WO2024027053A1 - 镁基合金及其制备方法 - Google Patents

镁基合金及其制备方法 Download PDF

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WO2024027053A1
WO2024027053A1 PCT/CN2022/135678 CN2022135678W WO2024027053A1 WO 2024027053 A1 WO2024027053 A1 WO 2024027053A1 CN 2022135678 W CN2022135678 W CN 2022135678W WO 2024027053 A1 WO2024027053 A1 WO 2024027053A1
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magnesium
alloy
content
based alloy
cao
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PCT/CN2022/135678
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English (en)
French (fr)
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邱鑫
田政
钞润泽
杨冰
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广东汇天航空航天科技有限公司
中国科学院长春应用化学研究所
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Publication of WO2024027053A1 publication Critical patent/WO2024027053A1/zh

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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
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • 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
    • 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
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent

Definitions

  • the present application relates to the technical field of magnesium alloys, and in particular to a high-strength and heat-resistant rare earth magnesium-based alloy.
  • the density of magnesium and magnesium alloys is 1.8g/cm3. It is the lightest structural metal material currently used. It has high specific strength and specific stiffness and is widely used in the automotive and aviation fields.
  • the Mg-Al series and Mg-Zn series magnesium alloys commonly used in the automotive industry, such as AZ91, AM50, AM60, etc. have a lower melting point due to their main strengthening phase Mg17Al12, which melts first in high-temperature environments, resulting in a decrease in the high-temperature strength of the alloy and making it impossible to It is used in working conditions above room temperature for a long time. Therefore, while developing high-strength magnesium alloys, it is also necessary to improve the high-temperature creep resistance of magnesium alloys.
  • rare earth elements and alkaline earth elements such as Ca and Sr have been one of the hot topics in magnesium-based material research in recent years.
  • the above elements can also improve the strength and high-temperature creep resistance of magnesium alloys, and related research results are relatively abundant.
  • the mechanical properties of the material are reduced; c) the addition of a single type of element cannot simultaneously take into account the multiple properties of high strength, high temperature resistance and flame retardancy; d) the addition of some elements has two-sided effects, such as the addition of Al alloy can significantly improve the strength of magnesium alloy, However, the flame retardant properties are deteriorated.
  • the main purpose of this application is to provide a magnesium-based alloy, aiming to solve the technical problem of poor comprehensive performance of magnesium-based alloys in the prior art.
  • the magnesium-based alloy proposed in this application includes the following components in terms of mass percentage: Al: 3%-9%, La: 1.5%-7%, RE except La: 0.02%-0.30%, Zn: 0.01 %-0.8%, Ca: 1.5%-4.0%, CaO: 0.01%-0.20%; the rest is magnesium and inevitable impurities.
  • the Al content range is 4-7%
  • the La content range is 2-4%
  • the RE content range is 0.05-0.20%
  • the Zn content range is 0.05-0.20%
  • the Ca content is The range is 2.0-3.0%
  • the CaO content range is 0.05-0.15%.
  • the RE is at least one of Gd, Ho, Er, Eu and Y.
  • the RE is at least one of Gd and Y.
  • the Al content ranges from 4.5% to 6.6%
  • the Gd content ranges from 0.02% to 0.10%
  • the Y content ranges from 0.03% to 0.10%.
  • the total content of the unavoidable impurities does not exceed 0.2% by mass percentage.
  • This application also proposes a preparation method of magnesium-based alloy, including the following steps:
  • the rare earth content in the Mg-Y/Gd alloy is 15-40 %.
  • the CaO is in the form of particles with a particle size of 20 ⁇ m to 100 ⁇ m.
  • the content of Ca in the Mg-Ca alloy is 15-40%
  • This application is a rare earth component matching scheme based on the multi-element microalloying effect of rare earth elements. Different rare earth elements will reduce each other's solid solubility in magnesium alloys, increase the nucleation density and increase the precipitation efficiency while the total amount remains unchanged, thereby improving strength performance and reducing plasticity loss.
  • the La element which is cheaper and does not generate sharp phases, is selected as the main alloying element. By adding a small amount of other rare earth elements such as Y/Gd, the amount of Al-La phase precipitated is effectively increased and the size of the precipitated phase is reduced.
  • the Al-La phase will grow significantly as the La content increases; on the premise of ensuring the overall performance of the alloy, the total amount of rare earth added to the alloy and proportions have also been restricted and optimized.
  • Figure 1 shows the as-cast microstructure morphology of the alloy of this application (A) optical OM analysis results, (B) scanning electron microscope analysis results;
  • Figure 2 shows the microstructure morphology of the alloy in the extruded state of this application (A) optical OM analysis results, (B) scanning electron microscope analysis results;
  • FIG. 3 shows the results of combustion experiments for the alloy of this application.
  • This application proposes a magnesium-based alloy, which includes the following components in terms of mass percentage: Al: 3%-9%, La: 1.5%-7%, RE except La: 0.02- 0.30%, Zn: 0.01%-0.8%, Ca: 1.5%-4.0%, CaO: 0.01-0.2%; the rest is magnesium and inevitable impurities.
  • Figure 1 shows the as-cast microstructure morphology of the present application. It can be seen from the optical metallographic structure in Figure 1A that the alloy microstructure is composed of ⁇ -Mg matrix, grain boundary network eutectic structure, and massive Al-RE. . It can be seen from the SEM structure morphology in Figure 1B that the eutectic precipitated phase is mainly distributed at the matrix grain boundary, consisting of discontinuous network ⁇ -Mg-Al eutectic, slender strip Al-Ca phase, and thick rod-shaped Al. -La phase composition, the massive phase is Al-La-RE phase, when the rare earth content is high, the number and volume of the massive phase will increase.
