CN113981259A - Novel magnesium-aluminum-tin-calcium alloy and preparation method thereof - Google Patents
Novel magnesium-aluminum-tin-calcium alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel magnesium-aluminum-tin-calcium alloy and a preparation method thereof, wherein the magnesium alloy comprises the following components in percentage by mass: 3 to 6 percent of aluminum, 0.5 to 3 percent of tin, 0.1 to 1 percent of calcium, 0 to 0.5 percent of manganese, 0 to 0.1 percent of rare earth, less than or equal to 0.02 percent of inevitable impurities, and the balance of magnesium. The preparation method comprises the following steps: preparing an as-cast plate blank by sub-rapid solidification; preparing a solid solution plate blank by deformation-assisted first gradient solid solution; preparing a solid solution plate blank by deformation-assisted second gradient solid solution; and (3) preparing the novel magnesium-aluminum-tin-calcium alloy by deformation-assisted third gradient solid solution. The invention effectively refines and spheroidizes the high-melting point eutectic phase formed in the alloy solidification process, and widens the design range of alloy components. In addition, the driving force of solute atom redissolution is increased to form a supersaturated solid solution, so that low-temperature short-time solid solution is realized. The magnesium alloy plate blank obtained by the invention can be applied to the field of metal material deformation processing, such as preparation of low-cost high-strength plastic magnesium alloy plates.
Description
Technical Field
The invention belongs to the field of metal material solidification and heat treatment, and particularly relates to a novel magnesium-aluminum-tin-calcium alloy and a preparation method thereof.
Background
The magnesium-aluminum alloy is used as a light engineering structure metal material and is widely applied to the fields of aerospace, mobile phone electronic components and the like. Alloy elements such as tin, calcium and the like are added into the magnesium-aluminum alloy, so that the room temperature strength and the high temperature thermal stability of the alloy can be effectively improved. In addition, the reserves of alloy elements such as tin, calcium and the like are rich, the price is low, and the method has good commercial application prospect. However, magnesium is liable to react with alloying elements such as aluminum, tin, calcium and the like during solidification to form a coarse eutectic phase (e.g., a CaMgSn phase, Mg phase) with a high melting point2(Al, Ca) phase and Al2Ca equals). Although these eutectic phases with high melting points can improve the thermal stability of the alloy; however, the alloy has large size and irregular shape, and is difficult to eliminate by conventional solution treatment, so that stress concentration is easy to generate in the subsequent deformation process, and the mechanical property of the alloy is seriously influenced.
The cooling rate in the solidification stage has a great influence on the morphology of the eutectic phase. In the conventional solidification process, due to the slow cooling speed, the atom diffusion time is sufficient, the eutectic phase grows sufficiently, and the morphology of the eutectic phase is generally in a thick rod shape or a feather shape.
Solution treatment is a common process for controlling the eutectic phase. At present, two solid solution methods for a high-melting point coarse eutectic phase exist, namely, the solid solution temperature is increased, and the solid solution time is prolonged. However, the matrix and partial eutectic phase (e.g., Mg) in the magnesium-aluminum-tin-calcium alloy17Al12) The melting point is low, and the material is easy to be over-sintered at high temperature; in addition, the overlong solid solution time (commonly 1440min, 2880min and the like) has large energy consumption, long period and high production cost.
In conclusion, the conventional solidification technology and the solution treatment process cannot effectively refine the coarse eutectic phase in the magnesium-aluminum-tin-calcium alloy, thereby seriously influencing the hot-working formability and the mechanical property of the alloy and limiting the large-scale industrial application of the alloy.
