WO2020199470A1 - 一种低稀土高耐蚀镁合金及其制备方法 - Google Patents

一种低稀土高耐蚀镁合金及其制备方法 Download PDF

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WO2020199470A1
WO2020199470A1 PCT/CN2019/102765 CN2019102765W WO2020199470A1 WO 2020199470 A1 WO2020199470 A1 WO 2020199470A1 CN 2019102765 W CN2019102765 W CN 2019102765W WO 2020199470 A1 WO2020199470 A1 WO 2020199470A1
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rare earth
magnesium alloy
magnesium
melt
mixed
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乐启炽
廖启宇
程春龙
胡成路
蒋燕超
陈星瑞
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

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  • the invention belongs to the technical field of light metal materials, and particularly relates to a low rare earth high corrosion resistance magnesium alloy and a preparation method thereof.
  • Magnesium alloy is by far the lightest metal structural material. Its density is only 2/3 that of aluminum and 1/4 that of steel, which makes it have high specific strength and specific stiffness; in addition, magnesium alloy also has good damping Many excellent properties, such as performance, machinability, thermal conductivity, easy recycling, regeneration, etc., make its application in automotive, aerospace, 3C, defense and other fields increasingly expanded; magnesium alloys are divided into cast magnesium alloys and wrought magnesium alloys. Magnesium alloys have higher strength, better ductility and more diverse sizes than cast magnesium alloys, and they are more widely used.
  • Wrought magnesium alloys are mainly based on Mg-Al-Zn series and Mg-Zn-Zr series magnesium alloys, while Mg-Al-Zn series are more widely used because of its lower preparation cost and easier preparation.
  • Zr series magnesium alloy; AZ80, as the highest strength magnesium alloy in the Mg-Al-Zn series, is more and more widely used in various extrusion and forging parts; due to the poor low-temperature formability of AZ80 magnesium alloy, some large specifications Complicated extruded parts are selected at higher temperatures; however, the Mg 17 Al 12 phase in AZ80 magnesium alloy is a high-temperature brittle phase. This phase cannot pin the matrix during the deformation process, making the The absolute strength of the alloy is not high when it is deformed at high temperature; on the other hand, AZ80 magnesium alloy has poor corrosion resistance, which also limits its wide application in industrialized products.
  • Rare earth elements have unique electronic arrangement structure and chemical characteristics. Adding proper amount of rare earth elements to magnesium alloys can enhance the bonding force between atoms, reduce the diffusion rate of magnesium atoms, increase the recrystallization temperature of magnesium alloys, and slow down the growth rate of recrystallization.
  • the main reason for the poor low-temperature formability and corrosion resistance of AZ80 magnesium alloy is the existence of too much Mg 17 Al 12 phase; too much brittle Mg 17 Al 12 phase is not conducive to deformation and reduces The deformation of the magnesium alloy matrix reduces the corrosion resistance of the alloy; at the same time, due to the poor low-temperature formability of the AZ80 magnesium alloy, the current industrial extrusion and forging products of the magnesium alloy are carried out at the temperature of 350°C ⁇ 400°C, which is too high. It will inevitably lead to the coarse internal structure of the product, and the temperature is too high and even the Mg 17 Al 12 phase will overburn, which has a great impact on the strength and corrosion resistance.
  • the purpose of the present invention is to provide a magnesium alloy with low rare earth and high corrosion resistance and a preparation method thereof.
  • AZ80 magnesium alloy several low-cost rare earth elements are added to improve the low-temperature formability and corrosion resistance of the alloy, so that It also maintains good formability at a low temperature of 300°C, while maintaining good mechanical properties at an extrusion temperature of 350°C to 400°C, providing a variety of industrially produced extrusions with good forming, excellent mechanical properties and resistance Magnesium alloy with good corrosion properties.
  • the composition of the low rare earth and high corrosion resistance magnesium alloy of the present invention is as follows: Al 6.5-7.5%, Zn 0.4-0.6%, Mn 0.1-0.4%, La-rich mixed rare earth 0.5-1.2%, the balance is Mg and Impurities are unavoidable; the La-rich mixed rare earth contains La and Ce, and the weight ratio of La/Ce is 2:1 to 3:1; the tensile strength is 320-340MPa, and the yield strength is 180-210MPa.
