CN116790932B - Preparation method of rare earth magnesium-based composite material - Google Patents

Preparation method of rare earth magnesium-based composite material Download PDF

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CN116790932B
CN116790932B CN202310751589.8A CN202310751589A CN116790932B CN 116790932 B CN116790932 B CN 116790932B CN 202310751589 A CN202310751589 A CN 202310751589A CN 116790932 B CN116790932 B CN 116790932B
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magnesium
sicp
alloy
composite material
rare earth
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CN116790932A (en
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邓坤坤
曹芳芳
王翠菊
聂凯波
徐超
王晓军
贾昌振
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Taiyuan University of Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/007—Semi-solid pressure die casting
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • 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

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Abstract

A preparation method of rare earth magnesium-based composite material belongs to the technical field of magnesium-based composite material, and aims at the characteristic of narrow semi-solid interval of rare earth magnesium alloy, so as to solve the technical problems of preparing high-strength and high-elastic modulus magnesium alloy composite material, and the solution is as follows: the method is characterized in that Mg-7 Gd-2Y-3 Zn alloy is selected as a matrix, siCp is used as an enhanced phase, a method of semi-solid stirring and liquid ultrasonic auxiliary dilution is adopted to prepare the rare earth magnesium-based composite material, the stirring temperature, the stirring speed and the stirring time are regulated and controlled to obtain the rare earth magnesium-based composite material with uniform SiCp distribution and no obvious agglomeration on the surface of crystal grains, the crystal grains are further refined through an extrusion deformation process on the basis, and the mechanical property of the material is improved. The yield strength of the rare earth magnesium-based composite material prepared by the invention is 340.6MPa, and the tensile strength is 354.4MPa.

Description

Preparation method of rare earth magnesium-based composite material
Technical Field
The invention belongs to the technical field of magnesium-based composite materials, and particularly relates to a preparation method of a rare earth magnesium-based composite material.
Background
The magnesium alloy has the advantages of low density, high specific strength, high specific rigidity and the like, and can be widely applied to industries such as automobiles, aviation, aerospace, 3C and the like. The room temperature tensile strength of the magnesium alloy can reach more than 400MPa, the elastic modulus is 45GPa, obvious strength-elastic modulus mismatch is presented, the magnesium alloy part is obviously elastically deformed in a high-stress service state, the service effect is seriously influenced, and therefore, the development of the magnesium alloy with high elastic modulus has important significance.
The rare earth magnesium alloy has excellent room temperature, high temperature mechanical properties, high elastic modulus and creep resistance, and although the rare earth magnesium alloy has the advantages, the contribution of the addition of rare earth elements to the elastic modulus reaches the bottleneck, and generally, the contribution of the addition of rare earth elements to the elastic modulus does not exceed 50GPa-55GPa. And the addition of a large amount of rare earth elements can lead to high density of the magnesium alloy, which is contrary to the advantage of light weight. The rare earth magnesium alloy compounding is another common method for improving the elastic modulus of magnesium alloy, and the elastic modulus and strength of the alloy can be further improved by adding SiCp enhanced phase to prepare the rare earth magnesium-based composite material, however, as the semi-solid interval of rare earth elements is narrower, the composite material with uniform particle distribution is difficult to obtain by adopting the traditional semi-solid stirring casting method, so that the urgent requirement of technological development on high-modulus high-strength magnesium alloy material is met, and a novel preparation process of the rare earth magnesium-based composite material needs to be developed.
Disclosure of Invention
Aiming at the characteristic of narrow semi-solid interval of the rare earth magnesium alloy, the invention mainly aims at solving the technical problem of preparing the magnesium alloy composite material with high strength and high elastic modulus due to uneven distribution of reinforcing phase particles in the rare earth magnesium composite material caused by the fact that the semi-solid interval is difficult to determine by adopting a traditional semi-solid stirring casting method.
The design concept of the invention is as follows:
on one hand, the method is improved on the basis of traditional semi-solid stirring, and the rare earth magnesium-based composite material with even SiCp dispersion and no obvious agglomeration on the surface is successfully prepared by a method of semi-solid stirring and liquid ultrasonic auxiliary dilution;
on the other hand, the mechanical property of the alloy is improved through the extrusion process, extrusion is an effective deformation mode for improving the structure and the property of the cast magnesium alloy, and because the material is subjected to strong three-dimensional compressive stress during extrusion deformation, the casting defect can be remarkably eliminated, the structure is thinned, and the plastic deformation of a blank is facilitated, so that the extrusion forming process is very important for controlling the structure and the property of the magnesium alloy;
in a word, the preparation method selects Mg-7Gd-2Y-3Zn alloy as a matrix, siCp as a reinforcing body, and the particle size of the SiCp is 10 um.
