CN114934217B - Micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy and preparation method thereof - Google Patents
Micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 166
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 144
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011777 magnesium Substances 0.000 claims abstract description 52
- 239000004033 plastic Substances 0.000 claims abstract description 32
- 238000012545 processing Methods 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 238000003723 Smelting Methods 0.000 claims abstract description 7
- 238000005242 forging Methods 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 34
- 229910052749 magnesium Inorganic materials 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 238000001125 extrusion Methods 0.000 claims description 26
- 239000000155 melt Substances 0.000 claims description 22
- 229910052726 zirconium Inorganic materials 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- 229910052797 bismuth Inorganic materials 0.000 claims description 19
- 229910052718 tin Inorganic materials 0.000 claims description 19
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 239000002893 slag Substances 0.000 claims description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 238000000265 homogenisation Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000007547 defect Effects 0.000 claims description 10
- 238000001192 hot extrusion Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000009749 continuous casting Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 7
- 229910052744 lithium Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000005728 strengthening Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910019021 Mg 2 Sn Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910019074 Mg-Sn Inorganic materials 0.000 description 1
- 229910019400 Mg—Li Inorganic materials 0.000 description 1
- 229910019382 Mg—Sn Inorganic materials 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 229910000706 light magnesium alloy Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- -1 magnesium-tin-yttrium-zirconium Chemical compound 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/02—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
- B21B1/024—Forging or pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J1/00—Preparing metal stock or similar ancillary operations prior, during or post forging, e.g. heating or cooling
- B21J1/02—Preliminary treatment of metal stock without particular shaping, e.g. salvaging segregated zones, forging or pressing in the rough
- B21J1/025—Preliminary treatment of metal stock without particular shaping, e.g. salvaging segregated zones, forging or pressing in the rough affecting grain orientation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/002—Hybrid process, e.g. forging following casting
-
- 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
-
- 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 application relates to the technical field of metal materials, in particular to a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following components in percentage by mass: sn:0.45-0.8%, bi:0.5-2.0%, gd:0.5-1.2%, zr:0.4-0.6%; the total amount of Fe, cu and Ni in the impurity elements is less than 0.02%; the balance of Mg. Through the optimized design of the components and the content of the magnesium alloy, the finally prepared alloy can be ensured to contain a small amount of second phase distribution which is uniformly distributed, and the second phase distribution can not be obviously coarsened, so that the alloy is ensured to have excellent plastic deformation capability and higher tensile mechanical property. The magnesium alloy is added with trace rare earth elements and alloy elements, the cost of the used raw materials is low, the plasticity of the magnesium alloy can be obviously changed, the alloy can be ensured to have higher strength, the use of expensive metal lithium and complex smelting protection measures are avoided, the preparation method is simple, complex processing technology and high-end equipment are not needed, and the actual industrial production is easy to realize.
Description
Technical Field
The application relates to the technical field of metal materials, in particular to a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy and a preparation method thereof.
Background
The magnesium resources in China are rich, the actual yield exceeds 60% of the world, but the actual application of magnesium still exists in protecting the magnesium alloy as alloying elements and sacrificial anodes. As is well known, magnesium and magnesium alloys have a number of remarkable characteristics that are incomparable with other structural metal alloy materials, such as light magnesium alloys having excellent damping and shock absorbing properties, electromagnetic shielding properties, and the like, and particularly having high specific strength and specific stiffness, and therefore have become the first choice materials for light weight and green weight reduction. However, since the crystal structure of magnesium is a close-packed hexagonal structure (hcp) structure, which determines that its plastic deformation forming ability is extremely limited at room temperature, how to prepare a magnesium alloy for a structure, which is inexpensive by a certain conventional means, has become a research hot spot in the art.
At present, in order to improve the room temperature high plasticity of magnesium alloys, a great deal of research is focused on adding metallic lithium into magnesium to obtain alloys with a biphase alpha-Mg and beta-Li structure, however, because the beta-Li phase in the magnesium-lithium alloy has extremely limited hardening and strengthening capacity, such as Xu Chunjie, etc., the research current state of the ultra-light Mg-Li alloy strengthening method and the application thereof, the content disclosed in weapon material science and engineering, 2012,35 (2): 97-100, the alloy elements are generally required to be added and then combined with large plastic deformation to ensure that the alloy has certain tensile mechanical properties. In addition, the limited resources of the metal lithium and the active characteristic of the lithium cause difficult preparation, so the price of the metal lithium is extremely high, which severely limits the practical industrial application value of the alloy. As another example, chinese patent No. 108425056A discloses a room temperature high plasticity magnesium alloy containing rare earth yttrium and a preparation method thereof; the application patent CN108796324A discloses a magnesium-tin-yttrium-zirconium alloy with high plasticity at room temperature and a preparation method thereof, both the patents adopt Sn and Y, but the strengthening capability of the alloy is limited because the adopted Sn content is lower,this limits the field of alloy applications. Meanwhile, the technology adopted by the application patent CN108796324A is simple, so that the mechanical property of the alloy is difficult to reach a certain height, and the industrial practical application is not facilitated. The application patent CN 113005347A discloses a high-plasticity Mg-Al-Ca magnesium alloy and a preparation method thereof, but the magnesium alloy needs to be rolled through 90 degrees of overturning, the process is complex, the rolling process is easy to crack, the production cost is higher, and the room temperature plasticity of the alloy is not ideal. The application patent CN 109161757A discloses a magnesium alloy with high strength and high plasticity and a preparation method thereof, which uses Mg x Zn y Ca z Metastable phase particles are used for controlling Laves phase or LPSO phase or recrystallization process, so that the strength and plasticity of the magnesium alloy are improved; however, the added alloy has a large variety and amount, the cost is high, and the room temperature plasticity is not ideal. Therefore, it is important to develop a preparation method of magnesium alloy which has high strength and high plasticity at room temperature and is easy to industrialize, and the problem of urgent need of industrial weight saving at present is also solved.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the application aims to provide the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy of the microalloy, and by adding and controlling the content of trace Sn, bi, gd and Zr elements into the magnesium alloy and combining plastic forming processing, the magnesium alloy prepared finally can be ensured to have high plasticity, and the elongation rate is up to more than 30 percent; in the application, the rare second phases are insufficient to become stress crack sources in the process of being subjected to tensile stress strain, so that the finally prepared alloy has high plasticity, and the alloy has higher elongation at room temperature. Meanwhile, the application also provides a preparation method of the modified starch.
