WO2022000893A1 - Rare earth element-free aluminum alloy for 3d printing - Google Patents

Rare earth element-free aluminum alloy for 3d printing Download PDF

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WO2022000893A1
WO2022000893A1 PCT/CN2020/125160 CN2020125160W WO2022000893A1 WO 2022000893 A1 WO2022000893 A1 WO 2022000893A1 CN 2020125160 W CN2020125160 W CN 2020125160W WO 2022000893 A1 WO2022000893 A1 WO 2022000893A1
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aluminum alloy
alloy
printing
balance
impurity elements
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PCT/CN2020/125160
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French (fr)
Chinese (zh)
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王国伟
沈显峰
杨家林
王利利
葛继强
张圣旺
黄姝珂
陈金明
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中国工程物理研究院机械制造工艺研究所
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Publication of WO2022000893A1 publication Critical patent/WO2022000893A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium

Definitions

  • the invention relates to the technical field of aluminum alloys and 3D printing, in particular to an aluminum alloy for 3D printing without rare earth elements.
  • Aluminum alloy has excellent properties such as high specific stiffness, high specific strength and low density, and has been widely used in aerospace, national defense and military industries, but traditional casting, forging, machining and other methods still cannot meet the processing of complex aluminum alloy parts. need. Therefore, metal 3D printing technology with the ability to directly form complex parts has developed rapidly in recent years, and aluminum alloy 3D printing technology represented by AlSi10Mg alloy has been widely used in various fields. However, the mechanical properties of AlSi10Mg are low, and it is not suitable for the working scene of high-strength aluminum alloys. Therefore, it is necessary to vigorously develop new high-strength aluminum alloys for 3D printing technology.
  • scandium-containing aluminum alloys have developed the most rapidly. Such alloys usually use aluminum as the matrix and scandium and zirconium elements as grain refiners to obtain 3D printed aluminum alloys with fine-grained structures. Material.
  • scandium and zirconium are important precipitation strengthening phase forming elements. Through solid solution aging or direct aging, a dispersed strengthening phase of several nanometers to tens of nanometers can be obtained, which further improves the properties of the alloy. The strength can exceed 500MPa.
  • the scandium element used in this alloy is a precious rare earth element, and the raw material price of this type of alloy is dozens of times that of ordinary aluminum alloys, which greatly limits the application range of this type of alloy.
  • the technical problem to be solved by the present invention is: the demand for high-strength aluminum alloys for 3D printing in civil and other fields, and the development of rare-earth-free high-strength aluminum alloy materials suitable for 3D printing is urgently needed. Therefore, the present invention provides a rare-earth element-free 3D aluminum alloy.
  • Aluminum alloy for printing which has excellent mechanical properties and good forming properties.
  • a rare earth element-free aluminum alloy for 3D printing comprising the following components by weight:
  • Mn 2.5% to 7.5%
  • Mg 1.5% to 9.5%
  • the balance is Al and impurity elements.
  • the aluminum alloy includes the following components by weight:
  • Mn 2.5% to 4.5%
  • Mg 1.5% to 9.5%
  • the balance is Al and impurity elements.
  • the aluminum alloy includes the following components by weight:
  • Mn 4.5% to 6.0%
  • Mg 1.5% to 7.0%
  • the balance is Al and impurity elements.
  • the aluminum alloy includes the following components by weight:
  • Mn 6.0% to 7.5%
  • Mg 1.5% to 4.5%
  • the balance is Al and impurity elements.
  • the aluminum alloy includes the following components by weight:
  • the total amount of Mn and Mg is less than 14%, the total amount of impurity elements is less than 0.5%, and the balance is Al.
  • the aluminum alloy includes the following components by weight:
  • the aluminum alloy includes the following components by weight:
  • the aluminum alloy includes the following components by weight:
  • the aluminum alloy includes the following components by weight:
  • the aluminum alloy includes the following components by weight:
  • the aluminum alloy includes the following components by weight:
  • Mn 6.6%
  • Mg 8.2%
  • the total weight percentage of impurity elements is less than 0.2%
  • the balance is Al.
  • the impurity elements include Fe, Si, Cu, Zn, Cr, Ni, Pb, Sn and O.
  • the preparation method of the aluminum alloy of the present invention is as follows:
  • the required ingredients are selected for batching; raw materials such as electrolytic aluminum and intermediate alloys are used for batching, and the raw materials are smelted by methods such as resistance heating to prepare the required alloy.
  • the alloy is processed into the required shape and size by casting or mechanical processing; then the alloy ingot is made into alloy powder by gas atomization or other suitable milling techniques; The powder inspection and other steps will obtain powder that meets the requirements of 3D printing. Or through the preparation methods of deformed alloys such as forging and extrusion, the alloys are processed into wires (wires), and finally aluminum alloy wires (wires) whose composition and specifications meet the requirements of wire-feeding 3D printing are obtained.
  • the conventional method of aluminum alloy 3D printing is as follows: take laser selective melting and forming equipment as an example, first place the aluminum powder in a drying oven or vacuum drying oven protected by an inert gas to dry it for use; build a three-dimensional model of the part to be processed, add Support, re-slicing and import into 3D printing equipment; select appropriate 3D printing process parameters, and process aluminum alloy powder into target parts under a protective atmosphere.
  • the aluminum alloy can be used in the fields of 3D printing, cladding, surfacing, powder metallurgy, spraying, injection molding, and powder forging.
  • the reason for the selection of Mn element is that the manganese content of the existing aluminum alloy is usually less than 2%, and its composition design is limited by the low cooling rate of the traditional process. When the manganese content is too high, it is easy to form coarse compounds and deteriorate the alloy. strength and plasticity. Facing the processing characteristics of 3D printing, the present invention designs a new aluminum alloy with a Mn element content higher than 2%.