  • the weight percentage of Fe in the impurities of the above-mentioned low rare earth high corrosion resistance magnesium alloy is 0.01-0.03%, and the total weight percentage of other impurities is less than or equal to 0.01%.
  • the elongation rate of the above-mentioned low rare earth and high corrosion resistance magnesium alloy is 18-28%.
  • the preparation method of the low rare earth high corrosion resistance magnesium alloy of the present invention includes the following steps:
  • Mg-La-rich misch rare earth master alloy prepared magnesium ingots, zinc blocks, aluminum blocks, manganese chloride particles, and Mg-La-rich misch rare earth master alloy according to the above composition; the Mg-La-rich misch rare earth master alloy contains La and Ce 20 ⁇ 30%, and the weight ratio of La/Ce is 2:1 to 3:1;
  • the electromagnetic semi-continuous casting system is used to cast the magnesium alloy melt.
  • the electromagnetic system is turned on to electromagnetically stir the magnesium alloy melt and the ingot.
  • the electromagnetic frequency is 15 to 30 Hz until the casting is completed to obtain the magnesium alloy.
  • the protective atmosphere is an argon atmosphere.
  • the amount of the above-mentioned No. 5 flux is 0.2-0.4% of the total weight of magnesium ingot, zinc block, aluminum block, manganese chloride and Mg-La-rich mixed rare earth master alloy.
  • the above-mentioned manganese chloride particles have a particle size of 1 to 3 mm.
  • the volume ratio of SF 6 to CO 2 in the mixed protective atmosphere of SF 6 and CO 2 is 1: (3 to 5).
  • AZ80 has poor formability at lower temperatures. Therefore, the general forging and extruding of large and complex profiles is carried out in the range of 350 to 400 °C. Because magnesium alloys are very sensitive to temperature, the structure is coarse and the performance is reduced;
  • the present invention is based on the AZ80 magnesium alloy and modified the alloy by adding a small amount of La-rich rare earth.
  • the lanthanum-cerium rare earth element has a certain solid solubility in the magnesium alloy, and preferentially forms a high melting point and high thermal stability with Al element.
  • Al 11 (La/Ce) 3 and Al 2 (La/Ce) rare earth phases these rare earth phases inhibit the precipitation and growth of the brittle second phase Mg 17 Al 12 , improve the formability of AZ80 magnesium alloy, and improve the Corrosion resistance
  • the preparation process is simple and easy, and the rare earth elements used are all cheap rare earths, so the preparation cost is low and it is suitable for industrial application.
  • Figure 1 is a metallographic structure diagram of the low rare earth high corrosion resistance magnesium alloy in Example 1 of the present invention.
  • Figure 2 shows the metallographic structure of AZ80 magnesium alloy
  • Example 3 is a scanning structure diagram of the low rare earth and high corrosion resistance magnesium alloy in Example 1 of the present invention.
  • Figure 4 is a scanning structure diagram of AZ80 magnesium alloy
  • FIG. 5 is an XRD diagram of the low rare earth high corrosion resistance magnesium alloy and the AZ80 magnesium alloy in Example 1 of the present invention.
  • the No. 5 flux in the embodiment of the present invention is a commercially available magnesium alloy refining agent product.
  • the impurity content of the magnesium ingot, zinc block, aluminum block, manganese chloride and Mg-La-rich mixed rare earth master alloy used in the embodiment of the present invention are all ⁇ 0.05%.
  • the electromagnetic semi-continuous casting system used in the embodiment of the present invention is an electromagnetic semi-continuous casting mold (see “Low Frequency Electromagnetic Semi-Continuous Casting AC52 Alloy” (Special Metals and Nonferrous Alloys, 2013 Vol. 33 No. 4).
  • the casting speed during casting in the embodiment of the present invention is 5-60 mm/min.
  • No. 5 fluxes are divided into at least 5 parts, which are added part by part during the smelting process, and for each ingredient added to the aluminum melt, at least 1 part No. 5 flux is added together .