Disclosure of Invention
In order to solve the technical problem, the invention provides a novel magnesium-aluminum-tin-calcium alloy, which comprises the following components in percentage by mass: 3-6% of aluminum, 0.5-3% of tin, 0.1-1% of calcium, 0-0.5% of manganese, 0-0.1% of rare earth, less than or equal to 0.02% of unavoidable impurity content and the balance of magnesium, wherein the preparation method of the magnesium-aluminum-tin-calcium alloy comprises the following steps:
(1) under the protection of argon, according to the component proportion, mixing commercial pure magnesium, commercial pure aluminum, commercial pure tin, magnesium-calcium intermediate alloy, magnesium-manganese intermediate alloy and magnesium-rare earth intermediate alloy, melting at the temperature of 600-;
(2) preheating the sub-rapid solidification cast magnesium alloy plate blank obtained in the step (1) at 20-300 ℃ for 2-20min, performing unidirectional deformation, wherein the deformation amount is 5-15%, the deformation direction is defined as the horizontal direction, performing first gradient solid solution at the temperature of 300-400 ℃, the solid solution time is 10-60min, and quenching in warm water at the temperature of 10-30 ℃ after solid solution to obtain a first gradient solid solution magnesium alloy plate blank;
(3) preheating the first gradient solid solution state magnesium alloy plate blank obtained in the step (2) at the temperature of 20-300 ℃ for 2-20min, performing unidirectional deformation, wherein the deformation amount is 5-15%, clockwise rotating the deformation direction along the horizontal direction by 45-90 degrees, then performing second gradient solid solution at the temperature of 350-450 ℃, the solid solution time is 10-60min, and quenching in warm water at the temperature of 10-30 ℃ after solid solution to obtain a second gradient solid solution state magnesium alloy plate blank;
(4) preheating the second gradient solid solution state magnesium alloy plate blank obtained in the step (3) at 20-300 ℃ for 2-20min, performing unidirectional deformation with the deformation amount of 5-15%, anticlockwise rotating the deformation direction along the horizontal direction for 45-90 degrees, performing third gradient solid solution at the temperature of 350-450 ℃ for 60-180min, and quenching in warm water at 10-30 ℃ after solid solution to obtain the novel magnesium-aluminum-tin-calcium alloy;
the accumulated deformation of the steps (2) to (4) is 14 to 39 percent.
Further, the rare earth is any combination of cerium or strontium.
Further, the magnesium-aluminum-tin-calcium alloy comprises the following components in percentage by mass: 4.5 to 5 percent of aluminum, 1 to 1.5 percent of tin, 0.2 to 0.5 percent of calcium, 0 to 0.2 percent of manganese and 0 to 0.05 percent of rare earth.
Further, the magnesium-rare earth master alloy in the step (1) is any combination of magnesium-cerium master alloy or magnesium-strontium master alloy.
Further, in the step (1), commercially pure magnesium, commercially pure aluminum, commercially pure tin, magnesium-calcium intermediate alloy, magnesium-manganese intermediate alloy and magnesium-rare earth intermediate alloy are mixed and melted at the temperature of 650-690 ℃, stirred for 6-8min at the temperature of 660-690 ℃ and kept warm for 6-10min to obtain the magnesium alloy melt with uniform components.
Further, the solidification cooling speed in the step (1) is 120-.
Further, the magnesium alloy plate blank in the step (2) is preheated at 20-250 ℃ for 5-10min and then is subjected to unidirectional deformation, the deformation direction is defined as the horizontal direction, the deformation amount is 5-10%, first gradient solid solution is carried out at the temperature of 300-350 ℃, and the solid solution time is 30-60 min.
Further, the magnesium alloy plate blank in the step (3) is preheated for 5-10min at 20-250 ℃, then is deformed in a single direction, the deformation direction rotates clockwise for 45-90 degrees along the horizontal direction, the deformation amount is 5-10 percent, and second gradient solid solution is carried out at the temperature of 350-400 ℃, and the solid solution time is 30-60 min.
Further, the magnesium alloy plate blank in the step (4) is preheated at 20-250 ℃ for 5-10min and then is deformed in a single direction, the deformation direction rotates 45-90 degrees along the horizontal direction anticlockwise, the deformation amount is 5-10 percent, and third gradient solid solution is carried out at the temperature of 400-450 ℃, and the solid solution time is 180 min.