In order to achieve the above purpose, the technical scheme provided by the application is as follows:
on one hand, the application provides a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following components in percentage by mass:
sn:0.45-0.8%, bi:0.5-2.0%, gd:0.5-1.2%, zr:0.4-0.6%; the impurity elements include Fe <0.005%, cu <0.015%, ni <0.002%; the total amount of unavoidable impurities is less than 0.02%; the balance of Mg.
More preferably, the alloy comprises the following components in percentage by mass:
sn:0.5-0.7%, bi:0.8-2.0%, gd:0.8-1.2%, zr:0.4-0.6%; the total amount of Fe, cu and Ni in the impurity elements is less than 0.02%; the balance of Mg.
The application provides a microalloyed Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which not only can ensure that the finally prepared magnesium alloy has high plasticity and the elongation is up to more than 30 percent, but also can ensure that the magnesium alloy exceeds the yield strength and the tensile strength possessed by commercial wrought magnesium alloys such as AZ31 or ZK60 and the like by adding and controlling the content of trace Sn, bi, gd and Zr elements into the magnesium alloy and combining plastic forming processing.
On one hand, the elements have higher solid solubility in the magnesium alloy and can play a role in solid solution strengthening to a certain extent because the addition amount of the elements such as Sn, bi, gd and Zr in pure magnesium is very small; on the other hand, the elements can be basically dissolved in the magnesium matrix in a solid solution manner in the homogenization process, so that the quantity of the second phase formed in the subsequent plastic deformation processing and heat treatment process is reduced, and the second phase is dispersed and distributed in the matrix; thirdly, the elements are harmless to human bodies, are green metal elements, and the prepared high-strength and high-toughness magnesium alloy can be used as a medical biological magnesium alloy material and has important significance on the theory and practical application research of the biological medical magnesium alloy material. Therefore, the rare second phases of the magnesium alloy in the application are not enough to become stress crack sources in the tensile stress strain process, so that the finally prepared alloy has high plasticity, and the alloy has high elongation at room temperature.
Specifically, as the solid solution limit of the rare earth Gd element in the magnesium matrix is as high as 23.49%, the rare earth Gd element mainly exists in the form of being dissolved in the magnesium matrix, the formation of the rare earth texture is promoted in the extrusion process, the basal plane texture of the alloy is weakened, the start of basal plane slip can be promoted when the alloy is subjected to tensile stress deformation, the plasticity of the alloy can be greatly improved, and the equilibrium solid solubility of the Gd element is reduced exponentially with the reduction of the temperature, so that an ideal precipitation strengthening system is formed with the Mg element; the limiting solid solubility of Sn element in magnesium matrix is 14.48%, and thus is mainly present in the form of solid solution in magnesium matrix; zr exists in an alpha-Zr form in the smelting process and is used as a nucleation point, the cast structure of the alloy can be obviously refined in the solidification process, the grain size is reduced, the homogenization structure is more thorough and uniform, the structure assurance is provided for forging, extrusion or rolling, the grain size after the alloy is deformed is finer, the structure is more uniform, the second phase is more dispersed and separated out in the aging process, and the improvement of the tensile mechanical property of the alloy is facilitated.
Therefore, sn, bi, gd and Zr elements which are solid-solved in the magnesium matrix can play a solid-solution strengthening effect to a certain extent, wherein the Sn, bi, gd and Zr elements which are solid-solved in the magnesium matrix are generally enriched at the grain boundary in an atomic form, so that the movement of the grain boundary can be effectively blocked, and the tensile strength is improved; on the other hand, the bonding capability of the grain boundary can be improved, and cracks are prevented from being generated at the grain boundary during stretching, so that the alloy strength is improved to a certain extent, and meanwhile, the plasticity of the alloy can be greatly improved.
At the same time, it should be noted that solidification under non-equilibrium conditions is likely to in turn form Gd with a high melting point 3 Sn (melting point: 1173 ℃ C.), gd 5 Sn 3 (melting point: 1243 ℃ C.) Mg 2 Sn (melting point: 771.5 ℃ C.) and Mg 3 Bi 2 (melting point: 821 ℃ C.) Mg 5 Gd (melting point: 642 ℃ C.) and MgGdSn phases, these small amounts of high melting point phases are extremely small or become solidified nucleation sites, and even multi-stage homogenization has little effect thereon. Thus, it is possible to remain in the room temperature structure, these second phases can pin the grain boundaries during the thermoplastic deformation dynamic recrystallization process, refining the grains; in the subsequent plastic deformation forming process and heat treatment process, a small amount of second phases of Sn, bi, gd and Zr elements can be separated out again, the second phases can deflect recrystallized grains to form rare earth textures, the textures of alloy basal planes are weakened, and non-basal plane sliding opening can be promoted. The addition of Sn, bi and Gd reduces the stacking fault energy of magnesium, promotes the opening of non-basal plane slip, and can coordinate the C axis directionStrain in the direction. In addition, the second phases obtained in the structure have high melting points, so that the alloy has certain high-temperature stability, good casting performance and relatively low cost. Meanwhile, when a proper amount of Zr element is added in the form of intermediate alloy, the Zr element is ensured to completely enter the melt without segregation, and the grain refining effect of the cast metal is achieved. The Zr element is added, and the main purpose is to be used as a refiner, refine the matrix structure and coarser Mg 3 Bi 2 Phase, exert fine crystal strengthening effect; and the content of the alloy needs to be strictly controlled and cannot be too high, so that the influence on the comprehensive performance of the alloy caused by the formation of compound phases with other alloy elements due to the too high content can be avoided.
