CN109943758B - High-strength high-toughness heat-resistant die-casting Mg-Er alloy and preparation method thereof - Google Patents
High-strength high-toughness heat-resistant die-casting Mg-Er alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-strength high-toughness heat-resistant die-casting Mg-Er alloy and a preparation method thereof, wherein the alloy comprises the following components in stoichiometric ratio: 4.0-8.5% of Er, 1.2-5.1% of Zn, 0.5-1.2% of Al, 0.1-0.3% of Mn, 0.01-0.08% of M and the balance of Mg; wherein M is Ti, and B is one or two elements. The preparation method comprises the following steps: 1) proportioning according to Mg-Er alloy components; 2) melting an industrial pure magnesium ingot; 3) heating to 720 ℃, adding the industrial pure zinc, Mg-Er and Mg-Mn intermediate alloy, and stirring until the industrial pure zinc, Mg-Er and Mg-Mn intermediate alloy are completely melted; 4) heating to 730 ℃, and refining to obtain a magnesium alloy melt after all the industrial pure aluminum ingot, the Al-Ti and the Al-Ti-B, Al-B intermediate alloy which are sequentially added are melted; (5) and cooling the magnesium alloy melt to a die-casting temperature for die-casting to obtain the die-casting alloy. After the alloy is subjected to pressure casting, the room-temperature tensile strength of the die-cast alloy reaches 302MPa, the high-temperature tensile strength at 200 ℃ reaches 205MPa, the room-temperature elongation reaches 15.0%, and the die-cast alloy can be used without aging and solution heat treatment, so that the high-end requirement of industries such as aerospace on light weight is met.
Description
Technical Field
The invention relates to a high-strength and high-toughness heat-resistant die-casting Mg-Er alloy which meets the high-end requirement of industries such as aerospace, automobiles, telecommunication and the like on light weight development. The invention also relates to a preparation method of the high-strength high-toughness heat-resistant die-casting Mg-Er alloy, belonging to the field of industrial magnesium alloy and manufacturing.
Background
The magnesium alloy is used as the lightest engineering metal material (the density of magnesium is 2/3 of aluminum and 1/4 of steel), the specific strength of the magnesium alloy is obviously higher than that of aluminum alloy and steel, the specific stiffness of the magnesium alloy is equivalent to that of the aluminum alloy and the steel but far higher than that of engineering plastics, and the magnesium alloy has a series of advantages of good castability, good cutting processability, good thermal conductivity, strong damping property and electromagnetic shielding capability, easy recovery and the like, and has wide application prospects in the fields of aviation, aerospace, automobiles, electronics, national defense war industry and the like. Magnesium alloys have become ideal materials to replace aluminum alloys, steel and engineering plastics to achieve light weight, with the most promising replacement potential being aluminum alloys.
Pressure casting is a casting method in which liquid or semi-solid metal is filled into a die-casting mold cavity at high speed under the action of high pressure and is solidified under pressure to form a casting. The die casting not only ensures that the casting has higher strength, dimensional accuracy and surface smoothness, but also is easy to realize mechanization and automation, has high production efficiency, and can produce thin-wall castings with complex shapes, thereby being widely applied to industries of automobiles, electronic instruments, telecommunication and the like.
Magnesium alloy die casting is the most competitive of all casting methods, and it is even lower in production cost than aluminum alloy die casting. The reason is that (1) the magnesium alloy has lower volume specific heat and thermal conductivity, the die casting has high productivity, the thermal shock of the alloy liquid to the die is small, and the service life of the die is long; (2) magnesium does not react with iron, the die sticking tendency is small, and the die filling speed is higher under the same die filling pressure, so that the smaller die drawing slope ensures that the casting with more complex appearance and higher tolerance precision can be produced. In recent years, the use of magnesium alloy die casting in the automobile and telecommunications industries has been rapidly increased due to the increased environmental pressure and the demand for lightweight and energy saving, and has accounted for the second place of magnesium consumption, of which 80% is used in the automobile industry.
AZ (such as AZ91) and AM series magnesium alloy (such as AM60 and AM50) are the most widely applied commercial die-casting magnesium alloy at present and are widely applied to automobile and 3C product die castings. AZ91D has excellent casting performance, can cast thin-wall die castings with precise and complex structures, but has poor plasticity, the elongation is only 3 percent, the plasticity of AM60 is good, the elongation reaches 8 percent, the product is commonly used for manufacturing shock-absorbing and impact-resistant automobile safety parts such as instrument panel supports, seat frames and the like, but has low strength and yield strength of only 130 MPa. In addition, AZ and AM series magnesium alloys have poor high temperature creep properties and rapidly decrease in tensile strength at temperatures above 150 ℃ due to the supersaturated alpha-Mg matrix Mg at grain boundaries during high temperature creep17Al12The phases are separated out discontinuously. By adding alloying elementsThe heat resistance of Mg-Al alloy is improved by improving the characteristics (crystal structure, form and thermal stability) of precipitated phases, and Mg-Al-RE die-cast magnesium alloy is developed on the basis. The commercial magnesium alloy AE44 with the best comprehensive mechanical property developed by the Dow chemical company in the United states at present has typical properties of yield strength of 140MPa, tensile strength of 247MPa and elongation of 11%. Although the AE magnesium alloy has relatively excellent elongation, the normal temperature and high temperature mechanical properties of the AE magnesium alloy can not reach the level of A380 die casting aluminum alloy which is widely applied at present, and the AE magnesium alloy is difficult to produce due to the die sticking tendency during die casting, thereby severely limiting the application development of the AE magnesium alloy.
