CN112974842B - A kind of nanometer multiphase reinforced aluminum matrix composite material and preparation method thereof - Google Patents
A kind of nanometer multiphase reinforced aluminum matrix composite material and preparation method thereofDownload PDFInfo
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Abstract
Translated fromChinese
Description
Translated fromChinese技术领域technical field
本发明属于纳米多相增强铝基复合材料领域，具体是一种高强度高承载纳米多相增强铝基复合材料及其制备方法。The invention belongs to the field of nanometer multiphase reinforced aluminum matrix composite material, in particular to a high-strength and high load bearing nanometer multiphase reinforced aluminum matrix composite material and a preparation method thereof.
背景技术Background technique
铝合金具有密度低、比强度高、耐蚀性好及导电导热性优异等特点，在航空航天、汽车、电力电子等领域中应用广泛。但铝合金有限的力学性能(极限拉伸强度＜400MPa，延伸率＜6％)难以满足迅速发展起来的航空航天、电子封装及汽车制造等高新技术领域的需求。为克服上述缺点，通过在铝合金基体中复合低密度、高强度、高模量的多相陶瓷增强体，有望协同提升基体的强度和模量。在众多陶瓷增强体中，碳纳米管(CNTs)因具有极大长径比(～1000)、低密度(1.7g/cm3)、高拉伸强度(～110GPa)、高弹性模量(～1TPa)、高热导率(～3000W m-1K-1)、良好导电性(～2×107S m-1)等特性，成为制备铝基复合材料较为理想的增强相。但目前采用单相陶瓷增强铝基复合材料，当增强相含量较多时，成形过程中液相粘度增加，流动性变差，增强相不能均匀分布，且会产生界面结合差、开裂等问题，导致零件成形质量较差。Aluminum alloy has the characteristics of low density, high specific strength, good corrosion resistance and excellent electrical and thermal conductivity, and is widely used in aerospace, automobile, power electronics and other fields. However, the limited mechanical properties of aluminum alloys (ultimate tensile strength <400MPa, elongation <6%) are difficult to meet the needs of the rapidly developing high-tech fields such as aerospace, electronic packaging and automobile manufacturing. In order to overcome the above shortcomings, it is expected to synergistically improve the strength and modulus of the matrix by compounding low-density, high-strength, and high-modulus multiphase ceramic reinforcements in the aluminum alloy matrix. Among many ceramic reinforcements, carbon nanotubes (CNTs) have a very large aspect ratio (~1000), low density (1.7g/cm3 ), high tensile strength (~110GPa), and high elastic modulus (~1000). 1TPa), high thermal conductivity (~3000W m-1 K-1 ), good electrical conductivity (~2×107 S m-1 ) and other characteristics, it becomes an ideal reinforcement phase for the preparation of aluminum matrix composites. However, at present, single-phase ceramic reinforced aluminum matrix composites are used. When the content of the reinforcing phase is large, the viscosity of the liquid phase increases during the forming process, the fluidity becomes poor, the reinforcing phase cannot be uniformly distributed, and problems such as poor interface bonding and cracking will occur, resulting in The forming quality of the parts is poor.
从加工工艺角度来看，目前制备单相陶瓷增强铝基复合材料的方法有很多，如熔铸法、粉末冶金、机械合金化法等，但陶瓷相与金属基体之间由于成分、晶体结构及物理化学性质的差异，而容易出现陶瓷增强体分布不均匀，尺寸和形状不易控制，陶瓷增强体与基体界面结合差等缺陷，致使复合材料的综合性能较差。选区激光熔化技术作为一种新型的激光增材制造技术，基于分层制造、累积叠加的局部成形原理，根据计算机辅助设计的三维零件模型，利用高能激光热源对金属粉末层以逐道逐层方式进行选择性快速熔化/凝固堆积成形，从而实现复杂结构金属构件的直接快速成形。选区激光熔化成形过程中，激光热源与预铺设的粉末层作用时间极短，因此熔融粉末具有相当高的冷却速度，这为纳米多相增强铝基复合材料晶粒细化提供了有利条件，并且粉末颗粒在高能激光束作用下完全熔化，使相邻扫描轨迹或层间冶金结合良好，改善纳米多相增强铝基复合材料零件的成形质量，从而提高材料的力学性能。选区激光熔化技术突破了传统制造工艺束缚，符合“近净成形”设计理念，有效地缩短了新产品的研发和制造周期，提高了生产效率，并且能够成形具有复杂几何形状的零件，因此采用选区激光熔化技术制备纳米多相增强铝基复合材料具有很大的发展潜力。From the point of view of processing technology, there are many methods for preparing single-phase ceramic reinforced aluminum matrix composites, such as casting method, powder metallurgy, mechanical alloying method, etc. Due to differences in chemical properties, it is prone to defects such as uneven distribution of ceramic reinforcements, difficult to control size and shape, and poor interface bonding between ceramic reinforcements and matrix, resulting in poor composite performance. As a new type of laser additive manufacturing technology, selective laser melting technology is based on the local forming principle of layered manufacturing and accumulation and superposition, according to the three-dimensional part model of computer-aided design, using high-energy laser heat source to metal powder layer by layer by layer. Selective rapid melting/solidification accumulation forming is carried out to realize direct rapid forming of complex structural metal components. In the process of selective laser melting and forming, the interaction time of the laser heat source and the pre-laid powder layer is extremely short, so the molten powder has a very high cooling rate, which provides favorable conditions for the grain refinement of nano-heterophase reinforced aluminum matrix composites, and The powder particles are completely melted under the action of the high-energy laser beam, so that the adjacent scanning trajectories or the interlayer metallurgical bonding are good, and the forming quality of the nano-multiphase reinforced aluminum matrix composite parts is improved, thereby improving the mechanical properties of the material. The selective laser melting technology breaks through the constraints of the traditional manufacturing process, conforms to the "near net shape" design concept, effectively shortens the development and manufacturing cycle of new products, improves production efficiency, and can form parts with complex geometric shapes, so the selective area is used. The preparation of nano-multiphase reinforced aluminum matrix composites by laser melting technology has great potential for development.
