CN113005346B - Corrosion-resistant fast extrusion magnesium alloy and preparation method thereof - Google Patents
Corrosion-resistant fast extrusion magnesium alloy and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of metal materials, and discloses a corrosion-resistant fast extrusion magnesium alloy and a preparation method thereof; the magnesium alloy comprises the following components in percentage by mass: aluminum: 0.1-2.0%, calcium: 0.05-0.5%, tin: 0.01-0.5%, yttrium: 0.01-0.45 percent of magnesium, additive elements and inevitable impurities, wherein the additive elements are one or any combination of cerium, neodymium and lanthanum, and the addition amount is as follows: cerium: 0-0.45%, neodymium: 0-0.45%, lanthanum: 0 to 0.45 percent. The preparation method comprises the following steps: after alloy smelting, pouring, rapid extrusion after homogenization heat treatment, solution heat treatment and artificial aging treatment, an atomic scale microstructure is formed in the magnesium alloy. The size, form, quantity and distribution of the microstructure can be regulated and controlled by the action of the rare earth elements and Al, Ca and Sn atoms, the micro-galvanic corrosion of the microstructure and a magnesium substrate is reduced, and the corrosion resistance is obviously improved.
Description
Technical Field
The invention relates to the field of metal materials, in particular to a corrosion-resistant fast extrusion magnesium alloy and a preparation method thereof.
Background
The magnesium alloy has the advantages of high specific strength, good shock absorption and the like as a light structural material, so the magnesium alloy has wide application prospect in the industries of automobiles, aerospace and the like. However, magnesium alloys are susceptible to corrosion due to the extremely high chemical and electrochemical activity of magnesium, which has a low equilibrium potential. Because the stability of the oxide film generated on the surface of the magnesium alloy is poor, and the impurity elements in the magnesium alloy, such as iron, and the like, can form galvanic corrosion with the magnesium base, the service life of the magnesium alloy is shortened, and the further wide application of the magnesium alloy is hindered. At present, the main approaches for improving the corrosion resistance of magnesium alloy are as follows: magnesium alloy surface treatment anticorrosion technology or addition of alloy elements. Alloying is an effective way for improving the corrosion resistance of magnesium and magnesium alloy, but the previous research mainly focuses on refining the grain size and the second phase by adding alloy elements and improving the stability of a surface film layer, and relatively few researches on the influence of the alloying elements on the size, shape, quantity and distribution of a primary-scale microstructure in the magnesium alloy and the corrosion resistance of the alloy are carried out. In addition, the extrusion speed of the existing commercial magnesium alloy is slow, for example, the extrusion speed of Mg-Al series and Mg-Zn series magnesium alloy is generally 1-5m/min, which is obviously lower than that of commercial 6XXX series aluminum alloy, and the extrusion cost of the magnesium alloy is higher. Therefore, from the idea of designing alloy components and regulating and controlling microstructure, it is a technical problem to be solved urgently at present to develop a novel magnesium alloy with high corrosion resistance and rapid extrusion deformation capability.
Disclosure of Invention
In order to solve the technical problem, the invention provides a corrosion-resistant fast extrusion magnesium alloy, which comprises the following components in percentage by mass: aluminum: 0.1-2.0%, calcium: 0.05-0.5%, tin: 0.01-0.5%, yttrium: 0.01 to 0.45 percent, and the balance of magnesium, additive elements and inevitable impurities; the additive element is one or any combination of cerium, neodymium and lanthanum, and the addition amount is as follows by mass percent: cerium: 0-0.45%, neodymium: 0-0.45%, lanthanum: 0 to 0.45 percent; the total amount of inevitable impurities is less than or equal to 0.05 percent; the balance being magnesium.
Further, the aluminum: 0.4-0.8%, calcium: 0.08-0.15%, tin: 0.05 to 0.1%, yttrium: 0.05-0.3 percent.
Further, the cerium: 0.05 to 0.3%, neodymium: 0.05-0.3%, lanthanum: 0.05-0.3 percent.
