EP3553199B1 - A method of preparing magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced magnesium-based composite material - Google Patents

A method of preparing magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced magnesium-based composite material Download PDF

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EP3553199B1
EP3553199B1 EP19153314.0A EP19153314A EP3553199B1 EP 3553199 B1 EP3553199 B1 EP 3553199B1 EP 19153314 A EP19153314 A EP 19153314A EP 3553199 B1 EP3553199 B1 EP 3553199B1
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magnesium
furnace
vacuum
frequency induction
medium frequency
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EP3553199A1 (en
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Yuhong Zhao
Jinzhong Tian
Hua HOU
Zhiqin Wen
Liwen Chen
Huijun GUO
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North University of China
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    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D18/00—Pressure casting; Vacuum casting
    • B22D18/02—Pressure casting making use of mechanical pressure devices, e.g. cast-forging
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C22C1/1052—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites by mixing and casting metal matrix composites with reaction
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1073—Infiltration or casting under mechanical pressure, e.g. squeeze casting
    • 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
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
    • C22C32/0057—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides based on B4C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • 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
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • 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

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • The application claims priority to Chinese Application No. 201810328616.X, filed on April 13, 2018 .
    • BACKGROUND Field of Invention
  • The present invention relates to a method of preparing magnesium-zinc-yttrium quasicrystal and boron carbide mixed enforced Mg-based composite materials, which belong to the technical area of preparing and applying the non-ferrous metal materials.
    • Background of the Invention
  • The magnesium alloy materials have widely applied in the automobile and aerospace area for it they are characterized in low density, high specific strength, excellent shock resistance, strong electromagnetic shielding capability and easy processing. However, the application of magnesium alloy in the industrial area is restricted for its low hardness, low anti-tensile strength and poor corrosion resistance. The Chinese patent CN 102618766B discloses a method of producing a quasicrystal enhanced Mg-Zn-Y alloy by means of conventional melting and subsequent thermal treatment.
  • As the quascicrystal has high hardness, high elastic modules, low expansion coefficient and excellent corrosion resistance, it is extremely suitable to be used as the enhance phase of the magnesium alloy and can efficiently improve the mechanical property of the magnesium alloy. The boron carbide particles are of great application potential for they have low density, excellent chemical stability, abrasive resistance and can be evenly distributed in the magnesium substrate with a stable interface. However, mixed particles reinforced Mg-based composite materials are still in the research phase and the process technology needs to be improved.
    • SUMMARY Invention Object
  • The present invention is done based on the situations introduced by the background art and aims at improving the mechanical property of the magnesium alloy by adopting the magnesium alloy as the substrate, the endogenous magnesium-zinc-yttrium quasicrystal and boron carbide as the reinforced phase, via smelting in the vacuum medium frequency induction melting furnace and then squeezing casting to prepare magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite materials.
    • Technical Solution
  • Chemical materials used in the present invention are: magnesium, zinc, magnesium yttrium interalloy, boron carbide, zinc oxide, talcum powder, water glass, deionized water, aluminum foil, absolute alcohol, argon, their amounts used in the composition are: (measured in gram, milliliter and centimeter3):
    magnesium Mg 4127gยฑ0.1g
    Zinc Zn 784gยฑ0.1g
    magnesium yttrium interalloy Mg89Y11 571gยฑ0.1g
    boron carbide B4C 300gยฑ0.1g
    zinc oxide ZnO 80gยฑ1g
    talcum powder Mg3Si4O10](OH)2 50gยฑ1g
    water glass Na2SiO3ยท9H2O 25gยฑ1g
    deionized water H2O 1000mLยฑ50mL
    aluminum foil Al 300mmร—0.5mmร—300mm
    absolute alcohol C2H5OH 3500mL ยฑ50mL
    argon Ar 800000cm3ยฑ100 cm3
    the preparation method comprises:
    1. (1) preparing the casting mold
      the open-close type squeeze casting mold is manufactured by hot working dies steel with a rectangle cavity, wherein the size of the cavity is 200mmร—160mmร—90mm and the surface roughness of the cavity is Ra 0.08-0.16ยตm;
    2. (2) preparing the coating agent
      weighing out zinc oxide 80gยฑ1g, talcum powder 50gยฑ1g, water glass 25gยฑ1g, measuring out deionized water 300mLยฑ1mL, adding zinc oxide 80gยฑ1g, talcum powder 50gยฑ1g, water glass 25gยฑ1g and deionized water 300mLยฑ1mL into the mixinghollander and stirring them to obtain the coating agent presenting as viscous liquid, wherein the stirring speed is 50r/min, stirring time is 80min.