Further, the novel magnesium-aluminum-tin-calcium alloy obtained in the step (4) has a refined and spheroidized eutectic phase with the length of 1-3 μm.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a sub-rapid solidification technology, a novel short-time solution treatment process and an alloy component optimization design, effectively refines and spheroidizes a high-melting point coarse eutectic phase formed by reaction with elements such as tin, calcium and the like in the solidification process of the magnesium-aluminum alloy, and can be seen from attached figures 1 and 2, the size of the eutectic phase is refined from 8-10 mu m to 1-3 mu m, and the appearance is changed from a coarse rod shape or a feather shape into a fine sphere shape and a similar sphere shape;
the method shortens the time of atomic diffusion and eutectic phase growth in the solidification process of the magnesium-aluminum-tin-calcium alloy, inhibits the growth of eutectic phase, and effectively refines and spheroidizes the eutectic phase through the synergistic effect of the sub-rapid solidification technology, the novel short-time solid solution treatment process and the optimized design of alloy components. Moreover, the synergistic effect enables the matrix to capture a large amount of solute atoms to form a supersaturated solid solution, reduces the temperature required by subsequent solid solution, and greatly shortens the solid solution time. In addition, the synergistic effect introduces crystal defects such as vacancies, dislocations, deformed twins and the like, increases the driving force of solute atom diffusion, and improves the solid solution efficiency. In a word, the method reduces the solid solution temperature and shortens the solid solution time, the temperature is reduced by 10-18%, the time is shortened by 80-83% (refer to a comparative example 1), the production efficiency is greatly improved, the energy consumption in the alloy processing process is reduced, and the method is more suitable for industrial batch production;
according to the invention, the deformation direction and the deformation amount are cooperatively regulated, on one hand, the texture is weakened and the anisotropy of the texture is improved through multidirectional deformation; on the other hand, the initial appearance of the magnesium alloy plate blank is kept through small deformation, compared with the common process (refer to a comparative example 2) with the deformation of 70-80%, the deformation of the magnesium alloy plate blank is reduced by more than 40%, and the possibility is provided for further processing the magnesium-aluminum-tin-calcium alloy plate blank;
the invention adopts a gradient solid solution process (first ladder) by synergistically regulating and controlling the solid solution temperature and the solid solution timeSolid solution: 300 ℃ and 400 ℃ for 10-60min, and carrying out second gradient solid solution: 350-450 ℃ for 10-60min, and performing third gradient solid solution: 350 ℃ and 450 ℃ for 60-180min), effectively avoiding the matrix and eutectic phase (such as Mg) with low melting point in the magnesium-aluminum-tin-calcium alloy17Al12) Burning loss;
according to the invention, through the synergistic effect of the sub-rapid solidification technology, the novel short-time solution treatment process and the optimization design of alloy components, the coarse eutectic phase with high melting point in the magnesium-aluminum-tin-calcium alloy is refined and spheroidized, the residual stress in the alloy is eliminated, the texture is weakened, and the initial morphology of a plate blank is kept, so that the magnesium-aluminum-tin-calcium alloy obtained by the invention can realize the synergistic improvement of the strong plasticity (see the attached figure 3 in detail).
Drawings
FIG. 1 shows the morphology of CaMgSn phase in the Mg-4.5Al-1.5Sn-0.5Ca alloy obtained in comparative example 1;
FIG. 2 shows the morphology of CaMgSn phase in the Mg-4.5Al-1.5Sn-0.5Ca alloy obtained in example 1;
FIG. 3 is a room temperature stress-strain curve of the Mg-4.5Al-1.5Sn-0.5Ca alloys obtained in comparative example 1 and example 1 after single pass rolling and stress relief annealing.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to the accompanying drawings and the detailed description.
Example 1
Mg-4.5Al-1.5Sn-0.5Ca alloy in percentage by mass: 4.5 percent of Al, 1.5 percent of Sn, 0.5 percent of Ca, less than or equal to 0.02 percent of unavoidable impurities and the balance of Mg. The preparation method specifically comprises the following steps:
(1) under the protection of argon, according to the component proportion, mixing commercial pure magnesium, commercial pure aluminum, commercial pure tin and magnesium-calcium intermediate alloy, melting at 670-680 ℃, stirring at 660-670 ℃ for 8min, and preserving heat for 10min to obtain a magnesium alloy melt with uniform components, casting the magnesium alloy melt into a copper water-cooling mold, wherein the water-cooling temperature is 30 ℃, the solidification cooling speed is 164K/s, so that a sub-rapid solidification casting state Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank with the thickness of 6mm is obtained;
(2) preheating the sub-rapid solidification cast Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (1) at 250 ℃ for 10min, carrying out unidirectional rolling, wherein the reduction is 10%, the rolling direction is defined as the horizontal direction, then carrying out first gradient solid solution at 350 ℃ for 60min, quenching in warm water at 25-30 ℃ after solid solution, and obtaining a first gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank;
(3) preheating the first gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (2) at 250 ℃ for 10min, carrying out unidirectional rolling, reducing the rolling amount to 10%, clockwise rotating the rolling direction along the horizontal direction by 90 degrees, then carrying out second gradient solid solution at 400 ℃ for 60min, quenching in warm water at 25-30 ℃ after solid solution, and obtaining a second gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank;
(4) preheating the second gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (3) at 250 ℃ for 10min, carrying out unidirectional rolling, reducing the rolling amount to 10%, rotating the rolling direction along the horizontal direction anticlockwise for 90 degrees, then carrying out third gradient solid solution at 450 ℃ for 180min, quenching in warm water at 25-30 ℃ after solid solution, and obtaining Mg-4.5Al-1.5Sn-0.5Ca alloy;
the cumulative deformation of steps (2) - (4) is 27%.
