse Has structure. If one compares this with those shown in FIGS. 3 and 4
  • Alloy composition in the area of the pseudo-eutectic point pE has a particularly high fine structuring of its eutectic structure, especially in comparison to the eutectic structure of alloy examples
  • FIG. 20 shows a flow stress diagram of the alloy example 10, the alloy composition of which is arranged at a somewhat greater distance from the pseudo-eutectic point pE. Slightly lower yield stress values and, in particular, a higher scatter between the individual measurement results can be seen. It is further shown in FIGS. 17 and 18 that, in comparison therewith, alloy example 1 and alloy example 2 with alloy compositions in the range of a
  • Liquidus boundary line however, both remote from the alloy composition of the pseudo-eutectic point pE and eutectic point E, have significantly poorer strength and deformation properties.
  • Fig. 19 is also a
  • the corresponding yield stress curves show clearly reduced yield stresses in comparison to the yield stresses of an alloy composition closer to the pseudo-eutectic point pE, such as that of the alloy example 8 shown in FIG. 13.
  • an alloy composition in an area around a pseudo-eutectic point pE corresponds to a finely structured eutectic microstructure or correspondingly high strength and pronounced formability.
  • alloy example 8 in FIG. 10 show large areas with a fine eutectic structure, in this case formed with Al mixed crystal and Mg Si.
  • a residual solidification of Al mixed crystal is also advantageous only very slightly or hardly present.
  • the aim is to keep residual solidification as small as possible or to avoid it.
  • the residual solidification is not connected in the manner of a network or is designed in the form of units separated from one another, which likewise promotes an advantageous design of high strength and pronounced formability. Alloy example 8 thus proves to be both low and low in terms of residual solidification
  • the alloy composition is chosen such that the primary solidification is formed with or from a mixed crystal phase and not with an intermetallic compound or phase, i.e. the primary solidification in the case of alloy example 8 is in the Al mixed crystal range .
  • alloy example 9 has an alloy composition practically at the pseudo-eutectic point pE. As can be seen in FIG. 11, alloy example 9 also shows a fine eutectic structure with hardly any residual solidification and hardly any primary solidification. The somewhat lower strength in comparison with alloy example 8 is explained by the lower dissolved content of Mg in the Al mixed crystal phase. A strength can advantageously be achieved by varying a proportion of dissolved elements in the mixed crystal phase, with the primary solidification, however, as stated above, preferably in
  • Solid solution range and not in the range of an intermetallic phase.
  • alloy example 10 which can be seen in FIG. 12, also shows a fine eutectic structure, but with a higher proportion of residual solidification, in the form of Al mixed crystal and Si, which is also characterized by a network. Due to the low Mg content, most of the Mg is bound in the form of Mg Si, so that solid solution hardening of the Al solid solution phase is very little pronounced. This corresponds to lower yield stresses in the yield stress diagram in FIG. 20. On further detailed consideration of the alloy examples arranged away from the pseudo-eutectic point pE with respect to an alloy composition, it can be seen that the alloy examples 4 and 5, which are in the region of the eutectic point E, shown in FIGS.
  • alloy examples 6 and 7 with the associated microscopy images shown in FIGS. 8 and 9 have coarse, polygonal primary solidifications. This is explained by the positioning of the associated
  • a particularly advantageous conversion range for such an Al-Mg-Si alloy is therefore given when the Al-Mg-Si alloy is arranged in the Al-Mg-Si phase diagram in an area around the pseudo-eutectic point, the
  • Fig. 21 shows a representation of a ternary phase diagram of an Al-Cu-Mg system.
  • An alloy example of the Al-Cu-Mg system was prepared and examined.
  • the associated alloy composition is shown in Table 2 as
  • Alloy example 13 indicated in weight percent and atomic percent and
  • reference number 13 which in particular denotes the alloy composition in the phase diagram of FIG. 21.
  • Table 2 Alloy example from the Al-Cu-Mg alloy system.
  • the alloy example 13 has an alloy composition which, in an area around a
  • pseudo-eutectic point pE is arranged. Using optical
  • FIG. 22 An associated microstructure is illustrated in FIG. 22 using microscopic images. A very fine-scale eutectic structure and a small amount of primary solidification formed with mixed crystal can be seen.