  • the magnesium alloy ingot is physically cut to a suitable size and then placed in the muffle furnace.
  • the current of the electromagnetic system during electromagnetic stirring is 100-140A.
  • the purity of the argon gas used in the embodiment of the present invention is ⁇ 99%.
  • the magnesium alloy ingot was subjected to a corrosion test, and was immersed in a NaCl solution with a weight concentration of 3.5% for ten days, and the measured corrosion weight of the equal area was 13-21 mg/cm 2 .
  • Mg-La-rich misch rare earth master alloy contains 20% La and Ce by weight, and La/Ce The weight ratio is 2:1; the particle size of the manganese chloride particles is 1 ⁇ 3mm;
  • the protective atmosphere Under the protective atmosphere, put the magnesium ingot into the smelting resistance furnace to melt, and set the material temperature to 750 ⁇ 5°C to obtain the magnesium melt;
  • the protective atmosphere is an argon atmosphere;
  • the aluminum block is melted in another smelting resistance furnace at a melting temperature of 750 ⁇ 5°C to obtain an aluminum melt; zinc block and manganese chloride are sequentially added to the aluminum melt Particles and Mg-rich La mixed rare earth master alloy, and add No. 5 flux at the same time; After all the materials are melted, a mixed melt is obtained; the amount of No. 5 flux is magnesium ingot, zinc block, aluminum block, manganese chloride and Mg-rich 0.2% of the total weight of La mixed rare earth master alloy;
  • the mixed solution is added to the magnesium melt, refined at 750 ⁇ 5°C for 30 minutes, then allowed to stand for 30 minutes, and the temperature is lowered to 700°C during the standing process to form a magnesium alloy melt body;
  • the volume ratio of SF 6 to CO 2 in the above-mentioned SF 6 and CO 2 mixed protective atmosphere is 1:3;
  • the electromagnetic semi-continuous casting system is used to cast the magnesium alloy melt.
  • the electromagnetic system is turned on to electromagnetically stir the magnesium alloy melt and the ingot.
  • the electromagnetic frequency is 15 to 30 Hz until the casting is completed, and the magnesium alloy ingot is obtained. ;
  • Carry out corrosion test on magnesium alloy ingot, soak it in NaCl solution with a weight concentration of 3.5% for ten days, and the corrosion weight of equal area is 24mg/cm 2 ;
  • the magnesium alloy ingot Place the magnesium alloy ingot in a muffle furnace, and then conduct a two-stage homogenization treatment; the temperature of the first-stage homogenization treatment is 180°C for 8 hours; the temperature of the second-stage homogenization treatment is 350°C and the time is 15 hours; After level homogenization, the surface oxide scale is removed to obtain the ingot;
  • the ingot is kept at 300°C for 3 hours, and then hot-extruded on a vertical extruder.
  • the extrusion outlet speed is 0.2mm/s.
  • the temperature of the extrusion cylinder and the die is 300°C, and the extrusion ratio is 15 :1; After the hot extrusion is completed, the low rare earth and high corrosion resistance magnesium alloy is obtained.
  • composition is as follows: Al 6.5%, Zn 0.4%, Mn 0.1%, La 0.36%, Ce 0.18%, and the balance is Mg and non Avoid impurities; the weight percentage of Fe in impurities is 0.01, the total weight percentage of other impurities is ⁇ 0.01%; the tensile strength is 340MPa, the yield strength is 210MPa, and the elongation is 18.8%; the metallographic structure is shown in Figure 1, and the scanning structure is shown in Figure 3. As shown, the XRD diagram is shown in Figure 5;
  • the traditional AZ80 magnesium alloy is cast, annealed and extruded in the above-mentioned manner.
  • the tensile strength is 322MPa
  • the yield strength is 210MPa
  • the elongation is 15.3%.
  • the corrosion test of AZ80 ingot is carried out, and the equal area corrosion weight is 60mg/cm. 2 ;
  • the metallographic structure is shown in Figure 2, the scanned structure is shown in Figure 4, and the XRD pattern is shown in Figure 5.