In addition, because the addition amount is controlled, the maximum liquid-solid temperature interval of Mg-Sn, mg-Bi and Mg-Gd is lower than 100 ℃, and the liquid-solid interval is small, which means that defects such as loose and hot cracks and the like formed in the solidification process are few. Meanwhile, the solid solubility change range of the elements along with the temperature change is extremely large, and a large space is provided for subsequent aging strengthening. In addition, precipitated Mg 2 Sn and Mg 3 Bi 2 Is of FCC structure, mg 3 Bi 2 The heat of formation is-3.5794 eV/atom, while Mg 17 Al 12 The alloy of the phases had a heat of formation of only-0.052 eV/atom, mg was seen 3 Bi 2 The structural stability of (C) is better than that of Mg 17 Al 12 Solid solutions. Thus, it is expected that the structural stability of the alloy of the present application is clearly superior to that of AZ-series alloys, i.e., mg—al—zn-series alloys. Furthermore, it should be noted that since the addition amounts of Sn, bi and Gd are small, the amount of the second phase or metal element compound formed is small, and the second phase or metal element compound is generally distributed in the grain boundary. The alloy is distributed in a streamline manner along the extrusion direction in the extrusion process, has limited effective pinning effect on the grain boundary, cannot prevent the growth effect of recrystallized grains, and has no dispersion strengthening effect, so that the comprehensive performance of the finally prepared alloy is not high. If the content of Sn, bi and Gd is increased, more and coarser second phases are formed, and the coarse second phases often break themselves or release between the particles and the matrix serves to induce the formation of micropores, thereby reducing plastic strain and thus breaking.
In a word, the preferred 0.5-0.7% Sn,0.8-2% Bi and 0.8-1.2% Gd can ensure that the finally prepared alloy contains a small amount of uniformly distributed second phase distribution without obvious coarsening, thereby ensuring that the alloy has excellent plastic deformation capability and higher tensile mechanical property. The magnesium alloy is added with trace rare earth elements and alloy elements, the cost of the used raw materials is low, the plasticity of the magnesium alloy can be obviously changed, the alloy can be ensured to have higher strength, the use of expensive metal lithium and complex smelting protection measures are avoided, the preparation method is simple, complex processing technology and high-end equipment are not needed, and the actual industrial production is easy to realize.
In one aspect, the application provides a method for preparing a microalloyed Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials according to the components and the mass percentages of the magnesium alloy, wherein the Mg, sn and Bi elements are added in the form of industrial pure magnesium ingots, industrial pure tin ingots and industrial pure bismuth particles, and the Gd and Zr elements are added in the form of Mg-Gd intermediate alloy and Mg-Zr intermediate alloy;
smelting and casting; melting, stirring and slagging off the industrial pure magnesium ingot in the first step at 700-720 ℃, adding the Mg-Gd intermediate alloy and the Mg-Zr intermediate alloy, heating to 740-780 ℃ while stirring, stirring for 10-15min after all the raw materials are melted, standing for 5min, adding the industrial pure tin ingot and the industrial pure bismuth particles and stirring for 10-15min when the slag in the melt floats upwards and the melt is cooled to 720-740 ℃, and then removing slag from the alloy melt and standing for 10-15min to facilitate impurity settlement; cooling the melt to 680-700 ℃, then skimming slag again, and then performing semi-continuous casting to obtain a semi-continuous cast ingot with the diameter of phi 100-350 mm; the semi-continuous casting process is adopted, the characteristic that the argon density is higher than that of air is utilized in the semi-continuous casting process, argon is always introduced to protect the surface of molten metal, and the liquid level of the magnesium alloy in the open crystallizer is prevented from being directly contacted with the air in the continuous casting process, so that the protection effect is achieved. In addition, the size and cross-sectional shape (e.g., circular cross-section, square cross-section, rectangular cross-section, or other profiled cross-section) of the semi-continuously cast ingot can be designed according to practical requirements. Since the alloy liquid required increases when the size of the ingot is large, the cooling and solidification speed is slow, and segregation of the alloy element in the ingot is more likely to occur, the size of the ingot is preferably designed in the present application.
Step three, homogenizing treatment; the semicontinuous ingot prepared in the second step is kept at 420 ℃ for 4 hours, then is heated to 460 ℃ for 4 hours, then is heated to 500 ℃ for 12 hours, is subjected to tissue homogenization treatment, is taken out and air-cooled to 200 ℃, and finally is put into warm water at 65 ℃ and is cooled to room temperature, so that an alloy blank is obtained;
fourthly, plastic working; and (3) removing an oxide layer and a surface skin on the surface of the homogenized cast ingot after the cast ingot is processed and removed, upsetting and then three-way forging are performed at 460-500 ℃ to refine crystal grains, further evenly organize and eliminate casting defects, and the cast ingot is directly forged to obtain a final magnesium alloy structural part or is forged and then is subjected to hot extrusion molding to obtain a magnesium alloy section or is forged and then is rolled to obtain a magnesium alloy plate.
The three-way forging process is to forge along the three directions of the x axis, the y axis and the z axis, so that the structure is kneaded, elongated and compressed, grains are forced to be elongated, upset, flowed, turned over, broken and dynamically recrystallized through the action generated by forging, the structure is thinned, and the possible inclusion or slag inclusion defects in the solidified structure are eliminated, so that the distribution of the solidified structure is more uniform. Meanwhile, the defects of casting shrinkage cavities, shrinkage porosity, air holes and the like possibly existing in the solidification process are closed, and the continuity of the tissue is promoted, so that the optimization of the microstructure structure is realized, and the tissue preparation is carried out for the subsequent extrusion or rolling process. In the specific forging process, the semi-continuous cast ingot is subjected to homogenization treatment, upsetting is firstly carried out along the Z direction of the length direction to form a cake shape, then rotary forging is carried out along the X and Y directions, and then the upsetted cake shape is forged into a cylinder shape. According to actual needs, the cake is repeatedly forged into a cake and then into a cylinder for 2-3 times, and finally the cake is turned into a cylinder, the surface oxide skin and the irregular surface are removed, fine crystal preparation is made for extrusion, and cracking is avoided in the extrusion process.
