CN113981288A - Die-casting magnesium alloy and preparation method thereof - Google Patents
Die-casting magnesium alloy and preparation method thereof Download PDFInfo
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- 238000004512 die casting Methods 0.000 title claims abstract description 113
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 136
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 135
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 64
- 239000011777 magnesium Substances 0.000 claims abstract description 61
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 60
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 47
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 43
- 239000011701 zinc Substances 0.000 claims description 102
- 239000007788 liquid Substances 0.000 claims description 52
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 39
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 22
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 238000003723 Smelting Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 8
- 229910052790 beryllium Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- MIOQWPPQVGUZFD-UHFFFAOYSA-N magnesium yttrium Chemical compound [Mg].[Y] MIOQWPPQVGUZFD-UHFFFAOYSA-N 0.000 description 20
- RRTQFNGJENAXJJ-UHFFFAOYSA-N cerium magnesium Chemical compound [Mg].[Ce] RRTQFNGJENAXJJ-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 19
- 238000001514 detection method Methods 0.000 description 14
- 238000005275 alloying Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- 239000007769 metal material Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000010998 test method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003120 Zn-Ce Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 240000001829 Catharanthus roseus Species 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- JTUZZGLMVUXHQL-UHFFFAOYSA-N [Y].[Sm] Chemical compound [Y].[Sm] JTUZZGLMVUXHQL-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001234 light alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000013079 quasicrystal Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—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
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Continuous Casting (AREA)
Abstract
The invention provides a die-casting magnesium alloy, which comprises the following components: 2-6 wt% of Zn, 1-4.5 wt% of Ce, 1.5-7 wt% of Y, the total content of Zn, Ce and Y is more than 7.5 wt%, the mass ratio of (Ce + Y)/Zn is more than 1, and the balance is magnesium. The application also provides a preparation method of the die-casting magnesium alloy. The die-casting magnesium alloy provided by the invention contains Zn, Ce and Y, the three components form a continuous reticular second phase structure distributed in a three-dimensional space after being melted, and the second phase has multiple structures, so that dislocation slippage and twin crystal formation can be effectively hindered under a high-temperature condition, and the high-temperature creep resistance of the alloy is improved. Experimental results show that the high-temperature creep-resistant die-casting magnesium alloy provided by the invention has the heat resistance temperature of more than 300 ℃, and the creep life of more than 1000h under the conditions of 300 ℃ and 30MPa, and is the first reported die-casting magnesium alloy capable of resisting the high-temperature creep of 300 ℃.
Description
Technical Field
The invention relates to the technical field of magnesium alloy, in particular to a die-casting magnesium alloy and a preparation method thereof.
Background
The magnesium alloy has small density, is the lightest metal structural material in the field of engineering application at present, and becomes one of the preferable materials for integrating the structural function due to the excellent specific strength, specific rigidity, damping performance, electromagnetic shielding performance and the like. With the development of the Chinese automobile industry, new energy vehicles, flying automobiles and the like become the trend of future development, so higher requirements on light weight are provided; the weight of the automobile mainly comes from automobile transmission parts and main bearing parts, and the parts have severe requirements on the absolute strength or heat resistance of the alloy and cannot be met by the existing magnesium alloy system at present. Therefore, the development of ultra-high strength magnesium alloys and super heat-resistant magnesium alloys has become a main direction of magnesium alloy development, and is also a precondition for the wide application of magnesium alloys in the fields of automobiles and the like.
At present, die-casting magnesium alloy is the main body of commercial magnesium alloy market, and the adopted alloy system is mainly Mg-Al-Zn, but the high-temperature creep resistance of the magnesium alloy of the system is poor, and the use temperature is strictly limited below 120 ℃ under general conditions. In recent decades, a great deal of researchers have been focusing on creep-resistant magnesium alloys and have successfully developed a plurality of heat-resistant magnesium alloy systems such as Mg-Al-RE system, and the main preparation method is cold chamber die casting, and the heat-resistant alloys have better heat resistance compared with Mg-Al alloy systems, and the use temperature can reach 175 ℃, even the use temperature of partial alloys can approach 200 ℃. But it is still difficult to meet the heat resistance requirements of the transmission parts. As for heat-resistant transmission parts, the service temperature is generally 150-300 ℃. Therefore, the development of a magnesium alloy or an aluminum alloy with 300 ℃ creep resistance becomes a new requirement of a novel light alloy material, and is a necessary trend for the development of a heat-resistant magnesium alloy/aluminum alloy.
The existing heat-resistant magnesium alloy mainly depends on adding rare earth elements, alkaline earth elements and the like, and when the using temperature is higher than 200 ℃, the creep resistance of the alloy is rapidly reduced; when the use temperature reaches 300 ℃, the creep stress with the creep life longer than 1000h is generally lower than 10MPa, and the use requirement of the power transmission structural part is far not met (the use stress is 30-50 MPa). Therefore, at present, no magnesium alloy can have a creep life of more than 1000 hours under the condition that the creep stress reaches 30MPa in an environment of 300 ℃. In other words, there is no creep-resistant magnesium alloy that is resistant to creep at 300 degrees celsius.
