CN114934217A - Microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy and preparation method thereof - Google Patents
Microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy and preparation method thereof Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000000956 alloy Substances 0.000 claims abstract description 133
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 110
- 239000011777 magnesium Substances 0.000 claims abstract description 56
- 238000012545 processing Methods 0.000 claims abstract description 34
- 239000004033 plastic Substances 0.000 claims abstract description 32
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 31
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 29
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 27
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000003723 Smelting Methods 0.000 claims abstract description 6
- 238000005242 forging Methods 0.000 claims description 59
- 229910052749 magnesium Inorganic materials 0.000 claims description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 28
- 238000005266 casting Methods 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 230000032683 aging Effects 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 18
- 238000005096 rolling process Methods 0.000 claims description 18
- 229910052718 tin Inorganic materials 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 12
- 238000009749 continuous casting Methods 0.000 claims description 11
- 238000000265 homogenisation Methods 0.000 claims description 11
- 230000007547 defect Effects 0.000 claims description 10
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 8
- 238000001192 hot extrusion Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 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
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 25
- 238000003756 stirring Methods 0.000 description 21
- 239000011159 matrix material Substances 0.000 description 12
- 238000005728 strengthening Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910019021 Mg 2 Sn Inorganic materials 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
- 238000013016 damping Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007788 liquid 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
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910019074 Mg-Sn Inorganic materials 0.000 description 1
- 229910019382 Mg—Sn Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending 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
- 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
- 239000001989 lithium alloy Substances 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
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Forging (AREA)
Abstract
The invention relates to the technical field of metal materials, in particular to a microalloy 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 percent; the balance being Mg. Through the optimization design of the components and the content of the magnesium alloy, the finally prepared alloy can be ensured to contain a small amount of uniformly distributed second phase distribution, and the second phase distribution can not be coarsened obviously, so that the alloy is ensured to have excellent plastic deformation capacity, and simultaneously has higher tensile mechanical property. The magnesium alloy is added with trace rare earth elements and alloy elements, the used raw materials have low cost, the plasticity of the magnesium alloy can be obviously changed, the high strength of the alloy can be ensured, 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 required, and the actual industrial production is easy to realize.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy and a preparation method thereof.
Background
China has abundant magnesium resources, and the actual yield exceeds 60 percent of the world, however, the practical application of magnesium still lies in serving as an alloying element and sacrificial anode to protect magnesium alloy. As is well known, magnesium and magnesium alloys have many remarkable characteristics that are incomparable with other structural metal alloy materials, for example, light magnesium alloys have excellent damping and damping properties, electromagnetic shielding properties and the like, and particularly have high specific strength and specific rigidity, so that magnesium and magnesium alloys have become the preferred materials for light weight and green weight reduction. However, since the crystal structure of magnesium is a hexagonal close-packed (hcp) structure, which determines that the plastic deformation forming ability at room temperature is very limited, it has become a research focus in the art how to prepare an inexpensive magnesium alloy for a structure by some conventional means.
At present, in order to improve the high plasticity of magnesium alloy at room temperature, a great deal of research is focused on adding metallic lithium into magnesium to obtain alloy with dual-phase alpha-Mg and beta-Li structures, however, because the beta-Li phase in the magnesium-lithium alloy has extremely limited work hardening strengthening capacity, such as Xunchojie and the likeThe elements are combined with large plastic deformation to ensure that the alloy has certain tensile mechanical property. In addition, because the resource of the metallic lithium is limited and the active characteristic of the lithium causes difficulty in preparation, the price of the metallic lithium is extremely high, which seriously limits the practical industrial application value of the alloy. For another example, chinese invention patent CN 108425056a discloses a high plasticity magnesium alloy containing rare earth yttrium at room temperature and its preparation method; the invention patent CN108796324A discloses a room temperature