  • the Mg-La-rich mixed rare earth master alloy contains 25% La and Ce by weight percentage, and the La/Ce weight ratio is 3:1;
  • No. 5 flux is 0.3% of the total weight of magnesium ingot, zinc block, aluminum block, manganese chloride and Mg-La-rich mixed rare earth master alloy;
  • the equal area corrosion weight of the corrosion test is 20 mg/cm 2 ;
  • the temperature of the first level of homogenization treatment is 210°C for 6 hours; the temperature of the second level of homogenization treatment is 390°C for 12 hours;
  • the composition of low rare earth and high corrosion resistance magnesium alloy is as follows: Al 7.0%, Zn 0.5%, Mn 0.2%, La 0.75%, Ce 0.25%, the balance is Mg and inevitable impurities; the impurities contain Fe The weight percentage is 0.02%; the tensile strength is 335MPa, the yield strength is 200MPa, and the elongation is 22.2%.
  • the Mg-La-rich mixed rare earth master alloy contains 30% La and Ce by weight percentage
  • No. 5 flux is 0.4% of the total weight of magnesium ingot, zinc block, aluminum block, manganese chloride and Mg-rich La-rich mixed rare earth intermediate alloy;
  • the equal area corrosion weight of the corrosion test is 18 mg/cm 2 ;
  • the temperature of the first level of homogenization treatment is 250°C for 5 hours; the temperature of the second level of homogenization treatment is 420°C for 10 hours;
  • the composition of low rare earth and high corrosion resistance magnesium alloy is as follows: Al 7.5%, Zn 0.6%, Mn 0.4%, La 1.0%, Ce 0.5%, the balance is Mg and inevitable impurities; the impurities contain Fe The weight percentage is 0.03%; the tensile strength is 328MPa, the yield strength is 195MPa, and the elongation is 25.8%.