Disclosure of Invention
The invention aims to provide a creep-resistant magnesium alloy capable of resisting 300 ℃ creep.
In view of the above, the present application provides a die-cast magnesium alloy, including:
Zn 2～6wt％；
Ce 1～4.5wt％；
Y 1.5～7wt％；
the total content of Zn, Ce and Y is more than 7.5 wt%, and (Ce + Y)/Zn is more than 1;
the balance of magnesium.
Preferably, the Zn content is 2.3-5.5 wt%, the Ce content is 1.5-4.0 wt%, and the Y content is 2.0-6.0 wt%.
Preferably, the total content of Zn, Ce and Y is 7.8-15.0 wt%.
Preferably, (Ce + Y)/Zn is 1.2 to 3.0.
Preferably, the total content of impurity elements Si, Fe, Ni, Cu, Be is less than 0.1 wt%.
The application also provides a preparation method of the die-casting magnesium alloy, which comprises the following steps:
mixing a magnesium source, a zinc source, a cerium source and an yttrium source according to the component ratio, and smelting to obtain an alloy liquid;
and carrying out high-pressure casting on the alloy liquid to obtain the die-casting magnesium alloy.
Preferably, the smelting temperature is 700-800 ℃.
Preferably, the temperature of the high-pressure casting is 700-750 ℃.
Preferably, the preparation process of the alloy liquid is specifically as follows:
smelting the preheated magnesium source, cerium source and yttrium source to obtain a first mixed molten metal;
and mixing the first mixed molten metal and the preheated zinc source to obtain alloy liquid.
Preferably, the temperature of the preheated magnesium source, the temperature of the preheated cerium source and the temperature of the preheated yttrium source are 280-400 ℃, and the temperature of the preheated zinc source is 280-400 ℃.
The invention provides a die-casting magnesium alloy, which contains Zn, Ce and Y, and second-phase grids which are formed by multiple crystal structures such as Mg-Zn-Ce, Mg-Zn-Y, Mg-Ce and the like and are continuously distributed in a three-dimensional space are formed after melting through limiting the content and the relation of the three components, the second phases have higher stability under the ultrahigh temperature condition, and the spatial network structure is maintained to effectively block dislocation glide and twin crystal formation, so that the resistance to alloy deformation is improved; in addition, Zn and Y in the magnesium matrix of the alloy can form basal plane precipitated phases with higher thermal stability in the creep process, thereby effectively hindering basal plane dislocation glide; therefore, the creep life of the alloy provided by the invention can meet the condition that the creep life is more than 1000h at 300 ℃ and 30 MPa.
Experimental results show that the 300 ℃ creep-resistant die-casting magnesium alloy provided by the invention has the creep stress of 30MPa at 300 ℃, the lasting creep life of more than 1000h and the minimum creep rate of less than 1 multiplied by 10-9/s。
Drawings
FIG. 1 is a photograph of a metallographic structure of a 300 ℃ creep resistant die-cast magnesium alloy obtained in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of die-cast magnesium alloy resistant to creep deformation at 300 ℃ obtained in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the problem that the use temperature and the creep resistance of the magnesium alloy in the prior art cannot be simultaneously combined, the application provides a 300 ℃ creep-resistant die-casting magnesium alloy, which contains Zn, Ce and Y, and the molten Zn, Ce and Y form second-phase grids which are formed by a plurality of crystal structures and are continuously distributed in a three-dimensional space, and the second-phase space network structures can effectively block dislocation slippage and twin crystal formation under the conditions of high temperature and high pressure, so that the resistance to alloy deformation is improved; in addition, Zn and Y in the magnesium matrix of the alloy can form basal plane precipitated phases in the creep process, thereby effectively hindering basal plane dislocation slippage; therefore, the alloy provided by the invention has extremely excellent 300 ℃ creep resistance. Specifically, the embodiment of the invention discloses a die-casting magnesium alloy, which comprises the following components:
Zn 2～6wt％；
Ce 1～4.5wt％；
Y 1.5～7wt％；
the total content of Zn, Ce and Y is more than 7.5 wt%, and (Ce + Y)/Zn is more than 1;
the balance of magnesium.
The 300 ℃ creep-resistant die-casting magnesium alloy provided by the invention comprises 2-6 wt% of Zn. Specifically, the mass content of the Zn in the high-temperature high-pressure creep-resistant alloy is 2.3 wt% to 5.5 wt%, and more specifically, the mass content of the Zn in the high-temperature high-pressure creep-resistant alloy is 3 wt% to 5 wt%. The content of Zn ensures that the high-temperature high-pressure creep-resistant die-casting magnesium alloy melt has very good flowing property, so that the high-temperature high-pressure creep-resistant alloy can be used for preparing a casting with a complex structure by a die-casting method.
