CN109628809B - Mg-Al series multi-element magnesium alloy and sub-rapid solidification preparation method thereof - Google Patents
Mg-Al series multi-element magnesium alloy and sub-rapid solidification preparation method thereof Download PDFInfo
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Abstract
An Mg-Al series multi-element magnesium alloy and a sub-rapid solidification preparation method thereof, in particular to a novel high-performance sub-rapid solidification magnesium alloy with a narrow solidification interval. According to the invention, by means of multi-component alloying and sub-rapid solidification, crystal grains and a coarse eutectic phase are refined, and meanwhile, component segregation is relieved, a solidification structure with high solid solubility is obtained, and the solid solution treatment time is shortened; high-solid-solution solute atoms are uniformly precipitated in the subsequent rolling treatment and the sub-rapid solidification process to form a deformation structure with fine grains and a dispersed second phase, so that the Mg-Al series multi-element magnesium alloy rolled plate with excellent mechanical property is obtained; the method is particularly suitable for Mg-Al series multi-element alloy with high aluminum content, simplifies the preparation process of the magnesium alloy rolled plate, and provides an effective way for improving the deformation capacity of the magnesium alloy and promoting the industrialization of the magnesium alloy plate. The Mg-Al series multi-element magnesium alloy comprises the following main chemical components in percentage by weight: 5.5-6.4 of All, 0.5-2.0 of Zn0, 0.5-2.0 of Sn0.2-1.0 of Bi0.1-0.5 of Mn0.5, and the balance of Mg.
Description
Technical Field
The invention relates to a Mg-Al series multi-element magnesium alloy and a sub-rapid solidification preparation method thereof, in particular to a novel high-performance sub-rapid solidification magnesium alloy with a narrow solidification interval.
Background
In recent years, energy conservation and environmental protection are increasingly emphasized at home and abroad. Because the automobile is energy consumption and CO2One of the important sources of emission is the light weight of automobiles. The magnesium alloy has the advantages of low density, high specific strength, high specific rigidity and the like, so that the magnesium alloy is an ideal material for realizing the lightweight of automobiles. Currently, magnesium alloy die castings have been used in automotive engine covers, instrument panel brackets, steering brackets, seat brackets, and transmission housings.
However, magnesium alloys have low formability at room temperature compared with aluminum alloys, and particularly magnesium alloy sheets are difficult to prepare, so that the wide application of wrought magnesium alloys in vehicle bodies is greatly limited. Magnesium alloys have poor room temperature formability mainly due to their close-packed hexagonal structure, low slip system and strong basal texture during rolling. Alloying can weaken basal plane texture of the magnesium alloy and activate a new sliding system, and is an effective means for improving the room temperature deformability of the magnesium alloy at present. The addition of rare earth elements has been proven to be helpful for activating non-basal plane slippage and improving the toughness of magnesium; however, rare earth elements are high in cost and have no wide application prospect, and development of a novel high-performance magnesium component system with low rare earth content or without rare earth is urgently needed. In the Mg-Al alloy, fine Mg can be formed by adding Sn element2Sn second phase, promoting dynamic recrystallization, refining grains and Mg17Al12Phase (1); zn element is added to improve the solid solution strengthening effect of the alloy; the addition of Bi element can refine crystal grains and a second phase; the addition of Mn element helps to remove Fe impurity elements and refine grains and a second phase. Therefore, the invention develops a novel Mg-Al series multi-element magnesium alloy with low cost by adding elements such as Sn, Zn, Bi and Mn to replace rare earth elements.
In addition, the cooling speed in the traditional solidification process is low, so that the solidification structure of the magnesium alloy is coarse and the composition segregation is serious; meanwhile, due to the influence of tissue inheritance, coarse dendrites and eutectic crystals generate adverse influence on the optimization of subsequent deformed structures, and the control of the solidification structure of the magnesium alloy needs to be developed urgentlyAnd (5) preparing. Increasing the cooling rate to the sub-rapid solidification range (10)2-103K/s) is beneficial to refining-Mg crystal grains and improving the solid solubility of alloy elements in a magnesium matrix, so that a supersaturated solidification structure is formed, the link of homogenization heat treatment is greatly shortened or omitted, and further, the production efficiency is improved and the energy consumption is saved. In order to better realize the sub-rapid solidification process and relieve the phenomena of component segregation and nonuniform structure, a novel magnesium alloy component system which has a narrow solidification interval and is suitable for sub-rapid solidification needs to be developed urgently.