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Abstract

一种低稀土高耐蚀镁合金及其制备方法，成分按重量百分比为：A1 6.5-7.5％，Zn 0.4-0.6％，Mn 0.1-0.4％，稀土0.5-1.2％，余量为Mg；稀土中La/Ce的重量比为2:1-3:1；方法为：（1）准备原料；（2）保护气氛条件下，将镁锭熔化获得镁熔体；（3）在混合保护气氛条件下，将其他原料熔化后获得混合熔体；（4）在混合保护气氛条件下，将混合溶体加入到镁熔体中，精炼后静置降温，制成镁合金熔体；（5）采用电磁半连续铸造系统，对镁合金熔体进行浇铸；（6）置于马弗炉中进行双级均匀化处理；（7）在300-400℃保温后进行热挤压。产品在较低温下挤锻时，能保持良好的成形性，在较高温下挤锻时，也可以保持良好的力学性能；制备工艺简单容易，适合工业化运用。

Description

一种低稀土高耐蚀镁合金及其制备方法 技术领域
本发明属于轻金属材料技术领域，特别涉及一种低稀土高耐蚀镁合金及其制备方法。
背景技术
镁合金是迄今为止最轻的金属结构材料，其密度仅相当于铝的2/3，钢的1/4，使其拥有很高的比强度与比刚度；此外，镁合金还具有良好的阻尼性、切削加工性和导热性以及易回收、再生等诸多优异的性能，使其在汽车、航空航天、3C、国防等领域的应用日益扩大；镁合金分为铸造镁合金与变形镁合金，变形镁合金比铸造镁合金具有更高的强度、更好的延展性以及更多样化的尺寸，应用也更为广泛。
变形镁合金主要以Mg-Al-Zn系与Mg-Zn-Zr系镁合金为主，而Mg-Al-Zn系因为其更低的制备成本与更易制备，运用要更广与Mg-Zn-Zr系镁合金；AZ80作为Mg-Al-Zn系中强度最高的一种镁合金，越来越广泛的运用与各种挤压以及锻造件中；由于AZ80镁合金低温成形性差，一些大规格较复杂的挤锻件都选择在较高温度下进行；然而，AZ80镁合金中的Mg 17Al 12相为一种高温脆性相，这种相在变形过程中无法对基体起到钉扎作用，使该合金在高温变形时绝对强度不高；另外一方面，AZ80镁合金具有较差的耐蚀性，同样限制了其在工业化产品中的广发运用。
稀土元素具有独特的电子排布结构和化学特征，在镁合金中加入适量的稀土元素可增强原子间结合力、减少镁原子扩散速度、提高镁合金的再结晶温度，减缓再结晶长大速度，能显著提高其成形性与耐蚀性；AZ80镁合金低温成形性差与耐蚀性差的主要原因是过多Mg 17Al 12相的存在；过多的脆性Mg 17Al 12相不利于变形，减少了镁合金基体的变形，降低了合金的耐蚀性；同时，由于AZ80镁合金的低温成形性较差，目前镁合金工业化挤锻产品都在350℃～400℃温度下进行，过高的变形温度必然会导致产品内部组织粗大，温度过高甚至会出现Mg 17 Al 12相过烧的情况，对强度以及耐蚀性都有很大影响。
发明概述
技术问题
问题的解决方案
技术解决方案
本发明的目的是提供一种低稀土高耐蚀镁合金及其制备方法，在AZ80镁合金的基础上添加几种微量廉价的稀土元素，改善合金的低温成形性与耐蚀性，使其在300℃低温下也保持较好的成形性，同时在350℃～400℃挤压温度下也能保持良好的力学性能，为各种工业化生产的挤锻件提供一种成型好、力学性能优良且耐蚀性好的镁合金。
本发明的低稀土高耐蚀镁合金的成分按重量百分比为：Al 6.5～7.5％，Zn 0.4～0.6％，Mn 0.1～0.4％，，富La混合稀土0.5～1.2％，余量为Mg和不可避免杂质；所述的富La混合稀土中含La和Ce，且La/Ce的重量比为2∶1～3∶1；抗拉强度320～340MPa，屈服强度180～210MPa。
上述的低稀土高耐蚀镁合金的杂质中含Fe的重量百分比0.01～0.03％，其他杂质的总重量百分比≤0.01％。
上述的低稀土高耐蚀镁合金的延伸率18～28％。
本发明的低稀土高耐蚀镁合金的制备方法包括以下步骤：
1、按上述成分准备镁锭、锌块、铝块、氯化锰颗粒和Mg-富La混合稀土中间合金；所述的Mg-富La混合稀土中间合金中按重量百分比含La和Ce 20～30％，并且La/Ce的重量比为2∶1～3∶1；