    3. (3) pre-treating the boron carbide particles
      • โ‘ ball milling: weighing boron carbide 300gยฑ0.1g, putting it into the ball mill tank of the ball mill and ball milling it to obtain fine powder with a particle size โ‰ค9ยตm, wherein the ball milling speed is 80r/min, the ball milling time is 3h;
      • โ‘กultrasonic dispersion washing: putting the fine powder after ball milling into a beaker and then adding absolute alcohol 500mLยฑ1mL, mixing;
        putting the beaker into an ultrasonic disperser and doing the ultrasonic dispersion washing to obtain the mixing liquid, wherein the ultrasonic frequency is 60kHz and the ultrasonic dispersion time is 80min;
      • โ‘ขfiltration: putting the mixing liquid into the cloth funnel of the filter bottle, filtering it with a microporous membrane, removing the supernatant, and keeping the filter cake;
      • โ‘ฃdrying and oxidation treatment: putting the filter cake into the thermal treatment furnace, conducting the drying and high temperature oxidation treatment, obtaining the boron carbide fine powderafter drying, wherein the drying and oxidation temperature is 500ยฐC and the drying and oxidation time is 2h;
    4. (4)pre-treating the magnesium, zinc and magnesium yttrium interalloy and the open-close type squeeze casting mold
      • โ‘ mechanically cutting the magnesium, zinc and magnesium yttrium interalloy into patches, wherein the size of the patch is โ‰ค30mmร—30mmร—10mm;
      • โ‘กwashing the surface of the magnesium, zinc and magnesium yttrium interalloy with absolute alcohol and then putting it into the vacuum drying oven after washing, wherein the drying temperature is 100ยฐC, the vacuum degree is 2 Pa and the drying period is 30min;
      • โ‘ขwrapping the boron carbide with aluminum foil, putting it into the vacuum drying ovenand drying, wherein the drying temperature is 100ยฐC, the vacuum degree is 2 Pa and the drying period is 60min;
        pre-heating the open-close type squeeze casting mold and coating the prepared coating agent on the inner surface of the mold cavity, wherein the thickness of the coating agent is 1mm; after the coating is completed, putting the open-close type squeeze casting mold into the heating furnace and preheating, wherein the pre-heating temperature is 150ยฐC and the pre-heating time is 1h;
    5. (5) smelting of the magnesium alloy
      smelting of the magnesium alloy is conducted in the vacuum medium frequency induction melting furnace and completed by processes of medium frequency induction heating, vacuumizing, bottom blowing argon and mechanical stirring;
      • โ‘ opening the vacuum medium frequency induction melting furnace and clearing the internal part of the graphite melting crucible to make the internal part of the crucible clean;
      • โ‘กweighing magnesium block 4127gยฑ0.1g, zinc block 784gยฑ0.1g and magnesium yttrium interalloy block 571gยฑ0.1g and putting them in the bottom of the crucible;
      • โ‘ขclosing the vacuum medium frequency induction melting furnace and getting it sealed;
        turning on the vacuum pump and extracting the air within to allow the pressure within the furnace to reach 1Pa;
        turning on the heater of the medium frequency induction melting furnace to start the heating, wherein the heating temperature is 610ยฐCยฑ1ยฐC;
      • โ‘ฃtuming on the argon bottom-blowing device to feed argon into the crucible, wherein the speed of the argon bottom-blowing is 200cm3/min; adjusting the pressure within the furnace to maintain the pressure within the furnace to be one bar pressure and it is regulated by the outlet valve;
      • โ‘คwhen the temperature of melt is 610ยฐCยฑ1ยฐC, adding boron carbide fine powder with the vacuum feeding device; turning on the mechanical agitator, wherein the stirring speed is 20r/min and the stirring time is 10min;
      • โ‘ฅstopping the stirring and continuing the heating; when the temperature of melt reaches 730ยฐCยฑ1ยฐC, turning off the mechanical agitator and the argon bottom blowing pipe, standing for 10 min to prepare for the casting;
    6. (6) squeeze casting
      • โ‘ opening the vacuum medium frequency induction melting furnace, removing the slag on the surface of the melt in the crucible, casting the alloy melt into the cavity of the squeeze casting mold; turning on the squeeze casting machine and squeezing the metal melt by the punch, wherein the squeeze pressure is 250MPa and the hold time is 20s;
        the alloying reaction occurs during the solidification of Mg-Zn-Y quascicrystal and stable quascicrystal Mg3Zn6Y phase can be produced, wherein the reaction formula is Mg + Zn + Mg 89 Y 11 + B 4 C โ†’ 250 MPa 20 s ฮฑ โˆ’ Mg + Mg 3 Zn 6 Y + B 4 C