Chinese patent CN103498086A discloses a high-strength high-toughness magnesium alloy and a preparation process thereof, wherein the alloy strength is improved by adding 3.0-10.0% of Zn, 1.0-6.0% of Y and 0-1.0% of Zr and a sub-rapid solidification method, wherein the sub-rapid solidification is realized by adopting a two-step method, a melt is poured into a mould to obtain a sub-rapid solidification master alloy, and then the master alloy melt is sent into a copper mould cavity through secondary remelting to obtain a sub-rapid solidification cooling speed (100 + 1000 ℃/s). Compared with the Chinese patent CN103498086A, the method adopts the non-rare earth element alloying combined copper mold chilling sub-rapid solidification method, wherein the cooling speed can reach 100 plus one temperature per second (500 ℃/s), although the control range of the cooling speed is lower than that of the Chinese patent CN103498086A, the non-rare earth element is adopted to reduce the alloy cost, and the magnesium alloy melt is directly poured in a water-cooling copper mold, so that the preparation process of the sub-rapid solidification is simplified. Chinese patent CN102181760A discloses a magnesium alloy containing multiple trace rare earths, which is an as-cast magnesium alloy with good mechanical properties obtained by adding 6-9.7 wt% of non-rare earth elements such as aluminum, 0.35-1.0 wt% of zinc and the like, 0.501-1.25 wt% of light rare earth elements and 0.006-0.06 wt% of heavy rare earth elements, wherein the room-temperature tensile strength is 273MPa, and the room-temperature elongation is 2.7%. Chinese patent CN103146972A discloses a multi-element rare earth magnesium alloy and a preparation method thereof, wherein the tensile strength and the use temperature of the as-cast magnesium alloy are improved by adding rare earth elements such as 2-6% of Gd, 2-3% of Y, 1-2.5% of Nd, 0.5-1.5% of Sm, 0.4-0.8% of Sb and the like into a magnesium matrix, wherein the tensile strength at room temperature is 274MPa, and the elongation at room temperature is 2.7%. Compared with the patent, the Mg-Al series multi-element magnesium alloy cast structure obtained by the sub-rapid solidification of the patent has the room temperature mechanical properties that: tensile strength of 200-257MPa and elongation of 16-20%. Although the tensile strength of the Mg-Al series multi-element magnesium alloy casting billet is lower than that of Chinese patents CN102181760A and CN103146972A, the elongation at break is obviously improved. Meanwhile, rare earth elements are not added in the invention, 0.5016-1.31% of the rare earth elements are added in Chinese patent CN102181760A, and 11% of the rare earth elements are added in Chinese patent CN 103146972A.
The existing novel multi-element magnesium alloy development mostly relates to the addition of rare earth elements, the production cost is increased, and the requirement of a narrow solidification interval required by sub-rapid solidification is not fully considered; meanwhile, the traditional solidification cooling speed is low, the homogenization heat treatment process is complex and long in period, and the mechanical properties of the prepared Mg-Al series multi-element magnesium alloy do not have remarkable advantages.
Disclosure of Invention
The invention aims to develop Mg-Al series multi-element magnesium alloy with a narrow solidification interval and provide a short-process magnesium rolled plate preparation method based on sub-rapid solidification, and the Mg-Al series multi-element magnesium alloy rolled plate with good mechanical property is obtained through multi-element alloying, sub-rapid solidification, short-time solution treatment and controlled rolling; wherein the multi-element alloying of Sn, Zn, Bi, Mn and other elements is helpful for reducing the solidification interval of Mg-Al alloy, and refining crystal grains and Mg17Al12A eutectic phase; the sub-rapid solidification can enlarge the solid solubility of alloy elements in a magnesium matrix, refine the solidification structure, relieve the component segregation and shorten the subsequent solid solution treatment time; short-time solution treatment is carried out, a small amount of coarse eutectic phase is further eliminated, solute atoms are uniformly distributed, and a precipitated phase is uniformly dispersed and precipitated in a magnesium matrix under the action of subsequent rolling stress, so that grain boundaries are effectively pinned, and a fine grain structure is obtained; the controlled rolling comprises two stages of high-temperature rolling and low-temperature rolling, wherein the high-temperature rolling enables the alloy to be quickly thinned at high temperature, and the efficiency is improved; and the low-temperature rolling is to refine crystal grains at low temperature and inhibit the crystal grains from growing up, so as to obtain the high-performance Mg-Al series multi-element magnesium alloy rolled plate.