The invention adopts the technical scheme that the preparation method of the rare earth magnesium-based composite material comprises the following steps:
s1, siCp pretreatment, namely, sequentially carrying out HF pickling, water washing, drying and sieving on SiCp powder, and reserving the SiCp powder for later use;
S2, selecting raw materials, namely weighing magnesium blocks, zinc particles, magnesium gadolinium intermediate alloy and magnesium yttrium intermediate alloy, wherein the components of the raw materials and the mass percentage content of the components are 3wt.% of zinc, 7wt.% of gadolinium, 2wt.% of yttrium and the balance of magnesium;
s3, placing the clean crucible into a smelting furnace for preheating, taking out the crucible after the clean crucible is preheated to 450-550 ℃, and uniformly coating a coating agent on the inner wall of the crucible to prevent impurities such as rust on the inner wall of the crucible from falling off;
s4, heating the smelting furnace to 730-750 ℃, and after the surface of the crucible turns yellow, placing the magnesium block prepared in the step S2 into the crucible, preserving heat of the smelting furnace until the magnesium block is completely melted, and continuously introducing protective gas into the smelting furnace in the process of melting the magnesium block to prepare magnesium liquid;
S5, cooling the smelting furnace to 710-720 ℃, removing an oxide layer on the surface of the magnesium liquid, adding zinc particles prepared in the step S2 into the magnesium liquid, stirring for 0.5-1.5 min, and then preserving heat for 10-20 min;
S6, firstly, placing SiCp powder pretreated in the step S1 into a crucible wrapped by aluminum foil (the crucible is made of stainless steel), preheating in a drying furnace, wherein the preheating temperature is 600-620 ℃, then, when alloy liquid prepared in the step S5 is cooled to a semi-solid state along with the furnace, namely, the temperature of melt is 610-630 ℃, removing an oxide layer on the surface of the alloy liquid, then, placing a stirring paddle in the melt, starting a stirring device for mechanical stirring for 3-5 min, and finally, after the semi-solid alloy melt forms a stable vortex, adding the preheated SiCp into the semi-solid alloy melt, wherein the adding amount of the SiCp powder accounts for 5% of the volume fraction of the total melt, and after stirring for 10-20 min, withdrawing from the stirring paddle;
S7, raising the temperature of the smelting furnace to 680-700 ℃ again, removing an oxide layer on the surface of the semi-solid alloy melt, then placing the magnesium-gadolinium intermediate alloy and the magnesium-yttrium intermediate alloy prepared in the step S2 into the semi-solid alloy melt, and placing the molten solid alloy into a stirring paddle again for mechanical stirring;
S8, firstly, preheating an ultrasonic working rod to 480-500 ℃, continuously heating a smelting furnace to 710-730 ℃ and then withdrawing from a stirring paddle, continuously stirring the stirring paddle in the heating process of the smelting furnace, then, removing an oxide layer on the surface of an alloy liquid, finally, stretching the preheated ultrasonic working rod to a position 20mm below the liquid surface of the alloy liquid, dispersing the ultrasonic working rod for 10-20 min, then, taking out the ultrasonic working rod, and keeping the ultrasonic working rod at a temperature for 5-15 min;
S9, firstly preheating a casting die to 400-500 ℃, then removing an oxide layer on the surface of the alloy liquid after ultrasonic dispersion treatment in the step S8, finally casting the alloy liquid into the preheated casting die, and carrying out die casting by using a press under the pressure of 450KN for 180-240 seconds, taking out an ingot after die casting, and naturally cooling to room temperature to obtain a rare earth magnesium-based composite ingot;
S10, cutting the cast ingot prepared in the step S9 to a certain size into a plurality of extrusion blocks, and then polishing the surfaces of the extrusion blocks cleanly and sealing and storing the extrusion blocks for later use;
And S11, extrusion forming, namely firstly preheating an extrusion die and the extrusion blocks stored in the step S10 to 360 ℃, then placing the extrusion blocks in the extrusion die, and carrying out hot extrusion forming on the extrusion blocks by using a press machine, wherein the extrusion rate is 0.1mm/S, the extrusion temperature is 360 ℃, and the extrusion ratio is 16:1, so as to prepare the rare earth magnesium-based composite material.
Further, in the step S1, siCp pretreatment includes the steps of:
S1-1, repeatedly cleaning SiCp for at least three times by using distilled water, taking out the SiCp after water washing, adding sufficient HF for acid washing, stirring and standing;
S1-2, cleaning SiCp subjected to HF acid washing by distilled water until the cleaning liquid is neutral;
s1-3, spreading SiCp cleaned in the step S1-2 in a baking pan and drying, wherein the drying temperature is 80-100 ℃, and the drying time is not less than 24 hours;
s1-4, dispersing SiCp dried in the step S1-3 in an ultrasonic vibration sieve, sieving with a sieve with the aperture of 20 mu m, sealing and preserving the sieved SiCp, and placing the SiCp in a drying dish for later use.
Further, in the step S2, the purity of the magnesium block is 99.9%, the purity of the zinc particles is 99.9%, the magnesium gadolinium intermediate alloy is Mg-30Gd, the purity of the magnesium gadolinium intermediate alloy is 99.9%, the magnesium yttrium intermediate alloy is Mg-30Y, and the purity of the magnesium yttrium intermediate alloy is 99.9%.
