EP2987874A1 - Feuerfeste magnesiumlegierung und herstellungsverfahren dafür - Google Patents

Feuerfeste magnesiumlegierung und herstellungsverfahren dafür Download PDF

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Publication number
EP2987874A1
EP2987874A1 EP14784615.8A EP14784615A EP2987874A1 EP 2987874 A1 EP2987874 A1 EP 2987874A1 EP 14784615 A EP14784615 A EP 14784615A EP 2987874 A1 EP2987874 A1 EP 2987874A1
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EP
European Patent Office
Prior art keywords
magnesium alloy
flame
atomic
retardant magnesium
total
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EP14784615.8A
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English (en)
French (fr)
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EP2987874A4 (de
EP2987874B1 (de
Inventor
Yoshihito Kawamura
Jonghyun Kim
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Kumamoto University NUC
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Kumamoto University NUC
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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
    • C22C23/06—Alloys based on magnesium with a rare earth metal 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • 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
    • 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

Definitions

  • the present invention relates to a flame-retardant magnesium alloy and a method of manufacturing the same.
  • a conventional long period stacking ordered (LPSO) magnesium alloy (refer to, for example, patent literatures 1 to 3) has mechanical properties of high strength and high ductility.
  • the melting and casting temperature of this long period stacking ordered magnesium alloy is 750°C. Since this temperature is close to an ignition temperature, it is dangerous to perform the melting and casting in the air. Therefore, in performing the melting and casting, there has been a necessity of performing an operation thereof under an atmosphere (for example, under an atmosphere of vacuum and an inert gas) in which the combustion of the magnesium alloy is prevented. This increases the cost.
  • SF 6 that is used as an inert gas has 23,900 times as high global warming potential as carbon dioxide, SF 6 is harmful to the environment, and thus the utilization needs to be prevented.
  • An aspect of the present invention has an object to provide a flame-retardant magnesium alloy having mechanical properties of a long period stacking ordered magnesium alloy and having an ignition temperature of 800°C or more and a method of manufacturing the same.
  • An aspect of the present invention is applied, and thus it is possible to provide a flame-retardant magnesium alloy having mechanical properties of a long period stacking ordered magnesium alloy and having an ignition temperature of 800°C or more and a method of manufacturing the same.
  • An alloy which contains a atomic% of Zn, b atomic% of Y and x atomic% of Ca and in which the remaining part is formed of Mg, and a, b and x satisfy formulae 1 to 4 below is melted and cast at a temperature of 800°C or less (preferably 850°C or less). Since this alloy has an ignition temperature of 800°C or more (preferably 850°C or more) by containing Ca. In this way, a magnesium alloy cast is made.
  • the cooling rate at the time of casting is 1000K/second or less, and is more preferably 100K/second or less.
  • Various processes can be used as the process for producing the magnesium alloy cast described above, and for example, high-pressure casting, roll casting, inclined plate casting, continuous casting, thixomolding, die-casting and the like can be used.
  • a product cut into a predetermined shape from an ingot may be used as the magnesium alloy cast.
  • homogenized heat treatment may be performed on the magnesium alloy cast.
  • the temperature is set at 400 to 550°C, and the treatment time is set at 1 to 1500 minutes (or 24 hours).
  • plastic processing is performed on the magnesium alloy cast.
  • methods of performing this plastic processing include extrusion, an ECAE (equal-channel-angular-extrusion) processing method, rolling, drawing and forging, processing of repeating these, FSW (friction stir welding) processing and the like.
  • the extrusion temperature is set to 250°C or more and 500°C or less, and the cross-section reduction rate by extrusion is set to 5% or more.
  • the ECAE processing method is a method of rotating the longitudinal direction of the sample by 90° per pass in order to introduce uniform distortion into the sample.
  • the ECAE processing method is the following method: a magnesium alloy cast serving as a molding material is forcibly made to enter a molding hole of a molding die where the molding hole whose cross section is in the shape of the letter L is formed, in particular, in a part of the L-shaped molding hole that is bent by 90°, a stress is applied to the magnesium alloy cast and thus a molded member having excellent strength and toughness is obtained.
  • the number of passes of the ECAE is preferably 1 to 8. The number is more preferably 3 to 5.
  • the temperature at the time of processing of the ECAE is preferably 250°C or more and 500°C or less
  • the rolling temperature is set to 250°C or more and 500°C or less, and the rolling reduction rate is set to 5% or more.