Currently, the conventional process is to directly perform rolling after the heat treatment by tissue homogenization. However, as a result, there is a possibility that cracking is caused by coarse grains in the structure. In addition, inclusions present in the structure may be distributed along the rolling streamline and the sheet may also have cracking problems. The present application does not have such a problem.
Step five, aging treatment; and (3) preserving the heat of the magnesium alloy material subjected to plastic processing in the step (IV) for 12-60 hours at the temperature of 150-200 ℃, performing aging treatment, and air-cooling to room temperature to obtain the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy. The purpose of the aging treatment is to make some strengthening phases dissolved in the matrix secondarily dispersed and separated out so as to improve the mechanical properties of the alloy. In addition, the aging treatment can also effectively eliminate the internal stress of the alloy in the plastic deformation process and improve the plastic deformation capacity of the alloy. The aging temperature and time are the temperature ranges and the length of time selected through comparison of the aging peaks.
Meanwhile, the application provides a preparation method of the magnesium alloy material, wherein Zr element is added in a form of intermediate alloy, and the dissolution and the distribution of the Zr element in magnesium liquid are promoted by stirring, so that the segregation of the Zr element is avoided; meanwhile, the Zr content is strictly controlled according to the solid solubility of Zr element in Mg, and the strict control of the adding time and the adding sequence of the elements is indispensable for synergism, so that the refinement effect of Zr element on the magnesium alloy structure is exerted.
More preferably, the Mg-Gd intermediate alloy adopts Mg-30% Gd intermediate alloy, and the Mg-Zr intermediate alloy adopts Mg-30% Zr intermediate alloy. The melting point of Gd element is higher (1313 ℃) and the difference between Gd element and Mg (649 ℃) is larger, so that the Gd element is added in a mode of intermediate alloy, and is beneficial to melting and even distribution of Gd element in the alloy; the Zr element adopts an Mg-Zr intermediate alloy form, and the same is not repeated. In particular, in the case of magnesium alloys, the higher the content of alloying elements, the higher the melting point of the master alloy, which is less favorable for smelting. However, the higher the alloy element is, the less the addition amount of the intermediate alloy is, so that the introduction of more impurity elements can be avoided; therefore, the intermediate alloy with proper proportion can also have a certain influence on the performance of the final magnesium alloy material.
More preferably, the final forging temperature of the three-way forging in the fourth step is 400-430 ℃. The material in the forging process generates heat due to deformation, and the material in the forging process is likely to crack due to heat dissipation of air convection from the outside. In order to avoid the adverse phenomena, in the three-way forging process, the temperature is detected for each forging, and if the temperature is too low, the material is put into a furnace to be heated again and then forged again. The final forging referred to herein means the final forging, since the former forging has been refined by elongating or crushing the crystal grains by kneading deformation, the plasticity of the material is significantly improved, and the influence on cracking is small, so that the final forging temperature is controlled to be lower than the final forging temperature, that is, the final forging temperature is 400-430 ℃, more preferably the final forging temperature is not more than 410-425 ℃, so as to control the size and orientation of the crystal grain size thereof, providing good tissue assurance for the subsequent processing. Mg may be present in the tissue 5 The Gd phase has better plasticity due to the existence of Sn and Bi elements. Therefore, forging can be performed at a relatively low temperature without cracking. The plastic deformation treatment of forging is carried out at a lower temperature, and the effect and the meaning are great for the tissue refinement degree, uniformity and secondary distribution of alloy elements and elimination of macroscopic and partial microscopic segregation of the alloy. Therefore, the lower the forging temperature is, the more advantageous the mechanical properties of the alloy are, while ensuring that no cracking is obtained.
More preferably, when the forging in the step four is performed again, hot extrusion molding is performed, turning is performed after cooling to room temperature, surface oxide layers, dirt and microcracks are removed, then the forged material after turning is put into an extrusion cylinder again, extrusion deformation processing is performed at the temperature of 250-330 ℃, the extrusion ratio is 12.5-40, and finally the micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material is obtained.
More preferably, when forging and then rolling in the fourth step, forging the alloy into a rectangular blank, removing the surface oxide layer and dirt, and rolling the rectangular blank into a plate at 420-440 ℃ to obtain the microalloyed Mg-Sn-Bi-Gd-Zr high plasticity magnesium alloy material.
In addition, the plastic forming process such as forging, extrusion or rolling and the additional heat treatment process are combined, so that the magnesium alloy material can be ensured to have good comprehensive mechanical properties, namely, the dispersion and precipitation of the second phase and the LPSO structure in the matrix are controlled by controlling the content of each component element in the magnesium alloy, so that the finally prepared fine-grain magnesium alloy not only has higher strength, high plasticity and high elongation rate of more than 30 percent, but also has the mechanical property indexes exceeding the properties such as ignition point, yield strength, tensile strength, elongation rate and the like of commercial wrought magnesium alloys such as AZ31 or ZK60 and the like.
The technical scheme provided by the application has the beneficial effects that:
the application provides a microalloyed Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which is characterized in that trace Sn, bi, gd and Zr element contents are added and controlled through the optimized design of the components and the contents of the magnesium alloy, so that the finally prepared alloy can be ensured to contain a small amount of uniformly distributed second phases without obvious coarsening, the alloy is ensured to have excellent plastic deformation capability, and meanwhile, the alloy has higher tensile mechanical property, and the elongation rate is up to more than 30%. The magnesium alloy is added with trace rare earth elements and alloy elements, the cost of the used raw materials is low, the plasticity of the magnesium alloy can be obviously changed, the alloy can be ensured to have higher strength, the use of expensive metal lithium and complex smelting protection measures are avoided, the preparation method is simple, complex processing technology and high-end equipment are not needed, and the actual industrial production is easy to realize.