  • Figure 2 shows the microstructure morphology of the extruded state of this application. It can be seen from Figure 2A that the alloy structure is distributed along the direction of plastic deformation, the precipitated phases are broken during the deformation process, and the alloy structure is significantly refined compared with the as-cast condition. As can be seen from Figure 2B, the alloy eutectic structure is broken and redistributed during the deformation process, and a recrystallized phase is generated between the remaining eutectics. The rare earth bulk phase is harder and remains relatively intact during the degeneration process.
  • Figure 3 shows the sample after the combustion test of the alloy of this application. It can be seen that the alloy did not undergo obvious oxidation after the combustion test.
  • the heat-affected zone of the sample is small, the structure is intact without deformation and cracking, and dense rare earth-containing dark oxidation is generated in the fire area. film, no gray oxide remains from the combustion of the magnesium matrix, which shows that the alloy of the present application has good flame retardant properties.
  • Al element is a commonly used strengthening element for magnesium alloys. It can not only effectively ensure the strength of magnesium alloys, but also improve the casting process performance of magnesium alloys. When the aluminum element is less than 3%, the strength of the alloy will be less improved and the casting performance will be poor; when the aluminum element is too high, it will have an adverse effect on the heat resistance. Therefore, the aluminum element used in this alloy ranges from 3% to 9%.
  • the La element in magnesium-aluminum alloys can significantly improve the room temperature mechanical properties of the alloy by forming a high melting point Al-La precipitation phase, and can effectively change the morphology and distribution of the Mg-Al precipitation phase.
  • the La content is too low There is no outstanding strengthening effect. If the content is too high, large-sized rod-shaped precipitates will be formed, splitting the matrix structure and causing a decrease in the mechanical properties of the material. In order to obtain the best strengthening effect, the range of La element is 1.5%-7%.
  • RE elements refer to light and heavy rare earth elements other than La added in order to adjust the comprehensive properties of magnesium alloys, including neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, ytterbium, yttrium, etc. It can be a single element above. It can be a combination of multiple elements, with a total range of 0.02-0.3%. Because heavy rare earth elements do not form sharp rod-like phases in magnesium, they have better multi-element microalloying strengthening effects.
  • the Zn element has a high solid solubility in magnesium alloys and can play a strengthening effect in magnesium alloys, which is beneficial to improving the casting properties of magnesium alloys.
  • higher Zn is detrimental to the material's resistance to thermal cracking and heat resistance. Therefore, a small amount of zinc is added to this alloy, with a content of 0.01%-0.8%.
  • Ca element can inhibit high-temperature oxidation of magnesium alloys, increase the ignition point of magnesium alloys, and promote the refinement of magnesium alloy grains during the solidification process.
  • calcium diffuses preferentially to the liquid surface and combines with oxygen before magnesium to form a dense oxide film, which hinders further oxidation of magnesium and thus improves the high-temperature performance of magnesium alloys.
  • excessive calcium content will lead to poor hot cracking performance of magnesium alloy casting and significantly reduce the mechanical properties of the material.
  • the calcium element addition range is 1.5%-4.0%.
  • the presence of CaO can increase the ignition point of magnesium alloys, but the addition of too much CaO will deteriorate the material flow properties, increase casting defects and reduce mechanical properties, so the range of adding CaO is 0.01-0.20%.
  • CaO can be added in the form of ordinary powder.
  • the uniformity of the distribution of CaO itself within the magnesium-based alloy has a greater impact on the flame retardant properties of the magnesium-based alloy.
  • the size of the CaO particle size is important for avoiding The agglomeration and increased dispersion in the molten metal have a great impact, so CaO particles with smaller particle sizes should be preferred.
  • impurities are unavoidable.
  • the unavoidable impurities include: Fe, Si, Cu, Ni, etc., and the total impurity content does not exceed 0.2%.
  • Example 1 In order to evaluate the properties of the materials of this application, the alloys of Examples 1-29 were melted and then die-cast to prepare test samples of various sizes.
  • CaO powder with an average particle size of about 50 ⁇ m was used as the raw material.
  • CaO coarse particle powder with an average particle size of about 100 ⁇ m was used as a raw material.
  • Conduct tensile strength test (GB/T228.1 room temperature tensile test method for metal materials) and flame retardant performance test (DOT/FAA/AR/00/12-Chapter 25, DOT/FAA/AR/00) on the samples of each example. /12-Chapter 26), the components and test results of each example are shown in Table 1 and Table 2.
  • the material yield strength increases with the increase in the number of strengthening phases, but because the Al11La3/Al2La phase will grow rapidly with the increase in the total amount of rare earth, This leads to the coarsening of the alloy microstructure, thereby reducing the material's plasticity.
  • the flame retardant properties of the material are directly related to the amount of Ca added.
  • the increase of Ca will significantly improve the flame retardant properties of the alloy (the weight loss rate gradually decreases); however, the Al2Ca phase formed by Ca will Aggregation occurs at grain boundaries, so an increase in Ca will reduce material plasticity (decreased elongation).
  • Comparative Examples D1 and D2 adopted the standard process scheme of their commercial brands, and Comparative Examples D3-D14 adopted the preferred process scheme of the alloy of this application.