  • the temperature at which the drawing processing is performed is set to 250°C or more and 500°C or less, and the cross-section reduction rate in the drawing processing is set to 5% or more.
  • the temperature at which the forging processing is performed is set to 250°C or more and 500°C or less, and the processing rate in the forging processing is set to 5% or more.
  • the amount of distortion for each processing is 0.002 or more and 4.6 or less, and the total amount of distortion is 15 or less.
  • the amount of distortion for each processing is 0.002 or more and 4.6 or less, and the total amount of distortion is 10 or less. The reason why the preferable total amount of distortion is set to 15 or less and the more preferable total amount of distortion is set to 10 or less is because even when the total amount of distortion is increased, the strength of the magnesium alloy is not always increased accordingly and as the total amount of distortion is made larger, the manufacturing cost is increased.
  • the amount of distortion in the extrusion processing is 0.92/ each processing when the extrusion ratio is 2.5, is 1.39/ each processing when the extrusion ratio is 4, is 2.30/ each processing when the extrusion ratio is 10, is 2.995/ each processing when the extrusion ratio is 20, is 3.91/ each processing when the extrusion ratio is 50, is 4.61/ each processing when the extrusion ratio is 100 and is 6.90/ each processing when the extrusion ratio is 1000.
  • the plastic-processed product obtained by performing the plastic processing on the magnesium alloy cast as described above has a crystalline structure of an hcp structure magnesium phase and a long period stacking ordered structural phase at room temperature, the volume fraction of the crystal grains of the long period stacking ordered structure is 5% or more (more preferably 10% or more) and the crystal grain size of the magnesium alloy is 100 nm or more and 500 ⁇ m or less.
  • the average grain size of the hcp structure magnesium phase is 2 ⁇ m or more, and the average grain size of the long period stacking ordered structural phase is 0.2 ⁇ m or more.
  • the dislocation density of the hcp structure magnesium phase is one or more digits larger than the dislocation density in the portions of the long period stacking ordered structural phase other than the random grain boundaries.
  • the plastic-processed product may have at least one type of precipitate selected from a precipitate group consisting of a compound of Mg and a rare-earth element, a compound of Mg and Zn, a compound of Zn and a rare-earth element, and a compound of Mg and Zn and a rare-earth element.
  • the total volume fraction of the precipitate is preferably more than 0% and not more than 40%.
  • the plastic-processed product has hcp-Mg. In a plastic-processed product after the plastic processing is performed, both the Vickers hardness and the yield strength are increased as compared with a cast before the plastic processing is performed.
  • Heat treatment may be performed on the plastic-processed product after the plastic processing is performed on the magnesium alloy cast.
  • the temperature is set to not less than 200°C and less than 500°C, and the heat treatment time is set at 10 to 1500 minutes (or 24 hours). The reason why the heat treatment temperature is set to less than 500°C is because when the heat treatment temperature is set to 500°C or more, the amount of distortion applied by the plastic processing is cancelled.
  • both the Vickers hardness and the yield strength are increased as compared with the plastic-processed product before the heat treatment is performed. Furthermore, the plastic-processed product after the heat treatment has, as with the plastic-processed product before the heat treatment, a crystalline structure of an hcp structure magnesium phase and a long period stacking ordered structural phase at room temperature, the volume fraction of the crystal grains of the long period stacking ordered structure becomes 5% or more (more preferably 10% or more), the average grain diameter of the hcp structure magnesium phase is 2 ⁇ m or more, and the average grain diameter of the long period stacking ordered structural phase is 0.2 ⁇ m or more.
  • the dislocation density of the hcp structure magnesium phase is one or more digits larger than the dislocation density in the portions of the long period stacking ordered structural phase other than the random grain boundaries.
  • the plastic-processed product may have at least one type of precipitate selected from a precipitate group consisting of a compound of Mg and a rare-earth element, a compound of Mg and Zn, a compound of Zn and a rare-earth element, and a compound of Mg and Zn and a rare-earth element.
  • the total volume fraction of the precipitate is preferably more than 0% and not more than 40%.
  • the processing of melting and casting for manufacturing a magnesium alloy including mechanical properties of high strength and high ductility by having the long period stacking ordered structural phase it becomes possible to carry out the processes in the air without setting an atmosphere in which combustion is prevented (an inert gas atmosphere having problems in cost and environment) .
