CN114318093A - Low-cost high-strength high-modulus cast magnesium alloy and preparation method thereof - Google Patents
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Abstract
The invention belongs to the field of metal material magnesium alloy, and discloses a low-cost high-strength high-modulus cast magnesium alloy and a preparation method thereof. The cast magnesium alloy comprises, based on the total weight of the cast magnesium alloy: 3.0-10.0% of Zn, 2-10.0% of Li, 1-6.0% of Al, 0.01-3.0% of Mn, 0.01-1.0% of Cu, 0.005% of impurity element Fe, 0.002% of impurity element Ni and the balance of Mg. According to the invention, rare earth elements such as Zn, Li, Al, Cu, Mn and the like are not contained, a new design method of a bi-component high-modulus-nano-phase reinforced high-strength high-modulus magnesium alloy is utilized, the alloy modulus is improved through micron-sized primary high-modulus secondary phase precipitation of the alloy, and the strength and toughness of the alloy are ensured by regulating and controlling a nano-sized secondary precipitation reinforced phase through a subsequent heat treatment process, so that the synergistic control of low cost, high modulus and high toughness is achieved.
Description
Technical Field
The invention belongs to the field of metal material magnesium alloy, and particularly relates to a low-cost high-strength high-modulus cast magnesium alloy and a preparation method thereof.
Background
The elastic modulus of the magnesium alloy is about 40GPa generally, and the magnesium alloy is easy to deform under stress to cause equipment function failure in a complex service environment, so that the development of the high-modulus magnesium alloy has important significance for light-weight application of the magnesium alloy in a bearing structural member. In recent years, the research on the high modulus magnesium alloy is receiving increasing attention, and the focus of the research is to ensure the toughness of the magnesium alloy and simultaneously improve the modulus of the magnesium alloy. Researches show that the enhancement of precipitated phases or composite phases with high elastic modulus is beneficial to improving the modulus of the magnesium alloy, so the key point for developing the high-modulus magnesium alloy lies in selecting the precipitated phases with high modulus and good compatibility with a matrix, and the precipitated phases are uniformly dispersed and distributed by fine control of a preparation process.
At present, the research on high modulus magnesium alloys mostly focuses on rare earth magnesium alloys, and high modulus second phase particles are generated to improve the alloy modulus by further adding elements such as Si and Li in the high-strength rare earth magnesium alloys. Among them, some researchers focused on the mechanism of magnesium alloy modulus, such as: and calculating the influence of LPSO (Long period of time) on the elastic modulus of the magnesium alloy by a first-property principle and an Eshelby micromechanics model. Some researchers are dedicated to developing high-strength high-modulus magnesium alloys, and have obtained certain research results at present, mainly focusing on the research and development of high-modulus rare earth magnesium alloys. However, the main problems of the current rare earth high modulus magnesium alloy are as follows: on one hand, the cost is high, on the other hand, the second phase of the rare earth with high melting point is easy to precipitate, the segregation is serious, and the precise control of the components of the alloy elements is difficult.
Disclosure of Invention
The invention aims to solve the problems of high cost and difficult component control of the conventional high-modulus rare earth magnesium alloy, and provides a low-cost high-strength high-modulus cast magnesium alloy and a preparation method thereof. The design idea of the invention is as follows: li and Cu elements are added into the rare earth-free low-cost Mg-Zn-Al-Mn alloy, a microstructure with double configuration (high modulus Li-containing phase-nano phase) characteristics is formed in the alloy, the modulus of the alloy is improved by precipitation of a micron-sized primary high modulus Li-containing second phase, and the strength and toughness of the alloy are ensured by regulating and controlling a nanoscale secondary precipitation strengthening phase through a subsequent heat treatment process, so that the alloy has higher modulus and higher room temperature toughness.