  • some Mn elements in the form of aluminum-manganese compounds solidify before the Al phase, which can play a role in grain refinement, thereby improving the strength and plasticity of the alloy and reducing the cracking tendency of the alloy; due to the rapid cooling of 3D printing Characteristic, some Mn elements are dissolved in the Al phase in the form of supersaturated solid solution, thus playing the role of solid solution strengthening; due to the rapid cooling characteristics of 3D printing, the manganese element in the alloy of the present invention will not form a coarse compound, Thereby avoiding performance degradation.
  • the alloy of the present invention uses Mn element and Mg element as the main alloy elements. These two alloy elements are in the composition range given by the present invention, which can greatly improve the strength of the aluminum matrix and retain a certain plasticity of the aluminum matrix. As alloying elements commonly used in aluminum alloys, the technological feasibility of adding Mn and Mg elements is extremely high.
  • the content of Mn element in the alloy of the invention is relatively high, which can play a certain role of grain refinement in the 3D printing process, thereby improving the plasticity of the alloy.
  • Al element in the alloy of the present invention is the matrix element, and Mg and Mn are alloying elements.
  • the alloy can be ensured to have good 3D printing forming performance, and at the same time Has excellent mechanical properties.
  • the alloy does not contain rare earth elements such as scandium, and the main alloy elements are commonly used magnesium and manganese, so that the alloy has good economy.
  • the alloy of the present invention can achieve excellent strength or plasticity. Compared with alloys such as Al-Mg-Sc-Zr, the alloy of the present invention does not contain rare earth elements such as scandium, which can greatly reduce the cost of the alloy.
  • the invention utilizes the synergistic strengthening effect of Mg and Mn elements to greatly improve the strength of the alloy while maintaining a certain elongation of the alloy.
  • the alloy of the present invention has a tensile strength and yield strength increased by about 100MPa when the plasticity is similar to that of the alloy of the present invention, which can be used for more important load-bearing components.
  • the alloy of the present invention has good technological feasibility and certain plasticity, and it is not easy to form defects such as cracks during the printing process.
  • the alloy of the present invention provides a new choice for 3D printing high-strength aluminum alloys, and provides a new alloy design ideas.
  • FIG. 1 is an engineering stress-strain curve diagram of Example 2 of the present invention.
  • a rare earth element-free aluminum alloy for 3D printing comprising the following components by weight:
  • Mn 2.5% to 7.5%
  • Mg 1.5% to 9.5%
  • the balance is Al and impurity elements.
  • the aluminum alloy includes the following components by weight:
  • Mn 2.5% to 4.5%
  • Mg 1.5% to 9.5%
  • the balance is Al and impurity elements.
  • the aluminum alloy includes the following components by weight:
  • Mn 4.5% to 6.0%
  • Mg 1.5% to 7.0%
  • the balance is Al and impurity elements.
  • the aluminum alloy includes the following components by weight:
  • Mn 6.0% to 7.5%
  • Mg 1.5% to 4.5%
  • the balance is Al and impurity elements.
  • the aluminum alloy includes the following components by weight:
  • the total amount of Mn and Mg is less than 14%, the total amount of impurity elements is less than 0.5%, and the balance is Al.
  • a rare earth element-free aluminum alloy for 3D printing comprising the following components by weight:
  • a rare earth element-free aluminum alloy for 3D printing comprising the following components by weight:
  • a rare earth element-free aluminum alloy for 3D printing comprising the following components by weight:
  • a rare earth element-free aluminum alloy for 3D printing comprising the following components by weight:
  • a rare earth element-free aluminum alloy for 3D printing comprising the following components by weight:
  • a rare earth element-free aluminum alloy for 3D printing comprising the following components by weight:
  • a rare earth element-free aluminum alloy for 3D printing comprising the following components by weight:
  • the impurity elements include Fe, Si, Cu, Zn, Cr, Ni, Pb, Sn and O.
  • the preparation method of the aluminum alloy of the present invention is as follows:
  • the required ingredients are selected for batching; raw materials such as electrolytic aluminum and intermediate alloys are used for batching, and the raw materials are smelted by methods such as resistance heating to prepare the required alloy.
  • the alloy is processed into the required shape and size by casting or mechanical processing; then the alloy ingot is made into alloy powder by gas atomization or other suitable milling techniques; The powder inspection and other steps will obtain powder that meets the requirements of 3D printing. Or through the preparation methods of deformed alloys such as forging and extrusion, the alloys are processed into wires (wires), and finally aluminum alloy wires (wires) whose composition and specifications meet the requirements of wire-feeding 3D printing are obtained.
  • the conventional method of aluminum alloy 3D printing is as follows: take laser selective melting and forming equipment as an example, first place the aluminum powder in a drying oven or vacuum drying oven protected by an inert gas to dry it for use; build a three-dimensional model of the part to be processed, add Support, re-slicing and import into 3D printing equipment; select appropriate 3D printing process parameters, and process aluminum alloy powder into target parts under a protective atmosphere.
  • the aluminum alloy can be used in the fields of 3D printing, cladding, surfacing, powder metallurgy, spraying, injection molding, and powder forging.
  • the alloy of the present invention uses Mn element and Mg element as the main alloy elements. These two alloy elements are in the composition range given by the present invention, which can greatly improve the strength of the aluminum matrix and retain a certain plasticity of the aluminum matrix. As alloying elements commonly used in aluminum alloys, the technological feasibility of adding Mn and Mg elements is extremely high.
  • the content of Mn element in the alloy of the invention is relatively high, which can play a certain role of grain refinement in the 3D printing process, thereby improving the plasticity of the alloy.
  • Al element in the alloy of the present invention is the matrix element, and Mg and Mn are alloying elements.