  • the reason for this is that it is possible to set the ignition temperature of the magnesium alloy to 800°C or more (preferably 850°C or more) by addition of a small amount of Ca.
  • the addition amount of Ca is 0 atomic% or more and 0.5 atomic% or less (is preferably more than 0.1 atomic% and not more than 0.5 atomic% and is further preferably 0.15 atomic% or more and 0.5 atomic% or less).
  • the magnesium alloy of the present embodiment is an alloy obtained by achieving flame retardance by the increase in the ignition temperature, conventional metal processing facilities may be utilized without being changed, and it is possible to reduce risk of igniting fine powder or cutting chips generated at the time of processing, with the result that problems related to the environment, the cost and the safety in the processing steps can be solved at the same time.
  • the magnesium alloy according to the present embodiment can increase the strength by having the long period stacking ordered structural phase, and has a property less likely to be combusted at the time of melting, casting and processing. Namely, it is possible to realize the magnesium alloy that is advantageous both in high strength and flame retardance.
  • the range of the application of the magnesium alloy in the present embodiment covers various fields such as an IT field (a smart phone, a notebook computer and the like), a medical field, an automobile field, an airplane field and a railway field.
  • the toughness tends to be lowered.
  • the toughness tends to be lowered.
  • the range of the content of zinc in the magnesium alloy of the present embodiment is at the widest range 0.5 atomic% or more and 5.0 atomic% or less.
  • Mg-Zn-Y magnesium alloy of the present embodiment has the content in the range described above, impurities to the extent of not affecting the properties of the alloy may be contained.
  • the magnesium alloy of the present embodiment may further contain y atomic% of Al, and y satisfies formula 5 below, preferably satisfies formula 51 below, further preferably satisfies formula 52 or formula 53 below and more preferably satisfies formula 54 or formula 55 below.
  • the upper limit of the content of Al is set to less than 0.35 atomic% (preferably 0.3 atomic% or less), and thus it is possible to maintain high strength at high temperature.
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of La, Ce, Pr, Eu, Mm and Gd, and c preferably satisfies formula 6 and formula 7 below or formula 7 and formula 8 below. 0 ⁇ c ⁇ 3.0 0.2 ⁇ b + c ⁇ 6.0 c / b ⁇ 1.5
  • Mm (misch metal) is a mixture or an alloy of a plurality of rare-earth elements each containing Ce and La as the main components, and is a residue after Sm, Nd and the like which are useful rare-earth elements are removed by being refined from ores, and its composition depends on the compositions of the ores before refinement.
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of Yb, Tb, Sm and Nd, and c preferably satisfies formula 8 and formula 9 below. 0 ⁇ c ⁇ 3.0 0.2 ⁇ b + c ⁇ 6.0
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of Yb, Tb, Sm and Nd, may contain, in total, d atomic% of at least one element selected from a group consisting of La, Ce, Pr, Eu, Mm and Gd, and c and d preferably satisfy formulae 6 to 8 or formulae 8 and 9 bellow.
  • the reason why the total content of Y, Yb and the like and La and the like is set to 6.0 atomic% or less is because, when the total content exceeds 6%, the weight of the magnesium alloy is increased, the cost of raw materials is increased and furthermore, the toughness is lowered.
  • the reason why Yb and the like and La and the like are contained is because an effect of miniaturizing crystal grains and an effect of precipitating an intermetallic compound are obtained.
  • the reason why formula 9 above is preferably satisfied is because when d/b is made greater than 1. 5 times, the effect of formation of the long period stacking ordered structural phase is reduced and the weight of the magnesium alloy is increased.
  • the magnesium alloy of the present embodiment preferably contains, in total, more than 0 atomic% and not more than 2.5 atomic% of at least one element selected from a group consisting of Th, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B, C, Sn, Au, Ba, Ge, Bi, Ga, In, Ir, Li, Pd, Sb and V.
  • Th and the like are added, it is possible to improve the other qualities while maintaining high strength and high toughness.
  • the addition of Th and the like is effective for, for example, corrosion resistance, grain miniaturization and the like.