According to the invention, Zn is adopted as a first component, as the addition of Zn precipitates MgZn strengthening phase in a magnesium matrix, and the MgZn strengthening phase is precipitated in a nanometer scale through the composite addition of 0.01-1.0% of Cu element, so that the strength and toughness of the alloy are ensured, the content of Zn cannot be too low, and meanwhile, the addition of Zn cannot be too high in order to ensure the casting performance, so that the addition amount of Zn is selected to be 3.0-10.0%;
according to the invention, Li is used as a second component, and Li-containing high-modulus primary precipitated phases such as AlLi, MgZnLi, beta-Li and the like are precipitated in a matrix through the composite addition of Zn and Al elements, so that the elastic modulus of the alloy is improved; the Al element of the invention forms a high modulus second phase with Li, and simultaneously improves the casting performance of the alloy, while the Mn element has the functions of grain refinement and corrosion resistance improvement.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a low-cost, high-strength and high-modulus cast magnesium alloy, comprising: 3.0-10.0% of Zn, 2-10.0% of Li, 1-6.0% of Al, 0.01-3.0% of Mn, 0.01-1.0% of Cu, 0.005% of impurity element Fe, 0.002% of impurity element Ni and the balance of Mg.
According to the present invention, preferably, the cast magnesium alloy includes, based on the total weight of the cast magnesium alloy: 6.0-9.0% of Zn, 3-8.0% of Li, 1-5.0% of Al, 0.5-2.0% of Mn, 0.005% of impurity element Fe, 0.002% of impurity element Ni and the balance of Mg.
The invention also provides a preparation method of the low-cost high-strength high-modulus cast magnesium alloy, which comprises the following steps: mixing the baked pure Mg, Mg-Li intermediate alloy, Mg-Mn intermediate alloy, pure Zn, pure Al and pure Cu, and carrying out vacuum melting treatment to obtain an alloy ingot; and sequentially carrying out solid solution treatment, quenching treatment and aging treatment on the alloy ingot to obtain the low-cost high-strength high-modulus cast magnesium alloy.
According to the invention, preferably, the Mg content in the pure Mg is > 99.99%; the Zn content in the pure Zn is more than 99.99 percent; the Al content in the pure Al is more than 99.99 percent; the Cu content in the pure Cu is more than 99.99 percent; the Mg-Li intermediate alloy is Mg-18-22% of Li; the Mg-Mn intermediate alloy is Mg-8-12% of Mn.
According to the present invention, preferably, the vacuum melting process comprises:
(1) placing baked pure Mg, Mg-Li intermediate alloy, Mg-Mn intermediate alloy, pure Zn, pure Al and pure Cu into a crucible of a vacuum induction melting furnace, closing the furnace, vacuumizing until the vacuum degree in the furnace is less than 1Pa, filling high-purity argon into the furnace to 0.3-0.5 atmospheric pressure, vacuumizing again until the vacuum degree in the furnace is less than 1Pa, and filling high-purity argon into the furnace to 0.3-0.5 atmospheric pressure;
(2) opening a heating power supply of the vacuum induction smelting furnace, and carrying out induction smelting until the baked pure Mg, Mg-Li intermediate alloy, Mg-Mn intermediate alloy, pure Zn, pure Al and pure Cu are completely cleaned;
(3) heating to a refining temperature, and carrying out refining treatment; and after the refining treatment is finished, pouring to obtain the alloy ingot.
According to the invention, the temperature of the baking treatment is preferably 120-160 ℃, and the time is preferably 1.5-2.5 h.
According to the present invention, preferably, the crucible of the vacuum induction melting furnace is selected from a graphite crucible, a metal crucible, or a calcium oxide crucible.
According to the invention, the temperature of the refining treatment is preferably 730-780 ℃ and the time is preferably 5-20 min.
According to the invention, the melt casting is preferably carried out at 680 to 720 ℃.
According to the invention, the cross section diameter of the alloy ingot is preferably 90-110 mm.
According to the invention, the temperature of the solution treatment is preferably 350-450 ℃ and the time is 16-60 h.
According to the present invention, preferably, the quenching process includes: and putting the alloy ingot subjected to the solution treatment into hot water at the temperature of 50-80 ℃ for quenching to room temperature.
According to the invention, preferably, the ageing treatment comprises: and pre-aging the alloy ingot subjected to quenching treatment at 60-100 ℃ for 6-24 h, then continuing to heat to 175-220 ℃ for aging for 5-30 h, and air-cooling to 18-30 ℃.