The 300 ℃ creep-resistant die-casting magnesium alloy provided by the invention comprises 1-4.5 wt% of Ce. Specifically, the mass content of Ce in the 300 ℃ creep-resistant die-casting magnesium alloy is 1.5% -4.0%, and more specifically, the mass content of Ce in the 300 ℃ creep-resistant die-casting magnesium alloy is 2% -3.5%. In the invention, the Ce can act together with the Zn in the technical scheme to further improve the fluidity of the alloy liquid, and simultaneously can inhibit the hot cracking behavior of the alloy in the die-casting process, so that the die-casting magnesium alloy with the creep resistance of 300 ℃ provided by the invention has better casting quality.
The die-casting magnesium alloy capable of resisting creep deformation at 300 ℃ provided by the invention comprises 1.5-7 wt% of Y. Specifically, the mass content of Y in the 300 ℃ creep-resistant die-casting magnesium alloy is 2.0 wt% -6.0 wt%, and more specifically, the mass content of Y in the 300 ℃ creep-resistant die-casting magnesium alloy is 2.5 wt% -4.5 wt%. In the invention, the Y can be combined with the Zn and the matrix Mg in the technical scheme to form a ternary phase, wherein the ternary phase also comprises a ternary long-range periodic phase and a quasicrystal phase, and the ternary phases are alternately distributed to form a spatially distributed continuous grid structure.
The die-casting magnesium alloy capable of resisting creep deformation at 300 ℃ provided by the invention can also contain other alloy elements, and the high-temperature high-pressure creep resistance of the alloy can not be obviously influenced by the other alloy elements. The total amount of impurity elements Si, Fe, Ni, Cu, Be, etc. is less than 0.1 wt%.
Furthermore, the total content of Zn, Ce and Y in the alloy is more than 7.5 wt%, and the mass ratio of (Ce + Y)/Zn is more than 1; specifically, the total content of Zn, Ce and Y is 7.8-15.0 wt%, and the (Ce + Y)/Zn is 1.2-3.0; more specifically, the total content of Zn, Ce and Y is 8.5-12.0 wt%, and the (Ce + Y)/Zn is 1.5-2.8. The total content of Zn, Ce and Y is limited to ensure the microstructure of the alloy, when the total amount of alloy elements is lower than a limited value, the number of second phases formed in the alloy is small, a continuous and complete second-phase network structure cannot be formed, the strength and the stability of the formed semi-continuous network structure are poor, and collapse can occur in the high-temperature creep process; therefore, a certain amount of alloying elements is required to ensure the microstructure of the alloy. The limitation of (Ce + Y)/Zn is the composition of the second phase, and when the content of Zn is high and the content of rare earth is low, the second phase with poor thermal stability such as Mg-Zn is formed, which is not beneficial to the high-temperature creep behavior of the alloy.
The invention provides a preparation method of the high-temperature high-pressure creep-resistant die-casting magnesium alloy, which comprises the following steps:
1) smelting a magnesium source, a zinc source, a cerium source and an yttrium source according to the component ratio to obtain an alloy liquid;
2) and (3) carrying out high-pressure casting on the alloy liquid to obtain the die-casting magnesium alloy with creep resistance of 300 ℃.
The invention smelts a magnesium source, a zinc source, a cerium source and an yttrium source (or other alloy element sources) to obtain alloy liquid. In the invention, the smelting temperature is 700-800 ℃, specifically 720-740 ℃, more specifically 730 ℃. The smelting method is not particularly limited in the invention, and the technical scheme of metal smelting known to those skilled in the art can be adopted. The smelting is preferably carried out under protective gas conditions. The present invention is not particularly limited in kind and source of the protective gas, and the protective gas used in the preparation of the magnesium alloy, which is well known to those skilled in the art, may be used and may be commercially available. In the present invention, the protective gas is preferably SF6And CO2. In the present invention, the SF6And CO2The volume ratio of (A) to (B) is preferably 1 (50-120), and most preferably 1: 80. In the present invention, the melting is preferably carried out under stirring.
In the application, the preparation process of the alloy liquid specifically comprises the following steps: smelting a magnesium source, a cerium source and an yttrium source to obtain a first mixed molten metal; and mixing the first mixed metal liquid with a zinc source (and other alloy element sources) to obtain an alloy liquid. The method for smelting the magnesium source, the zinc source, the cerium source and the yttrium source is not particularly limited, and the technical scheme of metal smelting known to those skilled in the art can be adopted. The invention preferably preheats the magnesium, cerium and yttrium sources prior to melting the sources. In the present invention, the temperature of the magnesium, cerium and yttrium sources is preferably 180 to 400 ℃, more preferably 240 to 360 ℃, and most preferably 300 ℃.
After obtaining the first mixed molten metal, the present invention preferably mixes the first mixed molten metal with other alloying element sources to obtain a second mixed molten metal; in the present invention, the mixing temperature of the first mixed molten metal and the other alloying element source is preferably 720 ℃ to 750 ℃, more preferably 725 ℃ to 740 ℃, and most preferably 730 ℃. In the present invention, the mixing time of the first mixed molten metal and the other alloying element source is preferably 5 minutes to 10 minutes, and more preferably 6 minutes to 8 minutes; there is no second mixed metal liquid if no other alloying element source is added.