  • Fig. 23 is a
  • Yield stress diagram as the result of dilatometric test series of Al-Cu-Mg alloy example 13 is shown, again showing a yield stress, in MPa, as a function of the degree of deformation. It can be seen that very high
  • Strengths or yield stresses can be achieved.
  • the elongation at break is also in the technologically relevant range for this alloy system.
  • Strength or Formability corresponds to the fine eutectic microstructure and in particular the small amount of primary solidification.
  • FIG. 24 shows a representation of a ternary phase diagram of a Mg-Al-Li system.
  • Three alloy examples of the Mg-Al-Li system were prepared and examined.
  • the alloy compositions of the alloy examples of the Mg-Al-Li system are in Table 3 as alloy examples 14, 15 and 16, respectively, in percent by weight and
  • Table 3 Three alloy examples from the Mg-Al-Li alloy system.
  • the alloy examples 14 to 16 each have an alloy composition which is arranged in a region around a pseudo-eutectic point pE.
  • the pseudo-eutectic point pE is illustrated in FIG. 24 with a reference line drawn in, the
  • Liquidus limit line and the reference line is located.
  • CaY in particular about 1 wt .-% Ca and about 0.5 wt .-% Y, can be practicable
  • Oxidation properties of the alloy examples of the Mg-Al-Li system are stabilized without adversely affecting a microstructure.
  • Alloy examples 14 and 15 lie somewhat closer in the phase diagram in a near area of the pseudo-eutectic point, alloy example 16 somewhat further away, the alloy composition of alloy example 14 being approximately at pseudo-eutectic point pE is positioned.
  • the alloy examples 14 to 16 are, according to the current data situation, in a mixed crystal region, in particular forming a body-centered cubic lattice, bcc.
  • FIGS. 25 to 27 With the aid of microscopic recordings, structural structures can be seen in FIGS. 25 to 27.
  • the microstructure morphology of FIGS. 25 and 26 indicates a
  • the microstructure of alloy example 16 was examined by means of scanning electron microscopy, shown in FIG. 27. Visible in FIG. 27 are, on the one hand, light grain boundary phases (in whitish-gray), which were identified as Al-Ca, and, on the other hand, pronounced fine crystal structures or
  • Alloy example 16 is arranged - is very flat in the phase diagram and also the three elements Mg, Al and Li have a high solubility in one another. This explains why there is a correspondingly extensive area around the
  • pseudo-eutectic point results in which an advantageous fine-scale eutectic microstructure can be formed with a high proportion.
  • FIG. 28 and 29 show flow stress diagrams of alloy examples 15 and 16 as the results of dilatometric test series, again showing a flow stress, in MPa, as a function of the degree of deformation, FIG. 28
  • Fig. 16 shows yield stress curves relating to alloy example 16. It can be seen that both alloy examples have high strengths or flow stresses as well as pronounced formability, corresponding to the fine eutectic microstructures determined.
  • FIG. 29 shows flow curves of alloy samples immediately after a production of the alloy example 16 (as-cast), shown in FIG. 29 as solid lines, identified by reference symbols 16-1, as well as flow curves from FIG. 29
  • samples of alloy example 16 were used
  • Heat treatment for strength, in particular compressive strength, and formability whereby the potential is given to optimize compressive strength and formability, in particular for a later application, through heat treatment
  • Magnesium-based alloy is, having, in particular consisting of, (in at .-%)
  • the alloy example 16 can be seen as a representative example for this alloy definition, as in the context of the European patent application with the
  • FIG. 24 a corresponding ratio of aluminum to magnesium (in at.%) Of 1: 6 is shown as a dashed line.
  • the aforementioned ratio range of aluminum to magnesium (in at.% Or mol%) from 1: 6 to 4: 6 is located in the phase diagram of FIG. 24 to the left of this line and in particular represents a special one
  • a particularly advantageous implementation range for a Mg-Li-Al alloy which can be used as an application alloy, in particular for a structural component, is given, if the Mg-Li-Al alloy in the Mg-Li-Al phase diagram is in a range between the line indicating a ratio of aluminum to magnesium (in at .-%) of 1: 6 and the monovariant line or liquidus boundary line, in particular with an aforementioned Li content range.
  • One such area is in
  • phase diagram of FIG. 24 is identified as a gray, flat area.