The invention also provides a preparation method of the corrosion-resistant fast extrusion magnesium alloy, which comprises the following steps:
(1) under the covering protection of argon or a second fusing agent, adding pure magnesium, pure aluminum, magnesium-calcium intermediate alloy, pure tin and magnesium-yttrium intermediate alloy in sequence, and heating and melting at 670-750 ℃; then, one or any combination of magnesium-cerium, magnesium-neodymium and magnesium-lanthanum intermediate alloys is added in sequence, the mixture is uniformly stirred at 670-;
(2) casting the alloy liquid obtained in the step (1) into a cast ingot in a semi-continuous casting or manual casting mode to obtain an as-cast alloy ingot;
(3) carrying out step homogenization heat treatment on the as-cast alloy ingot obtained in the step (2) under the protection of argon or nitrogen, and air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 300-480 ℃ to obtain an extruded section;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of argon or nitrogen, and then carrying out rapid air cooling or water quenching at 60-90 ℃ to obtain a solid solution extruded section;
(6) and (5) carrying out artificial aging treatment on the solid solution state extruded section obtained in the step (5) to obtain the corrosion-resistant fast extruded magnesium alloy.
Further, the steps of the step homogenization heat treatment in the step (3) are sequentially as follows: keeping the temperature at 350 ℃ for 2-5 hours in 300-;
further, the extrusion ratio of the rapid extrusion deformation in the step (4) is 15-200, and the extrusion speed is 8-80 m/min.
Further, the solution heat treatment temperature in the step (5) is 420-490 ℃ and the time is 10-120 min.
Further, the temperature of the artificial aging treatment in the step (6) is 155-198 ℃, and the time is 25-300 min.
Compared with the prior art, the invention has the following characteristics:
1) the magnesium alloy has low alloy element content, matrix magnesium content of more than 95.0 wt.%, main alloy element total amount of less than 5.0 wt.%, formed alloy has low melting point and eutectic phase content, added aluminum, calcium, tin, yttrium, cerium, neodymium, lanthanum and other rare earth elements can react to form high-melting point hard particles, such as calcium-containing phase, tin-containing calcium phase, rare earth-containing phase and composite phase thereof, and can effectively inhibit grain coarsening in the high-temperature extrusion process, so that rapid extrusion can be finally realized, the extrusion speed of the magnesium alloy is 10-20 times or more than that of commercial AZ31, AZ61 and AZ91 magnesium alloys, and the production efficiency is high.
2) Compared with the prior art, the artificial aging temperature required for forming the atomic scale microstructure is low, and the time is short, while the peak aging time required for forming the second phase by the traditional Mg-Al-Zn and Mg-Al-Sn magnesium alloys is usually ten to dozens of hours; for example, after a proper amount of rare earth elements are added into the alloy, the peak value can be reached after aging for 45min, the aging kinetics is obviously promoted, and the aging time is shortened.
3) According to the invention, the form, size, distribution and quantity of the atomic scale microstructure in the magnesium alloy can be regulated and controlled after the rare earth element is added; for example, when cerium, neodymium and yttrium are not added, the size of an atomic scale microstructure formed in the magnesium alloy is large, usually dozens to hundreds of nanometers, and the microstructure is not uniformly distributed, and the size of the microstructure formed after cerium, neodymium, yttrium and the like are added is small, the microstructure is dozens of nanometers to dozens of nanometers, and the microstructure is uniformly distributed in a dispersing manner, so that the corrosion resistance and the mechanical property of the alloy are obviously improved.