Further, in the step S3, the coating agent consists of talcum powder paint and zinc oxide paint, wherein the talcum powder paint comprises 80g of talcum powder, 20g of water glass and 250ml of water, and the zinc oxide paint comprises 45g of zinc oxide, 45g of water glass and 250ml of water.
Further, in the step S4, the shielding gas is a mixed gas formed by CO 2 and SF 6, and the volume ratio of CO 2 to SF 6 is 99:1.
Further, in the steps S5-S9, a slag ladle is adopted to remove an oxide layer on the surface of the semi-solid alloy melt or alloy liquid, and the surface of the slag ladle is coated with a coating agent.
Compared with the prior art, the invention has the beneficial effects that:
The composite material with SiCp uniformly dispersed and no obvious agglomeration on the surface of crystal grains is prepared by the method of semi-solid stirring and liquid ultrasonic auxiliary dilution, the structure of the composite material is further improved by an extrusion deformation process, the number of recrystallized crystal grains of the magnesium alloy after extrusion is obviously increased, the crystal grain size is fine and uniform, the mechanical property of the composite material is improved, the strength of the composite material is 354.4MPa after extrusion treatment, and the mechanical property of the composite material is improved by 163 percent compared with that of an as-cast composite material.
Drawings
FIG. 1 is a graph of temperature versus time for the preparation of SiCp/Mg-7Gd-2Y-3Zn composite material;
FIG. 2 is a microstructure topography of the as-cast SiCp/Mg-7Gd-2Y-3Zn composite material prepared;
FIG. 3 is a microstructure morphology of the prepared extruded SiCp/Mg-7Gd-2Y-3Zn composite material;
FIG. 4 is a graph comparing stress-strain curves of as-cast and as-extruded SiCp/Mg-7Gd-2Y-3Zn composites.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples.
Example 1
The preparation method of the rare earth magnesium-based composite material shown in fig. 1 comprises the following steps:
s1, siCp pretreatment, wherein the SiCp pretreatment specifically comprises the following steps:
s1-1, repeatedly cleaning SiCp (with the particle size of 10 mu m) for at least three times by using distilled water, taking out the SiCp after water washing, adding sufficient HF for acid washing, stirring and standing;
S1-2, cleaning SiCp subjected to HF acid washing by distilled water until the cleaning liquid is neutral;
s1-3, spreading SiCp cleaned in the step S1-2 in a baking pan and drying, wherein the drying temperature is 80 ℃ and the drying time is 24 hours;
S1-4, dispersing SiCp dried in the step S1-3 in an ultrasonic vibration sieve, sieving with a sieve with the aperture of 20 mu m, sealing and preserving the sieved SiCp, and placing the SiCp in a drying vessel for later use;
s2, selecting raw materials, wherein the purity of magnesium blocks is 99.9%, the purity of zinc particles is 99.9%, the purity of magnesium gadolinium intermediate alloy is Mg-30Gd, the purity of magnesium gadolinium intermediate alloy is 99.9%, the purity of magnesium yttrium intermediate alloy is Mg-30Y, the purity of magnesium yttrium intermediate alloy is 99.9%,
Weighing magnesium blocks, zinc particles, magnesium gadolinium intermediate alloy and magnesium yttrium intermediate alloy, wherein the composition of each element in the raw materials and the mass percentage content thereof are 3wt.% of zinc, 7wt.% of gadolinium and 2wt.% of yttrium, and the balance of magnesium;
S3, placing the clean crucible into a smelting furnace for preheating, taking out the crucible after the clean crucible is preheated to 450 ℃, and uniformly coating a coating agent on the inner wall of the crucible, wherein the coating agent consists of talcum powder paint and zinc oxide paint, the talcum powder paint comprises 80g of talcum powder, 20g of water glass and 250ml of water, and the zinc oxide paint comprises 45g of zinc oxide, 45g of water glass and 250ml of water;
S4, heating a smelting furnace to 730 ℃, after the surface of the crucible is yellowing, placing the magnesium block prepared in the step S2 into the crucible, and preserving heat in the smelting furnace until the magnesium block is completely melted, and continuously introducing a protective gas into the smelting furnace in the process of melting the magnesium block to prepare magnesium liquid, wherein the protective gas consists of CO 2 and SF 6 to form a mixed gas, and the volume ratio of CO 2 to SF 6 is 99:1;
S5, cooling the smelting furnace to 710 ℃, removing an oxide layer on the surface of the magnesium liquid, adding zinc particles prepared in the step S2 into the magnesium liquid, stirring for 0.5min, and then preserving heat for 10min;