The obtained Mg-4.5Al-1.5Sn-0.5Ca alloy has refined and spheroidized eutectic phase, and the length of the eutectic phase is 1-3 mu m.
Comparative example 1
Mg-4.5Al-1.5Sn-0.5Ca alloy in percentage by mass: 4.5 percent of Al, 1.5 percent of Sn, 0.5 percent of Ca, less than or equal to 0.02 percent of unavoidable impurities and the balance of Mg. The preparation method specifically comprises the following steps:
(1) under the protection of argon, according to the component proportion, mixing commercial pure magnesium, commercial pure aluminum, commercial pure tin and magnesium-calcium intermediate alloy, melting at 670-680 ℃, stirring at 660-670 ℃ for 8min, and preserving heat for 10min to obtain a magnesium alloy melt with uniform components, casting the magnesium alloy melt into an iron Y-shaped mold, wherein the solidification cooling speed is 11K/s, so that a conventional solidified casting state Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank with the thickness of 25mm is obtained;
(2) and (2) performing solid solution on the conventional solidified cast Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (1) at the temperature of 500 ℃ for 1440min, and quenching in warm water at the temperature of 25-30 ℃ after solid solution to obtain the Mg-4.5Al-1.5Sn-0.5Ca alloy.
In the embodiment 1, the sub-rapid solidification technology is combined with the three-pass rolling auxiliary solid solution process, and compared with the conventional solidification technology combined with the high-temperature long-time solid solution process adopted in the comparative example 1, the solid solution temperature of the embodiment 1 is reduced by 10%, and the time is shortened by 80%.
The comparative example 1 adopts the conventional solidification technology and combines the high-temperature long-time solid solution process, and the obtained CaMgSn phase is shown in the attached figure 1 in detail; in example 1, the sub-rapid solidification technology is combined with three rolling processes to assist the solid solution process, and the obtained CaMgSn phase is shown in the attached figure 2 in detail. As can be seen from figures 1 and 2: the length of the CaMgSn phase obtained in the comparative example 1 is 8-10 μm, and the length of the CaMgSn phase obtained in the example 1 is 1-3 μm, so that the CaMgSn phase is effectively refined by the method; in addition, the appearance of the CaMgSn phase obtained in the comparative example 1 is rod-shaped or feather-shaped, and the appearance of the CaMgSn phase obtained in the example 1 is spherical or sphere-like, so that the CaMgSn phase is effectively spheroidized by the method.
The following Mg-4.5Al-1.5Sn-0.5Ca alloys obtained in comparative example 1 and example 1 were subjected to single pass rolling and stress relief annealing, respectively, in the following manner:
(1) preheating the Mg-4.5Al-1.5Sn-0.5Ca alloy obtained in the comparative example 1 and the example 1 at the temperature of 250-300 ℃ for 5-15min, performing unidirectional rolling with the reduction of 30 percent, and horizontally rolling to obtain a rolled Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank;
(2) stress annealing the rolled Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (1) at the temperature of 200-300 ℃ for 10-30min, and quenching in warm water at the temperature of 25-30 ℃ after annealing to obtain the annealed Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank;
as can be seen from the attached FIG. 3, the annealed Mg-4.5Al-1.5Sn-0.5Ca alloy obtained in example 1 has the ultimate tensile strength 1.1 times that of comparative example 1 and the elongation 1.3 times that of comparative example 1, and the invention shows that the novel Mg-4.5Al-1.5Sn-0.5Ca alloy obtained in the invention can realize the synergistic improvement of the strong plasticity through the subsequent deformation processing.