4) In the prior art, alloying elements are added, mainly through refining the grain size of the magnesium alloy, changing the size distribution of a second phase and improving the stability of a corrosion product film, the corrosion resistance of the magnesium alloy is improved, and the required alloying elements have higher content; the invention improves the corrosion resistance by adding trace elements to regulate and control the shape, size, distribution and quantity of the internal atomic scale microstructure of the magnesium alloy. For example, after adding trace aluminum, calcium, tin, cerium, neodymium, yttrium, lanthanum and the like, the purpose of regulating and controlling the atomic scale microstructure of the magnesium alloy can be achieved, a solute atom aggregation region (GP region) microstructure or an element pinning dislocation microstructure or cluster microstructure which is distributed dispersedly and has the length of several nanometers to tens of nanometers and is in the aging process is formed, the corrosion resistance of the microstructure is obviously higher than that of a conventional second phase, and further propagation of corrosion is hindered. The dispersed microstructure can lead the magnesium alloy to be subjected to uniform corrosion instead of the conventional local severe point corrosion. The added trace elements can also participate in the microstructure of the GP zone, thereby reducing the potential difference between the microstructure and the magnesium alloy matrix and further improving the corrosion resistance of the alloy. In addition, because the total content of the alloy is low, the content of the second phase which can be introduced is small, so that the effective area of the cathode phase is reduced, and the corrosion rate of the magnesium alloy is obviously reduced. If yttrium, cerium, neodymium and other elements are added, compared with the magnesium alloy which is not added, the corrosion resistance after the microstructure is introduced is improved by more than two times, and the corrosion resistance is obviously superior to that of magnesium alloys such as pure magnesium and AZ 31.
5) After the trace alloying elements are added into the magnesium alloy, the corrosion resistance of the alloy can be obviously improved, the work hardening capacity and the forming capacity of the alloy can be further improved, and the structural function integration is realized.
Detailed Description
Example 1
Taking Mg-0.1Al-0.05Ca-0.2Sn-0.01Y-0.05Ce alloy as an example (according to the mass percentage of the components, 0.1 percent of Al, 0.05 percent of Ca, 0.2 percent of Sn, 0.01 percent of Y, 0.05 percent of Ce, less than or equal to 0.05 percent of the total amount of inevitable impurities and the balance of magnesium), the preparation method comprises the following steps:
(1) under the protection of argon, adding pure magnesium, pure aluminum, a magnesium-calcium intermediate alloy, pure tin and a magnesium-yttrium intermediate alloy in sequence, and heating and melting at the temperature of 680-730 ℃; then adding magnesium-cerium intermediate alloy, uniformly stirring at 670-;
(2) pouring the alloy liquid obtained in the step (1) into a cast ingot in a semi-continuous casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of argon, wherein the steps are as follows in sequence: keeping the temperature at 340-; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at 300 ℃ to obtain an extruded section; the extrusion ratio is 15-30, and the extrusion speed is 60-80 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of argon at the temperature of 450-490 ℃ for 10-30min, and then carrying out rapid air cooling to obtain a solid solution extruded section;
(6) and (3) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 185-198 ℃, and the time is 25-50min, so as to obtain the corrosion-resistant fast extrusion Mg-0.1Al-0.05Ca-0.2Sn-0.01Y-0.05Ce magnesium alloy.
Example 2
Taking Mg-0.6Al-0.18Ca-0.01Sn-0.06Y-0.07Nd alloy as an example (according to the mass percentage of the components, the Al is 0.6 percent, the Ca is 0.18 percent, the Sn is 0.01 percent, the Y is 0.06 percent, the Nd is 0.07 percent, the total amount of inevitable impurities is less than or equal to 0.05 percent, and the balance is magnesium), the preparation method comprises the following steps:
(1) under the protection of argon, adding pure magnesium, pure aluminum, magnesium-calcium intermediate alloy, pure tin and magnesium-yttrium intermediate alloy in sequence, and heating and melting at the temperature of 700-; then adding magnesium-neodymium intermediate alloy, stirring uniformly at the temperature of 690-710 ℃, refining, degassing and removing slag to obtain alloy liquid;
(2) casting the alloy liquid obtained in the step (1) into a cast ingot in a manual casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of nitrogen, wherein the steps are as follows in sequence: the temperature is maintained at 310-320 ℃ for 3 hours, at 410-425 ℃ for 7 hours and at 460-470 ℃ for 2 hours; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 330-350 ℃ to obtain an extruded section; the extrusion ratio is 40-60, and the extrusion speed is 40-60 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of nitrogen at the temperature of 430-450 ℃ for 30-60min, and then carrying out water quenching at the temperature of 60-70 ℃ to obtain a solid solution extruded section; (6) and (4) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 160-180 ℃, and the time is 45-60min, so as to obtain the corrosion-resistant fast extrusion Mg-0.6Al-0.18Ca-0.01Sn-0.06Y-0.07Nd magnesium alloy.