Zn is an important alloy element in magnesium alloy, the maximum solid solubility in Mg is as high as 6.2 wt%, and the Zn can play a role in solid solution strengthening and aging strengthening. Typical Mg-Zn-based cast magnesium alloys include ZK51A and ZK60A, and wrought alloys include ZK21A, ZK31, ZK40A, ZK60A, and ZK61, and the like. As the Zn content increases, the tensile strength and yield strength of the alloy increase, but the elongation after fracture thereof decreases, and the castability, process plasticity and weldability deteriorate, particularly because of the excessively wide solidification range (for example, the solidification range of ZK60 is as high as 265 ℃, Journal of Materials Science,45(14) (2010)3797-3803), so that the hot cracking tendency thereof is extremely severe and cannot be used for die casting.
The beneficial effect of rare earth element RE (rare earth element) on the strength performance of magnesium alloy and the grain refining effect of zirconium on the magnesium alloy are discovered in the thirties of the twentieth century, and in the Mg-RE-Zr system (EK30, EK31 and EK41), EK31 becomes the highest-developed high-temperature casting magnesium alloy in the Mg-Zr system. Magnesium rare earth alloys based on rare earth RE elements have excellent age hardening effect, and various novel magnesium alloys taking RE as a main element, such as WE54 and WE43 alloys of Mg-Y series, are developed in sequence. Patent document CN105525178A (high thermal conductivity die casting Mg-Y-Zr series multi-element magnesium alloy and preparation method thereof) discloses a high thermal conductivity die casting corrosion-resistant magnesium alloy, which comprises 1.5-4% of Y, 0.001-1% of Mn, 0.001-2% of Zn, 0.001-1% of Ca, 0.4-0.8% of Zr and the balance of Mg by mass percent; the addition of Ca element in the alloy sharply increases the solidification temperature range of the alloy, increases the hot cracking tendency, and the tensile strength of the die-casting ingot is only 140-190 MPa.
The solid solubility of the heavy rare earth element Er in the magnesium alloy is as high as 32.7 wt.%, which is far higher than other common rare earth elements, and the heavy rare earth element Er has strong solid solution strengthening and aging strengthening effects. Similar to Mg-Gd or Mg-Y alloy systems, the Mg-Er alloy is added with cheap Zn, which not only has more remarkable effect on regulating and controlling the aging precipitation structure of the alloy system, but also can form a plurality of strengthening phases under the conditions of different Zn/Er ratios: when the mass ratio of Zn to Er in the alloy is more than or equal to 2.35 (the atomic ratio is more than or equal to 6.0), an icosahedral quasicrystal structure I phase (Mg) is easily formed3Zn6Er); when the mass ratio of Zn to Er in the alloy is between 0.59 and 2.35 (the atomic ratio is between 1.5 and 6.0), a W phase (Mg) with a face-centered cubic structure is easily formed3Zn3Er2) And phase I; the W phase and the LPSO phase (Mg) with long period stacking ordered structure are easily formed when the Zn/Er mass ratio in the alloy is between 0.39 and 0.59 (the atomic ratio is between 1.0 and 1.5)12ZnEr); the LPSO phase is easily formed when the Zn/Er mass ratio in the alloy is less than or equal to 0.39 (atomic ratio less than or equal to 1.0) (Journal of Alloys and Compounds,602(2014) 32-39; Acta Materialia,68(2014) 325-338.). The alloy disclosed by patent document with application publication number CN104894447A (a layered/needle-shaped two-phase composite reinforced rare earth magnesium alloy and a preparation process thereof) comprises 6-25 wt% of Er, 4-10 wt% of Zn and the balance of Mg, wherein the mass addition ratio of Er to Zn is 1.5-3. The preparation method comprises the steps of placing the Mg-Er intermediate alloy in a crucible, and heating under a protective atmosphere; when the furnace temperature rises to the temperature range of 750-; then, reducing the smelting temperature to 740-; continuously reducing the temperature to 700-780 ℃, adding Zn, stirring and removing slag; continuously raising the temperature to 760 and 800 ℃, stirring the alloy liquid, and removing slag; finally, keeping the temperature of the alloy liquid at the temperature, standing for more than half an hour, and pouring the alloy liquid into a mold after the alloy liquid is cooled to 720-760 ℃, wherein the alloy generates a lamellar phase in the solidification process; the prepared alloy is put in a heat treatment furnace at 450 toAnd (3) carrying out solution treatment at 525 ℃, keeping the temperature for 5-30 h, and precipitating needle-shaped phases from the alloy after the solution treatment. The technical problems of the invention are as follows: because the alloy does not contain refined crystal grain elements, the crystal grain size in the figure description is up to more than 100 mu m, and the structure must be regulated and controlled through high-temperature solution treatment; the rare earth element Er with too high content leads to too high density, and the expensive price of the rare earth element leads to the difficulty in large-scale industrial application of the invention. Patent document No. CN104004979A (a microstructure refining method for improving room temperature plasticity of magnesium alloy) discloses a microstructure refining method for improving room temperature plasticity of magnesium alloy, which comprises the following steps: (1) firstly, cleaning the surface of a prepared Mg-Zn-Er alloy containing I phase, W phase or mixture of I phase and W phase, removing oxide skin, then cutting, placing in a resistance smelting furnace at the temperature of 720-800 ℃ for heat preservation, turning off a heating power supply after the alloy is melted, uniformly stirring, standing for 10-25 min, raising the temperature of the furnace to 720-800 ℃ again, keeping the temperature for 5-10 min, turning off the heating power supply, setting the temperature of the furnace to 650-720 ℃, adding 0.01-1.0 wt.