2、在保护气氛条件下，将镁锭加入熔炼电阻炉中熔化，设置化料温度为750±5℃，获得镁熔体；
3、在SF 6与CO 2混合保护气氛条件下，将铝块在另外一个熔炼电阻炉中熔化，熔化温度为750±5℃，获得铝熔体；向铝熔体中依次加入锌块、氯化锰颗粒和Mg-富La混合稀土中间合金，同时加入5号熔剂；待全部物料熔化后，获得混合熔体；
4、在SF 6与CO 2混合保护气氛条件下，将混合溶体加入到镁熔体中，在750±5 ℃精炼30～40min，然后静置30～60min，在静置过程中降温至690～700℃，制成镁合金熔体；
5、采用电磁半连续铸造系统，对镁合金熔体进行浇铸，浇铸开始的同时开启电磁系统对镁合金熔体及铸锭进行电磁搅拌，电磁频率为15～30Hz，直至浇铸完成，获得镁合金铸锭；
6、将镁合金铸锭置于马弗炉中，然后进行双级均匀化处理；其中第一级均匀化处理的温度180～250℃，时间5～8h；第二级均匀化处理的温度350～420℃，时间10～15h；双级均匀化处理后去除表面的氧化皮，获得锭坯；
7、将锭坯在300～400℃保温1～3小时，然后在立式挤压机上进行热挤压，挤压出口速度为0.2～1mm/s，热挤压时挤压筒与模具温度为300～400℃，挤压比≥15∶1；热挤压完成后获得低稀土高耐蚀镁合金。
上述的步骤2中，保护气氛为氩气气氛。
上述的5号熔剂的用量为镁锭、锌块、铝块、氯化锰和Mg-富La混合稀土中间合金总重量的0.2～0.4％。
上述的氯化锰颗粒的粒径1～3mm。
上述的步骤3和4中，SF 6与CO 2混合保护气氛的SF 6与CO 2的体积比为1∶(3～5)。
发明的有益效果
有益效果
本发明的优点及有益效果是：
1、传统AZ80在较低温下具有较差成形性，因此一般锻挤大型复杂型材时在350～400℃区间内进行，由于镁合金对温度敏感性很强，从而使组织粗大，导致性能下降；本发明在AZ80镁合金的基础上，通过添加微量富La稀土对合金进行改性，镧铈稀土元素在镁合金中具有一定的固溶度，与Al元素优先形成具有高熔点、高热稳定性的Al 11(La/Ce) 3和Al 2(La/Ce)稀土相，这些稀土相抑制了脆性第二相Mg 17Al 12的析出与长大，提高了AZ80镁合金的成形性，同时提高了耐蚀性；
2、只需添加0.5～1.2％稀土元素便可达到较为优良的成形性，并且在低温下也 可以保持良好的成形性与综合性能，扩大了AZ80镁合金的变形温度区间，在挤锻较为复杂的型材时，无需过多提高变形温度来达到变形效果；此外，在较高温下挤锻时，也可以保持良好的力学性能；
3、在Fe含量在0.03～0.1％时，依然保持很好的耐蚀性；
4、制备工艺简单容易，所用稀土元素均为廉价稀土，因此制备成本较低，适合工业化运用。
对附图的简要说明
附图说明
图1为本发明实施例1中的低稀土高耐蚀镁合金的金相组织图；
图2为AZ80镁合金的金相组织图；
图3为本发明实施例1中的低稀土高耐蚀镁合金的扫描组织图；
图4为AZ80镁合金的扫描组织图；
图5为本发明实施例1中的低稀土高耐蚀镁合金与AZ80镁合金的XRD图。
发明实施例
本发明的实施方式
本发明实施例中的5号熔剂为市购镁合金精炼剂产品。
本发明实施例中采用的镁锭、锌块、铝块、氯化锰和Mg-富La混合稀土中间合金的杂质含量均≤0.05％。
本发明实施例中采用的电磁半连续铸造系统为电磁半连续铸造结晶器(参见《低频电磁半连续铸造AC52合金》(特种金属及有色合金，2013年第33卷第4期)。
本发明实施例中浇铸时的浇铸速度为5～60mm/min。
本发明实施例中加入5号熔剂时，将全部5号熔剂分为至少5份，在熔炼过程中逐份加入，且向铝熔体中每加入一种成分，随同加入至少1份5号熔剂。
本发明实施例中镁合金铸锭物理切割至合适尺寸后，再置于马弗炉中。
本发明实施例中镁合金铸锭的尺寸为
Figure PCTCN2019102765-appb-000001
本发明实施例中进行电磁搅拌时电磁系统的电流为100～140A。
本发明实施例中采用的氩气纯度≥99％。