The invention adopts a method of combining multi-alloying and sub-rapid solidification means to realize narrow solidification intervalThe novel multi-element magnesium alloy is developed, alloy elements are dissolved in a magnesium matrix in a high-content manner, and-Mg dendrite and Mg are refined17Al12Eutectic phase, the solid solution treatment time is shortened; because the solidification-deformation structure has heredity, solute atoms with high solid solution are uniformly separated out under the action of subsequent rolling stress in the sub-rapid solidification process to form a deformation structure with fine grains and dispersed second phases, and the Mg-Al series multi-element magnesium alloy rolled plate with excellent mechanical property is obtained; the method is particularly suitable for high-aluminum-content multi-element Mg-Al series alloy, simplifies the preparation process of the magnesium alloy rolled plate, and provides an effective way for improving the deformation capacity of the magnesium alloy and promoting the industrialization of the magnesium alloy plate.
The technical scheme of the invention is as follows: by changing the types and contents of Sn, Zn, Bi, Mn and other elements, a novel sub-rapid solidification magnesium alloy component with a narrow solidification interval is developed; the sub-rapid solidification speed is obtained by regulating and controlling the size of the sub-rapid solidification mould and the temperature of cooling water, so that the alloy elements are uniformly dispersed and distributed in a magnesium matrix, and the-Mg dendrites and Mg are refined17Al12Eutectic phase, shortening the time of solution treatment; the high-performance Mg-Al series multi-element magnesium alloy rolled plate with fine grains and dispersed second phases is prepared by controlling the rolling reduction and the rolling temperature.
The Mg-Al series multi-element magnesium alloy comprises the following chemical components in percentage by mass: 5.5-6.4% of aluminum; 0.5-2.0% of zinc; 0.5-2.0% of tin; 0.2-1.0% of bismuth; 0.1-0.5% of manganese; the balance being magnesium and impurity elements, wherein the total content of all impurity elements is <0.02 wt.%.
The sub-rapid solidification preparation method of the Mg-Al series multi-element magnesium alloy comprises the following steps:
s1, grinding oxide skin of the raw materials such as magnesium ingots, aluminum ingots, zinc blocks, tin blocks, bismuth blocks, Al-10Mn intermediate alloy and the like by a grinding wheel machine and preheating the raw materials before use;
s2, placing the magnesium ingot in a pre-fired crucible, and introducing SF6And CO2Under the protection of gas, melting a magnesium ingot at 700 ℃ to obtain a magnesium melt;
s3, cooling the magnesium melt to 680 ℃, removing an oxide layer on the surface of the magnesium melt by using a preheated smelting tool, then simultaneously adding aluminum ingots, zinc blocks, tin blocks, bismuth blocks and Al-10Mn intermediate alloy raw materials, and preserving heat for 10-15 minutes to obtain a Mg-Al series multi-element magnesium alloy melt;
s4, blowing and refining the Mg-Al series multi-element magnesium alloy melt, and removing surface oxide skin;
s5, standing the smelted Mg-Al series multi-element magnesium alloy melt for 3-5 minutes, and pouring the melt into a water-cooled copper mold with well-regulated water temperature to obtain an Mg-Al series multi-element magnesium alloy casting blank;
s6, putting the Mg-Al series multi-element magnesium alloy casting blank into a heating box for short-time gradient solid solution heat treatment and carrying out warm quenching treatment to obtain a Mg-Al series multi-element magnesium alloy solid solution sample;
s7, performing surface pretreatment on the Mg-Al series multi-element magnesium alloy solid solution sample to remove a sample surface oxidation layer, and then performing controlled rolling on the sample to obtain a Mg-Al series multi-element magnesium alloy rolled plate;
s8, putting the Mg-Al series multi-element magnesium alloy rolled plate into a heating box for annealing heat treatment and air cooling.
In the step S5, the cooling rate of the Mg-Al series multi-element magnesium alloy melt in the water-cooling copper mould reaches more than 100 ℃/S, namely reaching the sub-rapid solidification range, and the obtained Mg-Al series multi-element magnesium alloy casting blank has high solid solubility.
In the step S1, all raw materials are dried in an oven at 120 ℃ and 100 ℃ for 0.5-1 hour.
In the step S5, the water-cooled copper mold material is red copper with high thermal conductivity, the thickness of the red copper is 3-10mm, and the temperature of the cooling water is controlled at 30-50 ℃.
In the step S5, the sub-rapid solidification experimental method may be implemented by using copper roll casting instead of copper mold chilling, thereby realizing industrial production.
In the step S6, the short time gradient solution treatment process comprises heat preservation at 215 ℃ for 2h, at 315 ℃ for 2h and at 415 ℃ for 2h, and the heat treatment time is 6 hours in total. The warm quenching treatment adopts 100 ℃ hot water and 25 ℃ hot water in a ratio of 1: 1.