The corrosion resistance of the magnesium alloy obtained in the step (6) of the embodiment is remarkably improved, and the average hydrogen evolution amount of the alloy after being soaked in a sodium chloride solution for 3 days is 4.2mL/cm2And same physical size and positionMg-0.6Al-0.18Ca-0.01Sn magnesium alloy (according to the mass percentage of the components, Al is 0.6 percent, Ca is 0.18 percent, Sn is 0.01 percent, the total amount of inevitable impurities is less than or equal to 0.05 percent, and the balance is magnesium) under the physical condition has the average hydrogen evolution of 15mL/cm2。
Example 3
Taking Mg-0.4Al-0.22Ca-0.1Sn-0.1Y-0.06La alloy as an example (according to the mass percentage of the components, the Al is 0.4 percent, the Ca is 0.22 percent, the Sn is 0.1 percent, the Y is 0.1 percent, the La is 0.06 percent, the total amount of inevitable impurities is less than or equal to 0.05 percent, and the balance is magnesium), the preparation method comprises the following steps:
(1) under the covering protection of a commercialized second flux, adding pure magnesium, pure aluminum, magnesium-calcium intermediate alloy, pure tin and magnesium-yttrium intermediate alloy in sequence, and heating and melting at 680-730 ℃; then adding magnesium-lanthanum intermediate alloy, stirring uniformly at the temperature of 680-700 ℃, refining, degassing and removing slag to obtain alloy liquid;
(2) pouring the alloy liquid obtained in the step (1) into a cast ingot in a semi-continuous casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of nitrogen, wherein the steps are as follows in sequence: keeping the temperature at 300-; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 380-400 ℃ to obtain an extruded section; the extrusion ratio is 25-40, and the extrusion speed is 20-30 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of argon at the temperature of 420-450 ℃ for 60-80min, and then carrying out water quenching at the temperature of 70-80 ℃ to obtain a solid solution extruded section; (6) and (4) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 185 ℃ and the time is 180 ℃ for 300min, and obtaining the corrosion-resistant fast extrusion Mg-0.4Al-0.22Ca-0.1Sn-0.1Y-0.06La magnesium alloy.
The magnesium alloy obtained in the step (6) of the embodiment has excellent corrosion resistance, and the average hydrogen evolution amount of the magnesium alloy after being soaked in the sodium chloride solution for 3 days is 3.3mL/cm2While the average hydrogen evolution amount of pure magnesium under the same external dimension and processing condition13mL/cm2。
Example 4
Taking Mg-2Al-0.5Ca-0.5Sn-0.45Y alloy as an example (according to the mass percentage of the components, the Al is 2 percent, the Ca is 0.5 percent, the Sn is 0.5 percent, the Y is 0.45 percent, the total amount of inevitable impurities is less than or equal to 0.05 percent, and the balance is magnesium), the preparation method comprises the following steps: (1) under the covering protection of a commercialized second flux, adding pure magnesium, pure aluminum, magnesium-calcium intermediate alloy, pure tin and magnesium-yttrium intermediate alloy in sequence, and heating and melting at 750 ℃ at 730-; stirring evenly at 710-;
(2) casting the alloy liquid obtained in the step (1) into a cast ingot in a manual casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of argon, wherein the steps are as follows in sequence: the temperature is maintained for 5 hours at the temperature of 330-; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 410-430 ℃ to obtain an extruded section; the extrusion ratio is 15-30, and the extrusion speed is 8-15 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of argon at the temperature of 440-450 ℃ for 120min, and then carrying out water quenching at the temperature of 70-80 ℃ to obtain a solid solution extruded section;
(6) and (4) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 180-.