% of Al into an alloy liquid after the temperature is stabilized to 650-720 ℃, stirring, keeping the temperature at 650-720 ℃ for standing for 10-25 min, and casting the alloy in a low-carbon steel mold; (2) and (2) carrying out solution treatment on the Mg-Zn-Er alloy containing a small amount of Al element prepared in the step (1), wherein the temperature of the solution treatment is 350-450 ℃, and after heat preservation is carried out for 2.5-15 h, spherical or/and island-shaped phases in the alloy disappear, a needle-shaped second phase is formed at a matrix and a crystal boundary, and the distribution of the needle-shaped second phase is more dispersed. The technical problems of the invention are as follows: in the Mg-Zn-Er alloy taking Zn as a main element, the mass ratio of Zn to Er is too high, a structure containing a quasicrystal I phase is formed, the solidification interval is large, only gravity casting can be performed, and the Mg-Zn-Er alloy is not suitable for die casting. The method needs to prepare an Mg-Zn-Er alloy ingot containing I, W phase or mixed I and W phases, remelting the alloy ingot, adding Al, performing gravity casting, performing solid solution homogenization and subsequent hot extrusion, and the complicated preparation process is difficult to industrially apply on a large scale. In addition, the magnesium crystal grains are coarse under the conventional solidification condition, and the Mg-Er-Zn precipitated phase often presents a coarse network structure, thereby deteriorating the mechanical property and being necessary to change by heatThe size of the precipitated phase is adjusted by solid solution or aging through heat treatment to play the role of the strengthening phase. At present, the Mg-Er-Zn alloy is generally limited to gravity casting and hot working processes, and a complex heat treatment process is required, so that no report is provided for die casting application.
Mg-Er-Zn alloys usually incorporate Zr as a grain refining element to refine their coarse microstructure. The currently reported Zr adding modes comprise sponge Zr, halogen salt of Zr, Zn-Zr, Mg-Zr intermediate alloy and the like, wherein the Mg-Zr intermediate alloy has the advantages of convenient use, less inclusion, good refining effect and the like, and is the currently main mode for adding Zr. However, the addition of the Mg-Zr intermediate alloy still has a plurality of problems: firstly, the preparation process of the Mg-Zr intermediate alloy is complex and has high energy consumption, so that the price of the Mg-Zr intermediate alloy is high, and the product cost can be increased by refining the crystal grains by using the Mg-Zr intermediate alloy; secondly, Zr has strong chemical activity and is easy to react with atmosphere and furnace gas at high temperature, and when a steel crucible is used and the temperature of a melt is higher than 750 ℃, Zr is easy to react with Fe in the crucible to generate a stable intermetallic compound Fe2Zr, all of which result in high Zr loss; much Zr in Mg-Zr intermediate alloy exists in the form of large-size simple substance particles, the Zr particles are difficult to dissolve in the melt due to the high melting point (1852 ℃) of Zr, and the density of Zr is much higher than that of magnesium melt (the density of Zr is 6.52 g/cm)3The density of the pure magnesium melt was 1.58g/cm3) And is liable to precipitate to the bottom of the crucible, resulting in a low yield of Zr.
Disclosure of Invention
The invention provides a high-strength-toughness heat-resistant die-casting Mg-Er alloy and a preparation method for pressure casting thereof, aiming at solving the industrial problem that the application of the existing die-casting magnesium alloy is greatly limited because the performance of the A380 constant-pressure die-casting aluminum alloy can not be achieved due to insufficient strength, toughness and heat resistance, and the die-casting magnesium alloy is subjected to pressure casting, wherein the room-temperature tensile strength of the die-casting alloy reaches 302MPa, the high-temperature tensile strength at 200 ℃ reaches 205MPa, and the room-temperature elongation reaches 15.0%.
In order to solve the technical problems, the invention adopts the following technical scheme:
the high-strength high-toughness heat-resistant die-casting Mg-Er alloy comprises the following elements in percentage by mass: 4.0-8.5% of Er, 1.2-5.1% of Zn, 0.5-1.2% of Al, 0.1-0.3% of Mn, 0.01-0.08% of M, and the balance of Mg and other inevitable impurities, wherein M is one or two of Ti and B.