After the first or second mixed metal liquid is obtained, the invention preferably mixes the first or second mixed metal liquid with a zinc source to obtain an alloy liquid; in the present invention, the mixing time of the first or second mixed metal liquid and the zinc source is preferably 8 minutes to 20 minutes, and more preferably 10 minutes to 15 minutes.
In the present invention, the zinc source is preferably pure zinc. In the present invention, the magnesium source is preferably pure magnesium. The zinc source and the magnesium source are not particularly limited in the present invention, and are commercially available. In the present invention, the cerium source is preferably a magnesium-cerium master alloy. In the present invention, the source of yttrium is preferably a magnesium-yttrium master alloy. In the invention, the mass fraction of cerium in the magnesium-cerium intermediate alloy is preferably 15-40%, and more preferably 20-30%. In the invention, the mass fraction of yttrium in the magnesium-yttrium master alloy is preferably 15-40%, and more preferably 20-30%. In the present invention, the other alloying element source is preferably a magnesium-other alloying element master alloy. In the invention, the mass fraction of the magnesium-other alloy element intermediate alloy is not particularly limited, and the alloy preparation conditions can be met. The sources of the cerium source, yttrium source and other alloying element sources are not particularly limited in the present invention, and may be commercially available from any sources known to those skilled in the art, including the above-mentioned types of metal sources. In an embodiment of the present invention, the cerium source, the yttrium source, and the other alloying element source are a magnesium-cerium intermediate alloy, a magnesium-yttrium intermediate alloy, and a magnesium-other alloying element intermediate alloy, respectively, provided by libanobacter limited of cismei magnesium, catharanthus roseus.
After obtaining the alloy liquid, introducing argon into the alloy liquid for refining; in the present invention, it is preferred not to refine; the alloy liquid is preferably allowed to stand. In the invention, the standing time is preferably 20-45 minutes, and the melt temperature during standing is preferably 700-720 ℃.
Before the magnesium source, the zinc source, the cerium source, the yttrium source and the other alloying element source are smelted, the magnesium source, the zinc source, the cerium source, the yttrium source and the other alloying element source are preferably preheated. In the invention, the temperature for preheating the magnesium source, the zinc source, the cerium source, the yttrium source and the other alloying element sources is preferably 180-400 ℃, more preferably 240-360 ℃, and most preferably 300 ℃.
After obtaining the alloy liquid, the invention carries out high-pressure casting on the alloy liquid by adopting a cold chamber die casting machine to obtain the die-casting magnesium alloy with creep resistance at 300 ℃, wherein the die-casting magnesium alloy with creep resistance at 300 ℃ comprises the following components: 2-6 wt% of Zn, 1-4.5 wt% of Ce, 1.5-7 wt% of Y, the total content of Zn, Ce and Y is more than 7.5 wt%, the mass ratio of (Ce + Y)/Zn is more than 1, and the balance is magnesium. In the present invention, the die casting melt temperature is 700 ℃ to 750 ℃, more preferably 705 ℃ to 720 ℃, and most preferably 710 ℃ to 720 ℃. In the invention, the die-casting injection rate is not particularly limited, and the quality of the die-casting sample can be ensured by adopting the technical scheme of magnesium alloy die-casting, which is well known to those skilled in the art. The preheating temperature of the die-casting die is preferably 180-300 ℃, more preferably 220-270 ℃, and most preferably 240-260 ℃.
In the invention, the 300 ℃ creep resistant die-casting magnesium alloy comprises 2-6 wt% of Zn, 1-4.5 wt% of Ce, 1.5-7 wt% of Y, the total content of Zn, Ce and Y is more than 7.5 wt%, the mass ratio of (Ce + Y)/Zn is more than 1, the total amount of impurity elements Si, Fe, Ni, Cu, Be and the like is less than 0.1 wt%, and the balance is magnesium. The invention can control the dosage of the magnesium source, the zinc source, the cerium source and the yttrium source (and other alloy element sources) in the technical scheme to obtain the high-temperature high-pressure creep resistance of the components.
Testing the creep property of the high-temperature high-pressure creep-resistant material under high temperature and high pressure according to the standard of GB/T2039-2012 'Metal Material uniaxial tensile creep test method'; the experimental results are as follows: at 300 deg.C, creep stress of 30MPa, endurance creep life of more than 1000h, and minimum creep rate of less than 1 × 10-9/s。
The invention provides a die-casting magnesium alloy capable of resisting creep deformation at 300 ℃, which comprises the following components: 2-6 wt% of Zn, 1-4.5 wt% of Ce, 1.5-7 wt% of Y, the total content of Zn, Ce and Y is more than 7.5 wt%, the mass ratio of (Ce + Y)/Zn is more than 1, the total amount of impurity elements Si, Fe, Ni, Cu, Be and the like is less than 0.1 wt%, and the balance is magnesium. The 300 ℃ creep-resistant die-casting magnesium alloy contains Zn, Ce and Y, and the molten Zn, Ce and Y form second-phase grids which are formed by various crystal structures such as Mg-Zn-Ce, Mg-Zn-Y, Mg-Ce and the like and are continuously distributed in a three-dimensional space, the second phases have higher thermal stability under the condition of ultrahigh temperature, and the spatial network structure is maintained to effectively block dislocation slippage and twin crystal formation, so that the resistance to alloy deformation is improved; in addition, Zn and Y in the magnesium matrix of the alloy can form basal plane precipitated phases in the creep process, thereby effectively hindering basal plane dislocation slip and twinning deformation; therefore, the alloy provided by the invention has extremely excellent performance of ultra-long creep life under high-temperature conditions.