  • the alloy can be ensured to have good 3D printing forming performance, and at the same time Has excellent mechanical properties.
  • the alloy does not contain rare earth elements such as scandium, and the main alloy elements are commonly used magnesium and manganese, so that the alloy has good economy.
  • Example 1 This comparative example is based on Example 1, and the main difference from Example 1 is:
  • Mn 1.1%
  • Mg 13.5%
  • Example 2 This comparative example is based on Example 2, and the main difference from Example 2 is:
  • Example 3 This comparative example is based on Example 3, and the main difference with Example 3 is:
  • Example 4 This comparative example is based on Example 4, and the main difference from Example 4 is:
  • Example 5 This comparative example is based on Example 5, and the main difference from Example 5 is:
  • the total weight percentage of impurity elements is 1.1%.
  • Comparative Example 1 Comparative Example 2 are difficult to form, not suitable for 3D printing, and cannot obtain mechanical property data; other test results are shown in Table 1:
  • Example 1 From Example 1 to Example 7, it can be seen that the alloy of the present invention has good forming properties, and 3D printing samples can be successfully prepared for mechanical property testing; the test results show that the alloy of the present invention has excellent resistance to Tensile strength and yield strength, and its elongation is better than 5%, which can be used for engineering applications.
  • Comparative Example 5 when the content of impurity elements is significantly higher than the range described in the present invention, compared with Example 5, the plasticity of the alloy of Comparative Example 5 is significantly reduced.
  • Example 2 a room temperature tensile experiment was performed after 3D printing, and the elongation was close to 7%, and the engineering stress-strain curve was shown in Figure 1.

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Abstract

A rare earth element-free aluminum alloy for 3D printing, comprising the following components in percentage by weight: Mn: 2.5%-4.5%, Mg: 1.5%-9.5%, and the balance of Al and impurity elements; or Mn: 4.5%-6.0% and Mg: 1.5%-7.5%. The alloy can achieve excellent strength or plasticity, and compared with Al-Mg-Sc-Zr aluminum alloys, rare earth resources can be saved and the raw material cost can be greatly reduced.

Description

一种无稀土元素的3D打印用铝合金A rare earth element-free 3D printing aluminum alloy 技术领域technical field
本发明涉及铝合金和3D打印技术领域，具体涉及一种无稀土元素的3D打印用铝合金。The invention relates to the technical field of aluminum alloys and 3D printing, in particular to an aluminum alloy for 3D printing without rare earth elements.
背景技术Background technique
铝合金拥有比刚度高、比强度高、密度低等优异性能，在航空航天、国防军工等领域得到了广泛应用，但是传统的铸造、锻造、机械加工等方法仍不能满足复杂铝合金零件的加工需求。因此，拥有复杂零件直接成形能力的金属3D打印技术近年来得到了快速发展，以AlSi10Mg合金为代表的铝合金3D打印技术在各领域得到了广泛应用。但是AlSi10Mg的力学性能偏低，无法胜任高强铝合金的工作场景，因此需要大力发展面向3D打印技术的新型高强铝合金。Aluminum alloy has excellent properties such as high specific stiffness, high specific strength and low density, and has been widely used in aerospace, national defense and military industries, but traditional casting, forging, machining and other methods still cannot meet the processing of complex aluminum alloy parts. need. Therefore, metal 3D printing technology with the ability to directly form complex parts has developed rapidly in recent years, and aluminum alloy 3D printing technology represented by AlSi10Mg alloy has been widely used in various fields. However, the mechanical properties of AlSi10Mg are low, and it is not suitable for the working scene of high-strength aluminum alloys. Therefore, it is necessary to vigorously develop new high-strength aluminum alloys for 3D printing technology.
在新型高强铝合金的开发方面，含钪铝合金的发展最为迅速，该类合金通常以铝为基体，以钪元素和锆元素作为晶粒细化剂，从而得到细晶组织的3D打印铝合金材料。并且，钪元素和锆元素是重要的沉淀强化相形成元素，通过固溶时效或直接时效，可以得到几纳米至几十纳米且弥散分布的强化相，进一步提高合金性能，该类合金的抗拉强度可以超过500MPa。但是该合金所使用的钪元素为贵重的稀土元素，该类合金的原材料价格是普通铝合金的数十倍，使得该类合金的应用范围受到了极大限制。为了解决民用等领域对3D打印用高强铝合金的需求，急需发展出适宜于3D打印的无稀土高强铝合金材料。In the development of new high-strength aluminum alloys, scandium-containing aluminum alloys have developed the most rapidly. Such alloys usually use aluminum as the matrix and scandium and zirconium elements as grain refiners to obtain 3D printed aluminum alloys with fine-grained structures. Material. In addition, scandium and zirconium are important precipitation strengthening phase forming elements. Through solid solution aging or direct aging, a dispersed strengthening phase of several nanometers to tens of nanometers can be obtained, which further improves the properties of the alloy. The strength can exceed 500MPa. However, the scandium element used in this alloy is a precious rare earth element, and the raw material price of this type of alloy is dozens of times that of ordinary aluminum alloys, which greatly limits the application range of this type of alloy. In order to solve the demand for high-strength aluminum alloys for 3D printing in civil and other fields, it is urgent to develop rare earth-free high-strength aluminum alloy materials suitable for 3D printing.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是：民用等领域对3D打印用高强铝合金的需求，急需发展出适宜于3D打印的无稀土高强铝合金材料，因此，本发明提供了一种无稀土元素的3D打印用铝合金，其拥有优异的力学性能和良好的成形特性。The technical problem to be solved by the present invention is: the demand for high-strength aluminum alloys for 3D printing in civil and other fields, and the development of rare-earth-free high-strength aluminum alloy materials suitable for 3D printing is urgently needed. Therefore, the present invention provides a rare-earth element-free 3D aluminum alloy. Aluminum alloy for printing, which has excellent mechanical properties and good forming properties.