high plasticity magnesium-tin-yttrium-zirconium alloy and a preparation method thereof, both of the two patents adopt Sn and Y, but the Sn content adopted is low, so the strengthening capability of the alloy is limited, and the application field of the alloy is limited. Meanwhile, the process adopted by the invention patent CN108796324A is simple, and the mechanical property of the alloy is difficult to reach a certain height, which is not beneficial to industrial practical application. The invention patent CN 113005347A discloses a high-plasticity Mg-Al-Ca magnesium alloy and a preparation method thereof, but the high-plasticity Mg-Al-Ca magnesium alloy needs to be rolled by 90-degree overturning, has complex process, is easy to crack in the rolling process, has higher production cost, and has unsatisfactory room temperature plasticity. The invention patent CN 109161757A discloses a magnesium alloy with high strength and high plasticity and a preparation method thereof, and Mg is used for preparing the magnesium alloy x Zn y Ca z Controlling a Laves phase or an LPSO phase or a recrystallization process by using metastable-phase particles, and improving the strength and the plasticity of the magnesium alloy; but the types and the amount of the added alloy are more, the cost is higher, and the room temperature plasticity is not ideal. Therefore, it is important to develop a preparation method for magnesium alloy with high strength, high plasticity at room temperature and easy industrialization, which is also a problem to be solved by the urgent need of industrial weight reduction.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a microalloyed Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, and not only can the finally prepared magnesium alloy be ensured to have high plasticity and the elongation rate is up to more than 30% by adding and controlling trace Sn, Bi, Gd and Zr element contents into the magnesium alloy and combining plastic forming processing; in the process of the tensile stress strain, the rare second phases of the magnesium alloy are not enough to become stress crack sources, so that the finally prepared alloy has high plasticity, and the alloy has higher elongation at room temperature. Meanwhile, the invention also provides a preparation method of the composition.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
on one hand, the invention provides a microalloy 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 comprise Fe < 0.005%, Cu < 0.015% and Ni < 0.002%; the total amount of unavoidable impurities is less than 0.02%; the balance being 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 percent; the balance being Mg.
The invention 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 reaches more than 30 percent, but also can ensure that the magnesium alloy exceeds the yield strength and the tensile strength of commercial wrought magnesium alloys such as AZ31 or ZK60 and the like by adding and controlling the content of trace elements such as Sn, Bi, Gd and Zr into the magnesium alloy and combining plastic forming processing.
Because the addition amount of Sn, Bi, Gd and Zr in pure magnesium is very small, on one hand, the elements have higher solid solubility in magnesium alloy and can play a role in solid solution strengthening to a certain extent; 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 second phases formed in the subsequent plastic deformation processing and heat treatment processes is reduced, and the second phases are dispersed in the matrix; thirdly, the elements are harmless to human bodies and 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 invention are not enough to be 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.
Specifically, as the solid solution limit of the rare earth Gd element in the magnesium matrix is up to 23.49 percent, the Gd element exists in a form of being dissolved in the magnesium matrix, the formation of a rare earth texture is promoted in the extrusion process, the basal plane texture of the alloy is weakened, the start of basal plane slippage can be promoted when the alloy is deformed by tensile stress, the plasticity of the alloy can be greatly improved, and the equilibrium solid solubility of the Gd element is reduced exponentially and rapidly along with the reduction of the temperature, so that an ideal precipitation strengthening system is formed with the Mg element; the limiting solid solubility of the Sn element in the magnesium matrix is 14.48%, and therefore, the Sn element is mainly present in the form of solid solution in the magnesium matrix; zr exists in the form of alpha-Zr in the smelting process and serves as nucleation particles, the as-cast structure of the alloy can be obviously refined and the grain size can be reduced in the solidification process, so that the homogenization structure is more thorough and uniform, the structure guarantee is provided for forging, extruding or rolling, the grain size after the alloy is deformed is finer, the structure is more uniform, a second phase is more dispersedly separated out in the aging process, and the improvement of the tensile mechanical property of the alloy is facilitated.
Therefore, the Sn, Bi, Gd and Zr elements which are dissolved in the magnesium matrix in a solid solution mode can play a role in solid solution strengthening to a certain extent, wherein the Sn, Bi, Gd and Zr elements which are dissolved in the magnesium matrix in a solid solution mode are usually enriched at a crystal boundary in an atomic mode, on one hand, the movement of the crystal boundary can be effectively hindered, 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 in the grain boundary during stretching, so that the alloy strength is improved to a certain extent, and the plasticity of the alloy can be greatly improved.