Detailed Description
The following description of the embodiments of the present application will clearly and fully describe the technical solutions of the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items. It is to be understood that various raw materials in the present application are commercially available unless otherwise specified.
Example 1
The application provides a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following components in percentage by mass:
sn:0.5%, bi:0.8%, gd:1.2%, zr:0.4%; the total amount of Fe, cu and Ni in the impurity elements is less than 0.02%; the balance of Mg.
The application provides a preparation method of a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials according to the components and mass percentages in the magnesium alloy, and preparing industrial pure magnesium ingots, industrial pure tin ingots, industrial pure bismuth particles, mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy;
melting, stirring and slagging off the industrial pure magnesium ingot in the first step at 720 ℃, adding the Mg-30% Gd intermediate alloy and the Mg-30% Zr intermediate alloy, heating to 780 ℃ while stirring, stirring for 10min after all the raw materials are melted, standing for 5min, adding the industrial pure tin ingot and the industrial pure bismuth particles and stirring for 10min when slag in the melt floats upwards and the melt is cooled to 720 ℃, and then standing for 10min after deslagging the alloy melt so as to facilitate impurity settlement; cooling the melt to 690 ℃, then skimming again, and then performing semicontinuous casting to obtain a semicontinuous cast ingot with the diameter of 250 mm;
step three, homogenizing treatment; the semicontinuous ingot prepared in the second step is kept at 420 ℃ for 4 hours, then is heated to 460 ℃ for 4 hours, then is heated to 500 ℃ for 12 hours, is subjected to tissue homogenization treatment, is taken out and air-cooled to 200 ℃, and finally is put into warm water at 65 ℃ and is cooled to room temperature, so that an alloy blank is obtained;
fourthly, plastic working; the oxide layer and the surface skin on the surface of the homogenized cast ingot are removed by the cast ingot processing obtained in the step three, and then upsetting and three-way forging are carried out at 500 ℃ to refine crystal grains, further uniformly organize and eliminate casting defects; the final forging temperature was 410 ℃. And when the hot extrusion molding is carried out after forging, the final forging size is limited to be 10mm larger than the diameter of the extrusion cylinder, turning a sheet after cooling to room temperature, removing the surface oxide layer and dirt, and then putting the forged material after turning the sheet again into the extrusion cylinder to carry out extrusion deformation processing at 330 ℃ with the extrusion ratio of 12.5, thereby obtaining the micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material.
Step five, aging treatment; and (3) preserving the heat of the magnesium alloy material subjected to plastic processing in the step (IV) for 24 hours at 180 ℃, performing aging treatment, and air-cooling to room temperature to obtain the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy.
Example 2
The application provides a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following components in percentage by mass:
sn:0.6%, bi:2.0%, gd:1.0%, zr:0.5%; the total amount of Fe, cu and Ni in the impurity elements is less than 0.02%; the balance of Mg.
The application provides a preparation method of a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials according to the components and mass percentages in the magnesium alloy, and preparing industrial pure magnesium ingots, industrial pure tin ingots, industrial pure bismuth particles, mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy;
melting, stirring and slagging off the industrial pure magnesium ingot in the first step, adding the Mg-30% Gd intermediate alloy and the Mg-30% Zr intermediate alloy, heating to 740 ℃ while stirring, stirring for 15min after all the raw materials are melted, standing for 5min, adding the industrial pure tin ingot and the industrial pure bismuth particles and stirring for 15min when slag in the melt floats up and the melt is cooled to 740 ℃, and then removing slag from the alloy melt and standing for 15min to facilitate impurity settlement; cooling the melt to 680 ℃, then skimming again, and then performing semicontinuous casting to obtain a semicontinuous cast ingot with the diameter of 350 mm;
step three, homogenizing treatment; the semicontinuous ingot prepared in the second step is kept at 420 ℃ for 4 hours, then is heated to 460 ℃ for 4 hours, then is heated to 500 ℃ for 12 hours, is subjected to tissue homogenization treatment, is taken out and air-cooled to 200 ℃, and finally is put into warm water at 65 ℃ and is cooled to room temperature, so that an alloy blank is obtained;
fourthly, plastic working; the oxide layer and the surface skin on the surface of the homogenized cast ingot are removed by the cast ingot processing obtained in the step three, and then upsetting and three-way forging are carried out at 460 ℃ to refine crystal grains, further uniformly organize and eliminate casting defects; the final forging temperature was 420 ℃.
When the magnesium alloy is rolled after forging, firstly forging the magnesium alloy into a rectangular blank, namely a rectangular section blank with the thickness of 100mm, then removing a surface oxide layer and dirt, rolling the rectangular blank into a plate at the rolling temperature of 440 ℃ to obtain a plate with the thickness of 6mm, and obtaining the micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material.
Step five, aging treatment; and (3) preserving the heat of the magnesium alloy material subjected to plastic processing in the step (IV) for 60 hours at 200 ℃, performing aging treatment, and air-cooling to room temperature to obtain the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy.
Example 3
The application provides a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following components in percentage by mass:
sn:0.7%, bi:1.8%, gd:0.9%, zr:0.6%; the total amount of Fe, cu and Ni in the impurity elements is less than 0.02%; the balance of Mg.