s6, firstly, placing SiCp powder pretreated in the step S1 into a crucible wrapped by aluminum foil (the crucible is made of stainless steel), preheating in a drying furnace, cooling the alloy liquid prepared in the step S5 to a semi-solid state along with the furnace, namely, when the temperature of the melt is 610 ℃, putting a stirring paddle into the melt after removing an oxide layer on the surface of the alloy liquid, and starting a stirring device to mechanically stir for 3min;
S7, heating the smelting furnace to 680 ℃ again, removing an oxide layer on the surface of the semi-solid alloy melt, then placing the magnesium-gadolinium intermediate alloy and the magnesium-yttrium intermediate alloy prepared in the step S2 into the semi-solid alloy melt, and placing the molten solid alloy into a stirring paddle again for mechanical stirring;
S8, firstly preheating an ultrasonic working rod to 480 ℃, continuously heating up the smelting furnace to 710 ℃ and then withdrawing the smelting furnace from the stirring paddle, continuously stirring the stirring paddle in the heating up process of the smelting furnace, then removing an oxide layer on the surface of the alloy liquid, finally extending the preheated ultrasonic working rod to a position 20mm below the liquid level of the alloy liquid, taking out the ultrasonic working rod after ultrasonic dispersion for 10min, and preserving heat and standing for 5min;
S9, firstly preheating a casting die to 400 ℃, then removing an oxide layer on the surface of the alloy liquid after ultrasonic dispersion treatment in the step S8, finally casting the alloy liquid into the preheated casting die, and carrying out die casting by using a press, wherein the pressure is 450KN, the dwell time is 180S, taking out the cast ingot after die casting is completed, and naturally cooling the cast ingot to room temperature to obtain a rare earth magnesium-based composite cast ingot, wherein a microstructure morphology diagram of the as-cast SiCp/Mg-7Gd-2Y-3Zn composite is shown in a graph as shown in FIG. 2, particles in the as-cast composite are uniformly dispersed, no obvious agglomeration and oxidation slag inclusion exist, siCp is distributed along the grain boundary in a necklace shape, and a second phase is distributed along the grain boundary in a discontinuous network shape;
S10, cutting the cast ingot prepared in the step S9 to a certain size into a plurality of extrusion blocks, and then polishing the surfaces of the extrusion blocks cleanly and sealing and storing the extrusion blocks for later use;
S11, extrusion forming, namely firstly preheating an extrusion die and an extrusion block stored in the step S10 to 360 ℃, then placing the extrusion block in the extrusion die, carrying out hot extrusion forming on the extrusion block by using a press machine, wherein the extrusion rate is 0.1mm/S, the extrusion temperature is 360 ℃, the extrusion ratio is 16:1, and the rare earth magnesium-based composite material is prepared, and the microstructure morphology graph of the extruded SiCp/Mg-7Gd-2Y-3Zn composite material is shown in FIG. 3, wherein the SiCp and the second phase are distributed along the extrusion direction after extrusion, obvious dynamic recrystallization occurs in a matrix, and the grain size is obviously thinned compared with that of the as-cast composite material.
Further, in the steps S5-S9, a slag ladle is adopted to remove an oxide layer on the surface of the semi-solid alloy melt or alloy liquid, and the surface of the slag ladle is coated with a coating agent.
As can be seen from FIG. 4, the yield strength, tensile strength and elongation of the as-cast composite material are respectively 99.0MPa, 134.5MPa and 0.93%, and the performance of the composite material is obviously improved after extrusion, and the yield strength, tensile strength and elongation are respectively improved to 340.6MPa, 354.4MPa and 1.82%.
Example 2
The preparation method of the rare earth magnesium-based composite material comprises the following steps:
s1, siCp pretreatment, wherein the SiCp pretreatment specifically comprises the following steps:
s1-1, repeatedly cleaning SiCp (with the particle size of 10 mu m) for at least three times by using distilled water, taking out the SiCp after water washing, adding sufficient HF for acid washing, stirring and standing;
S1-2, cleaning SiCp subjected to HF acid washing by distilled water until the cleaning liquid is neutral;
s1-3, spreading SiCp cleaned in the step S1-2 in a baking pan and drying, wherein the drying temperature is 90 ℃, and the drying time is 24 hours;
S1-4, dispersing SiCp dried in the step S1-3 in an ultrasonic vibration sieve, sieving with a sieve with the aperture of 20 mu m, sealing and preserving the sieved SiCp, and placing the SiCp in a drying vessel for later use;