At the same time, we should also note that, by solidifying under non-equilibrium conditions, it is possible in turn to form Gd, a high melting point 3 Sn (melting point: 1173 ℃), Gd 5 Sn 3 (melting point: 1243 ℃ C.), Mg 2 Sn (melting point: 771.5 ℃ C.), Mg 3 Bi 2 (melting point: 821 ℃ C.), Mg 5 Gd (melting point: 642 ℃ C.) and MgGdSn, and these small amounts of the high-melting-point phases are contained in extremely small amounts or becomeThe solidified nucleation particles have little effect even if multi-stage homogenization is carried out. Therefore, the structure can be retained in the room temperature structure, and the second phases can pin the grain boundaries and refine the grains in the process of thermoplastic deformation dynamic recrystallization; during subsequent plastic deformation forming and heat treatment, Sn, Bi, Gd and Zr elements may precipitate a small amount of second phases again, and the second phases can also deflect recrystallized grains to form rare earth textures, so that the texture of the basal plane of the alloy is weakened, and the opening of non-basal plane slippage can be promoted. The addition of Sn, Bi and Gd reduces the stacking fault energy of magnesium, promotes the opening of non-basal plane slippage and can coordinate the strain in the C axis direction. In addition, the high melting point of the second phase obtained in the structure ensures that the alloy also has certain high-temperature stability, has good casting performance and is relatively low in cost. Meanwhile, when a proper amount of Zr element is added in the form of master alloy, the Zr element is ensured to completely enter the melt without segregation, and the grain of the cast metal is refined. The Zr element is added mainly to be used as a refiner for refining the matrix structure and the thicker Mg 3 Bi 2 Phase, exerting fine crystal strengthening effect; and the content of the alloy is strictly controlled and cannot be too high, so that the influence on the comprehensive performance of the alloy caused by forming compound phases with other alloy elements can be avoided.
In addition, because the adding amount is controlled, the maximum liquid-solid temperature intervals of Mg-Sn, Mg-Bi and Mg-Gd are all lower than 100 ℃, and the liquid-solid intervals are small, which means that defects such as looseness, heat cracking and the like formed in the solidification process are few. Meanwhile, the solid solubility of the elements along with the temperature change has a large change range, and a large space is provided for the subsequent aging strengthening. In addition, precipitated Mg 2 Sn and Mg 3 Bi 2 Is of FCC structure, Mg 3 Bi 2 The heat formation is-3.5794 eV/atom, and Mg 17 Al 12 The alloy formation of the phases is only-0.052 eV/atom, Mg being visible 3 Bi 2 The structural stability of the alloy is obviously superior to that of Mg 17 Al 12 Solid solution. Therefore, it is expected that the structural stability of the alloy of the present application is clearly superior to that of the AZ series alloy, i.e., Mg-Al-Zn series alloy. Furthermore, we should also note that the amount of Sn, Bi and Gd added is due toAll are relatively small, and the amount of the formed second phase or metalwork compound is small, and the second phase or metalwork compound is generally distributed in the grain boundary. The alloy is distributed in a streamline shape along the extrusion direction in the extrusion process, has limited effective pinning effect on crystal boundary, can not hinder the growth effect of recrystallized grains, and has no dispersion strengthening effect, so that the finally prepared alloy has low comprehensive performance. If the contents of Sn, Bi and Gd are increased, more and coarser second phases are formed, and the coarse second phases often break by themselves or are detached from the matrix as induced micropores, thereby reducing plastic strain and causing breakage.
In conclusion, the preferable 0.5-0.7% of Sn, 0.8-2% of Bi and 0.8-1.2% of Gd can ensure that the finally prepared alloy contains a small amount of uniformly distributed second phase distribution, and the second phase distribution can not be coarsened obviously, 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 used raw materials have low cost, the plasticity of the magnesium alloy can be obviously changed, the high strength of the alloy can be ensured, 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 required, and the actual industrial production is easy to realize.
In one aspect, the invention provides a preparation method of 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 mass percentage in 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;
step two, smelting and casting; melting the industrial pure magnesium ingot in the step one at the temperature of 700-; cooling the melt to 680-700 ℃, slagging off again, and then carrying out 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, and the characteristic that the argon density is higher than that of air is utilized in the semi-continuous casting process, so that the argon is always introduced to the surface of the molten metal for protection, the magnesium alloy liquid level in the open crystallizer is prevented from directly contacting with the air in the continuous casting process, and the protection effect is achieved. In addition, the size and the cross-sectional shape (such as a round cross section, a square cross section, a rectangular cross section or other special-shaped cross sections) of the semi-continuously cast ingot can be designed according to actual requirements. Since the required molten alloy increases when the size of the continuous casting ingot blank is large, the cooling and solidification speed is slow, and segregation of the alloy elements in the ingot is more likely to occur, the size of the ingot is preferably designed in the present application.