For further understanding of the present invention, the die-cast magnesium alloy provided by the present invention will be described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
The raw materials used in the following examples of the present invention are all commercially available products, the mass fraction of cerium in the used magnesium-cerium intermediate alloy is 20%, the mass fraction of yttrium samarium in the used magnesium-yttrium intermediate alloy is 20%, and the used zinc is pure zinc.
Example 1
Preheating 10650g of pure magnesium, 600g of pure zinc, 1500g of magnesium-cerium intermediate alloy and 2250g of magnesium-yttrium intermediate alloy to 300 ℃; firstly, putting preheated pure magnesium, magnesium-cerium intermediate alloy and magnesium-yttrium intermediate alloy into a crucible preheated to 300 ℃, and introducing SF into the crucible6And CO2Is 1:80, heating the melt to 730 ℃ after the materials are melted, and then adding the pure zinc preheated to 300 ℃ into the crucible under the stirring condition for mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 715 ℃, and standing for 30 minutes;
and die-casting the alloy liquid after standing on a cold chamber die casting machine with 280 tons of die locking force to obtain the die-casting magnesium alloy with creep resistance of 300 ℃, wherein the die-casting temperature is 715 ℃, the die-casting die temperature is 240 +/-20 ℃, and the injection speed of die-casting is 2 m/s.
The die-casting magnesium alloy with creep resistance of 300 ℃ obtained in the embodiment 1 of the invention is subjected to component detection by using a spectrum analyzer, and the detection result is as follows: the die-casting magnesium alloy capable of resisting creep deformation at 300 ℃ obtained in embodiment 1 of the invention comprises the following components: 3.91 wt% of Zn, 2.02 wt% of Ce, 2.95 wt% of Y, less than 0.1 wt% of impurity elements of Fe, Cu, Si and Ni, and the balance of magnesium.
The die-casting magnesium alloy with 300 ℃ creep resistance obtained in example 1 of the present invention was observed by optical photograph and scanning photograph, and the observation results are shown in fig. 1 and fig. 2, and it can be seen that: the die-casting magnesium alloy with creep resistance of 300 ℃ obtained in the embodiment 1 of the invention has fine and uniform structure, and forms a continuous second phase space grid structure.
Testing the creep property of the alloy according to the standard of GB/T2039-2012 'test method for uniaxial tensile creep of metal materials'; the experimental results are as follows: at 300 deg.C, creep stress of 30MPa, endurance creep life of more than 1000h, and minimum creep rate of less than 1 × 10-9/s。
Example 2
Preheating 10575g of pure magnesium, 300g of pure zinc, 3000g of magnesium-cerium intermediate alloy and 1125g of magnesium-yttrium intermediate alloy to 300 ℃; firstly, putting preheated pure magnesium, magnesium-cerium intermediate alloy and magnesium-yttrium intermediate alloy into a crucible preheated to 300 ℃, and introducing SF into the crucible6And CO2Is 1:80, heating the melt to 730 ℃ after the materials are melted, and then adding the pure zinc preheated to 300 ℃ into the crucible under the stirring condition for mixing for 8 minutes to obtain alloy liquid; and cooling the alloy liquid to 715 ℃, and standing for 30 minutes.
And die-casting the alloy liquid after standing on a cold chamber die casting machine with 280 tons of die locking force to obtain the die-casting magnesium alloy with creep resistance of 300 ℃, wherein the die-casting temperature is 715 ℃, the die-casting die temperature is 240 +/-20 ℃, and the injection speed of die-casting is 2 m/s.
The die-casting magnesium alloy with creep resistance of 300 ℃ obtained in the embodiment 2 of the invention is subjected to component detection by using a spectrum analyzer, and the detection result is as follows: the die-casting magnesium alloy capable of resisting creep deformation at 300 ℃ obtained in embodiment 2 of the invention comprises the following components: 2.07 wt% of Zn, 3.95 wt% of Ce, 1.49 wt% of Y, less than 0.1 wt% of impurity elements of Fe, Cu, Si and Ni, and the balance of magnesium.
Testing the creep property of the alloy according to the standard of GB/T2039-2012 'test method for uniaxial tensile creep of metal materials'; the experimental results are as follows: the creep life at 300 ℃ and 30MPa is more than 1000 hours.