The technical scheme of the invention has the following beneficial effects:
(1) according to the invention, multiple alloying elements are introduced into the low-cost rare earth-free magnesium alloy to generate a new precipitated phase with high modulus, which is used as the most fundamental and most effective way for improving the modulus of the alloy, namely Li is used as a second component, and Li-containing high-modulus primary precipitated phases such as AlLi, MgZnLi, beta-Li and the like are precipitated in a matrix through the composite addition of Zn and Al elements, so that the elastic modulus of the alloy is improved; meanwhile, through solid solution strengthening of Zn, Al, Li, Mn and other elements in the matrix, the lattice constant is obviously reduced, and the elastic modulus of the alloy can also be improved. The elastic modulus of the alloy is improved to be more than 55GPa through the composite action of the two aspects.
(2) The invention adopts Zn as a first component, MgZn strengthening phase is precipitated in a magnesium matrix by adding Zn, the MgZn strengthening phase is precipitated in a nanometer scale by composite addition of 0.01-1.0% of Cu element, and the density, size and orientation of the nanometer precipitating phase are regulated and controlled by strengthening heat treatment, so that the strength and toughness of the alloy are ensured, the tensile strength of the alloy is more than 300MPa, and the elongation is more than 5%.
(3) According to the invention, rare earth elements such as Zn, Li, Al, Cu, Mn and the like are not contained, a new design method of a bi-component high-modulus-nano-phase reinforced high-strength high-modulus magnesium alloy is utilized, the alloy modulus is improved through micron-sized primary high-modulus secondary phase precipitation of the alloy, and the strength and toughness of the alloy are ensured by regulating and controlling a nano-sized secondary precipitation reinforced phase through a subsequent heat treatment process, so that the synergistic control of low cost, high modulus and high toughness is achieved. The low-cost high-strength high-modulus cast magnesium alloy provided by the invention does not contain precious rare earth elements, is low in alloy cost, and has the advantages of low density and accurate component control due to the fact that the alloy does not contain rare earth elements, and has a good application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
FIG. 1 shows a microscopic schematic diagram of a micron-sized high-modulus Li-containing phase in a low-cost high-strength high-modulus cast magnesium alloy Mg-8Zn-7Li-2Al-0.5Cu-0.5Mn provided by example 1 of the invention.
FIG. 2 shows a microscopic view of the nanoscale precipitated phase in the low-cost high-strength high-modulus cast magnesium alloy Mg-8Zn-7Li-2Al-0.5Cu-0.5Mn provided by example 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In each of the following examples and comparative examples, the Mg content in the pure Mg was > 99.99%; the Zn content in the pure Zn is more than 99.99 percent; the Al content in the pure Al is more than 99.99 percent; the Cu content in the pure Cu is more than 99.99%.
Example 1
The present embodiment provides a low-cost, high-strength, high-modulus cast magnesium alloy, comprising, based on the total weight of the cast magnesium alloy: 8.0% of Zn, 7.0% of Li, 2.0% of Al, 0.5% of Mn, 0.5% of Cu, 0.001% of impurity element Fe, 0.0005% of impurity element Ni and the balance of Mg, namely the cast magnesium alloy is Mg-8Zn-7Li-2Al-0.5Cu-0.5Mn alloy.
The preparation method of the Mg-8Zn-7Li-2Al-0.5Cu-0.5Mn alloy comprises the following steps:
s1: baking pure Mg, Mg-20% Li intermediate alloy, Mg-10% Mn intermediate alloy, pure Zn, pure Al and pure Cu at 150 ℃ for 2 h;
s2: putting baked pure Mg, Mg-20% Li intermediate alloy, Mg-10% Mn intermediate alloy, pure Zn, pure Al and pure Cu into a crucible of a vacuum induction smelting furnace, putting the crucible of the vacuum induction smelting furnace into the vacuum induction smelting furnace, closing the furnace, vacuumizing until the vacuum degree in the furnace is less than 1Pa, filling high-purity argon into the furnace to 0.4 atmosphere, vacuumizing again until the vacuum degree in the furnace is less than 1Pa, and filling the high-purity argon into the furnace to 0.4 atmosphere;
s3: opening a heating power supply of the vacuum induction smelting furnace, and carrying out induction smelting until the baked pure Mg, Mg-20% Li intermediate alloy, Mg-10% Mn intermediate alloy, pure Zn, pure Al and pure Cu are completely cleaned;
s4: heating to 740 ℃ for refining for 10 min; and after the refining treatment is finished, pouring the alloy into a metal mold with the diameter of 100mm at 700 ℃ to obtain an alloy ingot.