The invention has the innovation points of the high-strength high-toughness heat-resistant die-casting Mg-Er alloy:
(1) in the alloy design, except common metals of Zn, Al and Mn and a small amount of Ti and B elements, the heavy rare earth element Er is selected as an alloying element. The alloying elements Er and Zn and the matrix Mg element form a ternary Mg-Er-Zn strengthening phase, particularly within the mass ratio of Zn to Er of 0.2-0.6, on the one hand, the alloy mainly forms a long-period stacking ordered structure LPSO phase (Mg and Er are in the range of12ZnEr) and face-centered cubic structure W phase (Mg)3Zn3Er2) All are high melting point phases; compared with binary Mg-Er strengthening, the ternary Mg-RE-Zn strengthening phases LPSO and W have better high-temperature stability in a magnesium matrix, avoid performance reduction caused by dissolution of a precipitation strengthening phase, effectively enhance the room-temperature mechanical property and high-temperature property of the high-strength and high-toughness heat-resistant die-casting Mg-Er alloy, and particularly improve the room-temperature yield strength by one time. On the other hand, the invention overcomes the technical problems that the traditional Mg-Zn-Er alloy is easy to generate hot cracking due to the overlarge solidification interval caused by the overhigh Zn content, and the toughness and the die-casting performance of the alloy can not be ensured.
(2) The precipitated phases of Mg-Er-Zn alloy are often in a coarse network structure under the conventional solidification condition, the mechanical properties of the Mg-Er-Zn alloy are deteriorated, and the size of the precipitated phases must be adjusted to play the role of the strengthening phase through hot deformation or heat treatment solid solution and aging. Zr is usually added into the alloy as a grain refining element, the alloy element of the invention contains Al, Mn and rare earth Er alloy elements, and the elements are combined with Zr to form Al3Zr and the like are precipitated on the bottom of the crucible to prevent the crystal grain refinement of zirconium. On the other hand, researches show that the Mg-Er-Zn alloy refined by adding Zr has poor structure thermal stability, and crystal grains are rapidly coarsened when the temperature is kept at 550 ℃, so that the high-temperature performance is greatly reduced. In order to solve the problems, 0.5-1.2% of Al is added to the alloy of the invention to replace Zr to form dispersed high-melting-point Al3Er phase, not only refining the structure of the alloyAnd ensures the high-temperature stability of the magnesium alloy structure with LPSO and other high-temperature phases. Meanwhile, Al and a small amount of Ti and B play a role in composite grain refinement, the alloy structure is further refined, and the toughness of the alloy is improved. The alloy element of the invention is added with a small amount of Mn, which not only can promote the formation of LPSO phase, improve the high-temperature stability of the alloy, but also can improve the corrosion resistance of the magnesium alloy.
(3) In order to reduce the hot cracking tendency in the die casting process of Mg-Er-Zn alloy, the mass ratio of Zn to Er is 0.2-0.6, and the mass ratio of Zn + Al to Er is 0.3-0.7. Under the condition of the mass ratio, the alloy of the invention obtains a narrower solidification interval, thereby overcoming the hot cracking tendency in the die-casting process of Mg-Er-Zn alloy and improving the die-casting process performance of the alloy.
The preparation method of the high-strength high-toughness heat-resistant die-casting Mg-Er alloy comprises the following steps:
(1) properly considering the burning loss, calculating the consumption of required raw materials (industrial pure magnesium ingot, industrial pure zinc, industrial pure aluminum ingot, Mg-Er intermediate alloy, Mg-Mn intermediate alloy, Al-Ti-B intermediate alloy and Al-B intermediate alloy) according to the components and the stoichiometric ratio of the Mg-Er alloy; removing oxide layers of industrial pure magnesium ingots, industrial pure zinc, industrial pure aluminum ingots and Mg-Er and Mg-Mn intermediate alloys, drying and preheating to 200 ℃.
(2) Melting industrial pure magnesium ingot accounting for 25% of the height of the crucible into a molten pool at 680 ℃, introducing protective gas, and adding the rest magnesium ingot. The protective gas is argon or SF with volume fraction of 0.2%6And CO2Mixed gas (i.e. SF)6Volume fraction of 0.2%, CO299.8% by volume).
(3) After the magnesium ingot is completely melted, heating to 720 ℃, adding the industrial pure zinc, the Mg-Er and the Mg-Mn intermediate alloy for 2-4 times, keeping the temperature constant at 720 ℃, stirring until the industrial pure zinc, the Mg-Er and the Mg-Mn intermediate alloy are completely melted, and keeping the temperature for 30 min. Preferably, the Mg-Er master alloy is MgEr25 or MgEr30, and the Mg-Mn master alloy is MgMn 10.