Example 3
Preheating 9600g of pure magnesium, 900g of pure zinc, 3000g of magnesium-cerium intermediate alloy and 1500g of magnesium-yttrium intermediate alloy to 300 ℃; firstly, putting preheated pure magnesium, magnesium-cerium intermediate alloy and magnesium-yttrium intermediate alloy into a crucible preheated to 300 ℃, and introducing SF into the crucible6And CO2Is 1:80, heating the melt to 730 ℃ after the materials are melted, and then adding the pure zinc preheated to 300 ℃ into the crucible under the stirring condition for mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 715 ℃, and standing for 30 minutes;
and die-casting the alloy liquid after standing on a cold chamber die casting machine with 280 tons of die locking force to obtain the die-casting magnesium alloy with creep resistance of 300 ℃, wherein the die-casting temperature is 715 ℃, the die-casting die temperature is 240 +/-20 ℃, and the injection speed of die-casting is 2 m/s.
The die-casting magnesium alloy with creep resistance of 300 ℃ obtained in the embodiment 3 of the invention is subjected to component detection by a spectrum analyzer, and the detection result is as follows: the die-casting magnesium alloy capable of resisting creep deformation at 300 ℃ obtained in embodiment 3 of the invention comprises the following components: 5.83 wt% of Zn, 3.97 wt% of Ce, 1.91 wt% of Y, less than 0.1 wt% of impurity elements of Fe, Cu, Si and Ni, and the balance of magnesium.
Testing the creep property of the alloy according to the standard of GB/T2039-2012 'test method for uniaxial tensile creep of metal materials'; the experimental results are as follows: the creep life at 300 ℃ and 30MPa is more than 1000 h.
Example 4
Preheating 9150g of pure magnesium, 600g of pure zinc, 750g of magnesium-cerium intermediate alloy and 4500g of magnesium-yttrium intermediate alloy to 300 ℃; firstly, putting preheated pure magnesium, magnesium-cerium intermediate alloy and magnesium-yttrium intermediate alloy into a crucible preheated to 300 ℃, and introducing SF into the crucible6And CO2Is 1:80, heating the melt to 730 ℃ after the materials are melted, and then adding the pure zinc preheated to 300 ℃ into the crucible under the stirring condition for mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 715 ℃, and standing for 30 minutes;
and die-casting the alloy liquid after standing on a cold chamber die casting machine with 280 tons of die locking force to obtain the die-casting magnesium alloy with creep resistance of 300 ℃, wherein the die-casting temperature is 715 ℃, the die-casting die temperature is 240 +/-20 ℃, and the injection speed of die-casting is 2 m/s.
The die-casting magnesium alloy with creep resistance of 300 ℃ obtained in the embodiment 4 of the invention is subjected to component detection by a spectrum analyzer, and the detection result is as follows: the die-casting magnesium alloy capable of resisting creep deformation at 300 ℃ obtained in embodiment 4 of the invention comprises the following components: 3.97 wt% of Zn, 0.97 wt% of Ce, 5.92 wt% of Y, less than 0.1 wt% of impurity elements of Fe, Cu, Si and Ni, and the balance of magnesium.
Testing the creep property of the alloy according to the standard of GB/T2039-2012 'test method for uniaxial tensile creep of metal materials'; the experimental results are as follows: the creep life at 300 ℃ and 30MPa is more than 1000 h.
Example 5
9750g of pure magnesium, 375g of pure zinc, 1875g of magnesium-cerium intermediate alloy and 3000g of magnesium-yttrium intermediate alloy are preheated to 300 ℃; firstly, putting preheated pure magnesium, magnesium-cerium intermediate alloy and magnesium-yttrium intermediate alloy into a crucible preheated to 300 ℃, and introducing SF into the crucible6And CO2Is 1:80, heating the melt to 730 ℃ after the materials are melted, and then adding the pure zinc preheated to 300 ℃ into the crucible under the stirring condition for mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 715 ℃, and standing for 30 minutes;
and die-casting the alloy liquid after standing on a cold chamber die casting machine with 280 tons of die locking force to obtain the die-casting magnesium alloy with creep resistance of 300 ℃, wherein the die-casting temperature is 715 ℃, the die-casting die temperature is 240 +/-20 ℃, and the injection speed of die-casting is 2 m/s.
The die-casting magnesium alloy with creep resistance of 300 ℃ obtained in the embodiment 5 of the invention is subjected to component detection by using a spectrum analyzer, and the detection result is as follows: the die-casting magnesium alloy capable of resisting creep deformation at 300 ℃ obtained in embodiment 5 of the invention comprises the following components: 2.49 wt% of Zn, 2.37 t% of Ce, 3.92 wt% of Y, less than 0.1 wt% of impurity elements of Fe, Cu, Si and Ni, and the balance of magnesium.
Testing the creep property of the alloy according to the standard of GB/T2039-2012 'test method for uniaxial tensile creep of metal materials'; the experimental results are as follows: the creep life at 300 ℃ and 30MPa is more than 1000 h.