Example 2
The Mg-4.5Al-1.5Sn-0.5Ca-0.02Mn-0.025Ce-0.025Sr alloy comprises the following components in percentage by mass: 4.5 percent of Al, 1.5 percent of Sn, 0.5 percent of Ca, 0.02 percent of Mn, 0.025 percent of Ce, 0.025 percent of Sr, less than or equal to 0.02 percent of unavoidable impurities and the balance of Mg. The preparation method specifically comprises the following steps:
(1) under the protection of argon, according to the component proportion, mixing commercial pure magnesium, commercial pure aluminum, commercial pure tin, magnesium-calcium intermediate alloy, magnesium-manganese intermediate alloy, magnesium-cerium intermediate alloy and magnesium-strontium intermediate alloy, melting at 660-680 ℃, stirring at 660-670 ℃ for 8min, and preserving heat for 10min to obtain magnesium alloy melt with uniform components, casting the magnesium alloy melt into a copper water-cooling mold, wherein the water-cooling temperature is 30 ℃, the solidification cooling rate is 200K/s, and obtaining a sub-rapid solidification casting state Mg-4.5Al-1.5Sn-0.5Ca-0.02Mn-0.025Ce-0.025Sr alloy plate blank with the thickness of 5 mm;
(2) compressing the semi-rapidly solidified cast Mg-4.5Al-1.5Sn-0.5Ca-0.02Mn-0.025Ce-0.025Sr alloy plate blank obtained in the step (1) at room temperature, wherein the compression amount is 5%, and the compression direction is defined as the horizontal direction, then carrying out first gradient solid solution at the temperature of 320 ℃ for 60min, and quenching in warm water at the temperature of 25-30 ℃ after solid solution to obtain a first gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca-0.02Mn-0.025Ce-0.025Sr alloy plate blank;
(3) compressing the first gradient solid solution state Mg-4.5Al-1.5Sn-0.5Ca-0.02Mn-0.025Ce-0.025Sr alloy plate blank obtained in the step (2) at room temperature, wherein the compression amount is 5%, the compression direction rotates clockwise 90 degrees along the horizontal direction, then performing second gradient solid solution at the temperature of 400 ℃, the solid solution time is 60min, quenching in warm water at the temperature of 25-30 ℃ after solid solution, and obtaining a second gradient solid solution state Mg-4.5Al-1.5Sn-0.5Ca-0.02Mn-0.025Ce-0.025Sr alloy plate blank;
(4) compressing the second gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca-0.02Mn-0.025Ce-0.025Sr alloy plate blank obtained in the step (3) at room temperature, wherein the compression amount is 5%, the compression direction rotates anticlockwise for 90 degrees along the horizontal direction, then performing third gradient solid solution at the temperature of 420 ℃, the solid solution time is 120min, quenching in warm water at the temperature of 25-30 ℃ after solid solution, and obtaining Mg-4.5Al-1.5Sn-0.5Ca-0.02Mn-0.025Ce-0.025Sr alloy;
the cumulative deformation of steps (2) - (4) is 14%.
The obtained Mg-4.5Al-1.5Sn-0.5Ca-0.02Mn-0.025Ce-0.025Sr alloy has refined and spheroidized eutectic phase, and the length of the eutectic phase is 1-3 mu m.
Example 3
Mg-4.5Al-1.5Sn-0.5Ca alloy in percentage by mass: 4.5 percent of Al, 1.5 percent of Sn, 0.5 percent of Ca, less than or equal to 0.02 percent of unavoidable impurities and the balance of Mg. The preparation method specifically comprises the following steps:
(1) under the protection of argon, according to the component proportion, mixing commercial pure magnesium, commercial pure aluminum, commercial pure tin and magnesium-calcium intermediate alloy, melting at 670-680 ℃, stirring at 660-670 ℃ for 8min, and preserving heat for 10min to obtain a magnesium alloy melt with uniform components, casting the magnesium alloy melt into a copper water-cooling mold, wherein the water-cooling temperature is 30 ℃, the solidification cooling speed is 164K/s, so that a sub-rapid solidification casting state Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank with the thickness of 6mm is obtained;
(2) preheating the sub-rapid solidification cast Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (1) at 250 ℃ for 10min, carrying out unidirectional rolling, wherein the reduction is 10%, the rolling direction is defined as the horizontal direction, then carrying out first gradient solid solution at 350 ℃ for 60min, quenching in warm water at 25-30 ℃ after solid solution, and obtaining a first gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank;
(3) preheating the first gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (2) at 250 ℃ for 10min, carrying out unidirectional rolling, reducing the rolling amount to 10%, clockwise rotating the rolling direction along the horizontal direction by 45 degrees, then carrying out second gradient solid solution at 400 ℃ for 60min, quenching in warm water at 25-30 ℃ after solid solution, and obtaining a second gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank;
(4) preheating the second gradient solid solution Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (3) at 250 ℃ for 10min, carrying out unidirectional rolling, reducing the rolling amount to 10%, rotating the rolling direction along the horizontal direction anticlockwise for 45 degrees, then carrying out third gradient solid solution at 450 ℃ for 180min, quenching in warm water at 25-30 ℃ after solid solution, and obtaining Mg-4.5Al-1.5Sn-0.5Ca alloy;
the cumulative deformation of steps (2) - (4) is 27%.
The obtained Mg-4.5Al-1.5Sn-0.5Ca alloy has refined and spheroidized eutectic phase, and the length of the eutectic phase is 1-3 mu m.