  • an alloy composition is preferably selected such that the alloy composition is in the area of the pseudo-eutectic point pE and preferably also has primary solidification with or from a mixed crystal phase , i.e. the corresponding alloy composition is positioned in a mixed crystal area in the phase diagram.
  • Fig. 30 shows a representation of a ternary phase diagram of a Mg-Cu-Zn system.
  • An alloy example of the Mg-Cu-Zn system was prepared and examined.
  • the associated alloy composition is shown in Table 4 as
  • reference symbol 17 which in particular denotes the alloy composition in the phase diagram of FIG. 30.
  • Table 4 Alloy example from the Mg-Cu-Zn alloy system.
  • pseudo-eutectic point pE is arranged. Using optical
  • FIGS. 31 and 32 Microscopic recordings show an associated microstructure in FIGS. 31 and 32. A very fine-scale eutectic microstructure can be seen, which is at the limit of a light microscopic resolution. A relatively large proportion of primary solidification can be seen here. It is therefore advantageous for high strength and formability if an alloy composition is even closer to pseudoeutectic point pE or closer to the monovariant line or
  • Liquidus limit line is chosen.
  • Fig. 33 shows a yield stress diagram as results of dilatometric
  • Test series of alloy example 17 again showing a yield stress, in MPa, as a function of the degree of deformation. It can be seen that high strengths or yield stresses are achieved, which, however, in view of the pronounced proportion of primary solidification visible in the microscope images, can be further improved by choosing an alloy composition closer to the pseudo-eutectic point pE.
  • flow curves of the alloy example 17 are shown immediately after a production of the alloy example 17 (as-cast), denoted by the reference symbol 17-1, as well as flow curves of the
  • Alloy example 17 after the heat treatment has been carried out identified by reference symbol 17-2.
  • samples of alloy example 17 were used
  • Heat treatment for strength and formability which gives the potential to further optimize strength and formability by means of heat treatment.
  • alloy systems Al-Cu-Mg-Zn and Al-Mg-Si-Zn are considered.
  • Table 5 Alloy example from the Al-Cu-Mg-Zn alloy system.
  • 35 shows a flow stress diagram as a result of dilatometric
  • alloy example 18 Shown are flow curves before heat treatment carried out, denoted by reference number 18-1, and flow curves after carried out heat treatment, denoted by reference number 18-2, again showing a yield stress, in MPa, as a function of the degree of deformation. It can be seen that the alloy example 18 has a very high strength with a simultaneous elongation at break, with deformability by means of
  • Heat treatment is variable.
  • alloy example 19 located at the pseudo-eutectic point pE was examined by means of simulation.
  • the alloy composition is given in Table 6 as alloy example 19 and corresponds to reference symbol 19.
  • Table 6 Alloy example from the Al-Mg-Si-Zn alloy system.
  • FIG. 35 shows a representation of the solid fraction determined by means of the Scheil-Gulliver solidification calculation as a function of the temperature.
  • the equilibrium and Scheil-Gulliver solidification curves shown show an alloy system which shows binary eutectic solidification with four components or elements. Accordingly, there is again an increase in the thermodynamic degree of freedom from 1 to 3.
  • the Scheil-Gulliver calculation in FIG. 37 shows a very small proportion of primary solidification in the form of a mixed crystal with a proportion of less than 3 mol% or at% and also a virtually non-existent residual solidification.
  • An alloy according to the invention with more than three components with a eutectic structure produced by cooling from the liquid state to the solid state is therefore advantageous with a finely structured eutectic structure
  • the alloy in particular with a fine structure in the nanometer range, can be formed which has a forms dominant or substantial phase portion or structural portion in the alloy when an alloy composition of the alloy is arranged in the phase diagram in the area of or around a pseudo-eutectic point.
  • the alloy can be formed with advantageously high strength and pronounced formability. This is particularly true if there is very little primary solidification and / or residual solidification. In particular, it is favorable for this if the primary solidification is formed with or from a mixed crystal, in particular not with or from an intermetallic phase, or the alloy composition is selected in a corresponding area in the phase diagram.
  • An alloy formed in this way thus offers the potential for robust and resistant components, in particular
  • Construction elements in particular for a purpose in the
  • Automotive, aircraft and / or space industries are preferred.