Step three, homogenizing; keeping the temperature of the semicontinuous ingot casting prepared in the step two at 420 ℃ for 4h, then heating to 460 ℃ and keeping the temperature for 4h, then heating to 500 ℃ and keeping the temperature for 12h, carrying out tissue homogenization treatment, then taking out and air-cooling to 200 ℃, and finally putting the ingot casting into 65 ℃ warm water and cooling to room temperature to obtain an alloy blank;
step four, plastic processing; and (3) processing the ingot obtained in the third step to remove an oxide layer and a skin on the surface of the homogenized ingot, then performing upsetting at 460-500 ℃ and then performing three-way forging to refine grains, further uniformize the structure, eliminate casting defects, directly forging to obtain a final magnesium alloy structural part or performing hot extrusion molding after forging to obtain a magnesium alloy section or performing rolling after forging to obtain a magnesium alloy plate.
The three-way forging process is to forge along the x axis, the y axis and the z axis to knead, elongate and compress the structure, force the crystal grains to elongate, upset, flow, turn, break and dynamically recrystallize under the action of forging, thus thinning the structure, eliminating the possible inclusion or slag inclusion defect in the solidified structure and making the distribution more uniform. Meanwhile, hole defects such as casting shrinkage cavities, shrinkage porosity, air holes and the like possibly existing in the solidification process are closed, and continuity of the structure is promoted, so that optimization of the microstructure is realized, and the structure preparation is made for the subsequent extrusion or rolling process. In the specific forging process, firstly, after homogenizing a semi-continuous cast ingot, upsetting the semi-continuous cast ingot into a cake shape along the Z direction in the length direction, then, rotatably forging the semi-continuous cast ingot along the X direction and the Y direction, and forging the upset cake shape into a cylindrical shape. According to actual needs, the steel plate is repeatedly forged into a cake and then forged into a cylinder for 2-3 times, and finally the steel plate is turned into a cylinder, so that oxide skin and an irregular surface on the surface are removed, fine grain preparation is made for extrusion, and cracking in the extrusion process is avoided.
At present, the conventional process is to directly perform rolling after heat treatment for tissue homogenization. However, as a result, the crystal grains in the structure are coarse, and there is a possibility that cracking may occur. In addition, inclusions present in the structure may be distributed along the rolling flow lines, and the sheet material may also have cracking problems. And the present application does not have such a problem.
Step five, aging treatment; and (3) preserving the temperature of the magnesium alloy material subjected to plastic processing in the fourth step at the temperature of 150-. The purpose of the aging treatment is to ensure that some strengthening phases which are dissolved in the matrix are dispersed and precipitated for the second time so as to improve the mechanical property 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 range and length of time selected by comparison to the aging peak.
Meanwhile, the invention provides a preparation method of the magnesium alloy material, which adds Zr element in the form of intermediate alloy, promotes the dissolution and distribution of the Zr element in magnesium liquid by stirring, and avoids the segregation of the Zr element; meanwhile, the Zr content is strictly controlled according to the solid solubility of the Zr element in Mg, and the addition time and the addition sequence of the element are strictly controlled to realize the synergistic effect, so that the refining effect of the Zr element on the magnesium alloy structure is exerted.
More preferably, the Mg-Gd intermediate alloy is Mg-30% Gd intermediate alloy, and the Mg-Zr intermediate alloy is Mg-30% Zr intermediate alloy. Because the melting point of Gd element is higher (1313 ℃) and has larger difference with the melting point of Mg (649 ℃), the Gd element is favorably melted and uniformly distributed in the alloy by adopting the form of intermediate alloy; zr element adopts a Mg-Zr intermediate alloy form, and similarly, the description is not repeated. Specifically, in the case of magnesium alloys, the higher the content of alloying elements, the higher the melting point of the master alloy, and the more unfavorable the melting. But the higher the alloying element is, the less the addition amount of the intermediate alloy is, and more impurity elements can be avoided being introduced; therefore, the selection of the intermediate alloy with a proper proportion also has 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 ℃. During forging, the inside of the material generates heat due to deformation, and the outside of the material is subjected to heat dissipation due to air convection, so that the temperature difference between the inside and the outside can crack. In order to avoid the above-mentioned disadvantages, in the three-way forging, the temperature is detected for each forging, and if the temperature is too low, the material is heated again in the furnace and then forged again. The final forging referred to herein is the last forging, since the previous forging has been refined by kneading deformation to elongate or break the grains, 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, i.e. the final forging temperature is 400-430 ℃, and more preferably the final forging temperature does not exceed 410-425 ℃, so as to control the size and orientation of the grains, and provide good structural guarantee for subsequent processing. Mg may appear in the tissue 5 The Gd phase has better plasticity ratio due to the existence of Sn and Bi elements. Thus, 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 method has great effects and significance for the tissue refinement degree and uniformity of the alloy, the secondary distribution of alloy elements and the elimination of macroscopic and partial microscopic segregation. Therefore, the lower the forging temperature is, the more advantageous the mechanical properties of the alloy are, while ensuring that cracking is not caused.