  • the elemental components of each comparative example are shown in Table 2. After the alloy of the comparative example was melted, test samples of various sizes were prepared, and tensile strength tests (GB/T228.1 Room temperature tensile test method for metallic materials) and flame retardant properties tests (DOT/FAA/AR/00/12-Chapter 25 , DOT/FAA/AR/00/12-Chapter 26), among which comparative example D2 adopts gravity casting and T6 heat treatment, and the rest adopts die casting process. The test results are shown in Table 3.
  • Example 2 It can be seen from Example 2 and Comparative Examples D3 and D6 that adding the rare earth element La can effectively improve the material strength, but the flame retardant properties of the alloy are less improved.
  • the plasticity of the alloy first increases and then decreases with the increase of La element. When it exceeds the optimal range of the components , the alloy properties are significantly reduced.
  • Example 2 It can be seen from Example 2 and Comparative Examples D3, D5, D7, and D8 that the addition of metamorphic heavy rare earth elements can effectively refine the rare earth strengthening phase and disperse its distribution, and its improvement effect is better than that of multi-component alloys between light rare earth elements.
  • Gd/Y has the most significant effect, but with the further increase of metamorphic elements, its improvement effect tends to stagnate.
  • Example 2 It can be seen from Example 2 and Comparative Examples D9 and D10 that the flame retardant properties of the material are directly related to the amount of Ca added. However, although adding a high content of Ca element can improve the flame retardant properties of the material, the mechanical properties of the alloy are significantly reduced.
  • Example 2 Example 7, and Comparative Examples D11 and D12 that after adding CaO, a similar flame retardant effect can be achieved with a lower Ca content.
  • the amount of Ca can be reduced by about 30 %.
  • the process performance of the alloy deteriorates, resulting in a significant reduction in the mechanical properties of the alloy.
  • Example 2 It can be seen from Example 2 and Comparative Examples D13 and D14 that the Al content determines the number of main strengthening phases of the alloy and is directly related to the mechanical properties of the alloy. However, higher Al content leads to a reduction in the plasticity and flame retardant properties of the alloy, thereby reducing the overall strength of the alloy. performance.
  • this application proposes a technical solution for a high-strength and heat-resistant rare earth magnesium alloy and its manufacturing process.
  • This application solves the technical difficulties in the flame retardancy and mechanical properties of magnesium alloys by applying La and Ca elements, and effectively improves the mechanical properties and process suitability of the material by constructing a specifically compatible Mg-Al-La-Ca alloy system. , suitable for various preparation processes such as die-casting, extrusion, and forging.
  • this application uses the light and heavy rare earth composite application of adding La-Y/Gd to achieve multi-element microalloying of rare earth elements, with a maximum Improve the precipitation efficiency of rare earth elements and reduce the amount of alloying elements; this application uses Ca-CaO composite application and utilizes the mechanism that CaO can be dissolved in MgO on the surface of liquid magnesium alloy, effectively improving the anti-oxidation ability of the solid-liquid surface of the alloy.
  • the amount of Ca is reduced by about 30%, which avoids the aggregation of Ca at the grain boundaries in the microstructure, thus improving the mechanical properties of the alloy.
  • magnesium alloy material of the present application has better casting performance.
  • Rare earth elements can effectively improve the adverse effects of alkaline earth elements and silicon elements on casting performance.
  • the magnesium alloy in this application has lower rare-earth content, lower overall cost, and takes into account the effects of strength, high-temperature creep resistance, and fire retardancy.
  • This application also proposes a method for preparing the above-mentioned magnesium-based alloy, the steps of which are as follows:
  • the rare earth content in the Mg-RE alloy is 15-40 %; in the Mg-Ca alloy, the content of Ca is 15-40%, CaO is in the form of granules, and its particle size is 1 ⁇ m to 100 ⁇ m. In this way, CaO is dispersed more evenly.
  • This application is a rare earth component matching scheme based on the multi-element microalloying effect of rare earth elements. Different rare earth elements will reduce each other's solid solubility in magnesium alloys, increase the nucleation density and increase the precipitation efficiency while the total amount remains unchanged, thereby improving strength performance and reducing plasticity loss.
  • the La element which is cheaper and does not generate sharp phases, is selected as the main alloying element. By adding a small amount of other rare earth elements such as Y/Gd, the amount of Al-La phase precipitated is effectively increased and the size of the precipitated phase is reduced.
  • the Al-La phase will grow significantly as the La content increases; on the premise of ensuring the overall performance of the alloy, the total amount of rare earth added to the alloy and proportions have also been restricted and optimized.
  • the Mg-Al-Ca flame-retardant magnesium alloy system achieves its flame-retardant effect mainly through the action of Ca element forming a dense oxide film on the surface of the molten metal.
  • a lower content of Ca element cannot provide sufficient flame retardant effect.
  • too high Ca will accumulate at the grain boundaries of the microstructure, and the Al2Ca particles will also grow rapidly, resulting in a decrease in the strength and plasticity of the alloy. significantly reduced. It is difficult to achieve the flame retardant effect by adding only CaO.
  • a small amount of addition has no flame retardant effect, while a large amount of addition will cause oxide agglomeration and increase in melt viscosity, deteriorating mechanical properties and process suitability.
  • adding a small amount of CaO in an appropriate amount and utilizing the characteristic that CaO can be dissolved in a small amount in the MgO oxide film in the molten magnesium metal liquid can significantly enhance the flame retardant effect of Ca and reduce the amount of Ca by up to 30%. Based on the balance between mechanical properties and flame retardant effect, the total amount and proportion of Ca-CaO added have also been optimized.