s2, selecting raw materials, wherein the purity of magnesium blocks is 99.9%, the purity of zinc particles is 99.9%, the purity of magnesium gadolinium intermediate alloy is Mg-30Gd, the purity of magnesium gadolinium intermediate alloy is 99.9%, the purity of magnesium yttrium intermediate alloy is Mg-30Y, the purity of magnesium yttrium intermediate alloy is 99.9%,
Weighing magnesium blocks, zinc particles, magnesium gadolinium intermediate alloy and magnesium yttrium intermediate alloy, wherein the composition of each element in the raw materials and the mass percentage content thereof are 3wt.% of zinc, 7wt.% of gadolinium and 2wt.% of yttrium, and the balance of magnesium;
s3, placing the clean crucible into a smelting furnace for preheating, taking out the crucible after the clean crucible is preheated to 500 ℃, and uniformly coating a coating agent on the inner wall of the crucible, wherein the coating agent consists of talcum powder paint and zinc oxide paint, the talcum powder paint comprises 80g of talcum powder, 20g of water glass and 250ml of water, and the zinc oxide paint comprises 45g of zinc oxide, 45g of water glass and 250ml of water;
S4, heating a smelting furnace to 740 ℃, after the surface of the crucible is yellowing, placing the magnesium block prepared in the step S2 into the crucible, and preserving heat in the smelting furnace until the magnesium block is completely melted, and continuously introducing a protective gas into the smelting furnace in the process of melting the magnesium block to prepare magnesium liquid, wherein the protective gas consists of CO 2 and SF 6 to form a mixed gas, and the volume ratio of CO 2 to SF 6 is 99:1;
s5, cooling the smelting furnace to 715 ℃, removing an oxide layer on the surface of the magnesium liquid, adding zinc particles prepared in the step S2 into the magnesium liquid, stirring for 1min, and then preserving heat for 15min;
s6, firstly, placing SiCp powder pretreated in the step S1 into a crucible wrapped by aluminum foil (the crucible is made of stainless steel), preheating in a drying furnace, cooling the alloy liquid prepared in the step S5 to a semi-solid state along with the furnace, namely, when the temperature of the melt is 620 ℃, putting a stirring paddle into the melt after removing an oxide layer on the surface of the alloy liquid, and starting a stirring device to mechanically stir for 4min;
S7, heating the smelting furnace to 690 ℃ again, removing an oxide layer on the surface of the semi-solid alloy melt, then placing the magnesium-gadolinium intermediate alloy and the magnesium-yttrium intermediate alloy prepared in the step S2 into the semi-solid alloy melt, and placing the molten solid alloy into a stirring paddle again for mechanical stirring;
S8, firstly preheating an ultrasonic working rod to 490 ℃, simultaneously continuously heating the smelting furnace to 720 ℃, then withdrawing the smelting furnace from the stirring paddle, continuously stirring the stirring paddle in the heating process of the smelting furnace, then removing an oxide layer on the surface of the alloy liquid, finally extending the preheated ultrasonic working rod to a position 20mm below the liquid level of the alloy liquid, taking out the ultrasonic working rod after ultrasonic dispersion for 15min, and keeping the temperature for 10min;
S9, firstly preheating a casting die to 450 ℃, then removing an oxide layer on the surface of the alloy liquid after ultrasonic dispersion treatment in the step S8, finally casting the alloy liquid into the preheated casting die, and carrying out die casting by using a press, wherein the pressure is 450KN, the dwell time is 210S, and taking out the cast ingot after die casting is completed, and naturally cooling to room temperature to obtain a rare earth magnesium-based composite cast ingot, wherein in the step S5-S9, a slag ladle is adopted to remove the oxide layer on the surface of the semi-solid alloy melt or the alloy liquid, and the surface of the slag ladle is coated with a coating agent;
S10, cutting the cast ingot prepared in the step S9 to a certain size into a plurality of extrusion blocks, and then polishing the surfaces of the extrusion blocks cleanly and sealing and storing the extrusion blocks for later use;
And S11, extrusion forming, namely firstly preheating an extrusion die and the extrusion blocks stored in the step S10 to 360 ℃, then placing the extrusion blocks in the extrusion die, and carrying out hot extrusion forming on the extrusion blocks by using a press machine, wherein the extrusion rate is 0.1mm/S, the extrusion temperature is 360 ℃, and the extrusion ratio is 16:1, so as to prepare the rare earth magnesium-based composite material.