  • the magnesium alloy obtained by adding more than 0 atomic% and not more than 2.5 atomic% of Zr is melted and cast, in the magnesium alloy cast, the precipitation of a compound such as Mg 3 Zn 3 RE 2 is reduced, the formation of the long period stacking ordered structural phase is facilitated and the crystalline structure is miniaturized. Therefore, plastic processing such as extrusion is easily performed on this magnesium alloy cast, and the plastic-processed product on which the plastic processing is performed has a larger amount of long period stacking ordered structural phases and a more miniaturized crystalline structure than a plastic-processed product of the magnesium alloy to which Zr is not added.
  • the plastic-processed product has a large amount of long period stacking ordered structural phases, and thus it is possible to enhance strength and toughness.
  • a method of manufacturing a flame-retardant magnesium alloy according to one aspect of the present invention will be described. Note that, in the method of manufacturing a flame-retardant magnesium alloy according to the second embodiment, the description of the same parts as in the method of manufacturing a flame-retardant magnesium alloy according to the first embodiment will be omitted as much as possible.
  • An alloy which contains a atomic% of Zn, b atomic% of Y and x atomic% of Ca and in which the remaining part is formed of Mg and a, b and x satisfy formulae 1 to 4 below is melted and cast at a temperature of 800°C or less (preferably 850°C or less). Since this alloy has an ignition temperature of 800°C or more (preferably 850°C or more) by containing Ca. In this way, a magnesium alloy cast is formed. As the magnesium alloy cast, a product cut into a predetermined shape from an ingot is used.
  • a plurality of chip-shaped casts having a size of several mm square or less is produced by cutting the magnesium alloy cast.
  • the chip-shaped casts may be preliminarily molded using a compression means or a means of a plastic processing method, and thus may be subjected to homogenized heat treatment.
  • the temperature is set to 400 to 550°C, and the treatment time is set to 1 to 1500 minutes (or 24 hours).
  • heat treatment may be performed on the preliminarily molded product at a temperature of 150 to 450°C for 1 to 1500 minutes (or 24 hours).
  • the chip-shaped cast is generally used as, for example, the raw material of thixotropic mold.
  • a mixture of the chip-shaped cast and ceramic particles may be preliminarily molded using a compression means or a means of a plastic processing method, and thus may be subjected to homogenized heat treatment. Furthermore, before the chip-shaped cast is preliminarily molded, the cast may be additionally subjected to strong distortion processing.
  • plastic processing is performed on the chip-shaped cast, and thus the chip-shaped cast is solidified and molded.
  • Various methods can be used as the method of performing the plastic processing in the same way as in the first embodiment. Note that, before the chip-shaped cast is solidified and molded, repetition processing including: mechanical alloying such as a ball mill, a stamp mill, or a high-energy ball mill; or bulk mechanical alloying may be added. In addition, after the solidification and molding, plastic processing or blasting processing may further be added. Furthermore, the magnesium alloy cast may be complexed with intermetallic compound particles, ceramic particles, fibers or the like, or the cut product may be mixed with ceramic particles, fibers or the like.
  • the plastic-processed product obtained by performing the plastic processing as described above has, at room temperature, a crystalline structure of the hcp structure magnesium phase and the long period stacking ordered structural phase. At least a part of the long period stacking ordered structural phase is curved or bent.
  • both the Vickers hardness and the yield strength are increased as compared with the cast before the plastic processing is performed.
  • the total amount of distortion when the plastic processing is performed on the chip-shaped cast is preferably 15 or less, and is more preferably 10 or less.
  • the amount of distortion for each processing is preferably 0.002 or more and 4.6 or less.
  • the total amount of distortion here is the total amount of distortion that is not cancelled by heat treatment such as annealing, and means the total amount of distortion when the plastic processing is performed after the chip-shaped cast is preliminarily molded. Namely, distortion that is cancelled by performing heat treatment in the middle of the manufacturing process is not counted as the total amount of distortion, and the amount of distortion until the chip-shaped cast is preliminarily molded is not counted as the total amount of distortion.
  • Heat treatment may be performed on the plastic-processed product after the plastic processing is performed on the chip-shaped cast.
  • the temperature is set to not less than 200°C and less than 500°C, and the heat treatment time is set to 10 to 1500 minutes (or 24 hours).
  • the reason why the heat treatment temperature is set to less than 500°C is because, when the heat treatment temperature is set to 500°C or more, the amount of distortion applied by the plastic processing is cancelled.
  • both the Vickers hardness and the yield strength are increased as compared with the plastic-processed product before the heat treatment is performed.