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Abstract

一种镁基合金，其组成为（质量%）Al：3%-9%，La：1.5-7%，La除外的RE:0.2-0.3%，Zn：0.01-0.8%，Ca：1.5-4.0%，CaO:0.01-0.2%，其余为镁及不可避免的杂质。通过选用不生成尖锐相的La元素作为主合金化元素，通过添加少量Y/Gd等其他稀土元素，有效提高Al-La相的析出数量，缩小析出相尺寸，并提高其分布的弥散程度。由此提高强度性能，降低塑性损失。此外，还提供了该镁合金的制备方法。

Description

镁基合金及其制备方法
相关申请
本申请要求于2022年08月05日提交中国专利局、申请号为202210942910.6、发明名称为“镁基合金及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在申请中。
技术领域
本申请涉及镁合金技术领域，特别涉及一种高强耐热稀土镁基合金。
 背景技术
镁及镁合金密度为1.8g/cm3，是目前应用最轻的结构用金属材料，具有较高的比强度、比刚度，在汽车和航空领域被广泛应用。但汽车行业常用的Mg-Al系，Mg-Zn系镁合金，如AZ91、AM50、AM60等，由于其主强化相Mg17Al12熔点较低，在高温环境下最先熔解，导致合金高温强度下降，无法用于长期高于室温的工况环境中，所以在开发高强度镁合金的同时，还需要提高镁合金的耐高温蠕变性能。另外，随着新能源汽车的发展，电池包等动力零件在失效时有起火燃烧的风险，这就要求考虑镁合金的使用时，同时要满足高强度、耐高温性能和阻燃防火的需求；当镁合金用于航空器时，还需要满足航空法规更严格的阻燃防火要求。目前国内外，同时兼顾高强度、耐高温性能和阻燃防火的镁合金仍比较少，其中阻燃防火目标的实现最有挑战。
按满足FAA航空级阻燃要求考虑，目前国际上公开的经过试验验证的镁合金牌号仅有WE43及EV31两种，均为Mg-RE-Zr体系合金。虽然该体系合金具有优异的力学强度及阻燃特性，但存在两个缺陷：1、现有牌号合金应用高含量Gd、Y元素，造成合金成本高昂、制备工艺难度大；2、合金的析出强化机制导致材料塑性较低、且需经热处理，难以在压铸及精密加工领域进行应用。
通过添加稀土元素及Ca、Sr等碱土元素达到阻燃效果是近年来镁基材料研究的热点之一，以上元素同时可提高镁合金的强度和耐高温蠕变性能，相关研究成果比较丰富。但目前该领域存在一些技术瓶颈：a）具阻燃效果的元素用量低，则不具备显著的改良效果；b）而较高的合金化元素用量则会导致合金成本升高、工艺适性降低、材料力学性能降低；c）单一类型元素的添加无法同时兼顾高强度、耐高温和阻燃多种性能；d）部分元素的添加效果具有两面性，如Al合金的添加可显著提高镁合金强度，但恶化了阻燃性能。
 技术问题
本申请的主要目的是提供一种镁基合金，旨在解决现有技术中，镁基合金综合性能较差的技术问题。
 技术解决方案
本申请提出的一种镁基合金，按质量百分比计，包括如下组分：Al：3%-9%，La：1.5%-7%，La除外的RE：0.02%-0.30%，Zn：0.01%-0.8%，Ca：1.5%-4.0%，CaO：0.01%-0.20%；其余为镁以及不可避免的杂质。
在一实施例中，所述Al含量范围4-7%，所述La含量范围2-4 %，所述RE含量范围0.05-0.20 %，所述Zn含量范围0.05-0.20 %，所述Ca含量范围2.0-3.0 %，所述CaO含量范围0.05-0.15 %。
在一实施例中，所述RE为Gd、Ho、Er、Eu和Y中的至少一种。
在一实施例中，所述RE为Gd和Y中的至少一种。
在一实施例中，所述Al含量范围4.5%-6.6 %，所述Gd含量范围0.02%-0.10%，所述Y含量0.03%-0.10%。
在一实施例中，按质量百分比计，所述不可避免的杂质总含量不超过0.2%。
本申请还提出一种镁基合金的制备方法，包括如下步骤：
在保护气氛下，将所述Mg锭、Al锭熔化后，升温至700-730 ℃，依次加入所述Zn锭、Mg-La合金、Mg-Ca合金，熔化后充分搅拌均匀；
加入所述Mg-Y/Gd合金、CaO粉末，熔化后充分搅拌均匀，得到合金熔体；
静置20-35 min后，除气并加入熔剂，在700-710 ℃精炼处理20-35 Min；
精炼结束后，静置0.5-1.0 h，扒渣，浇铸成型，得到所述镁基合金。
在一实施例中，所述Mg-Y/Gd合金中，稀土含量为15-40 %。
在一实施例中，所述CaO呈颗粒状，粒径为20μm~100μm。
在一实施例中，所述Mg-Ca合金中，Ca的含量为15-40 %
 有益效果
本申请基于稀土元素多元微合金化效果的稀土组分搭配方案。不同稀土元素会降低彼此在镁合金中的固溶度，在总量不变的情况下提高形核密度、增加析出效率，由此带来提高强度性能、降低塑性损失的效果。在本申请中，选用价格较低、不生成尖锐相的La元素作为主合金化元素，通过添加少量Y/Gd等其他稀土元素，有效提高了Al-La相的析出数量、缩小析出相尺寸，并提高其分布的弥散程度；此外，由于Al-Y/Gd存在显著的损耗、Al-La相随La含量增加会明显长大；在保证合金综合性能的前提下，合金中添加的稀土总量及比例也受到了限制与优化。