In the step S7, the controlled rolling specifically comprises high-temperature rolling and low-temperature rolling, wherein in the high-temperature rolling process, the sample is subjected to heat preservation for 5-15 minutes at the temperature of 325-350 ℃, the roller temperature is 100 ℃, the roller speed is 50r/min, 6-9 passes of rolling are carried out, and the pass reduction is 15-25%; in the low-temperature rolling process, the sample is subjected to heat preservation for 5-10 minutes at the temperature of 275-;
in the step S8, the annealing heat treatment process is carried out at the temperature of 225-275 ℃ for 1.5 h.
The Mg-Al series multi-element magnesium alloy has a narrow solidification interval and is suitable for a sub-rapid solidification process; the finally obtained Mg-Al series multi-element magnesium alloy rolled plate has a fine crystal structure of 3 mu m and a plurality of uniformly dispersed spherical nano and submicron second phases, and has excellent mechanical properties.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the traditional AZ91 alloy, the solidification interval of the novel Mg-Al series multi-element magnesium alloy is shortened by 30-50 ℃, and the novel Mg-Al series multi-element magnesium alloy has higher cast state (tensile strength sigma)b>257MPa, elongation>20%) and as-rolled (tensile strength σ)b>329MPa, yield strength sigmas>194MPa, elongation>17%) mechanical properties.
(2) The invention prepares the Mg-Al series multi-element magnesium alloy casting blank with high solid solubility by a sub-rapid solidification method, solves the problems of thick solidification structure, serious component segregation, adverse influence on subsequent deformation structure optimization and the like in the traditional casting of high Al content magnesium alloy, shortens or omits the solid solution treatment time, simplifies the preparation process and is beneficial to improving the industrial competitiveness of magnesium alloy plates.
(3) According to the invention, through the combination of multi-component high alloying and sub-rapid solidification, alloy elements are solid-dissolved in magnesium matrix at high content, and an as-cast structure with good mechanical properties is obtained; due to the inheritance of the solidification-deformation structure, Mg is generated under the action of subsequent rolling stress17Al12And Mg2Sn and other various precipitated phases are uniformly and dispersedly precipitated in a magnesium matrix, a pinning effect is generated on recrystallized grains, a fine-grained deformed structure is obtained, and the mechanical property is excellent.
(4) After optimization, the Mg-6Al-1Zn-1Sn-0.5Bi-0.2Mn alloy has the best mechanical property and tensile strength sigmab>346MPa, yield strength sigmas>217MPa, elongation>19％。
Drawings
FIG. 1 is an SEM structure diagram of 1000 times of Mg-Al series multi-element magnesium alloy.
FIG. 2 is an SEM structure diagram of Mg-Al series multi-element magnesium alloy at 2000 times.
Detailed Description
Example 1:
taking Mg-6Al-1Zn-1Sn-0.5Bi-0.2Mn alloy as an example:
the raw materials comprise the following components in percentage by mass:
Al：6％
Zn：1％
Sn：1％
Bi：0.5％
Mn：0.2％
mg: and (4) the balance.
The preparation method comprises the following steps:
(1) before use, raw materials such as magnesium ingots, aluminum ingots, zinc blocks, tin blocks, bismuth blocks, Al-10Mn intermediate alloy and the like are ground into oxide skins by a grinding wheel machine and preheated in a 120 ℃ oven for 0.5 hour.
(2) Placing the magnesium ingot in a pre-fired crucible, and introducing SF with the volume ratio of 3:106And CO2Under the protection of gas, melting a magnesium ingot at 700 ℃ to obtain a magnesium melt;
(3) cooling the melt to 680 ℃, removing an oxide layer on the surface of the melt by using a preheated smelting tool, then adding aluminum ingots, zinc blocks, tin blocks, bismuth blocks and Al-10Mn intermediate alloy raw materials which are wrapped and preheated by aluminum foil, and preserving heat for 10 minutes to obtain Mg-Al series multi-element magnesium alloy melt;
(4) blowing and refining the Mg-Al series multi-element magnesium alloy melt, and removing surface oxide skin;
(5) standing the smelted Mg-Al series multi-element magnesium alloy melt for 3 minutes, and pouring the melt into a water-cooled copper mold with the water temperature of 45 ℃, the height of 80mm, the width of 50mm and the thickness of 5mm to obtain an Mg-Al series multi-element magnesium alloy casting blank;
(6) and (3) putting the Mg-Al series multi-element magnesium alloy casting blank into a heating box, carrying out heat preservation for 2h at 215 ℃, 2h at 315 ℃, 2h at 415 ℃ and short-time gradient solution heat treatment. Then quenching treatment is carried out by adopting 100 ℃ hot water and 25 ℃ hot water in a ratio of 1: 1. Obtaining a Mg-Al series multi-element magnesium alloy solid solution sample; (7) performing surface pretreatment on the Mg-Al series multi-element magnesium alloy solid solution sample, removing a surface oxide layer of the sample, and then performing high-temperature rolling and low-temperature rolling on the sample, wherein the sample is subjected to heat preservation at 350 ℃ for 5 minutes in the high-temperature rolling process, the roller temperature is 100 ℃, the roller speed is 50r/min, 6-pass rolling is performed, and the pass reduction is 25%; and (3) in the low-temperature rolling process, preserving the temperature of the sample at 275 ℃ for 10 minutes, controlling the temperature of the roller to be 100 ℃, controlling the speed of the roller to be 50r/min, performing 4-pass rolling, controlling the pass reduction to be 10%, and controlling the total reduction of the final sample to be about 78%, thereby obtaining the Mg-Al series multi-element magnesium alloy rolled plate.