(4) Heating to 730 ℃ 40-60 min before pressure casting, and adding industrial pure aluminum ingot, Al-Ti intermediate alloy, Al-Ti-B intermediate alloy and Al-B intermediate in sequenceAnd after the alloy is completely melted, adding a refining agent for refining, heating the furnace to 750 ℃, keeping the temperature and standing for 10-20min, and promoting the settlement of impurities to obtain the magnesium alloy melt. Preferably, the Al-Ti-B intermediate alloy is AlTi5B1, the Al-B intermediate alloy is AlB3 or AlB8, and the Al-Ti intermediate alloy is AlTi5 or AlTi 10. The refining agent comprises the following components in percentage by mass: 55% KCl and 25% CaCl2、5％CaF2、15％BaCl2. The addition amount of the refining agent is 1.0-3.5% of the total weight of the raw materials, the refining temperature is 720-730 ℃ when the refining agent is added for refining, and the stirring time of refining treatment is 10-15 min.
(5) And cooling the magnesium alloy melt to 720-740 ℃, skimming the surface scum, pressing the magnesium alloy melt into a die-casting die preheated to 180-250 ℃ at a speed of 4-15 m/s, and cooling to obtain the high-strength high-toughness heat-resistant die-casting Mg-Er alloy.
The preparation method of the high-strength high-toughness heat-resistant die-casting Mg-Er alloy has the following innovation points: (1) adding Mg-Er intermediate alloy which is easy to burn and lose at 720 ℃, and melting in the low-temperature melt in a heat preservation way, thereby improving the yield of the rare earth Er; (2) the refining treatment adopts MgCl-free2The special refining agent further reduces the burning loss of the rare earth Er in the refining process. The invention has the following beneficial effects:
after the high-strength high-toughness heat-resistant die-casting Mg-Er alloy is subjected to pressure casting, the room-temperature tensile strength sigma of the die-casting alloybThe tensile strength reaches 302MPa, the high-temperature tensile strength reaches 205MPa at 200 ℃, the room-temperature elongation delta reaches 15.0 percent, and the comprehensive performance reaches the performance of A380 isostatic cast aluminum alloy; the preparation method has the advantages of simple process, high efficiency, suitability for large-scale production and the like, can be used without aging and solution heat treatment, and meets the high-end requirements of industries such as aerospace, automobiles, telecommunication and the like on light weight development.
Drawings
FIG. 1 is an as-cast metallographic structure chart of a magnesium alloy obtained in example 3.
Detailed Description
Example 1
The high-strength and high-toughness heat-resistant die-casting Mg-Er alloy comprises the following components in percentage by weight: 4.0% of Er, 1.2% of Zn, 1.2% of Al, 0.3% of Mn, 0.01% of Ti and 0.01% of B, and the balance of Mg and other inevitable impurities according to the theoretical proportion. The preparation method comprises the following steps:
(1) properly considering the burning loss, calculating the consumption of the required raw materials according to the components of the Mg-Er alloy and the stoichiometric ratio; removing oxide layers of industrial pure magnesium ingots, industrial pure zinc, industrial pure aluminum ingots and intermediate alloys of MgEr25 and MgMn10, drying and preheating to 200 ℃.
(2) Melting industrial pure magnesium ingot accounting for 25% of the height of the crucible into a molten pool at 680 ℃, introducing protective gas argon, and adding the rest magnesium ingot.
(3) After the magnesium ingot is completely melted, heating to 720 ℃, adding the industrial pure zinc, MgEr25 and MgMn10 intermediate alloy for 2-4 times, keeping the temperature constant at 700 ℃ until the magnesium ingot is completely melted, and keeping the temperature for 30 min.
(4) Heating to 730 ℃ after 40-60 min before pressure casting, adding a refining agent accounting for 1% of the weight of the raw materials for refining after all the industrial pure aluminum ingot, the AlTi5B1 intermediate alloy and the AlB3 intermediate alloy which are sequentially added are melted, wherein the refining temperature is 730 ℃, the stirring time of refining treatment is 10min, and the refining agent comprises the following components in percentage by mass: 55% KCl and 25% CaCl2、5％CaF2、15％BaCl2. And (4) heating the furnace to 750 ℃, preserving heat and standing for 10min to promote the settlement of impurities, thereby obtaining the magnesium alloy melt.
(5) And cooling the magnesium alloy melt to 720 ℃, skimming surface scum, pressing the magnesium alloy melt into a die-casting die preheated to 180 ℃ at the speed of 4m/s, and cooling to obtain the high-strength high-toughness heat-resistant die-casting Mg-Er alloy.
Respectively carrying out a-room temperature tensile test on the prepared die-casting magnesium alloy; b, performing high-temperature tensile property test at 200 ℃ after 200-hour heat exposure treatment at 200 ℃, wherein the cast-state room-temperature tensile strength of the die-casting magnesium alloy obtained in the example is 275MPa, and the elongation is 18%; the tensile strength at high temperature of 200 ℃ is 185MPa, and the elongation is 30%.
Example 2
The high-strength and high-toughness heat-resistant die-casting Mg-Er alloy comprises the following components in percentage by weight: 8.5 percent of Er, 5.1 percent of Zn, 0.85 percent of Al, 0.1 percent of Mn, 0.08 percent of Ti, and the balance of Mg and other inevitable impurities according to the theoretical proportion. The preparation method comprises the following steps:
(1) properly considering the burning loss, calculating the consumption of the required raw materials according to the components of the Mg-Er alloy and the stoichiometric ratio; removing oxide layers of industrial pure magnesium ingots, industrial pure zinc, industrial pure aluminum ingots and intermediate alloys of MgEr30 and MgMn10, drying and preheating to 200 ℃.