Example 4
The Mg-5Al-1.5Sn-0.5Ca-0.2Mn-0.05Sr alloy comprises the following components in percentage by mass: 5 percent of Al, 1.5 percent of Sn, 0.5 percent of Ca, 0.2 percent of Mn, 0.05 percent of Sr, less than or equal to 0.02 percent of unavoidable impurities and the balance of Mg. The preparation method specifically comprises the following steps:
(1) under the protection of argon, according to the component proportion, mixing commercial pure magnesium, commercial pure aluminum, commercial pure tin, magnesium-calcium intermediate alloy, magnesium-manganese intermediate alloy and magnesium-strontium intermediate alloy, melting at 660-690 ℃, stirring at 670-690 ℃ for 6min, and keeping the temperature for 6min to obtain magnesium alloy melt with uniform components, casting the magnesium alloy melt into a copper water-cooling mold, wherein the water cooling temperature is 20 ℃, the solidification cooling rate is 200K/s, so that a sub-rapid solidification casting state Mg-5Al-1.5Sn-0.5Ca-0.2Mn-0.05Sr alloy plate blank with the thickness of 5mm is obtained;
(2) preheating the sub-rapid solidification cast Mg-5Al-1.5Sn-0.5Ca-0.2Mn-0.05Sr alloy plate blank obtained in the step (1) at 250 ℃ for 10min, carrying out unidirectional rolling, wherein the reduction is 10%, the rolling direction is defined as the horizontal direction, then carrying out first gradient solid solution at the temperature of 300 ℃ for 60min, and quenching in warm water at the temperature of 10-25 ℃ after solid solution to obtain a first gradient solid solution Mg-5Al-1.5Sn-0.5Ca-0.2Mn-0.05Sr alloy plate blank;
(3) preheating the first gradient solid solution Mg-5Al-1.5Sn-0.5Ca-0.2Mn-0.05Sr alloy plate blank obtained in the step (2) at 250 ℃ for 10min, then carrying out unidirectional rolling, wherein the reduction is 10%, the rolling direction clockwise rotates 45 degrees along the horizontal direction, then carrying out second gradient solid solution at 350 ℃ for 60min, and quenching in warm water at 10-25 ℃ after solid solution to obtain a second gradient solid solution Mg-5Al-1.5Sn-0.5Ca-0.2Mn-0.05Sr alloy plate blank;
(4) preheating the second gradient solid solution Mg-5Al-1.5Sn-0.5Ca-0.2Mn-0.05Sr alloy plate blank obtained in the step (3) at 250 ℃ for 10min, then carrying out unidirectional rolling, wherein the reduction is 10%, the rolling direction rotates anticlockwise for 45 degrees along the horizontal direction, then carrying out third gradient solid solution at 400 ℃ for 180min, and quenching in warm water at 10-25 ℃ after solid solution to obtain Mg-5Al-1.5Sn-0.5Ca-0.2Mn-0.05Sr alloy;
the cumulative deformation of steps (2) - (4) is 27%.
The obtained Mg-5Al-1.5Sn-0.5Ca-0.2Mn-0.05Sr alloy has refined and spheroidized eutectic phase, and the length of the eutectic phase is 1-3 mu m.
Example 5
Mg-4.5Al-1Sn-0.2Ca alloy in percentage by mass: 4.5 percent of Al, 1 percent of Sn, 0.2 percent of Ca, less than or equal to 0.02 percent of unavoidable impurities, and the balance of Mg. The preparation method specifically comprises the following steps:
(1) under the protection of argon, according to the component proportion, mixing commercial pure magnesium, commercial pure aluminum, commercial pure tin and magnesium-calcium intermediate alloy, melting at the temperature of 650 plus 670 ℃, stirring at the temperature of 660 plus 680 ℃ for 8min, and preserving heat for 10min to obtain a magnesium alloy melt with uniform components, casting the magnesium alloy melt into a copper water-cooling mold, wherein the water-cooling temperature is 40 ℃, the solidification cooling speed is 120K/s, and obtaining a sub-rapid solidification casting state Mg-4.5Al-1Sn-0.2Ca alloy plate blank with the thickness of 10 mm;
(2) preheating the sub-rapid solidification cast Mg-4.5Al-1Sn-0.2Ca alloy plate blank obtained in the step (1) at 250 ℃ for 5min, carrying out unidirectional rolling, wherein the reduction is 5%, the rolling direction is defined as the horizontal direction, then carrying out first gradient solid solution at 350 ℃ for 30min, quenching in warm water at 20-30 ℃ after solid solution, and obtaining a first gradient solid solution Mg-4.5Al-1Sn-0.2Ca alloy plate blank;
(3) preheating the first gradient solid solution Mg-4.5Al-1Sn-0.2Ca alloy plate blank obtained in the step (2) at 250 ℃ for 5min, carrying out unidirectional rolling, reducing the rolling amount to 5%, clockwise rotating the rolling direction to 45 degrees along the horizontal direction, then carrying out second gradient solid solution at 400 ℃ for 30min, quenching in warm water at 20-30 ℃ after solid solution, and obtaining a second gradient solid solution Mg-4.5Al-1Sn-0.2Ca alloy plate blank;
(4) preheating the second gradient solid solution Mg-4.5Al-1Sn-0.2Ca alloy plate blank obtained in the step (3) at 250 ℃ for 5min, carrying out unidirectional rolling with the reduction of 5%, anticlockwise rotating for 45 degrees along the horizontal direction in the rolling direction, then carrying out third gradient solid solution at 450 ℃ for 120min, quenching in warm water at 20-30 ℃ after solid solution to obtain Mg-4.5Al-1Sn-0.2Ca alloy;
the cumulative deformation of steps (2) - (4) is 14%.