Example 5
Taking Mg-1Al-0.25Ca-0.25Sn-0.3Y-0.05Nd alloy as an example (according to the mass percentage of the components, Al is 1 percent, Ca is 0.25 percent, Sn is 0.25 percent, Y is 0.3 percent, Nd is 0.05 percent, the total amount of inevitable impurities is less than or equal to 0.05 percent, and the balance is magnesium), the preparation method comprises the following steps:
(1) under the protection of argon, adding pure magnesium, pure aluminum, magnesium-calcium intermediate alloy, pure tin and magnesium-yttrium intermediate alloy in sequence, and heating and melting at 690-720 ℃; then adding magnesium-neodymium intermediate alloy, uniformly stirring at 670-710 ℃, refining, degassing and removing slag to obtain alloy liquid;
(2) pouring the alloy liquid obtained in the step (1) into a cast ingot in a semi-continuous casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of argon, wherein the steps are as follows in sequence: keeping the temperature at 300-; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 440-470 ℃ to obtain an extruded section; the extrusion ratio is 15-25, and the extrusion speed is 10-30 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of argon at the temperature of 440-460 ℃ for 90-110min, and then carrying out water quenching at the temperature of 80-90 ℃ to obtain a solid solution extruded section; (6) and (4) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 180 ℃ and the time is 200 ℃ and 250min, and obtaining the corrosion-resistant fast extrusion Mg-1Al-0.25Ca-0.25Sn-0.3Y-0.05Nd alloy.
Example 6
Taking Mg-0.33Al-0.2Ca-0.1Sn-0.08Y-0.1Ce alloy as an example (according to the mass percentage of the components, the Al is 0.33 percent, the Ca is 0.2 percent, the Sn is 0.1 percent, the Y is 0.08 percent, the Ce is 0.1 percent, the total amount of inevitable impurities is less than or equal to 0.05 percent, and the balance is magnesium), the preparation method comprises the following steps:
(1) under the protection of argon, adding pure magnesium, pure aluminum, a magnesium-calcium intermediate alloy, pure tin and a magnesium-yttrium intermediate alloy in sequence, and heating and melting at the temperature of 680-730 ℃; then adding magnesium-cerium intermediate alloy, uniformly stirring at 670-710 ℃, refining, degassing and removing slag to obtain alloy liquid;
(2) casting the alloy liquid obtained in the step (1) into a cast ingot in a manual casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of nitrogen, wherein the steps are as follows in sequence: keeping the temperature at 340-; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at 320 ℃ to obtain an extruded section; the extrusion ratio is 30-55, and the extrusion speed is 20-40 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of nitrogen at the temperature of 430-450 ℃ for 15-55min, and then carrying out rapid air cooling to obtain a solid solution extruded section;
(6) and (3) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 155-.
The corrosion resistance of the magnesium alloy obtained in the step (6) of the embodiment is remarkably improved, and the average hydrogen evolution amount after the magnesium alloy is soaked in a sodium chloride solution for 3 days is 5.0mL/cm2And the average hydrogen evolution amount of Mg-0.33Al-0.2Ca-0.1Sn magnesium alloy (according to the mass percentage of the components, Al is 0.33 percent, Ca is 0.2 percent, Sn is 0.1 percent, the total amount of inevitable impurities is less than or equal to 0.05 percent, and the balance is magnesium) under the same external dimension and treatment condition is 16.2mL/cm2。
Example 7
Taking Mg-0.3Al-0.3Ca-0.2Sn-0.21Y-0.05Ce-0.05Nd alloy as an example (according to the mass percentage of the components, Al is 0.3 percent, Ca is 0.3 percent, Sn is 0.2 percent, Y is 0.21 percent, Ce is 0.05 percent, Nd is 0.05 percent, the total amount of unavoidable impurities is less than or equal to 0.05 percent, and the balance is magnesium), the preparation method comprises the following steps:
(1) under the covering protection of a commercialized second flux, adding pure magnesium, pure aluminum, magnesium-calcium intermediate alloy, pure tin and magnesium-yttrium intermediate alloy in sequence, and heating and melting at the temperature of 700-; then adding magnesium-cerium and magnesium-neodymium intermediate alloys, uniformly stirring at 670-;
(2) pouring the alloy liquid obtained in the step (1) into a cast ingot in a semi-continuous casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of nitrogen, wherein the steps are as follows in sequence: preserving heat at 320-; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 320-350 ℃ to obtain an extruded section; the extrusion ratio is 25-50, and the extrusion speed is 45-70 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of nitrogen at the temperature of 460-480 ℃ for 30-70min, and then carrying out rapid air cooling to obtain a solid solution extruded section;
(6) and (3) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 180-190 ℃ and the time is 30-50min, so as to obtain the corrosion-resistant fast extrusion Mg-0.3Al-0.3Ca-0.2Sn-0.21Y-0.05Ce-0.05Nd alloy.