(2) Melting industrial pure magnesium ingot accounting for 25% of the height of the crucible into a molten pool at 680 ℃, and introducing protective gas containing 0.2% of SF by volume fraction6And CO2The remaining magnesium ingot is added to the mixed gas of (1).
(3) After the magnesium ingot is completely melted, heating to 720 ℃, adding the industrial pure zinc, MgEr30 and MgMn10 intermediate alloy for 2-4 times, keeping the temperature constant at 700 ℃ until the magnesium ingot is completely melted, and keeping the temperature for 30 min.
(4) Heating to 730 ℃ after 40-60 min before pressure casting, adding a refining agent accounting for 3.5% of the weight of the raw materials for refining after all the industrial pure aluminum ingot and the AlTi10 intermediate alloy which are sequentially added are melted, wherein the refining temperature is 730 ℃, the stirring time of the refining treatment is 10min, and the refining agent comprises the following components in percentage by mass: 55% KCl and 25% CaCl2、5％CaF2、15％BaCl2. And (4) heating the furnace to 750 ℃, preserving heat and standing for 20min to promote the settlement of impurities, thereby obtaining the magnesium alloy melt.
(5) And cooling the magnesium alloy melt to 740 ℃, skimming surface scum, pressing the magnesium alloy melt into a die-casting die preheated to 250 ℃ at the speed of 15m/s, and cooling to obtain the high-strength high-toughness heat-resistant die-casting Mg-Er alloy.
Respectively carrying out a-room temperature tensile test on the prepared die-casting magnesium alloy; b, performing high-temperature tensile property test at 200 ℃ after 200-hour heat exposure treatment at 200 ℃, wherein the as-cast room-temperature tensile strength of the die-casting magnesium alloy obtained in the example is 288MPa, and the elongation is 10%; the tensile strength at high temperature of 200 ℃ is 205MPa, and the elongation is 16%.
Example 3
The high-strength and high-toughness heat-resistant die-casting Mg-Er alloy comprises the following components in percentage by weight: 6.0% of Er, 3.0% of Zn, 0.5% of Al, 0.2% of Mn, 0.05% of Ti, 0.03% of B and the balance of Mg and other inevitable impurities according to the theoretical proportion. The preparation method comprises the following steps:
(1) properly considering the burning loss, calculating the consumption of the required raw materials according to the components of the Mg-Er alloy and the stoichiometric ratio; removing oxide layers from industrial pure magnesium ingots, industrial pure zinc ingots, industrial pure aluminum ingots and intermediate alloys of MgEr30 and MgMn10, drying and preheating to 200 DEG C
(2) Melting industrial pure magnesium ingot accounting for 25% of the height of the crucible into a molten pool at 680 ℃, introducing protective gas argon, and adding the rest magnesium ingot.
(3) After the magnesium ingot is completely melted, heating to 720 ℃, adding the industrial pure zinc, MgEr30 and MgMn10 intermediate alloy for 2-4 times, keeping the temperature constant at 700 ℃ until the magnesium ingot is completely melted, and keeping the temperature for 30 min.
(4) Heating to 730 ℃ after 40-60 min before pressure casting, adding a refining agent accounting for 2.5 percent of the weight of the raw materials for refining after all the industrial pure aluminum ingot, the AlTi10 intermediate alloy and the AlB8 intermediate alloy which are sequentially added are melted, wherein the refining temperature is 720 ℃, the stirring time of refining treatment is 15min, and the refining agent comprises the following components in percentage by mass: 55% KCl and 25% CaCl2、5％CaF2、15％BaCl2. And (4) heating the furnace to 750 ℃, preserving heat and standing for 15min to promote the settlement of impurities, thereby obtaining the magnesium alloy melt.
(5) And cooling the magnesium alloy melt to 730 ℃, skimming surface scum, pressing the magnesium alloy melt into a die-casting die preheated to 200 ℃ at the speed of 10m/s, and cooling to obtain the high-strength high-toughness heat-resistant die-casting Mg-Er alloy.
Respectively carrying out a-room temperature tensile test on the prepared die-casting magnesium alloy; b, performing high-temperature tensile property test at 200 ℃ after 200-hour heat exposure treatment, wherein the as-cast room-temperature tensile strength of the die-casting magnesium alloy obtained in the example is 298MPa, and the elongation is 12%; the tensile strength at high temperature of 200 ℃ is 192MPa, and the elongation is 25%. The obtained magnesium alloy as-cast metallographic structure is shown in fig. 1.
Example 4
The high-strength and high-toughness heat-resistant die-casting Mg-Er alloy comprises the following components in percentage by weight: according to the theoretical mixture ratio, 5.0% of Er, 2.5% of Zn, 1.0% of Al, 0.2% of Mn and 0.08% of B, and the balance of Mg and other inevitable impurities. The preparation method comprises the following steps:
(1) properly considering the burning loss, calculating the consumption of the required raw materials according to the components of the Mg-Er alloy and the stoichiometric ratio; removing oxide layers of industrial pure magnesium ingots, industrial pure zinc, industrial pure aluminum ingots and intermediate alloys of MgEr25 and MgMn10, drying and preheating to 200 ℃.