S5: carrying out solution treatment on the alloy cast ingot at 380 ℃ for 48h, and quenching the alloy cast ingot in hot water at 80 ℃ to room temperature; and then, pre-aging for 24 hours at 75 ℃, continuing heating to 175 ℃ for aging for 8 hours, and air-cooling to room temperature to obtain the Mg-8Zn-7Li-2Al-0.5Cu-0.5Mn alloy, as shown in figures 1 and 2.
Wherein:
FIG. 1 is a microscopic schematic view of a micron-sized high modulus Li-containing phase contained in the Mg-8Zn-7Li-2Al-0.5Cu-0.5Mn alloy;
FIG. 2 is a microscopic view of the nanoscale precipitated phase contained in the Mg-8Zn-7Li-2Al-0.5Cu-0.5Mn alloy.
As can be seen from FIGS. 1 and 2, the Mg-8Zn-7Li-2Al-0.5Cu-0.5Mn alloy of the present embodiment has a dual-configuration structure, i.e., includes both a high-modulus Li-containing phase and a nanoscale precipitate phase.
Example 2
The present embodiment provides a low-cost, high-strength and high-modulus cast magnesium alloy, and the difference between the present embodiment and embodiment 1 is: the cast magnesium alloy of the present embodiment does not include Cu, and includes, based on the total weight of the cast magnesium alloy: 8.0% Zn, 7.0% Li, 2.0% Al, 0.5% Mn, 0.0009% impurity element Fe, 0.0004% impurity element Ni, and the balance Mg.
Example 3
The present embodiment provides a low-cost, high-strength, high-modulus cast magnesium alloy, comprising, based on the total weight of the cast magnesium alloy: 7.0% of Zn, 8.0% of Li, 4.0% of Al, 0.5% of Mn, 0.0008% of impurity element Fe, 0.0006% of impurity element Ni and the balance of Mg, namely the cast magnesium alloy is Mg-7Zn-8Li-4Al-0.5Mn alloy.
The above Mg-7Zn-8Li-4Al-0.5Mn alloy was prepared by the method described in example 1, except that:
s4: heating to the refining temperature of 750 ℃ for refining for 12 min; after the refining treatment is completed, the alloy ingot is poured into a metal mold with the diameter of 100mm at the temperature of 710 ℃ to obtain an alloy ingot.
S5: carrying out solution treatment on the alloy cast ingot at 360 ℃ for 48h, and quenching the alloy cast ingot in hot water at 90 ℃ to room temperature; and then, pre-aging for 4 hours at 75 ℃, continuing to heat to 175 ℃ for aging for 24 hours, and air-cooling to room temperature to obtain the Mg-7Zn-8Li-4Al-0.5Mn alloy.
Comparative example 1
The comparative example provides a low-cost high-strength high-modulus cast magnesium alloy, and is different from the example 1 in that: the cast magnesium alloy of the present embodiment does not include Li, and includes, based on the total weight of the cast magnesium alloy: 8.0% of Zn, 2.0% of Al, 0.5% of Mn, 0.5% of Cu, 0.0014% of impurity element Fe, 0.0005% of impurity element Ni and the balance of Mg.
Test example
This test example the cast magnesium alloys of examples 1 to 3 and comparative example 1 were subjected to room temperature tensile property tests, and the results of tensile strength, elongation and elastic modulus of the cast magnesium alloys of examples 1 to 3 and comparative example 1 are shown in table 1.
Wherein the room-temperature tensile property of the alloy is determined according to GB/T228.1-2010 metallic material tensile experiment part 1: room temperature test method, INSTRON 55822 electronic Universal testing machine was used for the tests.
The elastic modulus of the alloy is measured by an RFDA-HTVP1750-C modulus instrument according to the GBT 22315-.
TABLE 1
From the comparison of the data of example 2 and example 1 in table 1, it is understood that example 2 lacks the accelerating effect of Cu on the precipitation of the nano-sized precipitate phase, and the tensile strength and elongation of the alloy are both significantly reduced, but the modulus is slightly increased.
As can be seen from the comparison between the data of comparative example 1 and example 1 in table 1, the elastic modulus of the alloy is greatly reduced, but the tensile strength and elongation are obviously improved in comparative example 1 without strengthening the micron-sized high-modulus Li-containing phase.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A low cost, high strength, high modulus cast magnesium alloy, comprising, based on the total weight of the cast magnesium alloy: 3.0-10.0% of Zn, 2-10.0% of Li, 1-6.0% of Al, 0.01-3.0% of Mn, 0.01-1.0% of Cu, 0.002% of impurity element Fe, 0.001% of impurity element Ni and the balance of Mg.