  • the plastic-processed product after the heat treatment has, as with the plastic-processed product before the heat treatment, a crystalline structure of an hcp structure magnesium phase and a long period stacking ordered structural phase at room temperature. At least a part of the long period stacking ordered structural phase is curved or bent.
  • the chip-shaped cast is produced by cutting the cast, and thus the structure is miniaturized, with the result that, as compared with the first embodiment, it becomes possible to produce, for example, the plastic-processed product having high strength, high ductility and high toughness.
  • the magnesium alloy of the present embodiment even when the concentrations of zinc and a rare-earth element are lower than in the magnesium alloy of the first embodiment, it is possible to obtain the properties of high strength and high toughness.
  • the lower limit of the content of zinc is set to 0.25 atomic%, and the lower limit of the total content of the rare-earth element is set to 0.5 atomic%.
  • the reason why the lower limit of the content of zinc can be as low as one half of that in the first embodiment is because the application to the chip-shaped cast is carried out.
  • the Mg-Zn-Y magnesium alloy of the present embodiment has the content in the range described above, impurities to the extent of not affecting the properties of the alloy may be contained.
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of La, Ce, Pr, Eu, Mm and Gd, and c preferably satisfies formula 6 and formula 7 below. 0 ⁇ c ⁇ 3.0 0.1 ⁇ b + c ⁇ 6.0
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of Yb, Tb, Sm and Nd, and c preferably satisfies formula 8 and formula 9 below. 0 ⁇ c ⁇ 3.0 0.1 ⁇ b + c ⁇ 6.0
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of Yb, Tb, Sm and Nd, may contain, in total, d atomic% of at least one element selected from a group consisting of La, Ce, Pr, Eu, Mm and Gd, and c and d preferably satisfy formulae 6 to 8 below. 0 ⁇ c ⁇ 3.0 0 ⁇ d ⁇ 2.0 0.1 ⁇ b + c + d ⁇ 6.0
  • a method of manufacturing a flame-retardant magnesium alloy according to one aspect of the present invention will be described. Note that, in the method of manufacturing a flame-retardant magnesium alloy according to the third embodiment, the description of the same parts as in the method of manufacturing a flame-retardant magnesium alloy according to the first embodiment will be omitted as much as possible.
  • a flame-retardant magnesium alloy which contains a atomic% of Zn, in total, b atomic% of at least one element selected from a group consisting of Gd, Tb, Tm and Lu, and x atomic% of Ca and in which a remaining part is formed of Mg and a, b and x satisfy Formulae 1 to 4 below is melted at a temperature of 800°C or less (preferably, 850°C or less) and cast.
  • This alloy has an ignition temperature of 800°C or more (preferably 850°C or more) by containing Ca. In this way, a magnesium alloy cast is made.
  • the cooling rate at the time of casting is 1000K/second or less, more preferably 100K/second or less.
  • homogenized heat treatment may be performed on the magnesium alloy cast.
  • the plastic-processed product obtained by performing the plastic processing on the magnesium alloy cast as described above has a crystalline structure of an hcp structure magnesium phase and a long period stacking ordered structural phase at room temperature, the volume fraction of the crystal grains of the long period stacking ordered structure is 5% or more (more preferably 10% or more).
  • At least a part of the long period stacking ordered structural phase is curved or bent.
  • Heat treatment may be performed on the plastic-processed product obtained by performing the plastic processing on the magnesium alloy cast.
  • the temperature is set to 400 to 550°C, and the heat treatment time is set to 1 to 1500 minutes (or 24 hours).
  • both the Vickers hardness and the yield strength are increased as compared with the plastic-processed product before the heat treatment is performed. Furthermore, the plastic-processed product after the heat treatment has, as with the plastic-processed product before the heat treatment, a crystalline structure of an hcp structure magnesium phase and a long period stacking ordered structural phase at normal temperature.
  • the Mg-Zn-(Gd, Tb, Tm, Lu)-based magnesium alloy of the present embodiment has the content in the range described above, impurities to the extent of not affecting the properties of the alloy may be contained.
  • the magnesium alloy of the present embodiment may further contain y atomic% of Al, and y satisfies Formula 5 below, preferably satisfies Formula 51 below, further preferably satisfies Formula 52 or Formula 53 below, and more preferably satisfies Formula 54 or Formula 55 below.