More preferably, when the hot extrusion molding is carried out after the forging in the fourth step, the forging material is skinned after being cooled to room temperature, the surface oxide layer, dirt and micro-cracks are removed, then the forged material which is skinned again is placed into an extrusion cylinder for extrusion deformation processing at the temperature of 250-330 ℃, the extrusion ratio is 12.5-40, and finally the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material is obtained.
More preferably, when rolling is carried out after forging in the fourth step, the magnesium alloy is forged into a rectangular blank, then a surface oxidation layer and dirt are removed, and then the rectangular blank is rolled to obtain the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material at the rolling temperature of 420-440 ℃.
In addition, the invention can ensure that the magnesium alloy material has good comprehensive mechanical property by combining the plastic forming process such as forging, extrusion or rolling and the like and the additional heat treatment process, namely, the dispersion precipitation of a second phase and an LPSO structure in a matrix is 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 and high plasticity and has the elongation rate of more than 30 percent, but also has the mechanical property indexes exceeding the properties of ignition point, yield strength, tensile strength, elongation rate and the like of commercial wrought magnesium alloys such as AZ31 or ZK 60.
The technical scheme provided by the invention has the beneficial effects that:
the invention provides a microalloyed Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which is characterized in that the components and the content of the magnesium alloy are optimally designed, namely trace Sn, Bi, Gd and Zr element contents are added and controlled, so that the finally prepared alloy can contain a small amount of uniformly distributed second phases without obvious coarsening, the excellent plastic deformation capability of the alloy is ensured, the tensile mechanical property is high, and the elongation is up to more than 30%. The magnesium alloy is added with trace rare earth elements and alloy elements, the used raw materials have low cost, the plasticity of the magnesium alloy can be obviously changed, the high strength of the alloy can be ensured, 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 required, and the actual industrial production is easy to realize.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the contents in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
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 invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. It is to be understood that the various starting materials of the present invention are commercially available, unless otherwise specified.
Example 1
The invention provides a microalloy 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 percent; the total amount of Fe, Cu and Ni in the impurity elements is less than 0.02 percent; the balance being Mg.
The invention provides a preparation method of a microalloyed Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials, namely an industrial pure magnesium ingot, an industrial pure tin ingot, an industrial pure bismuth particle, Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy according to the components and the mass percentage in the magnesium alloy;
step two, melting the industrial pure magnesium ingot in the step one at 720 ℃, stirring, slagging off, adding Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy, then heating to 780 ℃ while stirring, stirring for 10min after all the raw materials are melted, then standing for 5min, adding industrial pure tin ingot and industrial pure bismuth particles when the slag in the melt floats upwards and the melt is cooled to 720 ℃, stirring for 10min, and then standing for 10min after deslagging the alloy melt so as to facilitate impurity settlement; cooling the melt to 690 ℃, slagging off again, and then carrying out semi-continuous casting to obtain a semi-continuous cast ingot with the diameter of 250 mm;
step three, homogenizing; keeping the temperature of the semicontinuous ingot casting prepared in the step two at 420 ℃ for 4h, then heating to 460 ℃ and keeping the temperature for 4h, then heating to 500 ℃ and keeping the temperature for 12h, carrying out tissue homogenization treatment, then taking out and air-cooling to 200 ℃, and finally putting the ingot casting into 65 ℃ warm water and cooling to room temperature to obtain an alloy blank;
step four, plastic processing; processing the ingot obtained in the third step, removing an oxide layer and a skin on the surface of the homogenized ingot, and then performing upsetting and three-way forging at 500 ℃ to refine grains, further homogenizing the structure and eliminating casting defects; the finish forging temperature was 410 ℃. And when 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, the surface oxidation layer and dirt are removed after the final forging size is cooled to room temperature, then the forged material after re-skinning is placed into the extrusion cylinder for extrusion deformation processing at 330 ℃, the extrusion ratio is 12.5, and the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material is obtained.
Step five, aging treatment; and (3) preserving the temperature of the magnesium alloy material subjected to plastic processing in the fourth step at 180 ℃ for 24 hours, performing aging treatment, and performing air cooling to room temperature to obtain the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy.
Example 2
The invention provides a microalloy 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 percent; the total amount of Fe, Cu and Ni in the impurity elements is less than 0.02 percent; the rest is Mg.