 附图说明
图1为本申请合金铸态显微组织形貌（A）光学OM分析结果、（B）扫描电镜分析结果；
图2为本申请合金挤压态显微组织形貌（A）光学OM分析结果、（B）扫描电镜分析结果；
图3为本申请合金进行燃烧实验结果。
 本发明的实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请的一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
需要说明，本申请实施例中所有方向性指示（诸如上、下、左、右、前、后……）仅用于解释在某一特定姿态（如附图所示）下各部件之间的相对位置关系、运动情况等，如果该特定姿态发生改变时，则该方向性指示也相应地随之改变。
另外，在本申请中涉及“第一”、“第二”等的描述仅用于描述目的，而不能理解为指示或暗示其相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。另外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在，也不在本申请要求的保护范围之内。
请参阅图1至图3，本申请提出一种镁基合金，按质量百分比计，包括如下组分：Al：3%-9%，La：1.5%-7%，La除外的RE：0.02-0.30%，Zn：0.01%-0.8%，Ca：1.5%-4.0%，CaO：0.01-0.2 %；其余为镁以及不可避免的杂质。
附图说明：图1为本申请铸态显微组织形貌，由图1A光学金相组织可见，合金显微组织由α-Mg基体、晶界网状共晶组织、块状Al-RE组成。由图1B的SEM组织形貌可见，共晶析出相主要分布在基体晶界处，由不连续的网状β-Mg-Al共晶、细长条状Al-Ca相、较粗的棒状Al-La相组成，块状相为Al-La-RE相，当稀土含量较高时，块状相的数量与体积均会增加。图2为本申请挤压态显微组织形貌，由图2A可见，合金组织沿塑性变形方向分布，析出相在变形过程中破碎，合金组织较铸态条件下显著细化。由图2B可见，合金共晶组织在变形过程破碎并重新分布，并在残留共晶之间生成再结晶相，稀土块状相更加坚硬，在变性过程中保持相对完整。图3为本申请合金燃烧测试后的样品，可见合金经燃烧测试后并未发生明显的氧化，样品热影响区较小，结构完整未变形开裂，接火区域生成了致密的含稀土深色氧化膜，没有出现镁基体燃烧残留的灰白氧化物，由此说明本申请合金具有良好的阻燃特性。
针对各种元素的添加比重，下述内容将进一步概述：
Al元素是镁合金的常用强化元素，不仅可以有效保证镁合金的强度，还可以提高镁合金的铸造工艺性能。当铝元素低于3%时，对合金的强度提高较小，铸造性能也会较差；当铝元素过高，会对耐热性能产生不利影响。因而本合金采用铝元素范围在3%-9%。
La元素在镁铝系镁合金中通过形成高熔点的Al-La析出相，可以显著提高合金的室高温力学性能，可以有效改变Mg-Al析出相的形态和分布形式，但La含量过低时没有突出的强化效果，含量过高时则会形成大尺寸的棒状析出相、割裂基体组织造成材料力学性能的下降，为获得最佳的强化效果，La元素的范围在1.5%-7%。
RE元素指为了调节镁合金综合性能加入的除La外的轻重稀土等元素，包括了钕、钐、铕、钆、铽、镝、钬、铒、镱、钇等，可以是以上的单一元素也可以是其中多种元素的组合，其总范围0.02-0.3%。由于重稀土元素在镁中不会形成尖锐的棒状相，且具有更好的多元微合金化强化效果。
Zn元素在镁合金固溶度较高，在镁合金可以起到强化效果，有益于镁合金铸造性能的改善。但是较高的Zn对材料对抗热裂倾向及耐热性能不利。因而在本合金中添加少量的锌元素，含量为0.01%-0.8%。
Ca元素可以抑制镁合金的高温氧化，提高镁合金的着火点，在凝固过程中促进细化镁合金晶粒。在高温熔融状态，钙元素优先扩散到液体表面，先于镁元素与氧结合，形成致密的氧化膜，阻碍镁元素的进一步氧化，从而提高镁合金的高温性能。但钙含量过高会导致镁合金铸造热裂性能较差，显著降低材料的力学性能。本申请中，钙元素添加范围在1.5%-4.0%。
CaO的存在可以提高镁合金的着火点，但过多的CaO的添加会恶化材料流动性能、增加铸造缺陷和力学性能的下降，所以添加CaO的范围为0.01-0.20%。在此，CaO可以以普通粉末状添加，但是，CaO自身在镁基合金内部的分布的均匀性，对镁基合金的阻燃性能影响较大，实验发现，CaO粒径的大小，对避免在金属液中的团聚、提高弥散程度等方面影响甚大，应优选粒径较小的CaO颗粒。
对于合金而言，杂质是不可避免的，在本申请中，按质量百分比计，所述不可避免的杂质包括：Fe、Si、Cu、Ni等，总杂质含量不超过0.2%。
具体实施例