  • the strength at a high temperature can be maintained at a high level by setting the upper limit of the content of Al to less than 0.35 atomic% (preferably 0.3 atomic% or less). 0 ⁇ y ⁇ 0.5 0.05 ⁇ y ⁇ 0.5 0 ⁇ y ⁇ 0.35 0.05 ⁇ y ⁇ 0.35 0 ⁇ y ⁇ 0.3 0.05 ⁇ y ⁇ 0.3
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of La, Ce, Pr, Eu and Mm, and c preferably satisfies Formulae 6 and 7 bellow. 0 ⁇ c ⁇ 2.0 0.5 ⁇ b + c ⁇ 6.0
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of Yb, Sm and Nd, and c preferably satisfies Formulae 6 and 7 below. 0 ⁇ c ⁇ 2.0 0.5 ⁇ b + c ⁇ 6.0
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of Yb, Sm and Nd, may contain, in total, d atomic% of at least one element selected from a group consisting of La, Ce, Pr, Eu and Mm, and c and d satisfy Formulae 6 to 8 below. 0 ⁇ c ⁇ 2.0 0 ⁇ d ⁇ 2.0 0.5 ⁇ b + c + d ⁇ 6.0
  • the magnesium alloy of the present embodiment preferably contains, in total, more than 0 atomic% and not more than 2.5 atomic% of at least one element selected from a group consisting of Th, Si, Mn, Zr, Ti, Hf, Nb, Ag, Sr, Sc, B, C, Sn, Au, Ba, Ge, Bi, Ga, In, Ir, Li, Pd, Sb and V.
  • Th and the like are added, it is possible to improve the other qualities while maintaining high strength and high toughness.
  • the addition of Th and the like is effective for, for example, corrosion resistance, grain miniaturization and the like.
  • the magnesium alloy obtained by adding more than 0 atomic% and not more than 2.5 atomic% of Zr is melted and cast, in the magnesium alloy cast, the precipitation of a compound such as Mg 3 Zn 3 RE 2 is suppressed, the formation of the long period stacking ordered structural phase is facilitated, and the crystalline structure is miniaturized. Accordingly, plastic processing such as extrusion is easily performed on this magnesium alloy cast, and the plastic-processed product on which the plastic processing is performed has a larger amount of long period stacking ordered structural phases and a more miniaturized crystalline structure than a plastic-processed product of the magnesium alloy to which Zr is not added. In this way, the plastic-processed product has a large amount of the long period stacking ordered structural phases, and thus it is possible to enhance strength and toughness.
  • a method of manufacturing a flame-retardant magnesium alloy according to one aspect of the present invention will be described. Note that, in the method of manufacturing a flame-retardant magnesium alloy according to the fourth embodiment, the description of the same parts as in the method of manufacturing a flame-retardant magnesium alloy according to the first embodiment will be omitted as much as possible.
  • a flame-retardant magnesium alloy which contains a atomic% of Zn, in total, b atomic% of at least one element selected from a group consisting of Gd, Tb, Tm and Lu, and x atomic% of Ca and in which a remaining part is formed of Mg and a, b and x satisfy Formulae 1 to 4 below is melted at a temperature of 800°C or less (preferably, 850°C or less) and cast.
  • This alloy has an ignition temperature of 800°C or more (preferably 850°C or more) by containing Ca. In this way, a magnesium alloy cast is made.
  • the cooling rate at the time of casting is 1000K/second or less, more preferably 100K/second or less.
  • a method of manufacturing a flame-retardant magnesium alloy according to one aspect of the present invention will be described. Note that, in the method of manufacturing a flame-retardant magnesium alloy according to the fifth embodiment, the description of the same parts as in the method of manufacturing a flame-retardant magnesium alloy according to the third embodiment will be omitted as much as possible.
  • a flame-retardant magnesium alloy which contains a atomic% of Zn, in total, b atomic% of at least one element selected from a group consisting of Gd, Tb, Tm and Lu, and x atomic% of Ca and in which a remaining part is formed of Mg and a, b and x satisfy Formulae 1 to 4 below is melted at a temperature of 800°C or less (preferably, 850°C or less) and cast.
  • This alloy has an ignition temperature of 800°C or more (preferably 850°C or more) by containing Ca. In this way, a magnesium alloy cast is made.
  • a product cut into a predetermined shape from an ingot is used as the magnesium alloy cast.
  • a plurality of chip-shaped casts having a size of several mm square or less is produced by cutting the magnesium alloy cast.