本发明通过下述技术方案实现：The present invention is achieved through the following technical solutions:
一种无稀土元素的3D打印用铝合金，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, comprising the following components by weight:
Mn：2.5％～7.5％，Mg：1.5％～9.5％，余量为Al和杂质元素。Mn: 2.5% to 7.5%, Mg: 1.5% to 9.5%, and the balance is Al and impurity elements.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：2.5％～4.5％，Mg：1.5％～9.5％，余量为Al和杂质元素。Mn: 2.5% to 4.5%, Mg: 1.5% to 9.5%, and the balance is Al and impurity elements.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：4.5％～6.0％，Mg：1.5％～7.0％，余量为Al和杂质元素。Mn: 4.5% to 6.0%, Mg: 1.5% to 7.0%, and the balance is Al and impurity elements.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：6.0％～7.5％，Mg：1.5％～4.5％，余量为Al和杂质元素。Mn: 6.0% to 7.5%, Mg: 1.5% to 4.5%, and the balance is Al and impurity elements.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn和Mg的总量低于14％，杂质元素总量低于0.5％，余量为Al。The total amount of Mn and Mg is less than 14%, the total amount of impurity elements is less than 0.5%, and the balance is Al.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：3.7％，Mg：8.0％，杂质元素重量百分比总量为0.32％，余量为Al。Mn: 3.7%, Mg: 8.0%, the total weight percentage of impurity elements is 0.32%, and the balance is Al.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：5.8％，Mg：4.1％，杂质元素重量百分比总量为0.29％，余量为Al。Mn: 5.8%, Mg: 4.1%, the total weight percentage of impurity elements is 0.29%, and the balance is Al.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：6.8％，Mg：1.9％，杂质元素重量百分比总量为0.34％，余量为Al。Mn: 6.8%, Mg: 1.9%, the total weight percentage of impurity elements is 0.34%, and the balance is Al.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：2.5％，Mg：9.3％，杂质元素重量百分比总量为0.37％，余量为Al。Mn: 2.5%, Mg: 9.3%, the total weight percentage of impurity elements is 0.37%, and the balance is Al.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：4.6％，Mg：5.2％，杂质元素重量百分比总量为0.11％，余量为Al。Mn: 4.6%, Mg: 5.2%, the total weight percentage of impurity elements is 0.11%, and the balance is Al.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：6.6％，Mg：8.2％，杂质元素的重量百分比总量低于0.2％，余量为Al。Mn: 6.6%, Mg: 8.2%, the total weight percentage of impurity elements is less than 0.2%, and the balance is Al.
优选的，所述杂质元素包括Fe、Si、Cu、Zn、Cr、Ni、Pb、Sn和O。Preferably, the impurity elements include Fe, Si, Cu, Zn, Cr, Ni, Pb, Sn and O.
上述杂质元素含量的合理控制能够保证合金的性能稳定性。The reasonable control of the content of the above impurity elements can ensure the performance stability of the alloy.
本发明所述铝合金的制备方法如下：The preparation method of the aluminum alloy of the present invention is as follows:
根据上述的成分范围，选择需要的成分进行配料；配料时使用电解铝、中间合金等原材料，采用电阻加热等方法将原材料熔炼制备成所需合金。According to the above-mentioned composition range, the required ingredients are selected for batching; raw materials such as electrolytic aluminum and intermediate alloys are used for batching, and the raw materials are smelted by methods such as resistance heating to prepare the required alloy.
然后根据制粉工艺的需要，通过铸造或机械加工等方法将合金加工成所需的形状尺寸；再使用气雾化或其它适宜的制粉技术将合金锭制成合金粉；最后通过筛分、粉末送检等步骤得到符合3D打印使用要求的粉末。或通过锻造、挤压等变形合金的制备方法，将合金加工成丝材(线材)，最后得到成分及规格符合送丝类3D打印使用要求的铝合金丝(线)。Then, according to the needs of the milling process, the alloy is processed into the required shape and size by casting or mechanical processing; then the alloy ingot is made into alloy powder by gas atomization or other suitable milling techniques; The powder inspection and other steps will obtain powder that meets the requirements of 3D printing. Or through the preparation methods of deformed alloys such as forging and extrusion, the alloys are processed into wires (wires), and finally aluminum alloy wires (wires) whose composition and specifications meet the requirements of wire-feeding 3D printing are obtained.
铝合金3D打印的常规方法如下：以激光选区熔化成形设备为例，先将铝粉置于惰性气体保护的干燥箱或真空干燥箱中烘干以备用；建立待加工的零件的三维模型、添加支撑、再切片导入到3D打印设备；选用适宜的3D打印工艺参数，在保护气氛下将铝合金粉末加工成目标零件。The conventional method of aluminum alloy 3D printing is as follows: take laser selective melting and forming equipment as an example, first place the aluminum powder in a drying oven or vacuum drying oven protected by an inert gas to dry it for use; build a three-dimensional model of the part to be processed, add Support, re-slicing and import into 3D printing equipment; select appropriate 3D printing process parameters, and process aluminum alloy powder into target parts under a protective atmosphere.
所述铝合金可用于3D打印、熔覆、堆焊、粉末冶金、喷涂、注射成型、粉末锻造领域中。The aluminum alloy can be used in the fields of 3D printing, cladding, surfacing, powder metallurgy, spraying, injection molding, and powder forging.