Example 3
The preparation method of the rare earth magnesium-based composite material comprises the following steps:
s1, siCp pretreatment, wherein the SiCp pretreatment specifically comprises the following steps:
s1-1, repeatedly cleaning SiCp (with the particle size of 10 mu m) for at least three times by using distilled water, taking out the SiCp after water washing, adding sufficient HF for acid washing, stirring and standing;
S1-2, cleaning SiCp subjected to HF acid washing by distilled water until the cleaning liquid is neutral;
S1-3, spreading SiCp cleaned in the step S1-2 in a baking pan and drying, wherein the drying temperature is 100 ℃, and the drying time is 24 hours;
S1-4, dispersing SiCp dried in the step S1-3 in an ultrasonic vibration sieve, sieving with a sieve with the aperture of 20 mu m, sealing and preserving the sieved SiCp, and placing the SiCp in a drying vessel for later use;
s2, selecting raw materials, wherein the purity of magnesium blocks is 99.9%, the purity of zinc particles is 99.9%, the purity of magnesium gadolinium intermediate alloy is Mg-30Gd, the purity of magnesium gadolinium intermediate alloy is 99.9%, the purity of magnesium yttrium intermediate alloy is Mg-30Y, the purity of magnesium yttrium intermediate alloy is 99.9%,
Weighing magnesium blocks, zinc particles, magnesium gadolinium intermediate alloy and magnesium yttrium intermediate alloy, wherein the composition of each element in the raw materials and the mass percentage content thereof are 3wt.% of zinc, 7wt.% of gadolinium and 2wt.% of yttrium, and the balance of magnesium;
S3, placing the clean crucible into a smelting furnace for preheating, taking out the crucible after the clean crucible is preheated to 550 ℃, and uniformly coating a coating agent on the inner wall of the crucible, wherein the coating agent consists of talcum powder paint and zinc oxide paint, the talcum powder paint comprises 80g of talcum powder, 20g of water glass and 250ml of water, and the zinc oxide paint comprises 45g of zinc oxide, 45g of water glass and 250ml of water;
S4, heating a smelting furnace to 750 ℃, after the surface of a crucible is yellowing, placing the magnesium block prepared in the step S2 into the crucible, and preserving heat in the smelting furnace until the magnesium block is completely melted, and continuously introducing a protective gas into the smelting furnace in the process of melting the magnesium block to prepare magnesium liquid, wherein the protective gas consists of CO 2 and SF 6 to form a mixed gas, and the volume ratio of CO 2 to SF 6 is 99:1;
S5, cooling the smelting furnace to 720 ℃, removing an oxide layer on the surface of the magnesium liquid, adding zinc particles prepared in the step S2 into the magnesium liquid, stirring for 1.5min, and then preserving heat for 20min;
S6, firstly, placing SiCp powder pretreated in the step S1 into a crucible wrapped by aluminum foil (the crucible is made of stainless steel), preheating in a drying furnace, cooling the alloy liquid prepared in the step S5 to a semi-solid state along with the furnace, namely, when the temperature of the melt is 630 ℃, putting a stirring paddle into the melt after removing an oxide layer on the surface of the alloy liquid, and starting a stirring device to mechanically stir for 5min;
s7, raising the temperature of the smelting furnace to 700 ℃ again, removing an oxide layer on the surface of the semi-solid alloy melt, then placing the magnesium-gadolinium intermediate alloy and the magnesium-yttrium intermediate alloy prepared in the step S2 into the semi-solid alloy melt, and placing the molten solid alloy into a stirring paddle again for mechanical stirring;
S8, firstly preheating an ultrasonic working rod to 500 ℃, simultaneously continuously heating up the smelting furnace to 730 ℃, then withdrawing the smelting furnace from the stirring paddle, continuously stirring the stirring paddle in the heating up process of the smelting furnace, then removing an oxide layer on the surface of the alloy liquid, finally extending the preheated ultrasonic working rod to a position 20mm below the liquid level of the alloy liquid, taking out the ultrasonic working rod after ultrasonic dispersion for 20min, and preserving heat and standing for 15min;
S9, firstly preheating a casting mould to 500 ℃, then removing an oxide layer on the surface of the alloy liquid after ultrasonic dispersion treatment in the step S8, finally casting the alloy liquid into the preheated casting mould, and carrying out die casting by using a press under the pressure of 450KN for 240S, taking out the cast ingot after die casting is completed, and naturally cooling to room temperature to obtain a rare earth magnesium-based composite cast ingot, wherein in the step S5-S9, a slag ladle is adopted to remove the oxide layer on the surface of the semi-solid alloy melt or the alloy liquid, and the surface of the slag ladle is coated with a coating agent;
