CN108179336B - Ultra-light magnesium-lithium alloy and heat treatment method thereof - Google Patents
Ultra-light magnesium-lithium alloy and heat treatment method thereof Download PDFInfo
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- CN108179336B CN108179336B CN201810061133.8A CN201810061133A CN108179336B CN 108179336 B CN108179336 B CN 108179336B CN 201810061133 A CN201810061133 A CN 201810061133A CN 108179336 B CN108179336 B CN 108179336B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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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
- C22C1/02—Making non-ferrous alloys by melting
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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
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- 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
Abstract
The invention discloses an ultra-light magnesium-lithium alloy and a heat treatment method thereof, wherein the magnesium-lithium alloy comprises 10.5-16 wt.% of L i, 2-8 wt.% of Zn, 1-4 wt.% of Gd, 0.1-0.4 wt.% of Zr and the balance of Mg and inevitable impurities according to the mass percentage2ZrF6The mixed salt is used as a refiner, α -Mg crystal grains can be obviously refined, the ultra-light magnesium-lithium alloy adopts a heat treatment method of double-stage solution treatment and aging treatment, the solid solution strengthening and precipitation strengthening effects can be fully exerted, and the strength of the alloy is further improved.
Description
Technical Field
The invention relates to a preparation method of a magnesium-lithium alloy, in particular to an ultra-light magnesium-lithium alloy and a heat treatment method thereof, belonging to the technical field of metal materials.
Background
Along with the development of society, the energy problem is more and more emphasized by people, and the lightweight energy conservation and emission reduction gradually becomes the trend of the development of the traffic field, so that the preparation and the forming of the light metal material gradually become the research hotspots of scholars at home and abroad. The magnesium-lithium alloy is the lightest alloy material, and the density of the magnesium-lithium alloy is lower than that of the common AZ and ZK series magnesium alloys (the density of the AZ and ZK series magnesium alloys is about 1.8-1.9 g/cm)3) Has positive significance for light weight. Meanwhile, the magnesium-lithium alloy also has high specific rigidity and specific strength, excellent anti-seismic property, high-energy particle penetration resistance and good biocompatibility, and is suitable for aviation, aerospace and soldiersThe material is one of the most ideal structural materials with great development potential in the fields of appliance industry, nuclear industry, automobiles, 3C industry, medical appliances and the like.
The matrix phase of the magnesium-lithium alloy changes along with the change of L i content in the magnesium-lithium alloy, when L i content is lower than 5.7 wt%, L1 i is a six-row-close-square L2-Mg solid solution formed by dissolving Mg in solid solution, when L3 i content is higher than 10.3 wt%, the matrix phase is a body-centered cubic L0-L i solid solution formed by dissolving Mg in solid solution in L5 i, when L i content is between the two, a dual-phase structure formed by coexisting α -Mg solid solution and L4-L i solid solution is formed, when the matrix is α -Mg solid solution, the weight reduction effect brought by adding L i element is not obvious, meanwhile, the improvement of plastic deformation capability is not obvious, when the matrix is β -L i solid solution, the matrix is strong in plastic deformation capability, but the strength is low, and therefore, the improvement of the strength of the magnesium-lithium alloy with higher lithium content has important practical significance.
The strength of the magnesium-lithium alloy with higher lithium content in the current market is not ideal.
Disclosure of Invention
The invention provides an ultra-light magnesium-lithium alloy and a heat treatment method thereof, aiming at solving the problem of low strength of the existing magnesium-lithium alloy with higher lithium content. According to the invention, Zn and Gd elements with a certain mass ratio are added into the magnesium-lithium alloy to form a self-generated quasi-crystalline phase with high thermal stability so as to strengthen the alloy and improve the thermal stability of the alloy. In addition, Zr is selected and added as an element for refining crystal grains, so that the crystal grain size of the high-lithium magnesium-lithium alloy is reduced, and the strength can be further improved under the condition of keeping plasticity not to be reduced. And then further improving the alloy strength through a heat treatment process, thereby preparing the magnesium-lithium alloy with low density, high plasticity and high strength.
The purpose of the invention is realized by the following technical scheme:
the invention provides an ultra-light magnesium-lithium alloy which comprises, by mass, 10.5-16 wt.% of L i, 2-8 wt.% of Zn, 1-4 wt.% of Gd, 0.1-0.4 wt.% of Zr, and the balance of Mg and inevitable impurities.