        Figure imgb0001
        • ฮฑ-Mg : substrate magnesium phase
        • Mg3Zn6Y : magnesium zinc yttrium quasicrystalline phase
      • โ‘กejecting the cast and cooling it to 25ยฐC in the air to produce the magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite material blocks;
    7. (7)thermal treatment of the cast
      • โ‘ putting the magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite material blocks into the vacuum heat treatment furnace for thermal treatment, wherein the temperature of the thermal treatment is 420ยฐC, the vacuum degree is 2Pa, and the time of thermal treatment is15h; and then putting the cast into warm water of 50ยฐC fastly, quenching treatment, wherein the quenching time is 20s;
      • โ‘กputting the cast after quenching into the heat treatment furnace for aging treatment at 200ยฐC for 8h; and then stopping the heating and cooling it to 25ยฐC in the heat treatment furnace;
    8. (8) cleaning, detecting, analyzing and characterizing
      cleaning the surface of the cast to make it clean; detecting, analyzing and characterizing the microstructure and mechanical property;
      analyzing the metallographic structure with an optical microscope;
      conducting the tensile strength and hardness test with universal tensile testing machine and a hardness tester;
      conducting the fracture morphology analysis with a scanning electron microscope;
      conducting XRD analysis with X ray diffractometer;
      conclusion: magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite materials are rectangle blocks, wherein the tensile strength thereof is 315MPa, the elongation is 7%, the hardness reaches 108Hv.
    Beneficial effects
  • Compared with the background arts, the present invention has prominent advantages. Based on the situations that the Mg-based composite materials have poor mechanical properties, in the present invention, magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite materials are prepared by adopting the magnesium alloy as the substrate, the endogenous magnesium-zinc-yttrium quasicrystal and boron carbide as the reinforced phase, via smelting in the vacuum medium frequency induction melting furnace, protection of bottom blowing argon, mechanical stirring, squeeze casting and heat-treatment. The preparation method has advanced process and strict procedures, wherein the data is accurate and detailed, and the prepared Mg-based composite materials have 315MPa tensile strength, 7% elongation, 108Hv hardness, making it an advanced preparation method of mixed reinforced Mg-based composite materials.
    • BRIEF DESCRIPTION OF THE DRAWINGS
    • Figure 1 is the smelting state diagram of the Mg-based composite materials;
    • Figure 2 is the metallographic structure diagram of Mg-based composite materials;
    • Figure 3 is the fracture topography of Mg-based composite materials;
    • Figure 4 is is X-ray diffraction intensity spectrum of Mg-based composite materials;
      As shown in the figures, markers for the figures are listed as follow:
      1. 1. vacuum medium frequency induction melting furnace, 2. furnace base, 3. furnace chamber, 4. outlet pipe, 5. outlet valve, 6. worktable, 7. graphite melting crucible, 8. medium frequency induction heater, 9. alloy melt, 10. argon, 11. bottom blow motor, 12. bottom blow pipe, 13. vacuum pump, 14. vacuum pipe, 15. argon bottle, 16. argon pipe, 17. argon valve, 18. electric cabinet, 19. display screen, 20. indicator light, 21. power switch, 22. medium frequency induction heating controller, 23. bottom blow motor controller, 24. vacuum pump controller, 25. first cable, 26. second cable, 27. feed pipe, 28. feed valve, 29. mechanical agitator.
    DETAILED DESCRIPTION OF THE EMBODIMENTS
  • Now the present invention will be further described in combination with the figures:
    As shown in Figure 1, it shows the smelting state diagram of the Mg-based composite materials, wherein the location and connection relationship of each part should be correct and the ratio is conducted according to the amount and the process should be conducted according to the sequence.
  • The amount of the chemical materials used in the preparation of smelting is determined by the pre-configured scope, and they are measured in gram, milliliter and centimeter3.
  • The smelting of Mg-based composite materials is conducted in the vacuum medium frequency induction melting furnace, and finished by the process of mediate frequency induction heating, bottom blowing argon and mechanical stirring.