  • the chip-shaped casts may be preliminarily molded using a compression means or a means of a plastic processing method, and thus may be subjected to homogenized heat treatment.
  • the conditions of the heat treatment are the same as in the second embodiment.
  • the chip-shaped cast is generally used as, for example, the raw material of thixotropic mold.
  • a mixture of the chip-shaped cast and ceramic particles may be preliminarily molded using a compression means or a means of a plastic processing method, and thus may be subjected to homogenized heat treatment. Furthermore, before the chip-shaped cast is preliminarily molded, the cast may be additionally subjected to strong distortion processing.
  • plastic processing is performed on the chip-shaped cast, and thus the chip-shaped cast is solidified and molded.
  • Various methods can be used as the method of performing the plastic processing in the same way as in the third embodiment. Note that, before the chip-shaped cast is solidified and molded, repetition processing including: mechanical alloying such as a ball mill, a stamp mill, or a high-energy ball mill; or bulk mechanical alloying may be added. In addition, after the solidification and molding, plastic processing or blasting processing may further be added. Furthermore, the magnesium alloy cast may be complexed with intermetallic compound particles, ceramic particles, fibers or the like, or the cut product may be mixed with ceramic particles, fibers or the like.
  • the plastic-processed product obtained by performing the plastic processing as described above has, at room temperature, a crystalline structure of the hcp structure magnesium phase and the long period stacking ordered structural phase. At least a part of the long period stacking ordered structural phase is curved or bent.
  • both the Vickers hardness and the yield strength are increased as compared with the cast before the plastic processing is performed.
  • the total amount of distortion when the plastic processing is performed on the chip-shaped cast is the same as in the second embodiment.
  • Heat treatment may be performed on the plastic-processed product after the plastic processing is performed on the chip-shaped cast.
  • the conditions and effects of the heat treatment are the same as in the second embodiment.
  • the chip-shaped cast is produced by cutting the cast, and thus the structure is miniaturized, with the result that, as compared with the third embodiment, it becomes possible to produce, for example, the plastic-processed product having high strength, high ductility and high toughness.
  • the magnesium alloy of the present embodiment even when the concentrations of zinc and a rare-earth element are lower than in the magnesium alloy of the first embodiment, it is possible to obtain the properties of high strength and high toughness.
  • the magnesium alloy of the present embodiment may contain impurities to the extent of not affecting the properties of the alloy.
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of La, Ce, Pr, Eu and Mm, and c preferably satisfies Formulae 6 and 7 below. 0 ⁇ c ⁇ 2.0 0.25 ⁇ b + c ⁇ 6.0
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of Yb, Sm and Nd, and c preferably satisfies Formulae 6 and 7 below. 0 ⁇ c ⁇ 3.0 0.25 ⁇ b + c ⁇ 6.0
  • the magnesium alloy of the present embodiment may contain, in total, c atomic% of at least one element selected from a group consisting of Yb, Sm and Nd, may contain, in total, d atomic% of at least one element selected from a group consisting of La, Ce, Pr, Eu, and Mm, and c and d preferably satisfy Formulae 6 to 8 below. 0 ⁇ c ⁇ 2.0 0 ⁇ d ⁇ 2.0 0.25 ⁇ b + c + d ⁇ 6.0
  • a method of manufacturing a flame-retardant magnesium alloy according to one aspect of the present invention will be described. Note that, in the method of manufacturing a flame-retardant magnesium alloy according to the sixth embodiment, the description of the same parts as in the method of manufacturing a flame-retardant magnesium alloy according to the fifth embodiment will be omitted as much as possible.
  • a flame-retardant magnesium alloy which contains a atomic% of Zn, in total, b atomic% of at least one element selected from a group consisting of Gd, Tb, Tm and Lu, and x atomic% of Ca and in which a remaining part is formed of Mg and a, b and x satisfy Formulae 1 to 4 below is melted at a temperature of 800°C or less (preferably, 850°C or less) and cast.
  • This alloy has an ignition temperature of 800°C or more (preferably 850°C or more) by containing Ca. In this way, a magnesium alloy cast is made.
  • a product cut into a predetermined shape from an ingot is used as the magnesium alloy cast.
  • An ingot of a magnesium alloy having these alloy components was melted using a high frequency melting furnace in the atmosphere, and cast members each having a shape of ⁇ 32 ⁇ 70 mm were produced by being cut from the ingot. These cast members were extruded under conditions of a temperature of 350°C, an extrusion ratio of 10 and an extrusion rate of 2.5 mm/second.