本发明实施例中镁合金铸锭进行腐蚀试验，在重量浓度3.5％的Nacl溶液中浸泡十天，测得等面积腐蚀重量13～21mg/cm 2。
下面结合具体实施方式对本发明的优选方案进行描述，但是应当理解，这些描述只是为了进一步说明本发明的特征和优点而不是对本发明权利要求的限制。
实施例1
准备镁锭、锌块、铝块、氯化锰颗粒和Mg-富La混合稀土中间合金；所述的Mg-富La混合稀土中间合金中按重量百分比含La和Ce 20％，并且La/Ce的重量比为2∶1；氯化锰颗粒的粒径1～3mm；
在保护气氛条件下，将镁锭加入熔炼电阻炉中熔化，设置化料温度为750±5℃，获得镁熔体；保护气氛为氩气气氛；
在SF 6与CO 2混合保护气氛条件下，将铝块在另外一个熔炼电阻炉中熔化，熔化温度为750±5℃，获得铝熔体；向铝熔体中依次加入锌块、氯化锰颗粒和Mg-富La混合稀土中间合金，同时加入5号熔剂；待全部物料熔化后，获得混合熔体；5号熔剂的用量为镁锭、锌块、铝块、氯化锰和Mg-富La混合稀土中间合金总重量的0.2％；
在SF 6与CO 2混合保护气氛条件下，将混合溶体加入到镁熔体中，在750±5℃精炼30min，然后静置30min，在静置过程中降温至700℃，制成镁合金熔体；
上述的SF 6与CO 2混合保护气氛的SF 6与CO 2的体积比为1∶3；
采用电磁半连续铸造系统，对镁合金熔体进行浇铸，浇铸开始的同时开启电磁系统对镁合金熔体及铸锭进行电磁搅拌，电磁频率为15～30Hz，直至浇铸完成，获得镁合金铸锭；将镁合金铸锭进行腐蚀试验，在重量浓度3.5％的NaCl溶液中浸泡十天，等面积腐蚀重量24mg/cm 2；
将镁合金铸锭置于马弗炉中，然后进行双级均匀化处理；其中第一级均匀化处理的温度180℃，时间8h；第二级均匀化处理的温度350℃，时间15h；双级均匀化处理后去除表面的氧化皮，获得锭坯；
将锭坯在300℃保温3小时，然后在立式挤压机上进行热挤压，挤压出口速度为0.2mm/s，热挤压时挤压筒与模具温度为300℃，挤压比15∶1；热挤压完成后获得低稀土高耐蚀镁合金，其成分按重量百分比为：Al 6.5％，Zn 0.4％，Mn  0.1％，La 0.36％，Ce 0.18％，余量为Mg和不可避免杂质；杂质中含Fe的重量百分比0.01，其他杂质的总重量百分比≤0.01％；抗拉强度340MPa，屈服强度210MPa，延伸率18.8％；金相组织如图1所示，扫描组织如图3所示，XRD图如图5所示；
采用传统的AZ80镁合金，按上述方式经铸造、退火并挤压成形后，其抗拉强度322MPa，屈服强度210MPa；延伸率15.3％；其中AZ80铸锭进行腐蚀试验，等面积腐蚀重量60mg/cm 2；金相组织如图2所示，扫描组织如图4所示，XRD图如图5所示。
实施例2(Mg-7.0％Al-0.5％Zn-0.2％Mn-0.62％La-0.31％Ce)
方法同实施例1，不同点在于：
(1)Mg-富La混合稀土中间合金中按重量百分比含La和Ce 25％，并且La/Ce的重量比为3∶1；
(2)5号熔剂的用量为镁锭、锌块、铝块、氯化锰和Mg-富La混合稀土中间合金总重量的0.3％；
(3)在750±5℃精炼35min，然后静置40min，在静置过程中降温至695℃；
(4)SF 6与CO 2混合保护气氛的SF 6与CO 2的体积比为1∶4；
(5)腐蚀试验的等面积腐蚀重量20mg/cm 2；
(6)第一级均匀化处理的温度210℃，时间6h；第二级均匀化处理的温度390℃，时间12h；
(7)锭坯在350℃保温2h，热挤压的挤压出口速度为0.5mm/s，热挤压时挤压筒与模具温度为350℃，挤压比16∶1；
(8)低稀土高耐蚀镁合金的成分按重量百分比为：Al 7.0％，Zn 0.5％，Mn 0.2％，La 0.75％，Ce 0.25％，余量为Mg和不可避免杂质；杂质中含Fe的重量百分比0.02％；抗拉强度335MPa，屈服强度200MPa，延伸率22.2％。
实施例3
方法同实施例1，不同点在于：
(1)Mg-富La混合稀土中间合金中按重量百分比含La和Ce 30％；
(2)5号熔剂的用量为镁锭、锌块、铝块、氯化锰和Mg-富La混合稀土中间合 金总重量的0.4％；