Comparative example 1
Preheating 10650g of pure magnesium, 600g of pure zinc and 3750g of magnesium-cerium intermediate alloy to 300 ℃; firstly, putting preheated pure magnesium, magnesium and cerium intermediate alloy into a crucible preheated to 300 ℃, and introducing SF into the crucible6And CO2Is 1:80, heating the melt to 730 ℃ after the materials are melted, and then adding the pure zinc preheated to 300 ℃ into the crucible under the stirring condition for mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 715 ℃, and standing for 30 minutes;
and die-casting the alloy liquid after standing on a 280-ton mold clamping force cold chamber die-casting machine to obtain the comparative example die-casting magnesium alloy 1, wherein the die-casting temperature is 715 ℃, the die-casting mold temperature is 240 +/-20 ℃, and the injection speed of die-casting is 2 m/s.
And (3) detecting the components of the comparative example die-cast magnesium alloy 1 obtained in the comparative example 1 by using a spectrum analyzer, wherein the detection result is as follows: comparative example 1 the comparative example die-cast magnesium alloy 1 obtained according to the present invention includes: 3.88 wt% of Zn, 4.92 wt% of Ce, less than 0.1 wt% of the total amount of impurity elements Fe, Cu, Si and Ni, and the balance of magnesium.
Testing the creep property of the alloy according to the standard of GB/T2039-2012 'test method for uniaxial tensile creep of metal materials'; the experimental results are as follows: the creep life at 300 ℃ and 30MPa is less than 60 h.
Comparative example 2
Preheating 10650g of pure magnesium, 600g of pure zinc and 3750g of magnesium-yttrium master alloy to 300 ℃; firstly, putting preheated pure magnesium and magnesium-yttrium master alloy into a crucible preheated to 300 ℃, and introducing SF into the crucible6And CO2Is 1:80, heating the melt to 730 ℃ after the materials are melted, and then adding the pure zinc preheated to 300 ℃ into the crucible under the stirring condition for mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 715 ℃, and standing for 30 minutes;
and die-casting the alloy liquid after standing on a 280-ton mold clamping force cold chamber die-casting machine to obtain the comparative example die-casting magnesium alloy 2, wherein the die-casting temperature is 715 ℃, the die-casting mold temperature is 240 +/-20 ℃, and the injection speed of die-casting is 2 m/s.
And (3) detecting the components of the comparative example die-casting magnesium alloy 2 obtained in the comparative example 2 by using a spectrum analyzer, wherein the detection result is as follows: comparative example 2 the comparative example die-cast magnesium alloy 2 obtained according to the present invention includes: 3.92 wt% of Zn, 4.91 wt% of Y, less than 0.1 wt% of the total amount of impurity elements Fe, Cu, Si and Ni, and the balance of magnesium.
Testing the creep property of the alloy according to the standard of GB/T2039-2012 'test method for uniaxial tensile creep of metal materials'; the experimental results are as follows: the creep life at 300 ℃ and 30MPa is less than 200 h.
Comparative example 3
12050g of pure magnesium, 450g of pure zinc, 1000g of magnesium-cerium intermediate alloy and 1500g of magnesium-yttrium intermediate alloy are preheated to 300 ℃; firstly, putting preheated pure magnesium, magnesium-cerium intermediate alloy and magnesium-yttrium intermediate alloy into a crucible preheated to 300 ℃, and introducing SF into the crucible6And CO2Is 1:80, heating the melt to 730 ℃ after the materials are melted, and then adding the pure zinc preheated to 300 ℃ into the crucible under the stirring condition for mixing for 8 minutes to obtain alloy liquid; combining the above-mentioned materialsCooling the gold liquid to 715 ℃, and standing for 30 minutes;
and die-casting the alloy liquid after standing on a cold chamber die casting machine with 280 tons of die locking force to obtain the die-casting magnesium alloy with creep resistance of 300 ℃, wherein the die-casting temperature is 715 ℃, the die-casting die temperature is 240 +/-20 ℃, and the injection speed of die-casting is 2 m/s.
And (3) detecting the components of the die-casting magnesium alloy obtained in the comparative example 3 by using a spectrum analyzer, wherein the detection result is as follows: the die-cast magnesium alloy obtained in comparative example 3 of the present invention includes: 2.94 wt% of Zn, 1.26 wt% of Ce, 1.98 wt% of Y, less than 0.1 wt% of impurity elements of Fe, Cu, Si and Ni, and the balance of magnesium.
Testing the creep property of the alloy according to the standard of GB/T2039-2012 'test method for uniaxial tensile creep of metal materials'; the experimental results are as follows: the creep stress is 30MPa at 300 ℃, and the lasting creep life is less than 80 h.
Comparative example 4
11600g of pure magnesium, 900g of pure zinc, 1000g of magnesium-cerium intermediate alloy and 1500g of magnesium-yttrium intermediate alloy are preheated to 300 ℃; firstly, putting preheated pure magnesium, magnesium-cerium intermediate alloy and magnesium-yttrium intermediate alloy into a crucible preheated to 300 ℃, and introducing SF into the crucible6And CO2Is 1:80, heating the melt to 730 ℃ after the materials are melted, and then adding the pure zinc preheated to 300 ℃ into the crucible under the stirring condition for mixing for 8 minutes to obtain alloy liquid; cooling the alloy liquid to 715 ℃, and standing for 30 minutes;
and die-casting the alloy liquid after standing on a cold chamber die casting machine with 280 tons of die locking force to obtain the die-casting magnesium alloy with creep resistance of 300 ℃, wherein the die-casting temperature is 715 ℃, the die-casting die temperature is 240 +/-20 ℃, and the injection speed of die-casting is 2 m/s.