本发明中，Mn元素选取的原由，现有铝合金的锰含量通常低于2％，其成分设计受限于传统工艺的较低冷却速率，锰含量过高时容易形成粗大的化合物，恶化合金的强度与塑性。本发明面向3D打印的加工特点，设计了Mn元素含量高于2％的新型铝合金。在3D打印过 程，部分Mn元素以铝锰化合物的形式先于Al相凝固，可以起到晶粒细化的作用，从而提高合金的强度与塑性，降低合金的开裂倾向；由于3D打印快速冷却的特点，部分Mn元素以过饱和固溶体的形式固溶于Al相之中，从而起到固溶强化的作用；由于3D打印快速冷却的特点，本发明合金中的锰元素不会形成粗大的化合物，从而避免了性能恶化。In the present invention, the reason for the selection of Mn element is that the manganese content of the existing aluminum alloy is usually less than 2%, and its composition design is limited by the low cooling rate of the traditional process. When the manganese content is too high, it is easy to form coarse compounds and deteriorate the alloy. strength and plasticity. Facing the processing characteristics of 3D printing, the present invention designs a new aluminum alloy with a Mn element content higher than 2%. In the 3D printing process, some Mn elements in the form of aluminum-manganese compounds solidify before the Al phase, which can play a role in grain refinement, thereby improving the strength and plasticity of the alloy and reducing the cracking tendency of the alloy; due to the rapid cooling of 3D printing Characteristic, some Mn elements are dissolved in the Al phase in the form of supersaturated solid solution, thus playing the role of solid solution strengthening; due to the rapid cooling characteristics of 3D printing, the manganese element in the alloy of the present invention will not form a coarse compound, Thereby avoiding performance degradation.
本发明合金以Mn元素和Mg元素作为主要的合金元素，这两种合金元素在本发明给出的成分范围类，可以大幅度提高铝基体的强度同时保留一定的铝基体塑性。作为铝合金常用的合金化元素，添加Mn元素和Mg元素的工艺可行性极高。The alloy of the present invention uses Mn element and Mg element as the main alloy elements. These two alloy elements are in the composition range given by the present invention, which can greatly improve the strength of the aluminum matrix and retain a certain plasticity of the aluminum matrix. As alloying elements commonly used in aluminum alloys, the technological feasibility of adding Mn and Mg elements is extremely high.
本发明合金中Mn元素的含量较高，在3D打印过程能够起到一定的晶粒细化作用，从而提高合金的塑性。The content of Mn element in the alloy of the invention is relatively high, which can play a certain role of grain refinement in the 3D printing process, thereby improving the plasticity of the alloy.
本发明合金中Al元素为基体元素，Mg、Mn为合金元素，通过合理设置Mg、Mn的含量，并将杂质元素控制在合理范围内，便能够确保合金具有较好的3D打印成形性能，同时具有优异的力学性能。Al element in the alloy of the present invention is the matrix element, and Mg and Mn are alloying elements. By reasonably setting the content of Mg and Mn and controlling the impurity elements within a reasonable range, the alloy can be ensured to have good 3D printing forming performance, and at the same time Has excellent mechanical properties.
本发明与现有3D打印高强度铝合金相比，该合金中不含有钪等稀土元素，并且主要合金元素为常用的镁和锰，使得该合金具有很好的经济性。Compared with the existing 3D printing high-strength aluminum alloy, the alloy does not contain rare earth elements such as scandium, and the main alloy elements are commonly used magnesium and manganese, so that the alloy has good economy.
本发明具有如下的优点和有益效果：The present invention has the following advantages and beneficial effects:
1、本发明合金可以实现优异的强度或塑性，与Al-Mg-Sc-Zr这类合金相比，本发明合金中不含有钪等稀土元素，可以大幅降低合金成本。本发明利用Mg和Mn元素的协同强化作用，在大幅提高合金强度的同时还能使合金保持一定的延伸率。1. The alloy of the present invention can achieve excellent strength or plasticity. Compared with alloys such as Al-Mg-Sc-Zr, the alloy of the present invention does not contain rare earth elements such as scandium, which can greatly reduce the cost of the alloy. The invention utilizes the synergistic strengthening effect of Mg and Mn elements to greatly improve the strength of the alloy while maintaining a certain elongation of the alloy.
2、本发明合金与AlSi10Mg合金相比，本发明合金在塑性与其相近的情况下，抗拉强度和屈服强度提高了100MPa左右，可用于更加重要的承力构件。2. Compared with the AlSi10Mg alloy, the alloy of the present invention has a tensile strength and yield strength increased by about 100MPa when the plasticity is similar to that of the alloy of the present invention, which can be used for more important load-bearing components.
3、本发明合金具有较好的工艺可行性和一定的塑性，在打印过程中不容易形成裂纹等缺陷，本发明合金为3D打印高强度铝合金提供了新选择，并提供了新的合金设计思路。3. The alloy of the present invention has good technological feasibility and certain plasticity, and it is not easy to form defects such as cracks during the printing process. The alloy of the present invention provides a new choice for 3D printing high-strength aluminum alloys, and provides a new alloy design ideas.
附图说明Description of drawings
此处所说明的附图用来提供对本发明实施例的进一步理解，构成本申请的一部分，并不构成对本发明实施例的限定。在附图中：The accompanying drawings described herein are used to provide further understanding of the embodiments of the present invention, and constitute a part of the present application, and do not constitute limitations to the embodiments of the present invention. In the attached image:
图1为本发明的实施例2的工程应力应变曲线图。FIG. 1 is an engineering stress-strain curve diagram of Example 2 of the present invention.
具体实施方式detailed description
在对本发明的任意实施例进行详细的描述之前，应该理解本发明的应用不局限于下面的说明或附图中所示的结构的细节。本发明可采用其它的实施例，并且可以以各种方式被实施或被执行。基于本发明中的实施例，本领域普通技术人员在没有做出创造性改进前提下所获得的所有其它实施例，均属于本发明保护的范围。Before any embodiment of the invention is described in detail, it is to be understood that the invention is not limited to the details of construction shown in the following description or in the drawings. The invention is capable of other embodiments and of being carried out or being carried out in various ways. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative improvements shall fall within the protection scope of the present invention.