  • The vacuum medium frequency induction melting furnace is a vertical one. The bottom of the vacuum medium frequency induction melting furnace 1 is a furnace base 2, and the inside of the vacuum medium frequency induction melting furnace 1 is a furnace chamber 3; a worktable 6 is configured in the bottom of the furnace chamber 3 and a graphite melting crucible 7 is put on the worktable 6. The outside of the graphite melting crucible 7 is surrounded by the medium frequency induction heater 8 and the inside of the graphite melting crucible 7 is the alloy melt 9; an outlet pipe 4 is configured on the top right of the vacuum medium frequency induction melting furnace 1 and it is controlled by the outlet valve 5; the argon bottle 15 is configured on the top left of the vacuum medium frequency induction melting furnace 1 and an argon pipe 16 and an argon valve 17 are configured on the argon bottle 15. The argon pipe 16 is connected to the bottom blow motor 11. The bottom blow motor 11 is connected to the bottom blow pipe 12. The bottom blow pipe 12 communicates to the graphite melting crucible 7 through the furnace base 2 and worktable 6 and bottom blows the alloy melt 9; a vacuum pump 13 is configured in the bottom right of the furnace base 2 and communicates to the furnace chamber 3 through a vacuum pipe 14; a feed pipe 27, a feed valve 28 and a mechanical agitator 29 are configured on the top of the vacuum medium frequency induction melting furnace 1 and the feed pipe 27 and the mechanical agitator 29 extends to the graphite melt crucible 7 through the furnace top base.
  • A electric cabinet 18 is configured on the right of the vacuum medium frequency induction melting furnace 1 and a display screen 19, an indicator light 20, a power switch 21, a medium frequency induction heating controller 22, a bottom blow motor controller 23 and a vacuum pump controller 24 are configured on the electric cabinet 18; the electric cabinet 18 is connected to the medium frequency induction heater 8 through a first cable 25; The electric cabinet 18 is connected to the bottom blow motor 11 and a vacuum pump 13 through the second cable 26; the furnace cavity 3 is filled with argon 10.
  • As shown in Figure 2, it shows the metallographic structure diagram of Mg-based composite materials, wherein there are no defects such as inclusion and air holes in the metallographic structure diagram and the quascicrystal phase Mg3Zn6Y and boron carbide particles can be evenly distributed in particles.
  • As shown in Figure 3, it shows the fracture topography of Mg-based composite materials, wherein massive small dimples exist in the fracture topography and it demonstrates that it has excellent plasticity.
  • As shown in Figure 4, it shows X-ray diffraction intensity spectrum of Mg-based composite materials. In the figure, the ordinate is diffraction intensity index and the abscissa is the diffraction angle 2ฮธ. It can be seen that mainly ฮฑ-Mg substrate magnesium phase, Mg3Zn6Y quascicrystal phase and B4C reinforced phase exist in Mg-based composite materials.

Claims (2)

  1. A method of preparing a magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite materials, characterized in that, chemical materials used are: Magnesium, zinc, magnesium yittrium interalloy, boron carbide, zinc oxide, talcum powder, water glass which is Na2SiO3ยท9H2O, deionized water, aluminum foil, absolute alcohol, argon, their amounts are: magnesium Mg 4127gยฑ0.1g Zinc Zn 784gยฑ0.1g magnesium yttrium interalloy Mg89Y11 571gยฑ0.1g boron carbide B4C 300gยฑ0.1g zinc oxide ZnO 80gยฑ1g talcum powder Mg3[Si4O10](OH)2 50gยฑ1g water glass Na2SiO3ยท9H2O 25gยฑ1g deionized water H2O 1000mLยฑ50mL aluminum foil Al 300mmร—0.5mmร—300mm absolute alcohol C2H5OH 3500mL ยฑ50mL argon Ar 800000cm3ยฑ100 cm3
    the preparation method comprises:
    (1) preparing the casting mold
    the open-close type squeeze casting mold is manufactured by hot working dies steel with a rectangle cavity, wherein the size of the cavity is 200mmร—160mmร—90mm and the surface roughness of the cavity is Ra 0.08-0.16ยตm;
    (2) preparing the coating agent
    weighing out zinc oxide 80gยฑ1g, talcum powder 50gยฑ1g, water glass 25gยฑ1g, measuring out deionized water 300mLยฑ1mL, adding zinc oxide 80gยฑ1g, talcum powder 50gยฑ1g, water glass 25g+1g and deionized water 300mLยฑ1mL into the mixinghollander and stirring them to obtain the coating agent presenting as viscous liquid, wherein the stirring speed is 50r/min, stirring time is 80min;
    (3) pre-treating the boron carbide particles