(8) And (3) putting the Mg-Al series multi-element magnesium alloy rolled plate into a heating box, annealing at 275 ℃ for 1.5h, and air cooling. The solidification interval is 89 ℃, and the tensile strength is as follows: 346MPa, yield strength: 217MPa, elongation: 19 percent.
Example 2:
taking Mg-6.2Al-1.20Zn-1.27Sn-0.65Bi-0.25Mn alloy as an example:
the raw materials comprise the following components in percentage by mass:
Al：6.2％
Zn：1.2％
Sn：1.27％
Bi：0.65％
Mn：0.25％
mg: and (4) the balance.
The preparation method comprises the following steps:
(1) before use, raw materials such as magnesium ingots, aluminum ingots, zinc blocks, tin blocks, bismuth blocks, Al-10Mn intermediate alloy and the like are ground into oxide skins by a grinding wheel machine and preheated in an oven at 115 ℃ for 0.6 hour.
(2) Placing the magnesium ingot in a pre-fired crucible, and introducing SF with the volume ratio of 3:106And CO2Under the protection of gas, melting a magnesium ingot at 700 ℃ to obtain a magnesium melt;
(3) cooling the melt to 680 ℃, removing an oxide layer on the surface of the melt by using a preheated smelting tool, then adding aluminum ingots, zinc blocks, tin blocks, bismuth blocks and Al-10Mn intermediate alloy raw materials which are wrapped and preheated by aluminum foil, and preserving heat for 15 minutes to obtain Mg-Al series multi-element magnesium alloy melt;
(4) blowing and refining the Mg-Al series multi-element magnesium alloy melt, and removing surface oxide skin;
(5) standing the smelted Mg-Al series multi-element magnesium alloy melt for 5 minutes, and pouring the melt into a water-cooled copper mold with the water temperature of 30 ℃, the height of 80mm, the width of 50mm and the thickness of 8mm to obtain an Mg-Al series multi-element magnesium alloy casting blank;
(6) and (3) putting the Mg-Al series multi-element magnesium alloy casting blank into a heating box, carrying out heat preservation for 2h at 215 ℃, 2h at 315 ℃, 2h at 415 ℃ and short-time gradient solution heat treatment. Then quenching treatment is carried out by adopting 100 ℃ hot water and 25 ℃ hot water in a ratio of 1: 1. Obtaining a Mg-Al series multi-element magnesium alloy solid solution sample;
(7) performing surface pretreatment on the Mg-Al series multi-element magnesium alloy solid solution sample, removing a surface oxide layer of the sample, and then performing high-temperature rolling and low-temperature rolling on the sample, wherein the sample is subjected to heat preservation at 335 ℃ for 8 minutes in the high-temperature rolling process, the roller temperature is 100 ℃, the roller speed is 50r/min, 8-pass rolling is performed, and the pass reduction is 20%; and (3) in the low-temperature rolling process, keeping the temperature of the sample at 285 ℃ for 8 minutes, controlling the temperature of the roller to be 100 ℃, controlling the speed of the roller to be 50r/min, performing 3-pass rolling, wherein the pass reduction is 12%, and the total reduction of the final sample is about 78%, so as to obtain the Mg-Al series multi-element magnesium alloy rolled plate.
(8) And (3) putting the Mg-Al series multi-element magnesium alloy rolled plate into a heating box, annealing at 265 ℃ for 1.5h, and air cooling. The solidification interval is 89 ℃, and the tensile strength is as follows: 329MPa, yield strength: 235MPa, elongation: 22 percent.
Example 3:
taking Mg-6.4Al-1.65Zn-0.85Sn-0.44Bi-0.12Mn alloy as an example:
the raw materials comprise the following components in percentage by mass:
Al：6.4％
Zn：1.65％
Sn：0.85％
Bi：0.44％
Mn：0.12％
mg: and (4) the balance.