一种无稀土元素的3D打印用铝合金，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, comprising the following components by weight:
Mn：2.5％～7.5％，Mg：1.5％～9.5％，余量为Al和杂质元素。Mn: 2.5% to 7.5%, Mg: 1.5% to 9.5%, and the balance is Al and impurity elements.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：2.5％～4.5％，Mg：1.5％～9.5％，余量为Al和杂质元素。Mn: 2.5% to 4.5%, Mg: 1.5% to 9.5%, and the balance is Al and impurity elements.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：4.5％～6.0％，Mg：1.5％～7.0％，余量为Al和杂质元素。Mn: 4.5% to 6.0%, Mg: 1.5% to 7.0%, and the balance is Al and impurity elements.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn：6.0％～7.5％，Mg：1.5％～4.5％，余量为Al和杂质元素。Mn: 6.0% to 7.5%, Mg: 1.5% to 4.5%, and the balance is Al and impurity elements.
优选的，所述铝合金包括以下重量百分比组分：Preferably, the aluminum alloy includes the following components by weight:
Mn和Mg的总量低于14％，杂质元素总量低于0.5％，余量为Al。The total amount of Mn and Mg is less than 14%, the total amount of impurity elements is less than 0.5%, and the balance is Al.
实施例1：Example 1:
一种无稀土元素的3D打印用铝合金，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, comprising the following components by weight:
Mn：2.5％，Mg：9.3％，杂质元素重量百分比总量为0.37％，余量为Al。Mn: 2.5%, Mg: 9.3%, the total weight percentage of impurity elements is 0.37%, and the balance is Al.
实施例2：Example 2:
一种无稀土元素的3D打印用铝合金，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, comprising the following components by weight:
Mn：3.7％，Mg：8.0％，杂质元素重量百分比总量为0.32％，余量为Al。Mn: 3.7%, Mg: 8.0%, the total weight percentage of impurity elements is 0.32%, and the balance is Al.
实施例3：Example 3:
一种无稀土元素的3D打印用铝合金，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, comprising the following components by weight:
Mn：5.8％，Mg：4.1％，杂质元素重量百分比总量为0.29％，余量为Al。Mn: 5.8%, Mg: 4.1%, the total weight percentage of impurity elements is 0.29%, and the balance is Al.
实施例4：Example 4:
一种无稀土元素的3D打印用铝合金，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, comprising the following components by weight:
Mn：6.8％，Mg：1.9％，杂质元素重量百分比总量为0.34％，余量为Al。Mn: 6.8%, Mg: 1.9%, the total weight percentage of impurity elements is 0.34%, and the balance is Al.
实施例5：Example 5:
一种无稀土元素的3D打印用铝合金，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, comprising the following components by weight:
Mn：4.6％，Mg：5.2％，杂质元素重量百分比总量为0.11％，余量为Al。Mn: 4.6%, Mg: 5.2%, the total weight percentage of impurity elements is 0.11%, and the balance is Al.
实施例6：Example 6:
一种无稀土元素的3D打印用铝合金，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, comprising the following components by weight:
Mn：2.8％，Mg：1.7％，杂质元素重量百分比总量为0.43％，余量为Al。Mn: 2.8%, Mg: 1.7%, the total weight percentage of impurity elements is 0.43%, and the balance is Al.
实施例7：Example 7:
一种无稀土元素的3D打印用铝合金，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, comprising the following components by weight:
Mn：3.3％，Mg：3.8％，杂质元素重量百分比总量为0.36％，余量为Al。Mn: 3.3%, Mg: 3.8%, the total weight percentage of impurity elements is 0.36%, and the balance is Al.
优选的，所述杂质元素包括Fe、Si、Cu、Zn、Cr、Ni、Pb、Sn和O。Preferably, the impurity elements include Fe, Si, Cu, Zn, Cr, Ni, Pb, Sn and O.
上述杂质元素含量的合理控制能够保证合金的性能稳定性。The reasonable control of the content of the above impurity elements can ensure the performance stability of the alloy.
本发明所述铝合金的制备方法如下：The preparation method of the aluminum alloy of the present invention is as follows:
根据上述的成分范围，选择需要的成分进行配料；配料时使用电解铝、中间合金等原材料，采用电阻加热等方法将原材料熔炼制备成所需合金。According to the above-mentioned composition range, the required ingredients are selected for batching; raw materials such as electrolytic aluminum and intermediate alloys are used for batching, and the raw materials are smelted by methods such as resistance heating to prepare the required alloy.
然后根据制粉工艺的需要，通过铸造或机械加工等方法将合金加工成所需的形状尺寸；再使用气雾化或其它适宜的制粉技术将合金锭制成合金粉；最后通过筛分、粉末送检等步骤得到符合3D打印使用要求的粉末。或通过锻造、挤压等变形合金的制备方法，将合金加工成丝材(线材)，最后得到成分及规格符合送丝类3D打印使用要求的铝合金丝(线)。Then, according to the needs of the milling process, the alloy is processed into the required shape and size by casting or mechanical processing; then the alloy ingot is made into alloy powder by gas atomization or other suitable milling techniques; The powder inspection and other steps will obtain powder that meets the requirements of 3D printing. Or through the preparation methods of deformed alloys such as forging and extrusion, the alloys are processed into wires (wires), and finally aluminum alloy wires (wires) whose composition and specifications meet the requirements of wire-feeding 3D printing are obtained.