  • tensile yield strength and elongation were measured at room temperature with a tensile test, and the results thereof are shown in Fig. 1 .
  • ⁇ represents the tensile yield strength
  • ⁇ represents the elongation.
  • tensile yield strength and elongation were measured at a temperature of 523K with a tensile test, and the results thereof are shown in Fig. 2 .
  • ⁇ represents the tensile yield strength
  • ⁇ represents the elongation.
  • the ignition temperature of each of the cast members was measured.
  • a measurement method is as follows.
  • the ignition temperature of the magnesium alloy shown was 850°C or more.
  • the content of Ca is set to more than 0 atomic% and less than 0.75 atomic% (preferably set to not less than 0.1 atomic% and less than 0.75 atomic%), and thus the ignition temperature of 800°C or more can be expected.
  • the ignition temperature of a composition to which Ca is not added for example, an alloy of Mg 95.75 Zn 2 Y 1.9 La 0.1 Al 0.25 is approximately 775°C, and this ignition temperature is close to 750°C which is the temperature at the time of melting and casting of this alloy. Therefore, when this alloy is melted, it is necessary to use an atmosphere of an inert gas.
  • the ignition temperature is 800°C or more or 850°C or more, it becomes possible to perform melting processing even without the use of an inert gas since the ignition temperature is sufficiently higher than the melting point of the alloy.
  • the addition range of Ca having an ignition temperature of 800°C or more or 850°C or more while having excellent mechanical properties of the long period stacking ordered magnesium alloy is more than 0 atomic% and not more than 0.5 atomic% (preferably, 0.1 to 0.5 atomic%) by addition of Ca to the long period stacking ordered magnesium alloy.
  • An ingot of a magnesium alloy having these alloy components was melted using a high frequency melting furnace in an atmosphere of Ar, and cast members each having a shape of ⁇ 32 ⁇ 70 mm were produced by being cut from the ingot. These cast members were extruded under conditions of a temperature of 350°C, an extrusion ratio of 10 and an extrusion rate of 2.5 mm/second.
  • tensile strength and elongation were measured at room temperature with a tensile test, and the results thereof are shown in Fig. 6 .
  • ⁇ represents the tensile strength ( ⁇ UTS )
  • ⁇ represents a yield strength ( ⁇ 0.2 )
  • ⁇ represents the elongation (%).
  • tensile yield strength and elongation were measured at a temperature of 523K with a tensile test, and the results thereof are shown in Fig. 7 .
  • ⁇ represents the tensile strength ( ⁇ UTS )
  • ⁇ represents a yield strength ( ⁇ 0.2 )
  • ⁇ represents the elongation (%).
  • the content of Al is set to less than 0.35 atomic% (preferably set to 0.3 atomic% or less), and thus it is possible to maintain high strength at high temperature.
  • a creep test was performed on a sample of the extrusion member.
  • a sample of the extrusion member of the alloy of Mg 96 Zn 2 Y 2 was produced, and a creep test was performed.
  • the condition of the creep test was 200°C and 150 MPa. The results thereof are shown in Fig. 13 .
  • the alloy components of samples in the second Example are as shown in Table 1 and Table 2.
  • An ingot of a magnesium alloy having these alloy components was melted using a high frequency melting furnace in the atmosphere, and cast members each having a shape of ⁇ 32 ⁇ 70 mm were produced by being cut from the ingot. These cast members were extruded under conditions of a temperature of 350°C, an extrusion ratio of 10 and an extrusion rate of 2.5 mm/second.
  • the ignition temperature of each of the cast members was measured.
  • a measurement method is as follows.

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WO2014171550A9 (ja) 2015-12-30
US20160068933A1 (en) 2016-03-10
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US20160168666A1 (en) 2016-06-16
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JPWO2014171549A1 (ja) 2017-02-23
WO2014171549A1 (ja) 2014-10-23
JPWO2014171550A1 (ja) 2017-02-23
EP2987875B1 (de) 2018-10-10
WO2014171550A1 (ja) 2014-10-23
EP2987875A1 (de) 2016-02-24
JPWO2014171548A1 (ja) 2017-02-23
WO2014171548A1 (ja) 2014-10-23
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CN105283566A (zh) 2016-01-27
EP2987875A4 (de) 2016-11-30

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