The preparation method comprises the following steps:
(1) before use, raw materials such as magnesium ingots, aluminum ingots, zinc blocks, tin blocks, bismuth blocks, Al-10Mn intermediate alloy and the like are ground into oxide skins by a grinding wheel machine and preheated in a 110 ℃ oven for 0.75 hour.
(2) Placing the magnesium ingot in a pre-fired crucible, and introducing SF with the volume ratio of 3:106And CO2Under the protection of gas, melting a magnesium ingot at 700 ℃ to obtain a magnesium melt;
(3) cooling the melt to 680 ℃, removing an oxide layer on the surface of the melt by using a preheated smelting tool, then adding aluminum ingots, zinc blocks, tin blocks, bismuth blocks and Al-10Mn intermediate alloy raw materials which are wrapped and preheated by aluminum foil, and preserving heat for 12 minutes to obtain Mg-Al series multi-element magnesium alloy melt;
(4) blowing and refining the Mg-Al series multi-element magnesium alloy melt, and removing surface oxide skin;
(5) standing the smelted Mg-Al series multi-element magnesium alloy melt for 4 minutes, and pouring the melt into a water-cooled copper mold with the water temperature of 35 ℃, the height of 80mm, the width of 50mm and the thickness of 10mm to obtain an Mg-Al series multi-element magnesium alloy casting blank;
(6) and (3) putting the Mg-Al series multi-element magnesium alloy casting blank into a heating box, carrying out heat preservation for 2h at 215 ℃, 2h at 315 ℃, 2h at 415 ℃ and short-time gradient solution heat treatment. Then quenching treatment is carried out by adopting 100 ℃ hot water and 25 ℃ hot water in a ratio of 1: 1. Obtaining a Mg-Al series multi-element magnesium alloy solid solution sample;
(7) performing surface pretreatment on the Mg-Al series multi-element magnesium alloy solid solution sample, removing a surface oxide layer of the sample, and then performing high-temperature rolling and low-temperature rolling on the sample, wherein the sample is subjected to heat preservation at 325 ℃ for 10 minutes in the high-temperature rolling process, the roller temperature is 100 ℃, the roller speed is 50r/min, 9-pass rolling is performed, and the pass reduction is 15%; and (3) in the low-temperature rolling process, the sample is subjected to heat preservation at 295 ℃ for 5 minutes, the rolling temperature is 100 ℃, the rolling speed is 50r/min, 2-pass rolling is carried out, the pass reduction is 15%, and the final total reduction of the sample is about 78%, so that the Mg-Al series multi-element magnesium alloy rolled plate is obtained.
(8) And (3) putting the Mg-Al series multi-element magnesium alloy rolled plate into a heating box, annealing at 250 ℃ for 1.5h, and air cooling. The solidification interval is 87 ℃, and the tensile strength is as follows: 357MPa, yield strength: 232MPa, elongation: 17 percent.
Example 4:
taking Mg-5.5Al-0.65Zn-1.55Sn-0.75Bi-0.35Mn alloy as an example:
the raw materials comprise the following components in percentage by mass:
Al：5.5％
Zn：0.65％
Sn：1.55％
Bi：0.75％
Mn：0.35％
mg: and (4) the balance.
The preparation method comprises the following steps:
(1) before use, raw materials such as magnesium ingots, aluminum ingots, zinc blocks, tin blocks, bismuth blocks, Al-10Mn intermediate alloy and the like are ground into oxide skins by a grinding wheel machine and preheated in an oven at 100 ℃ for 1 hour.
(2) Placing the magnesium ingot in a pre-fired crucible, and introducing SF with the volume ratio of 3:106And CO2Under the protection of gas, melting a magnesium ingot at 700 ℃ to obtain a magnesium melt;
(3) cooling the melt to 680 ℃, removing an oxide layer on the surface of the melt by using a preheated smelting tool, then adding aluminum ingots, zinc blocks, tin blocks, bismuth blocks and Al-10Mn intermediate alloy raw materials which are wrapped and preheated by aluminum foil, and preserving heat for 13 minutes to obtain Mg-Al series multi-element magnesium alloy melt;
(4) blowing and refining the Mg-Al series multi-element magnesium alloy melt, and removing surface oxide skin;
(5) standing the smelted Mg-Al series multi-element magnesium alloy melt for 5 minutes, and pouring the melt into a water-cooled copper mold with the water temperature of 40 ℃, the height of 80mm, the width of 50mm and the thickness of 6mm to obtain an Mg-Al series multi-element magnesium alloy casting blank;
(6) and (3) putting the Mg-Al series multi-element magnesium alloy casting blank into a heating box, carrying out heat preservation for 2h at 215 ℃, 2h at 315 ℃, 2h at 415 ℃ and short-time gradient solution heat treatment. Then quenching treatment is carried out by adopting 100 ℃ hot water and 25 ℃ hot water in a ratio of 1: 1. Obtaining a Mg-Al series multi-element magnesium alloy solid solution sample;
(7) performing surface pretreatment on the Mg-Al series multi-element magnesium alloy solid solution sample, removing a surface oxide layer of the sample, and then performing high-temperature rolling and low-temperature rolling on the sample, wherein the sample is subjected to heat preservation at 345 ℃ for 6 minutes in the high-temperature rolling process, the roller temperature is 100 ℃, the roller speed is 50r/min, 7-pass rolling is performed, and the pass reduction is 22%; and (3) in the low-temperature rolling process, keeping the temperature of the sample at 300 ℃ for 6 minutes, controlling the temperature of the roller at 100 ℃ and the speed of the roller at 50r/min, performing 3-pass rolling, wherein the pass reduction is 13%, and the final total reduction of the sample is about 78%, so as to obtain the Mg-Al series multi-element magnesium alloy rolled plate.