铝合金3D打印的常规方法如下：以激光选区熔化成形设备为例，先将铝粉置于惰性气体保护的干燥箱或真空干燥箱中烘干以备用；建立待加工的零件的三维模型、添加支撑、再切片导入到3D打印设备；选用适宜的3D打印工艺参数，在保护气氛下将铝合金粉末加工成目标零件。The conventional method of aluminum alloy 3D printing is as follows: take laser selective melting and forming equipment as an example, first place the aluminum powder in a drying oven or vacuum drying oven protected by an inert gas to dry it for use; build a three-dimensional model of the part to be processed, add Support, re-slicing and import into 3D printing equipment; select appropriate 3D printing process parameters, and process aluminum alloy powder into target parts under a protective atmosphere.
所述铝合金可用于3D打印、熔覆、堆焊、粉末冶金、喷涂、注射成型、粉末锻造领域中。The aluminum alloy can be used in the fields of 3D printing, cladding, surfacing, powder metallurgy, spraying, injection molding, and powder forging.
本发明合金以Mn元素和Mg元素作为主要的合金元素，这两种合金元素在本发明给出的成分范围类，可以大幅度提高铝基体的强度同时保留一定的铝基体塑性。作为铝合金常用的合金化元素，添加Mn元素和Mg元素的工艺可行性极高。The alloy of the present invention uses Mn element and Mg element as the main alloy elements. These two alloy elements are in the composition range given by the present invention, which can greatly improve the strength of the aluminum matrix and retain a certain plasticity of the aluminum matrix. As alloying elements commonly used in aluminum alloys, the technological feasibility of adding Mn and Mg elements is extremely high.
本发明合金中Mn元素的含量较高，在3D打印过程能够起到一定的晶粒细化作用，从而提高合金的塑性。The content of Mn element in the alloy of the invention is relatively high, which can play a certain role of grain refinement in the 3D printing process, thereby improving the plasticity of the alloy.
本发明合金中Al元素为基体元素，Mg、Mn为合金元素，通过合理设置Mg、Mn的含量，并将杂质元素控制在合理范围内，便能够确保合金具有较好的3D打印成形性能，同时具有优异的力学性能。Al element in the alloy of the present invention is the matrix element, and Mg and Mn are alloying elements. By reasonably setting the content of Mg and Mn and controlling the impurity elements within a reasonable range, the alloy can be ensured to have good 3D printing forming performance, and at the same time Has excellent mechanical properties.
本发明与现有3D打印高强度铝合金相比，该合金中不含有钪等稀土元素，并且主要合金元素为常用的镁和锰，使得该合金具有很好的经济性。Compared with the existing 3D printing high-strength aluminum alloy, the alloy does not contain rare earth elements such as scandium, and the main alloy elements are commonly used magnesium and manganese, so that the alloy has good economy.
对比例1：Comparative Example 1:
本对比例基于实施例1，与实施例1的主要区别在于：This comparative example is based on Example 1, and the main difference from Example 1 is:
Mn：1.1％，Mg：13.5％。Mn: 1.1%, Mg: 13.5%.
对比例2：Comparative Example 2:
本对比例基于实施例2，与实施例2的主要区别在于：This comparative example is based on Example 2, and the main difference from Example 2 is:
Mn：3.4％，Mg：11.2％。Mn: 3.4%, Mg: 11.2%.
对比例3：Comparative Example 3:
本对比例基于实施例3，与实施例3的主要区别在于：This comparative example is based on Example 3, and the main difference with Example 3 is:
Mn：9.6％，Mg：4.3％。Mn: 9.6%, Mg: 4.3%.
对比例4：Comparative Example 4:
本对比例基于实施例4，与实施例4的主要区别在于：This comparative example is based on Example 4, and the main difference from Example 4 is:
Mn：1.3％，Mg：1.0％。Mn: 1.3%, Mg: 1.0%.
对比例5：Comparative Example 5:
本对比例基于实施例5，与实施例5的主要区别在于：This comparative example is based on Example 5, and the main difference from Example 5 is:
杂质元素重量百分比总量为1.1％。The total weight percentage of impurity elements is 1.1%.
将实施例1-实施例7，对比例1-对比例5所述的铝合金在激光选区熔化成形设备上，选用适宜的3D打印工艺将合金粉末加工块状样品，再将样品加工得到棒状拉伸试样并测试其力学性能。其中对比例1和对比例2均难以成形，不宜用于3D打印，无法得到力学性能数据；其它测试结果如表1所示：The aluminum alloys described in Example 1-Example 7, Comparative Example 1-Comparative Example 5 were processed by a suitable 3D printing process on the laser selective melting and forming equipment to process the alloy powder into a block sample, and then the sample was processed to obtain a rod-shaped drawing. The specimens were stretched and their mechanical properties were tested. Among them, Comparative Example 1 and Comparative Example 2 are difficult to form, not suitable for 3D printing, and cannot obtain mechanical property data; other test results are shown in Table 1:
Figure PCTCN2020125160-appb-000001
Figure PCTCN2020125160-appb-000001
根据表的数据可知：According to the data in the table:
1、从实施例1至实施例7可以看出，本发明所述合金具有良好的成形特性，均可以顺利 制备出3D打印样品用于力学性能测试；测试结果表明，本发明合金具有优异的抗拉强度及屈服强度，其延伸率优于5％，可用于工程应用。1. From Example 1 to Example 7, it can be seen that the alloy of the present invention has good forming properties, and 3D printing samples can be successfully prepared for mechanical property testing; the test results show that the alloy of the present invention has excellent resistance to Tensile strength and yield strength, and its elongation is better than 5%, which can be used for engineering applications.