    โ‘ ball milling: weighing boron carbide 300gยฑ0.1g, putting it into the ball mill tank of the ball mill and ball milling it to obtain fine powder with a particle size โ‰ค9ยตm, wherein the ball milling speed is 80r/min, the ball milling time is 3h;
    โ‘กultrasonic dispersion washing: putting the fine powder after ball milling into a beaker and then adding absolute alcohol 500mLยฑ1mL, mixing;
    putting the beaker into an ultrasonic disperser and doing the ultrasonic dispersion washing to obtain the mixing liquid, wherein the ultrasonic frequency is 60kHz and the ultrasonic dispersion time is 80min;
    โ‘ขfiltration: putting the mixing liquid into the cloth funnel of the filter bottle, filtering it with a microporous membrane, removing the supernatant, and keeping the filter cake;
    โ‘ฃdrying and oxidation treatment: putting the filter cake into the thermal treatment furnace, conducting the drying and high temperature oxidation treatment, obtaining the boron carbide fine powderafter drying, wherein the drying and oxidation temperature is 500ยฐC and the drying and oxidation time is 2h;
    (4)pre-treating the magnesium, zinc and magnesium yttrium interalloy and the open-close type squeeze casting mold
    โ‘ mechanically cutting the magnesium, zinc and magnesium yttrium interalloy into patches, wherein the size of the patch is โ‰ค30mmร—30mmร—10mm;
    โ‘กwashing the surface of the magnesium, zinc and magnesium yttrium interalloy with absolute alcohol and then putting it into the vacuum drying oven after washing, wherein the drying temperature is 100ยฐC, the vacuum degree is 2 Pa and the drying period is 30min;
    โ‘ขwrapping the boron carbide with aluminum foil, putting it into the vacuum drying ovenand drying, wherein the drying temperature is 100ยฐC, the vacuum degree is 2 Pa and the drying period is 60min;
    pre-heating the open-close type squeeze casting mold and coating the prepared coating agent on the inner surface of the mold cavity, wherein the thickness of the coating agent is 1mm; after the coating is completed, putting the open-close type squeeze casting mold into the heating furnace and preheating, wherein the pre-heating temperature is 150ยฐC and the pre-heating time is 1h;
    (5) smelting of the magnesium alloy
    smelting of the magnesium alloy is conducted in the vacuum medium frequency induction melting furnace and completed by processes of medium frequency induction heating, vacuumizing, bottom blowing argon and mechanical stirring;
    โ‘ opening the vacuum medium frequency induction melting furnace and clearing the internal part of the graphite melting crucible to make the internal part of the crucible clean;
    โ‘กweighing magnesium block 4127gยฑ0.1g, zinc block 784gยฑ0.1g and magnesium yttrium interalloy block 571gยฑ0.1g and putting them in the bottom of the crucible;
    โ‘ขclosing the vacuum medium frequency induction melting furnace and getting it sealed;
    turning on the vacuum pump and extracting the air within to allow the pressure within the furnace to reach 1Pa;
    turning on the heater of the medium frequency induction melting furnace to start the heating, wherein the heating temperature is 610ยฐCยฑ1ยฐC;
    โ‘ฃturning on the argon bottom-blowing device to feed argon into the crucible, wherein the speed of the argon bottom-blowing is 200cm3/min; adjusting the pressure within the furnace to allow the pressure within the furnace to be one bar pressure and it is regulated by the outlet valve;
    โ‘คwhen the temperature of melt is 610ยฐCยฑ1ยฐC, adding boron carbide fine powder with the vacuum feeding device; turning on the mechanical agitator, wherein the stirring speed is 20r/min and the stirring time is 10min;
    โ‘ฅstopping the stirring and continuing the heating; when the temperature of melt reaches 730ยฐCยฑ1ยฐC, turning off the mechanical agitator and the argon bottom blowing pipe, standing for 10 min and prepare for the casting;
    (6) squeeze casting
    โ‘ opening the vacuum medium frequency induction melting furnace, removing the slag on the surface of the melt in the crucible, casting the alloy melt into the cavity of the squeeze casting mold; turning on the squeeze casting machine and squeezing the metal melt by the punch, wherein the squeeze pressure is 250MPa and the hold time is 20s;
    the alloying reaction occurs during the solidification of Mg-Zn-Y quascicrystal and stable quascicrystal Mg3Zn6Y phase can be produced, wherein the reaction formula is Mg + Zn + Mg 89 Y 11 + B 4 C โ†’ 250 MPa 20 s ฮฑ โˆ’ Mg + Mg 3 Zn 6 Y + B 4 C
    Figure imgb0002