Example 8
Taking Mg-1.1Al-0.05Ca-0.01Sn-0.01Y alloy as an example (according to the mass percentage of the components, the Al is 1.1 percent, the Ca is 0.05 percent, the Sn is 0.01 percent, the Y is 0.01 percent, the total amount of inevitable impurities is less than or equal to 0.05 percent, and the balance is magnesium), the preparation method comprises the following steps:
(1) under the protection of argon, adding pure magnesium, pure aluminum, a magnesium-calcium intermediate alloy, pure tin and a magnesium-yttrium intermediate alloy in sequence, and heating and melting at the temperature of 680-720 ℃; stirring evenly at 670-;
(2) casting the alloy liquid obtained in the step (1) into a cast ingot in a manual casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of argon, wherein the steps are as follows in sequence: the temperature is maintained for 4 hours at the temperature of 310-; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 350-380 ℃ to obtain an extruded section; the extrusion ratio is 15-45, and the extrusion speed is 8-25 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of argon at the temperature of 420-440 ℃ for 10-45min, and then carrying out water quenching at the temperature of 60-70 ℃ to obtain a solid solution extruded section; (6) and (3) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 190-.
Example 9
Taking Mg-1.5Al-0.15Ca-0.15Sn-0.25Y-0.05La alloy as an example (according to the mass percentage of the components, 1.5 percent of Al, 0.15 percent of Ca, 0.15 percent of Sn, 0.25 percent of Y, 0.05 percent of La, less than or equal to 0.05 percent of the total amount of inevitable impurities and the balance of magnesium), the preparation method comprises the following steps:
(1) under the protection of argon, adding pure magnesium, pure aluminum, a magnesium-calcium intermediate alloy, pure tin and a magnesium-yttrium intermediate alloy in sequence, and heating and melting at the temperature of 680-730 ℃; then adding magnesium-lanthanum intermediate alloy, stirring uniformly at 670-710 ℃, refining, degassing and removing slag to obtain alloy liquid;
(2) pouring the alloy liquid obtained in the step (1) into a cast ingot in a semi-continuous casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of argon, wherein the steps are as follows in sequence: keeping the temperature at 340-; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 420-450 ℃ to obtain an extruded section; the extrusion ratio is 15-45, and the extrusion speed is 15-30 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of argon at the temperature of 470-480 ℃ for 20-50min, and then carrying out water quenching at the temperature of 70-80 ℃ to obtain a solid solution extruded section; (6) and (3) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 170-185 ℃, and the time is 100-150min, so as to obtain the corrosion-resistant fast extrusion Mg-1.5Al-0.15Ca-0.15Sn-0.25Y-0.05La magnesium alloy.
Example 10
Taking Mg-0.28Al-0.25Ca-0.01Sn-0.08Y-0.45Ce alloy as an example (according to the mass percentage of the components, the Al is 0.28 percent, the Ca is 0.25 percent, the Sn is 0.01 percent, the Y is 0.08 percent, the Ce is 0.45 percent, the total amount of inevitable impurities is less than or equal to 0.05 percent, and the balance is magnesium), the preparation method comprises the following steps:
(1) under the protection of argon, adding pure magnesium, pure aluminum, magnesium-calcium intermediate alloy, pure tin and magnesium-yttrium intermediate alloy in sequence, and heating and melting at the temperature of 700-; then adding magnesium-cerium intermediate alloy, uniformly stirring at 670-710 ℃, refining, degassing and removing slag to obtain alloy liquid;
(2) pouring the alloy liquid obtained in the step (1) into an ingot in a semi-continuous casting mode;
(3) carrying out step homogenization heat treatment on the ingot obtained in the step (2) under the protection of nitrogen, wherein the steps are as follows in sequence: heat preservation is carried out at 335-; then air-cooling to room temperature to obtain a homogeneous alloy ingot;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 380-420 ℃ to obtain an extruded section; the extrusion ratio is 45-65, and the extrusion speed is 30-65 m/min;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of nitrogen at the temperature of 430-450 ℃ for 30-60min, and then carrying out rapid air cooling to obtain a solid solution extruded section;
(6) and (3) carrying out artificial aging treatment on the solid solution state extrusion section obtained in the step (5), wherein the aging temperature is 180-.