2. The low cost, high strength and high modulus cast magnesium alloy of claim 1, wherein the cast magnesium alloy comprises, based on the total weight of the cast magnesium alloy: 6.0-9.0% of Zn, 3-8.0% of Li, 1-5.0% of Al, 0.5-2.0% of Mn, 0.001% of impurity element Fe, 0.0008% of impurity element Ni and the balance of Mg.
3. The method for preparing the low-cost high-strength high-modulus cast magnesium alloy according to claim 1 or 2, wherein the method comprises the following steps: mixing the baked pure Mg, Mg-Li intermediate alloy, Mg-Mn intermediate alloy, pure Zn, pure Al and pure Cu, and carrying out vacuum melting treatment to obtain an alloy ingot; and sequentially carrying out solid solution treatment, quenching treatment and aging treatment on the alloy ingot to obtain the low-cost high-strength high-modulus cast magnesium alloy.
4. The method of preparing a low cost high strength and high modulus cast magnesium alloy of claim 3, wherein the Mg content of the pure Mg is > 99.99%; the Zn content in the pure Zn is more than 99.99 percent; the Al content in the pure Al is more than 99.99 percent; the Cu content in the pure Cu is more than 99.99 percent; the Mg-Li intermediate alloy is Mg-18-22% of Li; the Mg-Mn intermediate alloy is Mg-8-12% of Mn.
5. The method for preparing the low-cost high-strength high-modulus cast magnesium alloy according to claim 3, wherein the vacuum melting treatment comprises:
(1) placing baked pure Mg, Mg-Li intermediate alloy, Mg-Mn intermediate alloy, pure Zn, pure Al and pure Cu into a crucible of a vacuum induction melting furnace, closing the furnace, vacuumizing until the vacuum degree in the furnace is less than 1Pa, filling high-purity argon into the furnace to 0.3-0.5 atmospheric pressure, vacuumizing again until the vacuum degree in the furnace is less than 1Pa, and filling high-purity argon into the furnace to 0.3-0.5 atmospheric pressure;
(2) opening a heating power supply of the vacuum induction smelting furnace, and carrying out induction smelting until the baked pure Mg, Mg-Li intermediate alloy, Mg-Mn intermediate alloy, pure Zn, pure Al and pure Cu are completely cleaned;
(3) heating to a refining temperature, and carrying out refining treatment; and after the refining treatment is finished, pouring to obtain the alloy ingot.
6. The preparation method of the low-cost high-strength high-modulus cast magnesium alloy according to claim 5, wherein the baking treatment temperature is 120-160 ℃ and the baking treatment time is 1.5-2.5 h.
7. The preparation method of the low-cost high-strength high-modulus cast magnesium alloy according to claim 5, wherein a crucible of the vacuum induction melting furnace is a graphite crucible, a metal crucible or a calcium oxide crucible;
the refining treatment temperature is 730-780 ℃, and the refining treatment time is 5-20 min;
the melt is poured at 680-720 ℃;
the diameter of the cross section of the alloy ingot is 90-110 mm.
8. The preparation method of the low-cost high-strength high-modulus cast magnesium alloy according to claim 3, wherein the temperature of the solution treatment is 350-450 ℃ and the time is 16-60 h.
9. The method of preparing a low cost high strength high modulus cast magnesium alloy of claim 3, wherein the quenching process comprises: and putting the alloy ingot subjected to the solution treatment into hot water at the temperature of 50-80 ℃ for quenching to room temperature.
10. The method of preparing a low cost high strength high modulus cast magnesium alloy of claim 3, wherein the aging treatment comprises: and pre-aging the alloy ingot subjected to quenching treatment at 60-100 ℃ for 6-24 h, then continuing to heat to 175-220 ℃ for aging for 5-30 h, and air-cooling to 18-30 ℃.
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Cited By (1)
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| CN114540684A (en) * | 2022-04-28 | 2022-05-27 | 北京理工大学 | High-strength high-modulus cast magnesium-lithium alloy containing two phases and preparation method thereof |
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