    ฮฑ-Mg : substrate magnesium phase
    Mg3Zn6Y : magnesium-zinc-yttrium quasicrystalline phase
    โ‘กejecting the cast and cooling it to 25ยฐC in the air to produce the magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite material blocks;
    (7)thermal treatment of the cast
    โ‘ putting the magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite material blocks into the vacuum heat treatment furnace for thermal treatment, wherein the temperature of the thermal treatment is 420ยฐC, the vacuum degree is 2Pa, and the time of thermal treatment is 15h; and then putting the cast into warm water of 50ยฐC fastly, quenching treatment, wherein the quenching time is 20s;
    โ‘กputting the cast after quenching into the heat treatment furnace for aging treatment at 200ยฐC for 8h; and then stopping the heating and cooling it to 25ยฐC in the heat treatment furnace;
    (8) cleaning, detecting, analyzing and characterizing
    cleaning the surface of the cast to make it clean; detecting, analyzing and characterizing the microstructure and mechanical property;
    analyzing the metallographic structure with an optical microscope;
    conducting the tensile strength and hardness test with universal tensile testing machine and a hardness tester;
    conducting the fracture morphology analysis with a scanning electron microscope;
    conducting XRD analysis with X ray diffractometer;
    conclusion: magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite materials are rectangle blocks, wherein the tensile strength is 315MPa, the elongation is 7%, the hardness reaches 108Hv.
  2. The method of preparing magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced Mg-based composite materials according to claim 1, characterized in that the smelting of Mg-based composite materials are conducted in the vacuum medium frequency induction melting furnace and completed through the process of the medium frequency induction heating, bottom blowing argon and mechanical stirring;
    the vacuum medium frequency induction melting furnace is a vertical one;
    The bottom of the vacuum medium frequency induction melting furnace (1) is nconfigured with a furnace base (2), and inside of the vacuum medium frequency induction melting furnace (1) is a furnace chamber (3); a worktable (6) is configured in the bottom of the furnace chamber (3) and a graphite melting crucible (7) is put on the worktable (6); The outside of the graphite melting crucible (7) is surrounded by the medium frequency induction heater (8) and the inside of the graphite melting crucible (7) is the alloy melt (9); an outlet pipe (4) is configured on the top right of the vacuum medium frequency induction melting furnace (1) and it is controlled by the outlet valve (5); the argon bottle (15) is configured on the top left of the vacuum medium frequency induction melting furnace (1) and an argon pipe (16) and an argon valve (17) are configured on the argon bottle (15). The argon pipe (16) is connected to the bottom blow motor (11). The bottom blow motor (11) is connected to the bottom blow pipe (12). The bottom blow pipe (12) communicates to the graphite melting crucible (7) through the furnace base(2) and worktable (6) and bottom blows the alloy melt (9); a vacuum pump (13) is configured in the bottom right of the furnace base (2) and communicates to the furnace chamber (3) through a vacuum pipe (14); a feed pipe (27), a feed valve (28) and a mechanical agitator (29) are configured on the top of the vacuum medium frequency induction melting furnace (1) and the feed pipe (27) and the mechanical agitator (29) extends to the graphite melt crucible (7) through the furnace top base;
    a electric cabinet (18) is configured on the right of the vacuum medium frequency induction melting furnace (1) and a display screen (19), an indicator light (20), a power switch (21), a medium frequency induction heating controller (22), a bottom blow motor controller (23) and a vacuum pump controller (24) are configured on the electric cabinet (18); the electric cabinet (18) is connected to the medium frequency induction heater (8) through a first cable (25); The electric cabinet (18) is connected to the bottom blow motor (11) and a vacuum pump (13) through the second cable (26); the furnace cavity (3) is filled with argon (10).
EP19153314.0A 2018-04-13 2019-01-23 A method of preparing magnesium-zinc-yttrium quasicrystal and boron carbide mixed reinforced magnesium-based composite material Active EP3553199B1 (en)

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