2、从对比例1至对比例4可以看出，当Mg、Mn元素的含量明显偏离本发明所述范围时，对比例1和对比例2均难以成形，不宜用于3D打印；与实施例3相比，对比例3的强度和塑性显著下降；对比例4的塑性很好，但其抗拉强度和屈服强度均大幅落后于本发明所述合金。2. From Comparative Example 1 to Comparative Example 4, it can be seen that when the content of Mg and Mn elements deviates significantly from the scope of the present invention, both Comparative Example 1 and Comparative Example 2 are difficult to form, and are not suitable for 3D printing; Compared with 3, the strength and plasticity of Comparative Example 3 decrease significantly; the plasticity of Comparative Example 4 is very good, but its tensile strength and yield strength are significantly behind the alloy of the present invention.
3、从对比例5可以看出，当杂质元素的含量明显高于本发明所述范围时，与实施例5相比，对比例5合金的塑性显著下降。3. It can be seen from Comparative Example 5 that when the content of impurity elements is significantly higher than the range described in the present invention, compared with Example 5, the plasticity of the alloy of Comparative Example 5 is significantly reduced.
4、本实施例采用多组正交实验，缩小数据范围。4. In this embodiment, multiple sets of orthogonal experiments are used to narrow the data range.
实施例2在3D打印后进行室温拉伸实验，其延伸率接近7％，其工程应力应变曲线如图1所示。In Example 2, a room temperature tensile experiment was performed after 3D printing, and the elongation was close to 7%, and the engineering stress-strain curve was shown in Figure 1.
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The specific embodiments described above further describe the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (9)

  1. 一种无稀土元素的3D打印用铝合金，其特征在于，包括以下重量百分比组分：A rare earth element-free aluminum alloy for 3D printing, characterized in that it comprises the following components by weight:
    Mn：2.5％～7.5％，Mg：1.5％～9.5％，余量为Al和杂质元素。Mn: 2.5% to 7.5%, Mg: 1.5% to 9.5%, and the balance is Al and impurity elements.
  2. 根据权利要求1所述的一种无稀土元素的3D打印用铝合金，其特征在于，所述铝合金包括以下重量百分比组分：The rare-earth element-free aluminum alloy for 3D printing according to claim 1, wherein the aluminum alloy comprises the following components by weight:
    Mn：2.5％～4.5％，Mg：1.5％～9.5％，余量为Al和杂质元素。Mn: 2.5% to 4.5%, Mg: 1.5% to 9.5%, and the balance is Al and impurity elements.
  3. 根据权利要求1所述的一种无稀土元素的3D打印用铝合金，其特征在于，所述铝合金包括以下重量百分比组分：The rare-earth element-free aluminum alloy for 3D printing according to claim 1, wherein the aluminum alloy comprises the following components by weight:
    Mn：4.5％～6.0％，Mg：1.5％～7.0％，余量为Al和杂质元素。Mn: 4.5% to 6.0%, Mg: 1.5% to 7.0%, and the balance is Al and impurity elements.
  4. 根据权利要求1所述的一种无稀土元素的3D打印用铝合金，其特征在于，所述铝合金包括以下重量百分比组分：The rare-earth element-free aluminum alloy for 3D printing according to claim 1, wherein the aluminum alloy comprises the following components by weight:
    Mn：6.0％～7.5％，Mg：1.5％～4.5％，余量为Al和杂质元素。Mn: 6.0% to 7.5%, Mg: 1.5% to 4.5%, and the balance is Al and impurity elements.
  5. 根据权利要求1-4任意一条所述的一种无稀土元素的3D打印用铝合金，其特征在于，所述铝合金包括以下重量百分比组分：The rare-earth element-free aluminum alloy for 3D printing according to any one of claims 1-4, wherein the aluminum alloy comprises the following components by weight:
    Mn和Mg的总量低于14％，杂质元素总量低于0.5％，余量为Al。The total amount of Mn and Mg is less than 14%, the total amount of impurity elements is less than 0.5%, and the balance is Al.
  6. 根据权利要求4所述的一种无稀土元素的3D打印用铝合金，其特征在于，所述铝合金包括以下重量百分比组分：The rare-earth element-free aluminum alloy for 3D printing according to claim 4, wherein the aluminum alloy comprises the following components by weight:
    Mn：6.8％，Mg：1.9％，杂质元素重量百分比总量为0.34％，余量为Al。Mn: 6.8%, Mg: 1.9%, the total weight percentage of impurity elements is 0.34%, and the balance is Al.
  7. 根据权利要求2所述的一种无稀土元素的3D打印用铝合金，其特征在于，所述铝合金包括以下重量百分比组分：The rare-earth element-free aluminum alloy for 3D printing according to claim 2, wherein the aluminum alloy comprises the following components by weight:
    Mn：2.5％，Mg：9.3％，杂质元素重量百分比总量为0.37％，余量为Al。Mn: 2.5%, Mg: 9.3%, the total weight percentage of impurity elements is 0.37%, and the balance is Al.
  8. 根据权利要求3所述的一种无稀土元素的3D打印用铝合金，其特征在于，所述铝合金包括以下重量百分比组分：The rare earth element-free aluminum alloy for 3D printing according to claim 3, wherein the aluminum alloy comprises the following components by weight:
    Mn：4.6％，Mg：5.2％，杂质元素重量百分比总量为0.11％，余量为Al。Mn: 4.6%, Mg: 5.2%, the total weight percentage of impurity elements is 0.11%, and the balance is Al.
  9. 根据权利要求1所述的一种无稀土元素的3D打印用铝合金，其特征在于，所述铝合金包括以下重量百分比组分：The rare-earth element-free aluminum alloy for 3D printing according to claim 1, wherein the aluminum alloy comprises the following components by weight:
    Mn：6.6％，Mg：8.2％，杂质元素的重量百分比总量低于0.2％，余量为Al。Mn: 6.6%, Mg: 8.2%, the total weight percentage of impurity elements is less than 0.2%, and the balance is Al.
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