The invention provides a preparation method of a microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials, namely an industrial pure magnesium ingot, an industrial pure tin ingot, an industrial pure bismuth particle, Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy according to the components and the mass percentage in the magnesium alloy;
step two, melting, stirring and slagging off the industrial pure magnesium ingot in the step one at 700 ℃, adding Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy, then heating to 740 ℃ while stirring, stirring for 15min after all the raw materials are melted, then standing for 5min, adding industrial pure tin ingot and industrial pure bismuth particles when the slag in the melt floats upwards and the melt is cooled to 740 ℃, stirring for 15min, and then standing for 15min after deslagging the alloy melt so as to facilitate impurity settlement; cooling the melt to 680 ℃, slagging off again, and then carrying out semi-continuous casting to obtain a semi-continuous cast ingot with the diameter of 350 mm;
step three, homogenizing; keeping the temperature of the semicontinuous ingot casting prepared in the step two at 420 ℃ for 4h, then heating to 460 ℃ and keeping the temperature for 4h, then heating to 500 ℃ and keeping the temperature for 12h, carrying out tissue homogenization treatment, then taking out and air-cooling to 200 ℃, and finally putting the ingot casting into 65 ℃ warm water and cooling to room temperature to obtain an alloy blank;
step four, plastic processing; processing the ingot obtained in the third step, removing an oxide layer and a skin on the surface of the homogenized ingot, and then performing upsetting and three-way forging at 460 ℃ to refine grains, further homogenizing the structure and eliminating casting defects; the finish forging temperature was 420 ℃.
When rolling is carried out after forging, the magnesium alloy is firstly forged into a rectangular blank, namely a blank with a rectangular section and a thickness of 100mm, then a surface oxidation layer and dirt are removed, then the rectangular blank is rolled into a 6mm plate at the rolling temperature of 440 ℃, and the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material is obtained.
Step five, aging treatment; and (3) preserving the temperature of the magnesium alloy material subjected to plastic processing in the fourth step 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 invention provides a microalloy 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 percent; the total amount of Fe, Cu and Ni in the impurity elements is less than 0.02 percent; the rest is Mg.
The invention provides a preparation method of a microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials, namely an industrial pure magnesium ingot, an industrial pure tin ingot, an industrial pure bismuth particle, Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy according to the components and the mass percentage in the magnesium alloy;
step two, melting the industrial pure magnesium ingot in the step one at 710 ℃, stirring, slagging off, adding Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy, then heating to 760 ℃ while stirring, stirring for 13min after all the raw materials are melted, then standing for 5min, adding industrial pure tin ingot and industrial pure bismuth particles when the slag in the melt floats upwards and the melt is cooled to 730 ℃, stirring for 13min, and then standing for 13min after deslagging the alloy melt so as to facilitate impurity settlement; cooling the melt to 680 ℃, slagging off again, and then carrying out semi-continuous casting to obtain a semi-continuous cast ingot with the diameter of 350 mm;
step three, homogenizing; keeping the temperature of the semicontinuous ingot casting prepared in the step two at 420 ℃ for 4h, then heating to 460 ℃ and keeping the temperature for 4h, then heating to 500 ℃ and keeping the temperature for 12h, carrying out tissue homogenization treatment, then taking out and air-cooling to 200 ℃, and finally putting the ingot casting into 65 ℃ warm water and cooling to room temperature to obtain an alloy blank;
step four, plastic processing; processing the ingot obtained in the third step, removing an oxide layer and a skin on the surface of the homogenized ingot, and then performing upsetting and three-way forging at 460 ℃ to refine grains, further homogenizing the structure and eliminating casting defects; the finish forging temperature was 425 ℃.
When rolling is carried out after forging, the magnesium alloy is firstly forged into a rectangular blank, namely a blank with a rectangular section and a thickness of 100mm, then a surface oxidation layer and dirt are removed, then the rectangular blank is rolled into a plate with a rolling temperature of 420 ℃ and a plate with a thickness of 8mm, and the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material is obtained.
Step five, aging treatment; and (3) preserving the temperature of the magnesium alloy material subjected to plastic processing in the fourth step 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 invention provides a microalloy 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 percent; the total amount of Fe, Cu and Ni in the impurity elements is less than 0.02 percent; the rest is Mg.