S10, cutting the cast ingot prepared in the step S9 to a certain size into a plurality of extrusion blocks, and then polishing the surfaces of the extrusion blocks cleanly and sealing and storing the extrusion blocks for later use;
And S11, extrusion forming, namely firstly preheating an extrusion die and the extrusion blocks stored in the step S10 to 360 ℃, then placing the extrusion blocks in the extrusion die, and carrying out hot extrusion forming on the extrusion blocks by using a press machine, wherein the extrusion rate is 0.1mm/S, the extrusion temperature is 360 ℃, and the extrusion ratio is 16:1, so as to prepare the rare earth magnesium-based composite material.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (6)

1.一种稀土镁基复合材料的制备方法，其特征在于，包括以下步骤：1. A method for preparing a rare earth magnesium-based composite material, characterized in that it comprises the following steps: S1、SiCp预处理：SiCp粉末依次经HF酸洗、水洗、烘干以及过筛，留待后步使用；S1. SiCp pretreatment: SiCp powder is successively HF pickled, water washed, dried and sieved for later use; S2、原料选取：称取镁块、锌粒、镁钆中间合金和镁钇中间合金，使原料中各元素的组成及其质量百分比含量为：锌：3wt.%，钆：7wt.%，钇：2wt.%，其余为镁；称取的块状原料经打磨去除表面的氧化皮，并用保鲜膜包裹，留待后步使用；S2. Raw material selection: weigh magnesium blocks, zinc particles, magnesium-gadolinium master alloys and magnesium-yttrium master alloys, so that the composition and mass percentage of each element in the raw materials are: zinc: 3wt.%, gadolinium: 7wt.%, yttrium: 2wt.%, and the rest is magnesium; the weighed block raw materials are polished to remove the oxide scale on the surface, and wrapped with plastic wrap for use in the next step; S3、将洁净的坩埚放入熔炼炉中预热，待洁净的坩埚预热至450℃~550℃后取出，向坩埚的内壁上均匀地涂刷涂覆剂；S3, putting the clean crucible into the melting furnace for preheating, taking out the clean crucible after it is preheated to 450°C~550°C, and evenly applying the coating agent on the inner wall of the crucible; S4、将熔炼炉升温至730℃~750℃，待坩埚的表面泛黄后，将步骤S2准备的镁块放入坩埚中，熔炼炉保温直至镁块完全熔化，镁块熔化过程中熔炼炉内持续通入保护气，制得镁液；S4, heating the smelting furnace to 730°C-750°C, and after the surface of the crucible turns yellow, placing the magnesium block prepared in step S2 into the crucible, and keeping the smelting furnace warm until the magnesium block is completely melted, and continuously introducing protective gas into the smelting furnace during the melting process of the magnesium block to obtain magnesium liquid; S5、熔炼炉降温至710℃~720℃，扒除镁液表面的氧化层，将步骤S2准备的锌粒加入镁液中并搅拌0.5min~1.5min，然后保温10min~20min；S5, the smelting furnace is cooled to 710°C-720°C, the oxide layer on the surface of the magnesium liquid is removed, the zinc particles prepared in step S2 are added to the magnesium liquid and stirred for 0.5min-1.5min, and then kept warm for 10min-20min; S6、首先，将步骤S1预处理后的SiCp粉末放入铝箔包裹的坩埚中，并放入烘干炉中预热，预热温度为600℃~620℃；然后，待步骤S5制得的合金液随炉冷却至半固态状态时，即熔体的温度为610℃~630℃时，扒除合金液表面的氧化层后在熔体中置入搅拌桨，启动搅拌装置进行机械搅拌，搅拌时间为3min~5min；最后，待半固态合金熔体形成稳定的涡流后，将预热后的SiCp加入半固态合金熔体中，SiCp粉末的添加量占总熔体的体积分数为5%，搅拌10min~20min后撤离搅拌桨；S6. First, put the SiCp powder pretreated in step S1 into a crucible wrapped in aluminum foil, and put it into a drying furnace for preheating at a temperature of 600°C to 620°C; then, when the alloy liquid obtained in step S5 is cooled to a semi-solid state with the furnace, that is, when the temperature of the melt is 610°C to 630°C, remove the oxide layer on the surface of the alloy liquid, place a stirring paddle in the melt, start the stirring device for mechanical stirring, and the stirring time is 3min to 5min; finally, after the semi-solid alloy melt forms a stable vortex, add the preheated SiCp into the semi-solid alloy melt, the added amount of SiCp powder accounts for 5% of the volume fraction of the total melt, stir for 10min to 20min, and then withdraw the stirring paddle; S7、熔炼炉再次升温至680℃~700℃，扒除半固态合金熔体表面的氧化层，然后将步骤S2准备的镁钆中间合金和镁钇中间合金放入半固态合金熔体中，待固体合金熔化后再次置入搅拌桨进行机械搅拌；S7, the melting furnace is heated up to 680°C-700°C again, the oxide layer on the surface of the semi-solid alloy melt is removed, and then the magnesium-gadolinium master alloy and the magnesium-yttrium master alloy prepared in step S2 are placed into the semi-solid alloy melt, and after the solid alloy is melted, a stirring paddle is placed again for mechanical stirring; S8、首先，将超声波工作杆预热到480℃~500℃，与此同时熔炼炉继续升温至710℃~730℃后撤离搅拌桨，熔炼炉升温过程中搅拌桨持续搅拌；然后，扒除合金液表面的氧化层；最后，将预热后的超声波工作杆伸入合金液液面下20mm处，超声波分散10min~20min后取出超声波工作杆，保温静置5min~15min；S8. First, preheat the ultrasonic working rod to 480℃~500℃. At the same time, the melting furnace continues to heat