The preparation method adopts L i (lithium) as a first component, L i is added to remarkably reduce alloy density and improve the alloy shaping, when the L i content is 10.5-16 wt.%, the magnesium alloy is a β -L i single-phase solid solution, the magnesium alloy with the structure has high plasticity, Zn (zinc) is adopted as a second component, the casting performance of the alloy can be improved by adding Zn element, and a strengthening phase can be formed with Mg and L i, Gd (gadolinium) is adopted as a third component, the mechanical property of the alloy can be effectively improved by adding Gd, a quasicrystal phase with a strengthening effect can be formed when the mass ratio of Zn to Gd is about 3: 1-5: 1, and Zr is adopted as a fourth component, crystal grains can be refined by adding Zr element, and the strength of the alloy can be further improved.
According to the invention, three elements of Zn, Gd and Zr are added simultaneously, the mass ratio of Zn to Gd is optimized, the self-generated quasi-crystalline phase is introduced into the magnesium-lithium alloy matrix, and more strengthening precipitated phases are formed through subsequent heat treatment. The solid solubility of Zn in magnesium is exceeded and the Zn simple substance is more due to too high Zn content, the quasi-crystalline phase is less due to too low Zn content, and the strengthening effect is insufficient; the Gd content is higher than the solid solubility of the Gd in magnesium and causes higher alloy density, and the Gd content is lower, causes less quasicrystal phase and insufficient strengthening effect; the Zr content is too high, so that the simple substance Zr is settled, the grain refining effect is reduced, and the grain refining effect is not obvious due to too low Zr content.
More preferably, the mass percent of Zr is 0.2-0.4 wt.%.
Preferably, the impurities are Si, Fe, Cu and Ni; the total mass percent of impurities is less than 0.03 wt.%.
Preferably, the mass ratio of Zn to Gd is 3: 1-5: 1.
The invention also provides a preparation method of the ultralight magnesium-lithium alloy, which comprises a smelting step and a heat treatment step;
the smelting step specifically comprises the steps of taking Mg, L i, Zn, Gd and Zr as raw materials of the alloy according to the proportion, heating to melt, heating to 660-720 ℃, mechanically stirring for 1-6 min, standing and preserving heat for 3-10 min, and casting.
Preferably, when the components of the alloy are added according to the mixture ratio, the Zr adopts K2ZrF6Mixed salt feedAnd (4) adding rows.
Preferably, said K2ZrF6The mixed salt is K2ZrF6-LiCl-LiF-CaF2，K2ZrF6Quality of the mixed salt according to the mixed salt K2ZrF6-LiCl-LiF-CaF2Determining the mass percent of the medium Zr in the magnesium-lithium alloy.
Preferably, said K2ZrF6-LiCl-LiF-CaF2K in mixed salt2ZrF6The content is 40-80 wt.%, L iCl, L iF and CaF2The mass percentage of (A) is 1:1: 1.
Preferably, the heat treatment step comprises a double-stage solution treatment and an aging treatment, and comprises the following steps:
solid solution is carried out for 1-10 hours at the temperature of 300-450 ℃, then solid solution is carried out for 8-32 hours at the temperature of 200-275 ℃, and finally aging is carried out for 1-60 hours at the temperature of 50-150 ℃.
According to the invention, Zn and Gd are introduced to form a quasicrystal phase, the mass ratio of Zn to Gd is 3: 1-5: 1, the strength and the thermal stability of the magnesium-lithium alloy can be obviously improved, and meanwhile, a trace amount of K is added into the alloy2ZrF6Mixed salt K2ZrF6-LiCl-LiF-CaF2As a Zr refiner, α -Mg grains can be refined significantly.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, by simultaneously adding two elements of Zn and Gd and controlling the proportion of the two elements, the authigenic quasicrystal phase containing Zn and Gd is introduced into the magnesium-lithium alloy matrix to play a role in strengthening and improve the heat-resistant stability of the alloy.
(2) Selection of K in the invention2ZrF6The mixed salt refiner is used for refining magnesium alloy grains, can achieve the refining effect achieved by adopting the Mg-Zr intermediate alloy as the refiner, is simpler than the refining process of the Mg-Zr intermediate alloy, has less Zr element segregation, high Zr element yield and stronger decay resistance, reduces the production cost of the magnesium alloy, and is suitable for experiments and industrial application.