(3)在750±5℃精炼40min，然后静置60min，在静置过程中降温至695℃；
(4)SF 6与CO 2混合保护气氛的SF 6与CO 2的体积比为1∶5；
(5)腐蚀试验的等面积腐蚀重量18mg/cm 2；
(6)第一级均匀化处理的温度250℃，时间5h；第二级均匀化处理的温度420℃，时间10h；
(7)锭坯在400℃保温1h，热挤压的挤压出口速度为1mm/s，热挤压时挤压筒与模具温度为400℃，挤压比17∶1；
(8)低稀土高耐蚀镁合金的成分按重量百分比为：Al 7.5％，Zn 0.6％，Mn 0.4％，La 1.0％，Ce 0.5％，余量为Mg和不可避免杂质；杂质中含Fe的重量百分比0.03％；抗拉强度328MPa，屈服强度195MPa，延伸率25.8％。

Claims (8)

  1. 一种低稀土高耐蚀镁合金，其特征在于成分按重量百分比为：Al 6.5～7.5％，Zn 0.4～0.6％，Mn 0.1～0.4％，，富La混合稀土0.5～1.2％，余量为Mg和不可避免杂质；所述的富La混合稀土中含La和Ce，且La/Ce的重量比为2∶1～3∶1；抗拉强度320～340MPa，屈服强度180～210MPa。
  2. 根据权利要求1所述的一种低稀土高耐蚀镁合金，其特征在于低稀土高耐蚀镁合金的杂质中含Fe的重量百分比0.01～0.03％，其他杂质的总重量百分比≤0.01％。
  3. 根据权利要求1所述的一种低稀土高耐蚀镁合金，其特征在于低稀土高耐蚀镁合金的延伸率18～28％。
  4. 一种权利要求1所述的低稀土高耐蚀镁合金的制备方法，其特征在于包括以下步骤：
    (1)按上述成分准备镁锭、锌块、铝块、氯化锰颗粒和Mg-富La混合稀土中间合金；所述的Mg-富La混合稀土中间合金中按重量百分比含La和Ce 20～30％，并且La/Ce的重量比为2∶1～3∶1；
    (2)在保护气氛条件下，将镁锭加入熔炼电阻炉中熔化，设置化料温度为750±5℃，获得镁熔体；
    (3)在SF 6与CO 2混合保护气氛条件下，将铝块在另外一个熔炼电阻炉中熔化，熔化温度为750±5℃，获得铝熔体；向铝熔体中依次加入锌块、氯化锰颗粒和Mg-富La混合稀土中间合金，同时加入5号熔剂；待全部物料熔化后，获得混合熔体；
    (4)在SF 6与CO 2混合保护气氛条件下，将混合溶体加入到镁熔体中，在750±5℃精炼30～40min，然后静置30～60min，在静置过程中降温至690～700℃，制成镁合金熔体；
    (5)采用电磁半连续铸造系统，对镁合金熔体进行浇铸，浇铸开始的同时开启电磁系统对镁合金熔体及铸锭进行电磁搅拌，电磁频率为15～30Hz，直至浇铸完成，获得镁合金铸锭；
    (6)将镁合金铸锭置于马弗炉中，然后进行双级均匀化处理；其中第一级均匀化处理的温度180～250℃，时间5～8h；第二级均匀化处理的温度350～420℃，时间10～15h；双级均匀化处理后去除表面的氧化皮，获得锭坯；
    (7)将锭坯在300～400℃保温1～3小时，然后在立式挤压机上进行热挤压，挤压出口速度为0.2～1mm/s，热挤压时挤压筒与模具温度为300～400℃，挤压比≥15∶1；热挤压完成后获得低稀土高耐蚀镁合金。
  5. 根据权利要求4所述的低稀土高耐蚀镁合金的制备方法，其特征在于步骤(2)中，保护气氛为氩气气氛。
  6. 根据权利要求4所述的低稀土高耐蚀镁合金的制备方法，其特征在于步骤(3)中，5号熔剂的用量为镁锭、锌块、铝块、氯化锰和Mg-富La混合稀土中间合金总重量的0.2～0.4％。
  7. 根据权利要求4所述的低稀土高耐蚀镁合金的制备方法，其特征在于所述的氯化锰颗粒的粒径1～3mm。
  8. 根据权利要求4所述的低稀土高耐蚀镁合金的制备方法，其特征在于步骤(3)和(4)中，SF 6与CO 2混合保护气氛的SF 6与CO 2的体积比为1∶(3～5)。
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