The obtained Mg-4.5Al-1Sn-0.2Ca alloy has refined and spheroidized eutectic phase, and the length of the eutectic phase is 1-3 mu m.
Comparative example 2
Mg-4.5Al-1.5Sn-0.5Ca alloy in percentage by mass: 4.5 percent of Al, 1.5 percent of Sn, 0.5 percent of Ca, less than or equal to 0.02 percent of unavoidable impurities and the balance of Mg. The preparation method specifically comprises the following steps:
(1) under the protection of argon, according to the component proportion, mixing commercial pure magnesium, commercial pure aluminum, commercial pure tin and magnesium-calcium intermediate alloy, melting at 670-680 ℃, stirring at 660-670 ℃ for 8min, and preserving heat for 10min to obtain a magnesium alloy melt with uniform components, casting the magnesium alloy melt into an iron Y-shaped mold, wherein the solidification cooling speed is 11K/s, so that a conventional solidified casting state Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank with the thickness of 25mm is obtained;
(2) homogenizing the conventional solidified cast Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (1) at the temperature of 350 ℃ for 60min, and quenching the homogenized cast Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank in warm water at the temperature of 40 ℃ after homogenizing to obtain a homogenized Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank;
(3) preheating the homogeneous Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (2) at 300 ℃ for 20min, and performing unidirectional rolling, wherein the rolling reduction is 20%, and the rolling direction is defined as the horizontal direction, so as to obtain a first-pass rolling Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank;
(4) preheating the first-pass rolling-state Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (3) at 250 ℃ for 15min, and then performing unidirectional rolling, wherein the rolling reduction is 30%, the rolling direction rotates clockwise by 90 degrees along the horizontal direction, so that a second-pass rolling-state Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank is obtained;
(5) preheating the second-pass rolling-state Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (4) at 300 ℃ for 15min, and performing unidirectional rolling, wherein the rolling reduction is 33%, the rolling direction rotates clockwise 180 degrees along the horizontal direction, so that a third-pass rolling-state Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank is obtained;
(6) preheating the third rolling state Mg-4.5Al-1.5Sn-0.5Ca alloy plate blank obtained in the step (5) at 350 ℃ for 20min, performing unidirectional rolling with the reduction of 50%, clockwise rotating the rolling direction along the horizontal direction by 270 degrees, and obtaining the heating rotating four-pass rolled Mg-4.5Al-1.5Sn-0.5Ca alloy;
the accumulated deformation of the steps (3) to (6) is 81 percent;
comparative example 2 also yielded a crushed and spheroidized CaMgSn phase as compared to example 1. However, compared with the heat preservation and temperature-raising rotation four-pass rolling adopted in the comparative example 2, the process flow of the example 1 is shorter; in addition, compared with the large reduction rolling (the reduction is 81%) adopted in the comparative example 2, the small reduction rolling (the reduction is 27%) adopted in the example 1 greatly retains the initial appearance of the alloy slab, and the Mg-4.5Al-1.5Sn-0.5Ca alloy obtained in the example 1 has higher processability and provides possibility for subsequent large deformation processing.