(3) The invention selects two-stage solid solution and aging treatment, can fully play the roles of solid solution strengthening and precipitation strengthening, and further improves the strength of the alloy.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides an ultra-light magnesium-lithium alloy, which comprises, by mass, 10.5 wt.% L i, 3wt.% Zn, 1 wt.% Gd, 0.1 wt.% Zr, a total content of impurity elements Fe, Si, Cu, and Ni being less than 0.03wt.%, and the balance Mg., wherein a ratio of Zn to Gd is 3: 1.
The smelting preparation method of the alloy comprises the steps of taking Mg, L i, Zn, Gd and Zr as raw materials of the alloy according to the proportion, heating to 720 ℃ after melting, mechanically stirring for 1min, standing and preserving heat for 10min, and casting2ZrF6Addition of mixed salts, K2ZrF6The mixed salt is 55K2ZrF6-15LiCl-15LiF-15CaF2。
The heat treatment method of the alloy comprises the following steps: solid solution is carried out for 10 hours at 300 ℃, then for 32 hours at 200 ℃, and finally, aging is carried out for 60 hours at 50 ℃.
The density of the ultra-light magnesium-lithium alloy Mg-10.5L i-3Zn-1Gd-0.1Zr is 1.44g/cm3The mechanical properties are as follows:
yield strength at room temperature: 171MPa, tensile strength: 195MPa, elongation: 35 percent.
Example 2
The embodiment provides an ultra-light magnesium-lithium alloy, which comprises, by mass, 16wt.% L i, 8wt.% Zn, 2wt.% Gd, 0.4wt.% Zr, and a total content of impurity elements Fe, Si, Cu, and Ni less than 0.03wt.%, and the balance Mg., wherein a ratio of Zn to Gd is 4: 1.
The smelting preparation method of the alloy comprises the steps of taking raw materials of Mg, L i, Zn and Al in proportion,And (3) melting Gd and Zr, heating to 660 ℃, mechanically stirring for 6min, standing, preserving heat for 3min, and casting. The Zr adopts K2ZrF6Addition of mixed salts, K2ZrF6The mixed salt is 40K2ZrF6-20LiCl-20LiF-20CaF2。
The heat treatment method of the alloy comprises the following steps: solid solution is carried out for 1 hour at the temperature of 450 ℃, then solid solution is carried out for 8 hours at the temperature of 270 ℃, and finally aging is carried out for 1 hour at the temperature of 150 ℃.
The density of the ultra-light magnesium-lithium alloy Mg-16L i-8Zn-2Gd-0.4Zr is 1.38g/cm3The mechanical properties are as follows:
yield strength at room temperature: 178MPa, tensile strength: 209MPa, elongation: 41 percent.
Example 3
The embodiment provides an ultra-light magnesium-lithium alloy, which comprises, by mass, 13 wt.% L i, 6wt.% Zn, 1.2 wt.% Gd, 0.2 wt.% Zr, a total content of impurity elements Fe, Si, Cu, and Ni being less than 0.03wt.%, and the balance Mg., wherein a ratio of Zn to Gd is 5: 1.
The smelting preparation method of the alloy comprises the steps of taking Mg, L i, Zn, Gd and Zr as raw materials of the alloy according to the proportion, heating to 690 ℃ after melting, mechanically stirring for 3.5min, standing and preserving heat for 6.5min, and casting, wherein the Zr adopts K2ZrF6Addition of mixed salts, K2ZrF6The mixed salt is 70K2ZrF6-10LiCl-10LiF-10CaF2。
The heat treatment method of the alloy comprises the following steps: solid solution is carried out for 5.5 hours at 375 ℃, then for 20 hours at 250 ℃, and finally aging is carried out for 30 hours at 100 ℃.
The density of the ultra-light magnesium-lithium alloy Mg-13L i-6Zn-3Gd-0.2Zr is 1.42g/cm3The mechanical properties are as follows:
yield strength at room temperature: 182MPa, tensile strength: 204MPa, elongation: 39 percent.
Comparative example 1
The present embodiment provides an ultra-light magnesium-lithium alloy, which comprises, by mass, 13 wt.% L i, 5.1 wt.% Zn, 2.1 wt.% Gd, 0.2 wt.% Zr, a total content of impurity elements Fe, Si, Cu, and Ni being less than 0.03wt.%, and a balance Mg., wherein a ratio of Zn to Gd is about 2.5: 1.
The preparation method of the ultralight magnesium-lithium alloy is the same as that of the example 3.