The application provides a preparation method of a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials according to the components and mass percentages in the magnesium alloy, and preparing industrial pure magnesium ingots, industrial pure tin ingots, industrial pure bismuth particles, mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy;
melting, stirring and slagging off the industrial pure magnesium ingot in the first step at 710 ℃, adding the Mg-30% Gd intermediate alloy and the Mg-30% Zr intermediate alloy, heating to 760 ℃ while stirring, stirring for 13min after all the raw materials are melted, standing for 5min, adding the industrial pure tin ingot and the industrial pure bismuth particles and stirring for 13min when slag in the melt floats up and the melt is cooled to 730 ℃, and then removing slag from the alloy melt and standing for 13min again to facilitate impurity settlement; cooling the melt to 680 ℃, then skimming again, and then performing semicontinuous casting to obtain a semicontinuous cast ingot with the diameter of 350 mm;
step three, homogenizing treatment; the semicontinuous ingot prepared in the second step is kept at 420 ℃ for 4 hours, then is heated to 460 ℃ for 4 hours, then is heated to 500 ℃ for 12 hours, is subjected to tissue homogenization treatment, is taken out and air-cooled to 200 ℃, and finally is put into warm water at 65 ℃ and is cooled to room temperature, so that an alloy blank is obtained;
fourthly, plastic working; the oxide layer and the surface skin on the surface of the homogenized cast ingot are removed by the cast ingot processing obtained in the step three, and then upsetting and three-way forging are carried out at 460 ℃ to refine crystal grains, further uniformly organize and eliminate casting defects; the final forging temperature was 425 ℃.
When the alloy is rolled after forging, firstly forging the alloy into a rectangular blank, namely a rectangular section blank with the thickness of 100mm, then removing a surface oxide layer and dirt, rolling the rectangular blank into a plate at the rolling temperature of 420 ℃, and rolling the plate into a plate with the thickness of 8mm to obtain the micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material.
Step five, aging treatment; and (3) preserving the heat of the magnesium alloy material subjected to plastic processing in the step (IV) for 48 hours at 150 ℃, performing aging treatment, and air-cooling to room temperature to obtain the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy.
Example 4
The application provides a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following components in percentage by mass:
sn:0.55%, bi:1.2%, gd:0.8%, zr:0.5%; the total amount of Fe, cu and Ni in the impurity elements is less than 0.02%; the balance of Mg.
The application provides a preparation method of a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials according to the components and mass percentages in the magnesium alloy, and preparing industrial pure magnesium ingots, industrial pure tin ingots, industrial pure bismuth particles, mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy;
melting, stirring and slagging off the industrial pure magnesium ingot in the first step at 710 ℃, adding the Mg-30% Gd intermediate alloy and the Mg-30% Zr intermediate alloy, heating to 770 ℃ while stirring, stirring for 12min after all the raw materials are melted, standing for 5min, adding the industrial pure tin ingot and the industrial pure bismuth particles and stirring for 12min when slag in the melt floats up and the melt is cooled to 730 ℃, and then removing slag from the alloy melt and standing for 12min again to facilitate impurity settlement; cooling the melt to 700 ℃, then removing slag again, and then performing semicontinuous casting to obtain a semicontinuous cast ingot with the diameter of 150 mm;
step three, homogenizing treatment; the semicontinuous ingot prepared in the second step is kept at 420 ℃ for 4 hours, then is heated to 460 ℃ for 4 hours, then is heated to 500 ℃ for 12 hours, is subjected to tissue homogenization treatment, is taken out and air-cooled to 200 ℃, and finally is put into warm water at 65 ℃ and is cooled to room temperature, so that an alloy blank is obtained;
fourthly, plastic working; the oxide layer and the surface skin on the surface of the homogenized cast ingot are removed by the cast ingot processing obtained in the step three, and then upsetting and three-way forging are carried out at 460 ℃ to refine crystal grains, further uniformly organize and eliminate casting defects; the final forging temperature was 420 ℃.
And when the hot extrusion molding is carried out after forging, the final forging size is limited to be 10mm larger than the diameter size of the extrusion cylinder, turning a sheet after cooling to room temperature, removing the surface oxide layer and dirt, and then putting the forged material after turning the sheet again into the extrusion cylinder to carry out extrusion deformation processing at 250 ℃ with the extrusion ratio of 40, thus obtaining the micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material.
Step five, aging treatment; and (3) preserving the heat of the magnesium alloy material subjected to plastic processing in the step (IV) for 12 hours at 200 ℃, performing aging treatment, and air-cooling to room temperature to obtain the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy.
Example 5
The application provides a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following components in percentage by mass:
sn:0.65%, bi:1.0%, gd:1.1%, zr:0.55%; the total amount of Fe, cu and Ni in the impurity elements is less than 0.02%; the balance of Mg.
The application provides a preparation method of a micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials according to the components and mass percentages in the magnesium alloy, and preparing industrial pure magnesium ingots, industrial pure tin ingots, industrial pure bismuth particles, mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy;
melting, stirring and slagging off the industrial pure magnesium ingot in the first step at 720 ℃, adding the Mg-30% Gd intermediate alloy and the Mg-30% Zr intermediate alloy, heating to 750 ℃ while stirring, stirring for 15min after all the raw materials are melted, standing for 5min, adding the industrial pure tin ingot and the industrial pure bismuth particles and stirring for 15min when slag in the melt floats upwards and the melt is cooled to 740 ℃, and standing for 10min after deslagging the alloy melt so as to facilitate impurity settlement; cooling the melt to 690 ℃, then skimming again, and then performing semicontinuous casting to obtain a semicontinuous cast ingot with the diameter of 200 mm;
step three, homogenizing treatment; the semicontinuous ingot prepared in the second step is kept at 420 ℃ for 4 hours, then is heated to 460 ℃ for 4 hours, then is heated to 500 ℃ for 12 hours, is subjected to tissue homogenization treatment, is taken out and air-cooled to 200 ℃, and finally is put into warm water at 65 ℃ and is cooled to room temperature, so that an alloy blank is obtained;
fourthly, plastic working; the oxide layer and the surface skin on the surface of the homogenized cast ingot are removed by the cast ingot processing obtained in the step three, and then upsetting and three-way forging are carried out at 470 ℃ to refine crystal grains, further uniformly organize and eliminate casting defects; the final forging temperature was 415 ℃.