The invention provides a preparation method of a microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials, namely an industrial pure magnesium ingot, an industrial pure tin ingot, an industrial pure bismuth particle, Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy according to the components and the mass percentage in the magnesium alloy;
step two, melting the industrial pure magnesium ingot in the step one at 710 ℃, stirring, slagging off, adding Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy, then heating to 770 ℃ while stirring, stirring for 12min after all the raw materials are melted, then standing for 5min, adding industrial pure tin ingot and industrial pure bismuth particles when the slag in the melt floats upwards and the melt is cooled to 730 ℃, stirring for 12min, and then standing for 12min after deslagging the alloy melt so as to facilitate impurity settlement; cooling the melt to 700 ℃, slagging off again, and then carrying out semi-continuous casting to obtain a semi-continuous cast ingot with the diameter of 150 mm;
step three, homogenizing; keeping the temperature of the semicontinuous ingot casting prepared in the step two at 420 ℃ for 4h, then heating to 460 ℃ and keeping the temperature for 4h, then heating to 500 ℃ and keeping the temperature for 12h, carrying out tissue homogenization treatment, then taking out and air-cooling to 200 ℃, and finally putting the ingot casting into 65 ℃ warm water and cooling to room temperature to obtain an alloy blank;
step four, plastic processing; processing the ingot obtained in the third step, removing an oxide layer and a skin on the surface of the homogenized ingot, and then performing upsetting and three-way forging at 460 ℃ to refine grains, further homogenizing the structure and eliminating casting defects; the finish forging temperature was 420 ℃.
And when 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, the surface oxidation layer and dirt are removed after the final forging size is cooled to room temperature, then the forged material after re-skinning is placed into the extrusion cylinder to carry out extrusion deformation processing at 250 ℃, the extrusion ratio is 40, and the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material is obtained.
Step five, aging treatment; and (3) preserving the temperature of the magnesium alloy material subjected to plastic processing in the fourth step at 200 ℃ for 12h, performing aging treatment and air cooling to room temperature to obtain the Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy.
Example 5
The invention provides a microalloy 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 percent; the total amount of Fe, Cu and Ni in the impurity elements is less than 0.02 percent; the rest is Mg.
The invention provides a preparation method of a microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy, which comprises the following steps:
step one, batching; weighing raw materials, namely an industrial pure magnesium ingot, an industrial pure tin ingot, an industrial pure bismuth particle, Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy according to the components and the mass percentage in the magnesium alloy;
step two, melting the industrial pure magnesium ingot in the step one at 720 ℃, stirring, slagging off, adding Mg-30% Gd intermediate alloy and Mg-30% Zr intermediate alloy, then heating to 750 ℃ while stirring, stirring for 15min after all the raw materials are melted, then standing for 5min, adding industrial pure tin ingot and industrial pure bismuth particles when the slag in the melt floats upwards and the melt is cooled to 740 ℃, stirring for 15min, and then standing for 10min after deslagging the alloy melt so as to facilitate impurity settlement; cooling the melt to 690 ℃, slagging off again, and then carrying out semi-continuous casting to obtain a semi-continuous cast ingot with the diameter of 200 mm;
step three, homogenizing; keeping the temperature of the semicontinuous ingot casting prepared in the step two at 420 ℃ for 4h, then heating to 460 ℃ and keeping the temperature for 4h, then heating to 500 ℃ and keeping the temperature for 12h, carrying out tissue homogenization treatment, then taking out and air-cooling to 200 ℃, and finally putting the ingot casting into 65 ℃ warm water and cooling to room temperature to obtain an alloy blank;
step four, plastic processing; processing the ingot obtained in the third step, removing an oxide layer and a skin on the surface of the homogenized ingot, and then performing upsetting and three-way forging at 470 ℃ to refine grains, further homogenizing the structure and eliminating casting defects; the finish forging temperature was 415 ℃.
And when 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, the rolling is carried out after the final forging size is cooled to room temperature, a surface oxidation layer and dirt are removed, then the forged material after re-rolling is placed into the extrusion cylinder for extrusion deformation processing at 280 ℃, the extrusion ratio is 25, and the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material is obtained.
Step five, aging treatment; and (3) preserving the temperature of the magnesium alloy material subjected to plastic processing in the fourth step at 175 ℃ for 48h, 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 plaques of 4mm thickness were selected for tensile strength UTS of 250MPa, yield strength YTS of 177MPa and elongation of 15% at room temperature.
Comparative example 2
A commercially available 5mm thick ZK60 plate was selected for use, which had a tensile strength UTS of 285MPa, a yield strength YTS of 200MPa and an elongation of 19% at room temperature.