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Abstract

L'invention concerne un alliage, en particulier un alliage de métaux légers, présentant une composition d'alliage comprenant au moins trois composants et une structure eutectique, laquelle est obtenue par le refroidissement d'un état liquide à un état solide de l'alliage, tant qu'une composition de l'alliage se situe dans une zone autour d'un point pseudo-eutectique (pE) d'un diagramme de phase de l'alliage, de sorte que l'alliage contient au moins 85% en moles de structure eutectique. L'invention concerne en outre un procédé pour la production d'un tel alliage.
EP20735621.3A 2019-07-08 2020-07-07 Alliage comprenant des structures eutectiques fines, en particulier nano-eutectiques, et production de celui-ci Pending EP3997251A1 (fr)

Applications Claiming Priority (3)

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EP19184999.1A EP3763845B1 (fr) 2019-07-08 2019-07-08 Alliage de magnesium et son procédé de fabrication
PCT/EP2020/058280 WO2021004662A1 (fr) 2019-07-08 2020-03-25 Alliage de magnésium et son procédé de fabrication
PCT/EP2020/069131 WO2021005062A1 (fr) 2019-07-08 2020-07-07 Alliage comprenant des structures eutectiques fines, en particulier nano-eutectiques, et production de celui-ci

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GB683813A (en) * 1949-09-29 1952-12-03 Magnesium Elektron Ltd Improvements in or relating to magnesium base alloys
DE1255928B (de) * 1966-01-13 1967-12-07 Metallgesellschaft Ag Verfahren zur Erzielung eines langanhaltenden Veredelungseffektes in Aluminium-Silicium-Legierungen
CN104060137A (zh) * 2014-06-29 2014-09-24 应丽红 一种耐磨硅铝合金
US10900103B2 (en) * 2015-01-27 2021-01-26 Santokij Corporation Magnesium-lithium alloy, rolled material and shaped article
JP6768637B2 (ja) * 2015-03-25 2020-10-14 株式会社Ｓｕｂａｒｕ マグネシウム−リチウム合金、マグネシウム−リチウム合金からなる圧延材及びマグネシウム−リチウム合金を素材として含む被加工品
JP6583426B2 (ja) * 2015-11-10 2019-10-02 日産自動車株式会社 電気デバイス用負極活物質、およびこれを用いた電気デバイス
JP6290520B1 (ja) * 2016-07-26 2018-03-07 株式会社三徳 マグネシウム−リチウム合金及びマグネシウム空気電池
CN106148786B (zh) * 2016-08-22 2018-12-18 上海交通大学 高强度铸造镁锂合金及其制备方法

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JP2022540544A (ja) 2022-09-16
CA3138658A1 (fr) 2021-01-14
WO2021004662A1 (fr) 2021-01-14
KR20220030244A (ko) 2022-03-10
CN114026260B (zh) 2023-06-20
US20220259705A1 (en) 2022-08-18
CN114026260A (zh) 2022-02-08
EP3763845B1 (fr) 2021-08-18
CA3137604A1 (fr) 2021-01-14
KR20220030243A (ko) 2022-03-10
EP3763845A1 (fr) 2021-01-13
US20220267881A1 (en) 2022-08-25
CN114096690A (zh) 2022-02-25
JP2022540542A (ja) 2022-09-16

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