为评价本申请材料性能，对实施例1-29的合金熔化后进行压铸制备各尺寸测试样品，其中实施例1-28中采用平均粒径为约50μm的CaO粉末作为原料，实施例29中采用平均粒径为约100μm的CaO粗颗粒粉末作为原料。对各实施例样品进行拉伸强度测试（GB/T228.1 金属材料室温拉伸试验方法）、阻燃性能测试（DOT/FAA/AR/00/12-Chapter 25、DOT/FAA/AR/00/12-Chapter 26），各实施例组分与测试结果如表1和表2所示。
表1 各实施例合金元素组分 (%)
表2 各实施例力学及阻燃性能测试结果
由表1实施例1-7的测试结果可知，各实施例合金均具有良好的力学性能及阻燃特性，且本申请合金的各项性能与合金Al含量、稀土总量、Ca含量密切相关。
其中，由实施例2、8-11可见，材料力学性能与稀土元素的总含量关系密切，材料屈服强度随稀土元素的增加而提高（实施例8-实施例11提现了屈服强度逐渐增加），但较高含量时抗拉强度增长趋于停滞甚至下降（抗拉强度在实施例8-实施例10是逐渐增加的，但是实施例11是降低了延伸率逐渐减小），而材料塑性则随稀土含量的增加而先增长后降低（实施例2中的稀土含量增加至实施例8中的稀土含量时，合金的塑性是提升的，当稀土含量继续增加至实施例9、10、11时，塑性反而降低），这是由于合金主强化相Al11La3/Al2La相增加所导致的，材料屈服强度随强化相数量增加而升高，但由于Al11La3/Al2La相会随稀土总量增加而迅速长大，导致合金显微组织粗化，由此导致材料塑性降低。
由实施例2、12-15可见，材料阻燃特性与Ca的加入量直接相关，Ca的增加会明显改善合金阻燃特性（失重率逐渐降低）；但由于Ca所形成的的Al2Ca相会在晶界处聚集，因此Ca的增加会降低材料塑性（延伸率降低）。
对比实施例2、16-19可见，合金的力学性能随着Al含量的增加而提高，但材料塑性与阻燃特性则呈现相反趋势（两个强度指标增加，塑性降低，阻燃降低），这是由于Al含量增加导致脆性强化相Mg17Al12增加，因此合金强度性能提高；但由于Mg17Al12相较脆、呈网状分布于晶界处，且在较低温度下即发生分解，故材料的塑性与阻燃性能随Mg17Al12相的增多而降低。
对比实施例2、20、21、26-28可见，变质重稀土元素的添加可以有效细化稀土强化相、并使其分布弥散化，在重稀土添加上，Ho、Er、Eu对应的效果是不如Gd和Y的，且混合添加比添加单一元素效果更好（在塑性上，Gd与Y的混合效果优于单独的Gd和Y）。
对比实施例2、22、23可见，CaO则强化了Ca元素的阻燃效果，随着CaO添加量的增加，合金阻燃性能提高。（从实施例2、22、23可以看出，阻燃性达到实施例2的5.0%之后，虽然继续增加CaO，但是阻燃性没有得到明显提升）
对比实施例2、24、25可见，Zn含量增加可以提高材料屈服强度。
对比实施例2、29可见，CaO原料的粒径对其添加效果存在影响，使用粒径越小的CaO颗粒，越容易溶解于材料固液界面的氧化膜中，进而具有更好的强化阻燃性能效果。
对比例设计与分析
为进一步对本申请进行评价，设计并制备了对比例，其中对比例D1、D2采用了其商用牌号的标准工艺方案，对比例D3-D14采用了本申请合金的优选工艺方案。各对比例元素组分如表2所示。对比例合金熔化后进行制备各尺寸测试样品，并进行拉伸强度测试（GB/T228.1 金属材料室温拉伸试验方法）、阻燃性能测试（DOT/FAA/AR/00/12-Chapter 25、DOT/FAA/AR/00/12-Chapter 26），其中对比例D2采用重力铸造及T6热处理，其余采用压铸工艺。测试结果如表3所示。
表3各对比例合金的元素组分
对比例 Al La Ca Y Gd Zn CaO Mn Nd Zr Er Eu Sm Mg
D1 (AZ91) 8.9 - - - - 0.85 - 0.27 - - - - - 余量
D2 (WE43) - - - 4.3 0.8 - - - 2.3 0.46 - - - 余量
D3 6.5 - 3.0 0.04 0.07 0.09 0.10 - - - - - - 余量
D4 6.7 3.7 3.4 - - 0.12 0.10 - 0.1 - - - 0.09 余量
D5 6.7 3.9 3.2 - - 0.08 0.10 - - - 0.08 0.11 - 余量
D6 6.6 12.1 2.5 0.07 0.05 0.11 0.10 - - - - - - 余量
D7 6.5 4.0 3.3 - - 0.11 0.10 - - - - - - 余量
D8 5.5 4.1 3.2 0.50 0.39 0.08 0.10 - - - - - - 余量
D9 6.5 3.9   0.06 0.10 0.11 0.10 - - - - - - 余量
D10 6.4 3.6 7.0 0.05 0.07 0.09 0.10 - - - - - - 余量
D11 6.5 3.9 4.3 0.08 0.04 0.08 - - - - - - - 余量
D12 - 4.1 3.2 0.05 0.07 0.11 1.00 - - - - - - 余量
D13 - 4.3 3.0 0.07 0.04 0.09 0.10 - - - - - - 余量
D14 12.0 4.0 3.0 0.06 0.04 0.12 0.10 - - - - - - 余量