up to 710℃~730℃ and then remove the stirring paddle. The stirring paddle continues to stir during the heating process of the melting furnace. Then, remove the oxide layer on the surface of the alloy liquid. Finally, extend the preheated ultrasonic working rod to 20mm below the alloy liquid surface. After ultrasonic dispersion for 10min~20min, take out the ultrasonic working rod and keep it warm for 5min~15min. S9、首先，将浇铸模具预热至400℃~500℃；然后，扒除步骤S8超声波分散处理后合金液表面的氧化层；最后，将合金液浇铸至预热后的浇铸模具中，并用压力机进行压铸，压力为450KN，保压时间为180s~240s，压铸完成后取出铸锭自然冷却至室温，制得稀土镁基复合材料铸锭；S9, first, preheat the casting mold to 400°C~500°C; then, remove the oxide layer on the surface of the alloy liquid after the ultrasonic dispersion treatment in step S8; finally, cast the alloy liquid into the preheated casting mold, and use a press to perform die casting, the pressure is 450KN, the pressure holding time is 180s~240s, after the die casting is completed, take out the ingot and naturally cool it to room temperature to obtain a rare earth magnesium-based composite material ingot; S10、将步骤S9制得的铸锭定尺切分成若干挤压块，然后将挤压块表面打磨干净并密封保存，留待后步使用；S10, cutting the ingot obtained in step S9 into a plurality of extruded blocks, then polishing the surface of the extruded blocks and sealing and preserving them for use in the next step; S11、挤压成形：首先，将挤压模具以及步骤S10保存的挤压块分别预热至360℃；然后，将挤压块放置于挤压模具中，使用压力机对挤压块进行热挤压成形，挤出速率为0.1mm/s，挤出温度为360℃，挤压比为16:1，制得稀土镁基复合材料。S11, extrusion forming: first, preheat the extrusion die and the extrusion block saved in step S10 to 360°C respectively; then, place the extrusion block in the extrusion die, and use a press to hot extrude the extrusion block, with an extrusion rate of 0.1 mm/s, an extrusion temperature of 360°C, and an extrusion ratio of 16:1 to obtain a rare earth magnesium-based composite material. 2.根据权利要求1所述的一种稀土镁基复合材料的制备方法，其特征在于：在所述步骤S1中，SiCp预处理包括以下步骤：2. The method for preparing a rare earth magnesium-based composite material according to claim 1, characterized in that: in the step S1, the SiCp pretreatment comprises the following steps: S1-1、采用蒸馏水反复清洗SiCp至少三次，取出水洗后的SiCp并加入足量HF进行酸洗，搅拌后静置；S1-1. Wash SiCp repeatedly with distilled water for at least three times, take out the washed SiCp and add sufficient HF for acid washing, stir and let stand; S1-2、用蒸馏水清洗HF酸洗后的SiCp，直至清洗液呈中性；S1-2, clean the SiCp after HF pickling with distilled water until the cleaning solution becomes neutral; S1-3、将步骤S1-2清洗后的SiCp平铺在烘盘中并烘干，烘干温度为80℃-100℃，烘干时间为24h；S1-3, spreading the SiCp cleaned in step S1-2 on a baking tray and drying it at a temperature of 80°C-100°C for 24 hours; S1-4、将步骤S1-3烘干后的SiCp在超声波振动筛中分散后过孔径为20μm的筛网，将过筛后的SiCp密封保存，置于干燥皿中留待后步使用。S1-4, the SiCp dried in step S1-3 is dispersed in an ultrasonic vibration screen and passed through a sieve with a pore size of 20 μm. The sieved SiCp is sealed and stored in a drying dish for use in the next step. 3.根据权利要求1所述的一种稀土镁基复合材料的制备方法，其特征在于：在所述步骤S2中，所述镁块的纯度为99.9%，锌粒的纯度为99.9%；所述镁钆中间合金为Mg-30Gd，镁钆中间合金的纯度为99.9%；所述镁钇中间合金为Mg-30Y，镁钇中间合金的纯度为99.9%。3. The method for preparing a rare earth magnesium-based composite material according to claim 1, characterized in that: in the step S2, the purity of the magnesium block is 99.9%, the purity of the zinc particles is 99.9%; the magnesium-gadolinium master alloy is Mg-30Gd, and the purity of the magnesium-gadolinium master alloy is 99.9%; the magnesium-yttrium master alloy is Mg-30Y, and the purity of the magnesium-yttrium master alloy is 99.9%. 4.根据权利要求1所述的一种稀土镁基复合材料的制备方法，其特征在于：在所述步骤S3中，所述涂覆剂由滑石粉涂料和氧化锌涂料组成，所述滑石粉涂料的配比为：滑石粉80g、水玻璃20g和水250ml；所述氧化锌涂料的配比为：氧化锌45g、水玻璃45g和水250ml。4. The method for preparing a rare earth magnesium-based composite material according to claim 1, characterized in that: in the step S3, the coating agent is composed of a talcum powder coating and a zinc oxide coating, and the ratio of the talcum powder coating is: 80g of talcum powder, 20g of water glass and 250ml of water; the ratio of the zinc oxide coating is: 45g of zinc oxide, 45g of water glass and 250ml of water. 5.根据权利要求1所述的一种稀土镁基复合材料的制备方法，其特征在于：在所述步骤S4中，所述保护气由CO2和SF6组成混合气体，CO2和SF6的体积比为99:1。5. The method for preparing a rare earth magnesium-based composite material according to claim 1, characterized in that: in the step S4, the protective gas is a mixed gas consisting of CO 2 and SF 6 , and the volume ratio of CO 2 to SF 6 is 99:1. 6.根据权利要求1所述的一种稀土镁基复合材料的制备方法，其特征在于：在所述步骤S5-S9中，采用扒渣勺扒除半固态合金熔体或者合金液表面的氧化层，所述扒渣勺表面涂覆涂覆剂。6. The method for preparing a rare earth magnesium-based composite material according to claim 1, characterized in that: in the steps S5-S9, a slag scoop is used to scrape off the oxide layer on the surface of the semi-solid alloy melt or alloy liquid, and the surface of the slag scoop is coated with a coating agent.
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