Claims (10)
1. The novel magnesium-aluminum-tin-calcium alloy is characterized by comprising the following components in percentage by mass: 3-6% of aluminum, 0.5-3% of tin, 0.1-1% of calcium, 0-0.5% of manganese, 0-0.1% of rare earth, less than or equal to 0.02% of unavoidable impurity content and the balance of magnesium, wherein the preparation method of the magnesium-aluminum-tin-calcium alloy comprises the following steps:
(1) under the protection of argon, according to the component proportion, mixing commercial pure magnesium, commercial pure aluminum, commercial pure tin, magnesium-calcium intermediate alloy, magnesium-manganese intermediate alloy and magnesium-rare earth intermediate alloy, melting at the temperature of 600-;
(2) preheating the sub-rapid solidification cast magnesium alloy plate blank obtained in the step (1) at 20-300 ℃ for 2-20min, performing unidirectional deformation, wherein the deformation amount is 5-15%, the deformation direction is defined as the horizontal direction, performing first gradient solid solution at the temperature of 300-400 ℃, the solid solution time is 10-60min, and quenching in warm water at the temperature of 10-30 ℃ after solid solution to obtain a first gradient solid solution magnesium alloy plate blank;
(3) preheating the first gradient solid solution state magnesium alloy plate blank obtained in the step (2) at the temperature of 20-300 ℃ for 2-20min, performing unidirectional deformation, wherein the deformation amount is 5-15%, clockwise rotating the deformation direction along the horizontal direction by 45-90 degrees, then performing second gradient solid solution at the temperature of 350-450 ℃, the solid solution time is 10-60min, and quenching in warm water at the temperature of 10-30 ℃ after solid solution to obtain a second gradient solid solution state magnesium alloy plate blank;
(4) preheating the second gradient solid solution state magnesium alloy plate blank obtained in the step (3) at 20-300 ℃ for 2-20min, performing unidirectional deformation with the deformation amount of 5-15%, anticlockwise rotating the deformation direction along the horizontal direction for 45-90 degrees, performing third gradient solid solution at the temperature of 350-450 ℃ for 60-180min, and quenching in warm water at 10-30 ℃ after solid solution to obtain the novel magnesium-aluminum-tin-calcium alloy;
the accumulated deformation of the steps (2) to (4) is 14 to 39 percent.
2. The magnesium-aluminum-tin-calcium alloy as claimed in claim 1, wherein the rare earth is any combination of cerium or strontium.
3. The novel magnesium-aluminum-tin-calcium alloy as claimed in claim 1, wherein the magnesium-aluminum-tin-calcium alloy comprises the following components in percentage by mass: 4.5 to 5 percent of aluminum, 1 to 1.5 percent of tin, 0.2 to 0.5 percent of calcium, 0 to 0.2 percent of manganese and 0 to 0.05 percent of rare earth.
4. The novel magnesium-aluminum-tin-calcium alloy as claimed in claim 1, wherein the magnesium-rare earth master alloy in step (1) is magnesium-cerium master alloy or any combination of magnesium-strontium master alloys.
5. The novel magnesium-aluminum-tin-calcium alloy as claimed in claim 1, wherein step (1) is carried out by mixing commercially pure magnesium, commercially pure aluminum, commercially pure tin, magnesium-calcium intermediate alloy, magnesium-manganese intermediate alloy and magnesium-rare earth intermediate alloy, melting at 650-.
6. The magnesium-aluminum-tin-calcium alloy as claimed in claim 1, wherein the solidification cooling rate in step (1) is 120-200K/s, and the slab thickness is 5-10 mm.
7. The magnesium-aluminum-tin-calcium alloy as claimed in claim 1, wherein the magnesium alloy slab in step (2) is preheated at 20-250 ℃ for 5-10min and then is deformed unidirectionally, the deformation direction is defined as the horizontal direction, the deformation amount is 5-10%, the first gradient solid solution is carried out at the temperature of 300-350 ℃, and the solid solution time is 30-60 min.
8. The novel magnesium-aluminum-tin-calcium alloy as claimed in claim 1, wherein the magnesium alloy slab in step (3) is preheated at 20-250 ℃ for 5-10min and then is deformed unidirectionally, the deformation direction is rotated clockwise at 45-90 ° along the horizontal direction, the deformation amount is 5-10%, and the second gradient solid solution is carried out at the temperature of 350-400 ℃ for 30-60 min.
9. The novel magnesium-aluminum-tin-calcium alloy as claimed in claim 1, wherein the magnesium alloy slab in step (4) is preheated at 20-250 ℃ for 5-10min and then is deformed unidirectionally, the deformation direction is rotated counterclockwise by 45-90 ° along the horizontal direction, the deformation amount is 5-10%, and the third gradient solid solution is carried out at the temperature of 400-450 ℃ for 180 min.
10. The novel magnesium-aluminum-tin-calcium alloy according to any one of claims 1 to 9, wherein the novel magnesium-aluminum-tin-calcium alloy obtained in step (4) has a refined and spheroidized eutectic phase having a length of 1 to 3 μm.
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