And when the hot extrusion molding is carried out after forging, the final forging size is limited to be 10mm larger than the diameter size of the extrusion cylinder, turning a sheet after cooling to room temperature, removing the surface oxide layer and dirt, and then putting the forged material after turning the sheet again into the extrusion cylinder to carry out extrusion deformation processing at 280 ℃ with the extrusion ratio of 25, thereby obtaining the micro-alloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material.
Step five, aging treatment; and (3) preserving the heat of the magnesium alloy material subjected to plastic processing in the step (IV) for 48 hours at 175 ℃, performing aging treatment, and air-cooling to room temperature to obtain the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy.
Comparative example 1
Commercial AZ31 plates with the thickness of 4mm are selected, the tensile strength UTS is 250MPa, the yield strength YTS is 177MPa and the elongation is 15 percent at room temperature.
Comparative example 2
Commercially available ZK60 plates with the thickness of 5mm are selected, the tensile strength UTS is 285MPa, the yield strength YTS is 200MPa, and the elongation is 19%.
Experimental results and performance analysis
The magnesium alloy materials prepared in examples 1 to 5 were subjected to the following performance tests:
tensile strength test: the magnesium alloy of the examples 1-5 is subjected to room temperature mechanical property test, the mechanical property test is processed and tested according to national standard GB 6397-86 Metal tensile test sample, the testing equipment is a precision universal experiment machine stretcher, and the stretching speed is 1mm/min; the test results are shown in Table 1.
Table 1 results of performance test for preparing magnesium alloys in examples 1 to 5
| Material | Ultimate tensile Strength (MPa) | Yield strength (MPa) | Elongation (%) |
| Example 1 | 317 | 223 | 31.2 |
| Example 2 | 296 | 212 | 32.4 |
| Example 3 | 330 | 208 | 34.0 |
| Example 4 | 312 | 221 | 35.6 |
| Example 5 | 349 | 224 | 36.1 |
| Commercial AZ31 plate (4 mm thick) | 250 | 177 | 15 |
| Commercial ZK60 plate (5 mm thick) | 285 | 200 | 19 |
As can be seen from Table 1, the room temperature tensile strength and elongation of the microalloyed high-plasticity magnesium alloy are greatly improved compared with those of commercial AZ31 and ZK60 alloys, the magnesium alloy shows very high room temperature plasticity, and the alloy obtained by adopting the magnesium alloy component design and preparation process can meet the requirement of room temperature primary plastic deformation on the elongation of the material, and the alloy cannot crack and fail during plastic deformation. At the same time, the alloy has enough strength. Therefore, the plate rolled by the alloy can achieve the bending and stamping processes adopted by the processing of the steel plate, realize further plastic deformation forming and meet the requirement of plastic forming of magnesium alloy at room temperature.
While the fundamental and principal features of the application and advantages of the application have been shown and described, it will be apparent to those skilled in the art that the application is not limited to the details of the foregoing exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (5)
1. The Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy of the micro alloy is characterized by comprising the following components in percentage by mass:
sn:0.5-0.7%, bi:0.8-2.0%, gd:0.8-1.2%, zr:0.4-0.6%; the impurity elements comprise Fe <0.005%, cu <0.015%, ni <0.002%, and the total amount of Fe, cu and Ni in the impurity elements is less than 0.02%; the balance of Mg;
the preparation method of the magnesium alloy comprises the following steps:
step one, batching; weighing raw materials according to the components and the mass percentages of the magnesium alloy, wherein the Mg, sn and Bi elements are added in the form of industrial pure magnesium ingots, industrial pure tin ingots and industrial pure bismuth particles, and the Gd and Zr elements are added in the form of Mg-Gd intermediate alloy and Mg-Zr intermediate alloy;
smelting and casting; melting, stirring and slagging off the industrial pure magnesium ingot in the first step at 700-720 ℃, adding the Mg-Gd intermediate alloy and the Mg-Zr intermediate alloy, heating to 740-780 ℃ while stirring, stirring for 10-15min after all the raw materials are melted, standing for 5min, adding the industrial pure tin ingot and the industrial pure bismuth particles and stirring for 10-15min when the slag in the melt floats upwards and the melt is cooled to 720-740 ℃, and then removing slag from the alloy melt and standing for 10-15min to facilitate impurity settlement; cooling the melt to 680-700 ℃, then skimming again, and then performing semi-continuous casting to obtain a semi-continuous cast ingot with the diameter of 100-350 mm;
step three, homogenizing treatment; the semicontinuous ingot prepared in the second step is kept at 420 ℃ for 4 hours, then is heated to 460 ℃ for 4 hours, then is heated to 500 ℃ for 12 hours, is subjected to tissue homogenization treatment, is taken out and air-cooled to 200 ℃, and finally is put into warm water at 65 ℃ and is cooled to room temperature, so that an alloy blank is obtained;
fourthly, plastic working; removing an oxide layer and a surface skin on the surface of the homogenized cast ingot after the cast ingot is processed and removed, upsetting and then three-way forging are performed at 460-500 ℃ to refine crystal grains, further evenly organize and eliminate casting defects, and the cast ingot is directly forged to obtain a final magnesium alloy structural part or is forged and then is subjected to hot extrusion molding to obtain a magnesium alloy section or is forged and then is rolled to obtain a magnesium alloy plate;
step five, aging treatment; and (3) preserving the heat of the magnesium alloy material subjected to plastic processing in the step (IV) for 12-60 hours at the temperature of 150-200 ℃, performing aging treatment, and air-cooling to room temperature to obtain the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy.
2. The micro-alloyed Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy according to claim 1, wherein Mg-Gd intermediate alloy is Mg-30% Gd intermediate alloy and Mg-Zr intermediate alloy is Mg-30% Zr intermediate alloy.