(8) And (3) putting the Mg-Al series multi-element magnesium alloy rolled plate into a heating box, annealing at 240 ℃ for 1.5h, and air cooling. The solidification interval is 80 ℃, and the tensile strength is as follows: 337MPa, yield strength: 194MPa, elongation: 21 percent.
Example 5:
taking Mg-5.8Al-0.9Zn-1.09Sn-0.35Bi-0.4Mn alloy as an example:
the raw materials comprise the following components in percentage by mass:
Al：5.8％
Zn：0.9％
Sn：1.09％
Bi：0.35％
Mn：0.4％
mg: and (4) the balance.
The preparation method comprises the following steps:
(1) before use, raw materials such as magnesium ingots, aluminum ingots, zinc blocks, tin blocks, bismuth blocks, Al-10Mn intermediate alloy and the like are ground into oxide skins by a grinding wheel machine and preheated in an oven at 105 ℃ for 1 hour.
(2) Placing the magnesium ingot in a pre-fired crucible, and introducing SF with the volume ratio of 3:106And CO2Under the protection of gas, melting a magnesium ingot at 700 ℃ to obtain a magnesium melt;
(3) cooling the melt to 680 ℃, removing an oxide layer on the surface of the melt by using a preheated smelting tool, then adding aluminum ingots, zinc blocks, tin blocks, bismuth blocks and Al-10Mn intermediate alloy raw materials which are wrapped and preheated by aluminum foil, and preserving heat for 11 minutes to obtain Mg-Al series multi-element magnesium alloy melt;
(4) blowing and refining the Mg-Al series multi-element magnesium alloy melt, and removing surface oxide skin;
(5) standing the smelted Mg-Al series multi-element magnesium alloy melt for 5 minutes, and pouring the melt into a water-cooled copper mold with the water temperature of 50 ℃, the height of 80mm, the width of 50mm and the thickness of 3mm to obtain an Mg-Al series multi-element magnesium alloy casting blank;
(6) and (3) putting the Mg-Al series multi-element magnesium alloy casting blank into a heating box, carrying out heat preservation for 2h at 215 ℃, 2h at 315 ℃, 2h at 415 ℃ and short-time gradient solution heat treatment. Then quenching treatment is carried out by adopting 100 ℃ hot water and 25 ℃ hot water in a ratio of 1: 1. Obtaining a Mg-Al series multi-element magnesium alloy solid solution sample;
(7) performing surface pretreatment on the Mg-Al series multi-element magnesium alloy solid solution sample, removing a surface oxide layer of the sample, and then performing high-temperature rolling and low-temperature rolling on the sample, wherein the sample is subjected to heat preservation for 7 minutes at 330 ℃ in the high-temperature rolling process, the roller temperature is 100 ℃, the roller speed is 50r/min, 8-pass rolling is performed, and the pass reduction is 17%; and (3) in the low-temperature rolling process, keeping the temperature of the sample at 280 ℃ for 7 minutes, controlling the temperature of the roller to be 100 ℃, controlling the speed of the roller to be 50r/min, performing 4-pass rolling, controlling the pass reduction to be 11%, and controlling the total reduction of the final sample to be about 78%, thereby obtaining the Mg-Al series multi-element magnesium alloy rolled plate.
(8) And (3) putting the Mg-Al series multi-element magnesium alloy rolled plate into a heating box, annealing at 225 ℃ for 1.5h, and air-cooling.
The method has the main advantages that the preparation process is simple and safe, so that the method is suitable for industrial production, and the prepared magnesium alloy sample is an alloy with higher strength and narrow solidification interval.