Experimental results and Performance analysis
The magnesium alloy materials prepared in examples 1 to 5 were subjected to the following performance tests:
and (3) testing tensile strength: the magnesium alloy of the embodiment 1-5 is subjected to room temperature mechanical property test, the mechanical property test is processed and tested according to the national standard GB 6397-86 metal tensile test sample, the test equipment is a precision universal tester tensile machine, and the tensile speed is 1 mm/min; the test results are shown in table 1.
TABLE 1 results of performance tests on magnesium alloys prepared 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 board (4mm thick) | 250 | 177 | 15 |
| Commercial ZK60 board (5mm thick) | 285 | 200 | 19 |
As can be seen from the table 1, the room temperature tensile strength and the elongation of the microalloyed high-plasticity magnesium alloy are greatly improved compared with commercial AZ31 and ZK60 alloys, the magnesium alloy shows high room temperature plasticity, the alloy obtained by adopting the magnesium alloy component design and preparation process can meet the requirement of one-time plastic deformation at room temperature on the elongation of the material, and the alloy cannot crack and fail during plastic deformation. At the same time, the alloy has sufficient strength. Therefore, the sheet rolled by the alloy can achieve the bending and stamping processes adopted by steel plate processing, realize further plastic deformation forming and meet the room-temperature plastic forming requirement of the magnesium alloy.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of 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 invention 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 description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (7)
1. The microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy is characterized by comprising 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 comprise Fe < 0.005%, Cu < 0.015% and Ni < 0.002%; the balance being Mg.
2. The microalloyed Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy according to claim 1, is characterized in that the components and the preferred mass percentages thereof in the alloy are as follows:
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 percent; the balance being Mg.
3. A method for preparing a microalloyed Mg-Sn-Bi-Gd-Zr high plasticity magnesium alloy according to claim 1 or 2, characterized by comprising the steps of:
step one, batching; weighing raw materials according to the components and mass percentage in 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;
step two, smelting and casting; melting the industrial pure magnesium ingot in the step one at the temperature of 700-; cooling the melt to 680-700 ℃, slagging off again, and then carrying out semi-continuous casting to obtain a semi-continuous cast ingot with the diameter of 100-350 mm;
step three, homogenizing; keeping the temperature of the semicontinuous ingot casting prepared in the step two at 420 ℃ for 4h, then heating to 460 ℃ and keeping the temperature for 4h, then heating to 500 ℃ and keeping the temperature for 12h, carrying out tissue homogenization treatment, then taking out and air-cooling to 200 ℃, and finally putting the ingot casting into 65 ℃ warm water and cooling to room temperature to obtain an alloy blank;
step four, plastic processing; processing the ingot obtained in the third step to remove an oxide layer and a skin on the surface of the homogenized ingot, then performing upsetting at 460-500 ℃ and then performing three-way forging to refine grains, further uniformizing the structure, eliminating casting defects, directly forging to obtain a final magnesium alloy structural part or performing hot extrusion molding after forging to obtain a magnesium alloy section or rolling after forging to obtain a magnesium alloy plate;
step five, aging treatment; and (3) preserving the temperature of the magnesium alloy material subjected to plastic processing in the fourth step at the temperature of 150-.
4. The method for producing a microalloyed Mg-Sn-Bi-Gd-Zr high plasticity magnesium alloy according to claim 3, wherein the Mg-Gd intermediate alloy is a Mg-30% Gd intermediate alloy, and the Mg-Zr intermediate alloy is a Mg-30% Zr intermediate alloy.
5. The method for preparing the microalloyed Mg-Sn-Bi-Gd-Zr high plasticity magnesium alloy according to claim 3, wherein the finish forging temperature of the three-way forging in the fourth step is 400-430 ℃.
6. The method for preparing the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy according to claim 3, wherein the hot extrusion molding is carried out after the forging in the fourth step, the surface oxidation layer, dirt and microcracks are removed after the cooling to the room temperature, then the forged material after the re-skinning is placed into an extrusion cylinder for extrusion deformation processing at the temperature of 250 ℃ and 330 ℃, the extrusion ratio is 12.5-40, and finally the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material is obtained.
7. The method for preparing the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy according to claim 3, wherein the step four is carried out after forging, the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy material is obtained by forging the microalloy Mg-Sn-Bi-Gd-Zr high-plasticity magnesium alloy into a rectangular blank, removing a surface oxidation layer and dirt, and then rolling the rectangular blank at the rolling temperature of 420-440 ℃.
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| CN114934217B (en) | 2023-09-26 |
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