And (3) detecting the components of the die-casting magnesium alloy obtained in the comparative example 3 by using a spectrum analyzer, wherein the detection result is as follows: the die-casting magnesium alloy with 300 ℃ creep resistance obtained by the comparative example 3 of the invention comprises: 5.84 wt% of Zn, 1.23 wt% of Ce, 2.02 wt% of Y, less than 0.1 wt% of impurity elements of Fe, Cu, Si and Ni, and the balance of magnesium.
Testing the creep property of the alloy according to the standard of GB/T2039-2012 'test method for uniaxial tensile creep of metal materials'; the experimental results are as follows: the creep stress is 30MPa at 300 ℃, and the lasting creep life is less than 30 h.
As can be seen from the above examples and comparative examples, the present invention provides a die-cast magnesium alloy resistant to creep deformation at 300 degrees celsius, comprising: 2-6 wt% of Zn, 1-4.5 wt% of Ce, 1.5-7 wt% of Y, the total content of Zn, Ce and Y is more than 7.5 wt%, the mass ratio of (Ce + Y)/Zn is more than 1, the total amount of impurity elements Si, Fe, Ni, Cu, Be and the like is less than 0.1 wt%, and the balance is magnesium.
The 300 ℃ creep-resistant die-casting magnesium alloy contains Zn, Ce and Y, and the Zn, the Ce and the Y form second-phase grids which are formed by a plurality of crystal structures and are continuously distributed in a three-dimensional space after being melted, and the second-phase space network structures can effectively hinder dislocation slippage and twin crystal formation under the conditions of high temperature and high pressure, so that the resistance to alloy deformation is improved; in addition, Zn and Y in the magnesium matrix of the alloy can form basal plane precipitated phases in the creep process, thereby effectively hindering basal plane dislocation slippage; therefore, the alloy provided by the invention has extremely excellent performance of resisting ultrahigh temperature creep.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A die cast magnesium alloy comprising:
Zn 2～6wt％；
Ce 1～4.5wt％；
Y 1.5～7wt％；
the total content of Zn, Ce and Y is more than 7.5 wt%, and (Ce + Y)/Zn is more than 1;
the balance of magnesium.
2. The die-cast magnesium alloy according to claim 1, wherein the Zn content is 2.3 to 5.5 wt%, the Ce content is 1.5 to 4.0 wt%, and the Y content is 2.0 to 6.0 wt%.
3. The die-cast magnesium alloy according to claim 1, wherein the total content of Zn, Ce and Y is 7.8-15.0 wt%.
4. The die-cast magnesium alloy according to claim 1, wherein (Ce + Y)/Zn is 1.2 to 3.0.
5. Die-cast magnesium alloy according to claim 1, characterized in that the total content of the impurity elements Si, Fe, Ni, Cu, Be is less than 0.1 wt%.
6. The method for producing a die-cast magnesium alloy as claimed in claim 1, comprising the steps of:
mixing a magnesium source, a zinc source, a cerium source and an yttrium source according to the component ratio, and smelting to obtain an alloy liquid;
and carrying out high-pressure casting on the alloy liquid to obtain the die-casting magnesium alloy.
7. The preparation method according to claim 1, wherein the temperature of the smelting is 700-800 ℃.
8. The method according to claim 1, wherein the temperature of the high-pressure casting is 700 to 750 ℃.
9. The preparation method according to claim 1, wherein the preparation process of the alloy liquid is specifically as follows:
smelting the preheated magnesium source, cerium source and yttrium source to obtain a first mixed molten metal;
and mixing the first mixed molten metal and the preheated zinc source to obtain alloy liquid.
10. The method according to claim 9, wherein the temperature of the preheated magnesium source, the temperature of the preheated cerium source and the temperature of the preheated yttrium source are 280 to 400 ℃, and the temperature of the preheated zinc source is 280 to 400 ℃.
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| CN101240391A (en) * | 2008-02-04 | 2008-08-13 | 中国科学院长春应用化学研究所 | Equilibrium optimized binary reinforcement damping magnesium alloy and preparation method thereof |
| CN113337765A (en) * | 2021-05-27 | 2021-09-03 | 长春理工大学 | High-temperature and high-pressure creep-resistant die-casting magnesium alloy and preparation method thereof |
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| CN101240391A (en) * | 2008-02-04 | 2008-08-13 | 中国科学院长春应用化学研究所 | Equilibrium optimized binary reinforcement damping magnesium alloy and preparation method thereof |
| CN113337765A (en) * | 2021-05-27 | 2021-09-03 | 长春理工大学 | High-temperature and high-pressure creep-resistant die-casting magnesium alloy and preparation method thereof |
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