3. The Mg-Sn-Bi-Gd-Zr high plasticity magnesium alloy according to claim 1, wherein the final forging temperature of the three-way forging in step four is 400-430 ℃.
4. The Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy according to claim 1, wherein the step four is a hot extrusion molding process after forging, wherein the hot extrusion molding process is performed after cooling to room temperature, the surface oxide layer, dirt and micro-cracks are removed, the forged material after the hot extrusion molding process is performed in an extrusion container at 250-330 ℃ for extrusion deformation processing, the extrusion ratio is 12.5-40, and finally the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material of the micro alloy is obtained.
5. The Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy according to claim 1, wherein the step four is performed with forging to form a rectangular blank, removing the surface oxide layer and dirt, and rolling the rectangular blank at 420-440 ℃.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010056130A1 (en) * | 2008-11-14 | 2010-05-20 | Auckland Uniservices Limited | Magnesium based alloys and processes for preparation thereof |
| JP2017206757A (en) * | 2016-05-20 | 2017-11-24 | 不二ライトメタル株式会社 | Resolvable magnesium alloy |
| JP2018012888A (en) * | 2016-07-11 | 2018-01-25 | 国立研究開発法人物質・材料研究機構 | Magnesium based alloy extension material and method for producing the same |
| CN107747014A (en) * | 2017-10-26 | 2018-03-02 | 东北大学 | One kind has high ductibility high-strength magnesium alloy and preparation method thereof |
| CN108425056A (en) * | 2018-05-03 | 2018-08-21 | 重庆大学 | A kind of room temperature high plastic magnesium alloy and preparation method thereof containing rare-earth yttrium |
| CN108796324A (en) * | 2018-07-03 | 2018-11-13 | 重庆大学 | A kind of room temperature high-ductility magnesium-tin-yttrium-zircaloy and preparation method thereof |
| WO2019013226A1 (en) * | 2017-07-10 | 2019-01-17 | 国立研究開発法人物質・材料研究機構 | Magnesium-based wrought alloy material and manufacturing method therefor |
| CN109266930A (en) * | 2018-11-19 | 2019-01-25 | 河北工业大学 | A kind of high tough wrought magnesium alloy and preparation method thereof |
| CN109280826A (en) * | 2018-10-17 | 2019-01-29 | 余炜 | A kind of non-rare earth high-strength magnesium alloy materials of nanostructure-containing and preparation method thereof |
| CN110945154A (en) * | 2017-07-18 | 2020-03-31 | 国立研究开发法人物质·材料研究机构 | Magnesium-based alloy ductile material and method for producing same |
| EP3650561A1 (en) * | 2018-11-08 | 2020-05-13 | Citic Dicastal Co., Ltd. | Plastic wrought magnesium alloy and preparation method thereof |
| CN113444944A (en) * | 2021-06-30 | 2021-09-28 | 赣州虔博新材料科技有限公司 | Low-cost high-strength high-ductility rare earth magnesium alloy and preparation method thereof |
| WO2021215666A1 (en) * | 2020-04-22 | 2021-10-28 | 경북대학교 산학협력단 | High-quality magnesium alloy processed material and manufacturing method therefor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101159790B1 (en) * | 2012-01-30 | 2012-06-26 | 한국기계연구원 | Magnesium alloy having high ductility and high toughness and process for preparing the same |
-
2022
- 2022-05-25 CN CN202210575408.6A patent/CN114934217B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010056130A1 (en) * | 2008-11-14 | 2010-05-20 | Auckland Uniservices Limited | Magnesium based alloys and processes for preparation thereof |
| JP2017206757A (en) * | 2016-05-20 | 2017-11-24 | 不二ライトメタル株式会社 | Resolvable magnesium alloy |
| JP2018012888A (en) * | 2016-07-11 | 2018-01-25 | 国立研究開発法人物質・材料研究機構 | Magnesium based alloy extension material and method for producing the same |
| WO2019013226A1 (en) * | 2017-07-10 | 2019-01-17 | 国立研究開発法人物質・材料研究機構 | Magnesium-based wrought alloy material and manufacturing method therefor |
| CN110945154A (en) * | 2017-07-18 | 2020-03-31 | 国立研究开发法人物质·材料研究机构 | Magnesium-based alloy ductile material and method for producing same |
| CN107747014A (en) * | 2017-10-26 | 2018-03-02 | 东北大学 | One kind has high ductibility high-strength magnesium alloy and preparation method thereof |
| CN108425056A (en) * | 2018-05-03 | 2018-08-21 | 重庆大学 | A kind of room temperature high plastic magnesium alloy and preparation method thereof containing rare-earth yttrium |
| CN108796324A (en) * | 2018-07-03 | 2018-11-13 | 重庆大学 | A kind of room temperature high-ductility magnesium-tin-yttrium-zircaloy and preparation method thereof |
| CN109280826A (en) * | 2018-10-17 | 2019-01-29 | 余炜 | A kind of non-rare earth high-strength magnesium alloy materials of nanostructure-containing and preparation method thereof |
| EP3650561A1 (en) * | 2018-11-08 | 2020-05-13 | Citic Dicastal Co., Ltd. | Plastic wrought magnesium alloy and preparation method thereof |
| CN109266930A (en) * | 2018-11-19 | 2019-01-25 | 河北工业大学 | A kind of high tough wrought magnesium alloy and preparation method thereof |
| WO2021215666A1 (en) * | 2020-04-22 | 2021-10-28 | 경북대학교 산학협력단 | High-quality magnesium alloy processed material and manufacturing method therefor |
| CN113444944A (en) * | 2021-06-30 | 2021-09-28 | 赣州虔博新材料科技有限公司 | Low-cost high-strength high-ductility rare earth magnesium alloy and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张建新等.《Mg：xSn：Si合金的组织演变和强韧化机理研究铸铁冶金》.中国矿业大学出版社,2017,第11页. * |
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