(2) Melting industrial pure magnesium ingot accounting for 25% of the height of the crucible into a molten pool at 680 ℃, and introducing SF containing 0.2% of volume fraction6And CO2The remaining magnesium ingot is added to the mixed protective gas of (1).
(3) After the magnesium ingot is completely melted, heating to 720 ℃, adding the industrial pure zinc, MgEr25 and MgMn10 intermediate alloy for 2-4 times, keeping the temperature constant at 700 ℃ until the magnesium ingot is completely melted, and keeping the temperature for 30 min.
(4) Heating to 730 ℃ after 40-60 min before pressure casting, adding a refining agent accounting for 3.0 percent of the weight of the raw materials for refining after all the industrial pure aluminum ingot and the AlB8 intermediate alloy which are sequentially added are melted, wherein the refining temperature is 720 ℃, the stirring time of the refining treatment is 15min, and the refining agent comprises the following components in percentage by mass: 55% KCl and 25% CaCl2、5％CaF2、15％BaCl2. And (4) heating the furnace to 750 ℃, preserving heat and standing for 15min to promote the settlement of impurities, thereby obtaining the magnesium alloy melt.
(5) And cooling the magnesium alloy melt to 720 ℃, skimming surface scum, pressing the magnesium alloy melt into a die-casting die preheated to 220 ℃ at the speed of 8m/s, and cooling to obtain the high-strength high-toughness heat-resistant die-casting Mg-Er alloy.
Respectively carrying out a-room temperature tensile test on the prepared die-casting magnesium alloy; b, performing high-temperature tensile property test at 200 ℃ after 200-hour heat exposure treatment, wherein the as-cast room-temperature tensile strength of the die-casting magnesium alloy obtained in the example is 302MPa, and the elongation is 15%; the tensile strength at high temperature of 200 ℃ is 201MPa, and the elongation is 22%.
Example 5
The high-strength and high-toughness heat-resistant die-casting Mg-Er alloy comprises the following components in percentage by weight: 7.0% of Er, 1.4% of Zn, 0.7% of Al, 0.3% of Mn, 0.04% of Ti, 0.04% of B and the balance of Mg and other inevitable impurities according to the theoretical proportion. The preparation method comprises the following steps:
(1) properly considering the burning loss, calculating the consumption of the required raw materials according to the components of the Mg-Er alloy and the stoichiometric ratio; removing oxide layers of industrial pure magnesium ingots, industrial pure zinc, industrial pure aluminum ingots and intermediate alloys of MgEr25 and MgMn10, and drying and preheating to 200 ℃; and calculating the consumption of the required raw materials according to the components and the stoichiometric ratio of the alloy.
(2) Melting industrial pure magnesium ingot accounting for 25% of the height of the crucible into a molten pool at 680 ℃, introducing protective gas argon, and adding the rest magnesium ingot.
(3) After the magnesium ingot is completely melted, heating to 720 ℃, adding the industrial pure zinc, MgEr25 and MgMn10 intermediate alloy for 2-4 times, keeping the temperature constant at 700 ℃ until the magnesium ingot is completely melted, and keeping the temperature for 30 min.
(4) Heating to 730 ℃ after 40-60 min before pressure casting, adding a refining agent accounting for 2.0 percent of the weight of the raw materials for refining after all the industrial pure aluminum ingot, the AlTi10 intermediate alloy and the AlB8 intermediate alloy which are sequentially added are melted, wherein the refining temperature is 730 ℃, the stirring time of refining treatment is 10min, and the refining agent comprises the following components in percentage by mass: 55% KCl and 25% CaCl2、5％CaF2、15％BaCl2. And (4) heating the furnace to 750 ℃, preserving heat and standing for 20min to promote the settlement of impurities, thereby obtaining the magnesium alloy melt.
(5) And cooling the magnesium alloy melt to 740 ℃, skimming surface scum, pressing the magnesium alloy melt into a die-casting die preheated to 250 ℃ at the speed of 15m/s, and cooling to obtain the high-strength high-toughness heat-resistant die-casting Mg-Er alloy.
Respectively carrying out a-room temperature tensile test on the prepared die-casting magnesium alloy; b, performing high-temperature tensile property test at 200 ℃ after 200-hour heat exposure treatment at 200 ℃, wherein the cast-state room-temperature tensile strength of the die-casting magnesium alloy obtained in the example is 295MPa, and the elongation is 13%; the tensile strength at high temperature of 200 ℃ is 198MPa, and the elongation is 27%.
The above embodiments do not limit the present invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent transformation fall within the protection scope of the present invention.