表4 各对比例合金的力学性能与阻燃性能
由表3的测试结果可知，对比商用镁合金（D1、D2），各主要合金化元素脱离本申请范围后，材料性能出现显著的变化，特别是合金对的塑性及阻燃特性，随材料组分变化出现了显著的下降。
由实施例2、对比例D3、D6可见，添加稀土元素La可以有效提高材料强度，但合金阻燃特性改善较少，合金塑性随La元素增加而先增加后降低，当超过组分优选范围后，合金性能出现显著降低。
由实施例2、对比例D3、D5、D7、D8可见，变质重稀土元素的添加可以有效细化稀土强化相、并使其分布弥散化，其改良效果优于轻稀土元素之间的多元合金化，在重稀土的搭配组合中，Gd/Y具有最显著的效果，但随着变质元素的进一步增加，其改良效果趋于停滞。
由实施例2、对比例D9、D10可见，材料阻燃特性与Ca的加入量直接相关，但添加高含量Ca元素虽然可以改善材料阻燃特性，但合金力学性能显著下降。
由实施例2、实施例7、对比例D11、D12可见，添加CaO后，可通过更低的Ca含量实现相近的阻燃效果，在保证合金阻燃效果的前提下，可降低Ca用量约30%。但当添加过多CaO时，合金工艺性能恶化，导致合金力学性能显著降低。
由实施例2、对比例D13、D14可见，Al含量决定合金主要强化相的数量，与合金力学性能直接相关，但较高的Al含量导致合金塑性及阻燃特性降低，从而降低了合金的综合性能。
综上所述，基于多种化学元素对镁合金室温及高温力学性能的作用机理，以及在成形工艺性能的影响，本申请提出了一种高强耐热稀土镁合金及其制造工艺的技术方案。
本申请通过应用La及Ca元素解决了镁合金阻燃性与力学性能上的技术难点，并通过构建特定配伍的Mg-Al-La-Ca的合金体系，有效提高材料的力学性能与工艺适性，适用于压铸、挤压、锻压等多种制备工艺。
为解决添加较多含量合金化元素所带来的成本上升、力学性能降低、工艺适性差等问题，本申请通过添加La-Y/Gd 的轻重稀土复合应用，实现稀土元素多元微合金化，最大程度提高稀土元素的析出效率，减低合金化元素用量；本申请通过Ca-CaO复合应用，利用CaO在液态镁合金表面可溶解于MgO的机制，有效提高了合金固液表面的抗氧化能力，在保证合金阻燃效果的前提下，降低Ca用量约30%，避免了Ca在显微组织中晶界处的聚集，从而提高了合金的力学性能。
与AZ91、AM60、AM50等铝锌/铝锰相比较，本申请大幅提高了镁合金材料力学性能。主要是在镁铝系合金的基础上同时引入了钙元素和稀土元素，改变了铝镁相的形态和分布。与其他镁铝碱土镁合金、镁铝硅镁合金相比，本申请的镁合金材料具有更优异的铸造性能。稀土元素可以有效的改善碱土元素、硅元素对铸造性能的不利影响。与WE43和EV31等已商业化的高稀土镁合金相比，本申请中的镁合金稀土含量更低，综合成本更低，且兼顾强度、耐高温蠕变和防火阻燃的效果。
本申请还提出一种制备上述镁基合金的方法，其步骤如下：
S1、按各实施例组分所规定的质量百分比，配置Mg锭、Al锭、Zn锭、Mg-La合金、Mg-Ca合金、Mg-Y/Gd合金、Mg-Y合金以及高纯CaO粉末。
S2、在保护气氛下，升温将所述Mg锭、Al锭熔化后，升温至700-730 ℃，依次加入所述Zn锭、Mg-La合金、Mg-Ca合金，熔化后充分搅拌均匀；随后加入所述Mg-RE合金、高纯CaO粉末，熔化后充分搅拌均匀，得到合金熔体。
S3、静置20-35 min后，除气并加入熔剂，在700-710 ℃精炼处理20-35 Min。
S4、精炼结束后，静置0.5-1.0 h，扒渣，浇铸成型，得到所述各组镁基合金。
其中，所述Mg-RE合金中，稀土含量为15-40 %；所述Mg-Ca合金中，Ca的含量为15-40 %，CaO呈颗粒状，且其粒径为1μm至100μm，如此，CaO分散更就均匀。
本申请基于稀土元素多元微合金化效果的稀土组分搭配方案。不同稀土元素会降低彼此在镁合金中的固溶度，在总量不变的情况下提高形核密度、增加析出效率，由此带来提高强度性能、降低塑性损失的效果。在本申请中，选用价格较低、不生成尖锐相的La元素作为主合金化元素，通过添加少量Y/Gd等其他稀土元素，有效提高了Al-La相的析出数量、缩小析出相尺寸，并提高其分布的弥散程度；此外，由于Al-Y/Gd存在显著的损耗、Al-La相随La含量增加会明显长大；在保证合金综合性能的前提下，合金中添加的稀土总量及比例也受到了限制与优化。
本申请在传统Ca作用于镁合金效果的基础上，优化为Ca+CaO特性的复合应用阻燃设计。Mg-Al-Ca阻燃镁合金体系主要通过Ca元素会在熔融金属表面形成致密氧化膜的作用来实现其阻燃效果。一方面较低含量的Ca元素不能形成足够的阻燃效果，另一方面，过高的Ca会在显微组织晶界处聚集，Al2Ca颗粒也会迅速长大，由此造成合金强度与塑性的显著降低。仅添加CaO也难以实现阻燃效果，少量添加没有阻燃作用，大量添加则会导致氧化物团聚及熔体粘度的增加，恶化力学性能与工艺适性。综上，适量少量添加CaO，利用CaO可以在熔融镁金属液中少量溶解于MgO氧化膜的特性，可以显著增强Ca的阻燃效果，最高可以降低30%的Ca用量。基于力学性能与阻燃效果的平衡，Ca-CaO的添加总量与比例也经过了优化。