The 1000-fold SEM structural diagram of the Mg-Al series multi-element magnesium alloy is shown in figure 1. The SEM structure diagram of the Mg-Al series multi-element magnesium alloy with the magnification of 2000 is shown in figure 2.
Claims (2)
1. A sub-rapid solidification preparation method of Mg-Al series multi-element magnesium alloy comprises the following chemical components in percentage by mass: 5.5-6.4% of aluminum; 0.5-2.0% of zinc; 0.5-2.0% of tin; 0.2-1.0% of bismuth; 0.1-0.5% of manganese; the balance being magnesium and impurity elements, wherein the total content of all impurity elements is <0.02 wt.%; the method is characterized in that: the method comprises the following steps:
s1, grinding oxide skins of the magnesium ingot, the aluminum ingot, the zinc block, the tin block, the bismuth block and the Al-10Mn intermediate alloy raw materials by a grinding wheel machine and preheating the raw materials before use;
s2, placing the magnesium ingot in a pre-fired crucible, and introducing SF6And CO2Under the protection of gas, melting a magnesium ingot at 700 ℃ to obtain a magnesium melt;
s3, cooling the magnesium melt to 680 ℃, removing an oxide layer on the surface of the magnesium melt by using a preheated smelting tool, then simultaneously adding aluminum ingots, zinc blocks, tin blocks, bismuth blocks and Al-10Mn intermediate alloy raw materials, and preserving heat for 10-15 minutes to obtain a Mg-Al series multi-element magnesium alloy melt;
s4, blowing and refining the Mg-Al series multi-element magnesium alloy melt, and removing surface oxide skin;
s5, standing the smelted Mg-Al series multi-element magnesium alloy melt for 3-5 minutes, and pouring the melt into a water-cooled copper mold with well-regulated water temperature to obtain an Mg-Al series multi-element magnesium alloy casting blank;
s6, putting the Mg-Al series multi-element magnesium alloy casting blank into a heating box for short-time gradient solid solution heat treatment and carrying out warm quenching treatment to obtain a Mg-Al series multi-element magnesium alloy solid solution sample;
s7, performing surface pretreatment on the Mg-Al series multi-element magnesium alloy solid solution sample to remove a sample surface oxidation layer, and then performing controlled rolling on the sample to obtain a Mg-Al series multi-element magnesium alloy rolled plate;
s8, putting the Mg-Al series multi-element magnesium alloy rolled plate into a heating box for annealing heat treatment and air cooling;
in step S1, all raw materials need to be dried in an oven at 120 ℃ of 100 ℃ and 0.5-1 hour;
in the step S5, the cooling rate of the Mg-Al series multi-element magnesium alloy melt in the water-cooling copper mould reaches more than 100 ℃/S, namely the sub-rapid solidification range is reached, and the obtained Mg-Al series multi-element magnesium alloy casting blank has high solid solubility;
in step S5, the water-cooled copper mold material is red copper with high thermal conductivity, the thickness of the red copper is 3-10mm, and the temperature of cooling water is controlled at 30-50 ℃.
In the step S5, the sub-rapid solidification experimental method can replace copper mold chilling by copper roller casting and rolling, so that industrial production is realized;
in step S6, the short time gradient solution treatment process comprises heat preservation at 215 ℃ for 2h, 315 ℃ for 2h and 415 ℃ for 2h, and the heat treatment time is 6 hours in total; the warm quenching treatment adopts 100 ℃ hot water and 25 ℃ hot water in a ratio of 1: 1;
in the step S7, the controlled rolling specifically comprises high-temperature rolling and low-temperature rolling, wherein in the high-temperature rolling process, the sample is subjected to heat preservation for 5-15 minutes at the temperature of 325-350 ℃, the roller temperature is 100 ℃, the roller speed is 50r/min, 6-9 passes of rolling are carried out, and the pass reduction is 15-25%; in the low-temperature rolling process, the sample is subjected to heat preservation for 5-10 minutes at the temperature of 275-;
in step S8, the annealing heat treatment process is carried out at 225-275 ℃ for 1.5 h.
2. The sub-rapid solidification preparation method of the Mg-Al series multi-element magnesium alloy according to claim 1, characterized in that: the Mg-Al series multi-element magnesium alloy has a narrow solidification interval and is suitable for a sub-rapid solidification process; the Mg-Al series multi-element magnesium alloy rolled plate finally obtained has a 3 mu m fine crystal structure and a plurality of uniformly dispersed spherical nano and submicron second phases.
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| CN102337437A (en) * | 2011-09-13 | 2012-02-01 | 四川大学 | High-plasticity casting Mg-Sn-Zn-Al series magnesium alloy |
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