Claims (6)
1. The high-strength and high-toughness heat-resistant die-casting Mg-Er alloy is characterized by comprising the following elements in percentage by mass: 4.0-8.5% of Er, 1.2-5.1% of Zn, 0.5-1.2% of Al, 0.1-0.3% of Mn, 0.01-0.08% of M, and the balance of Mg and other inevitable impurities; wherein M is one or two of Ti and B; the mass ratio of Zn to Er is 0.2-0.6, and the mass ratio of (Zn + Al)/Er is 0.3-0.7;
the preparation method of the high-strength high-toughness heat-resistant die-casting Mg-Er alloy comprises the following steps:
(1) calculating the use amounts of an industrial pure magnesium ingot, an industrial pure zinc ingot, an industrial pure aluminum ingot, an Mg-Er intermediate alloy, an Mg-Mn intermediate alloy, an Al-Ti-B intermediate alloy and an Al-B intermediate alloy according to the components of the Mg-Er alloy and the stoichiometric ratio; removing oxide layers of an industrial pure magnesium ingot, an industrial pure zinc ingot, an industrial pure aluminum ingot, a Mg-Er intermediate alloy and a Mg-Mn intermediate alloy, and drying and preheating to 200 ℃;
(2) melting an industrial pure magnesium ingot accounting for 25% of the height of the crucible into a molten pool, introducing protective gas, and adding the rest magnesium ingot;
(3) after the magnesium ingot is completely melted, heating to 720 ℃, adding industrial pure zinc, Mg-Er intermediate alloy and Mg-Mn intermediate alloy for multiple times, keeping the temperature constant at 720 ℃, stirring until the industrial pure zinc, Mg-Er intermediate alloy and Mg-Mn intermediate alloy are completely melted, and keeping the temperature for 30 min;
(4) heating to 730 ℃ after 40-60 min before pressure casting, adding a refining agent for refining after all the industrial pure aluminum ingot, the Al-Ti intermediate alloy, the Al-Ti-B intermediate alloy and the Al-B intermediate alloy which are sequentially added are melted, heating the furnace to 750 ℃, keeping the temperature and standing for 10-20min, and promoting the settlement of impurities to obtain a magnesium alloy melt;
(5) and cooling the magnesium alloy melt to 720-740 ℃, skimming the surface scum, pressing the magnesium alloy melt into a die-casting die preheated to 180-250 ℃ at a speed of 4-15 m/s, and cooling to obtain the high-strength high-toughness heat-resistant die-casting Mg-Er alloy.
2. The high strength and toughness heat-resistant die-cast Mg-Er alloy according to claim 1, wherein: the Mg-Er master alloy is MgEr25 or MgEr 30; the Mg-Mn intermediate alloy is MgMn 10; the Al-Ti-B intermediate alloy is AlTi5B 1; the Al-B intermediate alloy is AlB3 or AlB8, and the Al-Ti intermediate alloy is AlTi5 or AlTi 10.
3. The high strength and toughness heat-resistant die-cast Mg-Er alloy according to claim 1, wherein: the refining agent comprises the following components in percentage by mass: 55% KCl and 25% CaCl2、5% CaF2、15% BaCl2。
4. The high strength and toughness heat-resistant die-cast Mg-Er alloy according to claim 1, wherein: the addition amount of the refining agent is 1.0-3.5% of the total weight of the raw materials.
5. The high strength and toughness heat-resistant die-cast Mg-Er alloy according to claim 1, wherein: the refining temperature when the refining agent is added for refining is 720-730 ℃, and the stirring time of the refining treatment is 10-15 min.
6. The high strength and toughness heat-resistant die-cast Mg-Er alloy according to claim 1, wherein: the protective gas is argon or SF with volume fraction of 0.2%6And CO2The mixed gas of (1).
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| CN102618763A (en) * | 2012-04-13 | 2012-08-01 | 江汉大学 | Heat resistant magnesium alloy |
| EP2550377A1 (en) * | 2010-03-25 | 2013-01-30 | Magnesium Elektron Limited | Magnesium alloys containing heavy rare earths |
| CN102994835A (en) * | 2011-09-09 | 2013-03-27 | 江汉大学 | Heatproof magnesium alloy |
| CN104894447A (en) * | 2015-04-03 | 2015-09-09 | 北京工业大学 | Layered/acicular two-phase composite enhanced rare earth magnesium alloy and preparation technology thereof |
| CN105220041A (en) * | 2014-06-18 | 2016-01-06 | 中国科学院金属研究所 | A kind of high-strength wrought magnesium alloys and preparation method thereof |
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| EP2550377A1 (en) * | 2010-03-25 | 2013-01-30 | Magnesium Elektron Limited | Magnesium alloys containing heavy rare earths |
| CN102994835A (en) * | 2011-09-09 | 2013-03-27 | 江汉大学 | Heatproof magnesium alloy |
| CN102618763A (en) * | 2012-04-13 | 2012-08-01 | 江汉大学 | Heat resistant magnesium alloy |
| CN105220041A (en) * | 2014-06-18 | 2016-01-06 | 中国科学院金属研究所 | A kind of high-strength wrought magnesium alloys and preparation method thereof |
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Denomination of invention: High strength and toughness heat-resistant die-casting Mg-Er alloy and its preparation method Effective date of registration: 20230109 Granted publication date: 20210917 Pledgee: Anhui Fengyang Rural Commercial Bank Co.,Ltd. Pledgor: FENGYANG L-S LIGHT ALLOY NET FORMING Co.,Ltd. Registration number: Y2023980030740 |