合金组分的优化设计。根据镁合金材料的一般规律，合金化元素的种类/用量越多，由于生成物的总量增加与作用机制的互相影响，其强化效果收益越低、材料塑性与工艺适性越差。基于此，本申请合金组分经过了整体优化，不仅降低了元素总量，也去除了功能重复、收益较低的元素，比如Mg-Al中常见的Mn元素，去除Mn可以避免形成Al-Mn-RE大颗粒相，消除其降低塑性及争夺稀土元素的影响，Mn元素的除铁和析出强化功能由添加稀土元素来代替实现。
以上所述仅为本申请的优选实施例，并非因此限制本申请的专利范围，凡是在本申请的发明构思下，利用本申请说明书及附图内容所作的等效结构变换，或直接/间接运用在其他相关的技术领域均包括在本申请的专利保护范围内。

Claims (15)

  1. 一种镁基合金，其中，按质量百分比计，包括如下组分：Al：4.5%-6.6%，La：2%-4%，La除外的RE：0.05%-0.20%，Zn：0.05%-0.20%，Ca：2.0%-3.0%，CaO：0.05%-0.15%；其余为镁以及不可避免的杂质，所述RE为Gd和Y，所述Gd含量范围0.02%-0.10%，所述Y含量0.03-0.10%，所述不可避免的杂质总含量不超过0.2%。
  2. 一种镁基合金，其中，按质量百分比计，包括如下组分：Al：3%-9%，La：1.5%-7%，La除外的RE：0.02%-0.30%，Zn：0.01%-0.8%，Ca：1.5%-4.0%，CaO：0.01%-0.20%；其余为镁以及不可避免的杂质，所述RE为Gd和Y，所述Gd含量范围0.02%-0.10%，所述Y含量0.03-0.10%。
  3. 根据权利要求2所述的一种镁基合金，其中，所述Al含量范围4.5%-6.6%。
  4. 一种镁基合金，其中，按质量百分比计，包括如下组分：Al：3%-9%，La：1.5%-7%，La除外的RE：0.02%-0.30%，Zn：0.01%-0.8%，Ca：1.5%-4.0%，CaO：0.01%-0.20%；其余为镁以及不可避免的杂质，所述RE为Gd、Ho、Er、Eu和Y中的至少一种，所述不可避免的杂质总含量不超过0.2%。
  5. 一种镁基合金，其中，按质量百分比计，包括如下组分：Al：3%-9%，La：2%-4%，La除外的RE：0.05%-0.20%，Zn：0.05%-0.20%，Ca：2.0%-3.0%，CaO：0.05%-0.15%；其余为镁以及不可避免的杂质，所述RE为Gd、Ho、Er、Eu和Y中的至少一种，所述Gd含量范围0.02%-0.10%，所述Y含量0.03-0.10%，所述不可避免的杂质总含量不超过0.2%。
  6. 一种镁基合金，其中，按质量百分比计，包括如下组分：Al：3%-9%，La：1.5%-7%，La除外的RE：0.02%-0.30%，Zn：0.01%-0.8%，Ca：1.5%-4.0%，CaO：0.01%-0.20%；其余为镁以及不可避免的杂质。
  7. 根据权利要求6所述的一种镁基合金，其中，所述Al含量范围4%-7%，所述La含量范围2%-4%，所述RE含量范围0.05%-0.20%，所述Zn含量范围0.05%-0.20%，所述Ca含量范围2.0%-3.0%，所述CaO含量范围0.05%-0.15%。
  8. 根据权利要求7所述的一种镁基合金，其中，所述RE为Gd、Ho、Er、Eu和Y中的至少一种。
  9. 根据权利要求8所述的一种镁基合金，其中，所述RE为Gd和Y中的至少一种。
  10. 根据权利要求9所述的一种镁基合金，其中，所述Al含量范围4.5%-6.6%，所述RE为Gd和Y，所述Gd含量范围0.02%-0.10%，所述Y含量0.03-0.10%。
  11. 根据权利要求6所述的一种镁基合金，其中，按质量百分比计，所述不可避免的杂质总含量不超过0.2%。
  12. 一种如权利要求6所述镁基合金的制备方法，其中，包括如下步骤：
    在保护气氛下，将所述Mg锭、Al锭熔化后，升温至700-730℃，依次加入所述Zn锭、Mg-La合金、Mg-Ca合金，熔化后充分搅拌均匀；
    加入所述Mg-RE合金、CaO粉末，熔化后充分搅拌均匀，得到合金熔体；
    静置20-35min后，除气并加入熔剂，在700-710℃精炼处理20-35Min；
    精炼结束后，静置0.5-1.0h，扒渣，浇铸成型，得到所述镁基合金。
  13. 如权利要求12所述的镁基合金的制备方法，其中，所述Mg-RE合金中，稀土含量为15%-40%。
  14. 如权利要求12所述的镁基合金的制备方法，其中，所述CaO呈颗粒状，粒径为20μm~100m。
  15. 如权利要求12所述的镁基合金的制备方法，其中，所述Mg-Ca合金中，Ca的含量为15%-40%。
PCT/CN2022/135678 2022-08-05 2022-11-30 镁基合金及其制备方法 WO2024027053A1 (zh)

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