The density of the ultra-light magnesium-lithium alloy Mg-13L i-3Zn-3Gd-0.2Zr is 1.39g/cm3The mechanical properties are as follows:
yield strength at room temperature: 148MPa, tensile strength: 166MPa, elongation: 29 percent.
Comparative example 2
The embodiment provides an ultra-light magnesium-lithium alloy, which comprises, by mass, 16wt.% L i, 8wt.% Zn, 1 wt.% Gd, 0.4wt.% Zr, a total content of impurity elements Fe, Si, Cu, and Ni is less than 0.03wt.%, and the balance Mg., wherein a ratio of Zn to Gd is 8: 1.
The preparation method of the ultralight magnesium-lithium alloy is the same as that of the example 2.
The density of the ultra-light magnesium-lithium alloy Mg-13L i-3Zn-3Gd-0.2Zr is 1.37g/cm3The mechanical properties are as follows:
yield strength at room temperature: 158MPa, tensile strength: 179MPa, elongation: 5.4 percent.
Comparative example 3
This example provides an ultra-light magnesium-lithium alloy, which has the same composition and mass percentage as those of example 3.
The preparation method of the ultralight magnesium-lithium alloy is basically the same as that of the example 3. The difference lies in that: k adopted2ZrF6The mixed salt refiner is 40K2ZrF6-30LiCl-10LiF-20CaF2。
The density of the ultra-light magnesium-lithium alloy Mg-13L i-6Zn-1.2Gd-0.2Zr is 1.41g/cm3The mechanical properties are as follows:
yield strength at room temperature: 156MPa, tensile strength: 171MPa, elongation: 25 percent.
Comparative example 4
This example provides an ultra-light magnesium-lithium alloy, which has the same composition and mass percentage as those of example 3.
Preparation method and embodiment of the ultra-light magnesium-lithium alloy3 are substantially the same, except that: k adopted2ZrF6The mixed salt refiner is 30K2ZrF6-30LiCl-20LiF-20CaF2。
The density of the ultra-light magnesium-lithium alloy Mg-13L i-6Zn-1.2Gd-0.2Zr is 1.42g/cm3The mechanical properties are as follows:
yield strength at room temperature: 166MPa, tensile strength: 181MPa, elongation: 13.1 percent.
Comparative example 5
The embodiment provides an ultra-light magnesium-lithium alloy, the components and the mass percentage of which are the same as those of the embodiment 3, and the preparation method is basically the same as that of the embodiment 3, except that: the adopted heat treatment method comprises the following steps: solid solution is carried out for 25.5 hours at the temperature of 300 ℃, and then aging is carried out for 30 hours at the temperature of 100 ℃.
The density of the ultra-light magnesium-lithium alloy Mg-13L i-3Zn-3Gd-0.2Zr is 1.42g/cm3The mechanical properties are as follows:
yield strength at room temperature: 161MPa, tensile strength: 177MPa, elongation: 9.7 percent.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (2)
1. The ultra-light magnesium-lithium alloy is characterized by comprising the following components, by mass, 13-16 wt.% of L i, 6-8 wt.% of Zn, 1.2-2 wt.% of Gd, 0.2-0.4 wt.% of Zr, and the balance of Mg and inevitable impurities, wherein the mass ratio of Zn to Gd is 4: 1-5: 1;
the preparation method of the ultralight magnesium-lithium alloy comprises a smelting step and a heat treatment step;
the smelting step is specifically that the raw materials of Mg, L i, Zn, Gd and Zr of the alloy are taken according to the proportion, heated and melted, heated to 660-720 ℃, mechanically stirred for 1-6 min, kept stand and insulated for 3-10 min, and cast;
when the components of the alloy are added according to the proportion, Zr adopts K2ZrF6Adding mixed salt; said K2ZrF6The mixed salt is K2ZrF6-LiCl-LiF-CaF2；
Said K2ZrF6-LiCl-LiF-CaF2K in mixed salt2ZrF6The content is 40-80 wt.%, L iCl, L iF and CaF2The mass percentage of (A) is 1:1: 1;
the heat treatment steps comprise two-stage solution treatment and aging treatment, and comprise the following steps:
solid solution is carried out for 1-10 hours at the temperature of 300-450 ℃, then solid solution is carried out for 8-32 hours at the temperature of 200-275 ℃, and finally aging is carried out for 1-60 hours at the temperature of 50-150 ℃.
2. The ultra-light magnesium-lithium alloy of claim 1, wherein the impurities are Si, Fe, Cu and Ni; the total mass percent of impurities is less than 0.03 wt.%.
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