The corrosion resistance of the magnesium alloy is obviously improved, and the average hydrogen evolution amount after the magnesium alloy is soaked in a sodium chloride solution for 3 days is 1.9mL/cm2While the average hydrogen evolution amount of the commercial AZ31 magnesium alloy under the same external dimension condition is 26mL/cm2。
Claims (5)
1. A corrosion-resistant fast extrusion magnesium alloy is characterized in that: the alloy comprises the following components in percentage by mass: aluminum: 0.1-2.0%, calcium: 0.05-0.5%, tin: 0.01-0.5%, yttrium: 0.01 to 0.45 percent, and the balance of magnesium, additive elements and inevitable impurities; the additive element is one or any combination of cerium, neodymium and lanthanum, and the addition amount is as follows by percentage: cerium: 0-0.45%, neodymium: 0-0.45%, lanthanum: 0 to 0.45 percent; the total amount of inevitable impurities is less than or equal to 0.05 percent; the balance being magnesium; the preparation method comprises the following steps:
(1) under the covering protection of argon or a second fusing agent, adding pure magnesium, pure aluminum, magnesium-calcium intermediate alloy, pure tin and magnesium-yttrium intermediate alloy in sequence, and heating and melting at 670-750 ℃; then, one or any combination of magnesium-cerium, magnesium-neodymium and magnesium-lanthanum intermediate alloys is added in sequence, the mixture is uniformly stirred at 670-;
(2) casting the alloy liquid obtained in the step (1) into a cast ingot in a semi-continuous casting or manual casting mode to obtain an as-cast alloy ingot;
(3) carrying out step homogenization heat treatment on the as-cast alloy ingot obtained in the step (2) under the protection of argon or nitrogen, and air-cooling to room temperature to obtain a homogeneous alloy ingot; the steps of the step homogenization heat treatment are as follows in sequence: keeping the temperature at 350 ℃ for 2-5 hours in 300-;
(4) carrying out rapid extrusion deformation on the homogeneous alloy ingot obtained in the step (3) at the temperature of 300-480 ℃ to obtain an extruded section;
(5) carrying out solid solution heat treatment on the extruded section obtained in the step (4) under the protection of argon or nitrogen, and then carrying out rapid air cooling or water quenching cooling at 60-90 ℃ to obtain a solid solution extruded section;
(6) carrying out artificial aging treatment on the solid solution state extruded section obtained in the step (5) to obtain corrosion-resistant fast extruded magnesium alloy; the artificial aging treatment comprises the following steps: the temperature is 155-198 ℃, and the time is 25-300 min.
2. A corrosion resistant fast extruded magnesium alloy as claimed in claim 1, wherein: the aluminum is as follows by mass percent: 0.4-0.8%, calcium: 0.08-0.15%, tin: 0.05 to 0.1%, yttrium: 0.05-0.3 percent.
3. A corrosion resistant fast extruded magnesium alloy as claimed in claim 1, wherein: the weight percentage of the cerium: 0.05 to 0.3%, neodymium: 0.05-0.3%, lanthanum: 0.05-0.3 percent.
4. A corrosion resistant fast extruded magnesium alloy according to any of claims 1 to 3, characterized in that: the extrusion ratio of the rapid extrusion deformation in the step (4) is 15-200, and the extrusion speed is 8-80 m/min.
5. A corrosion resistant fast extruded magnesium alloy according to any of claims 1 to 3, characterized in that: the solution heat treatment temperature in the step (5) is 420-490 ℃ and the time is 10-120 min.
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