发明内容SUMMARY OF THE INVENTION
发明目的：本发明所要解决的技术问题是针对现有技术的不足，提供一种高强度高承载纳米多相增强铝基复合材料及其制备方法。Purpose of the invention: The technical problem to be solved by the present invention is to provide a high-strength and high-load-bearing nano-multiphase reinforced aluminum-based composite material and a preparation method thereof, aiming at the deficiencies of the prior art.
为了实现上述目的，本发明采取的技术方案如下：In order to achieve the above object, the technical scheme adopted by the present invention is as follows:
一种高强度高承载纳米多相增强铝基复合材料，包括铝合金基体以及分散在铝合金基体内的Al3Sc纳米增强相、Al3Zr纳米增强相和Al4C3纳米增强相；A high-strength and high-load bearing nano-multiphase reinforced aluminum-based composite material, comprising an aluminum alloy matrix and Al3 Sc nano-enhancing phase, Al3 Zr nano-enhancing phase and Al4 C3 nano-enhancing phase dispersed in the aluminum alloy matrix;
所述铝合金基体为铝-硅-钪-锆-锰合金，其中，硅含量为0.5～2.0wt.％，钪含量0.5～1.5wt.％，锆含量0.2～1.0wt.％，锰含量为0.4～1.0wt.％，余量为铝。The aluminum alloy substrate is an aluminum-silicon-scandium-zirconium-manganese alloy, wherein the silicon content is 0.5-2.0 wt.%, the scandium content is 0.5-1.5 wt.%, the zirconium content is 0.2-1.0 wt.%, and the manganese content is 0.4～1.0wt.%, the balance is aluminum.
本发明进一步提供上述高强度高承载纳米多相增强铝基复合材料的制备方法，包括如下步骤：The present invention further provides a method for preparing the above-mentioned high-strength and high-load-bearing nano-multiphase reinforced aluminum-based composite material, comprising the following steps:
(1)取铝合金基体粉末、多壁碳纳米管通过球磨机在惰性气体保护下进行球磨混合均匀，得到复合粉体；(1) Take the aluminum alloy matrix powder and the multi-walled carbon nanotubes through a ball mill under the protection of an inert gas for ball milling and mixing to obtain a composite powder;
(2)使用Soildworks软件建立目标零件的三维实体几何模型，然后利用Magics软件对该模型进行分层切片并规划激光扫描路径，将三维实体离散成一系列二维数据，保存并导入选区激光熔化成形设备中；(2) Use Soildworks software to establish a three-dimensional solid geometric model of the target part, and then use Magics software to slice the model and plan the laser scanning path, discretize the three-dimensional solid into a series of two-dimensional data, save and import the selected area laser melting forming equipment middle;
(3)通过选区激光熔化成形设备，根据步骤(2)所导入的数据，将步骤(1)中的复合粉体逐层熔化并凝固，成形为三维实体零件；(3) through the selective laser melting and forming equipment, according to the data imported in the step (2), the composite powder in the step (1) is melted and solidified layer by layer, and formed into a three-dimensional solid part;
(4)通过热处理设备将步骤(3)成形的三维实体零件在特定温度、时间下时效处理，即得。(4) Ageing treatment of the three-dimensional solid parts formed in step (3) at a specific temperature and time by means of heat treatment equipment to obtain the result.
优选地，步骤(1)中，所述铝合金基体粉末粒径分布范围在25～60μm，纯度大于99.0％，粉末流动性65～74s/50g。Preferably, in step (1), the particle size distribution range of the aluminum alloy base powder is 25-60 μm, the purity is greater than 99.0%, and the powder fluidity is 65-74s/50g.
优选地，步骤(1)中，所述的多壁碳纳米外径10-40nm，长度10-50μm。Preferably, in step (1), the outer diameter of the multi-wall carbon nanometer is 10-40 nm and the length is 10-50 μm.
优选地，步骤(1)中，所述的多壁碳纳米管添加量占复合材料总质量的0.1～1.0wt.％。Preferably, in step (1), the added amount of the multi-walled carbon nanotubes accounts for 0.1-1.0 wt.% of the total mass of the composite material.
优选地，步骤(1)中，所述的球磨机采用QM系列行星式球磨机，球料比为2:1，球磨转速为150～300rpm，球磨时间为3～6h。为防止球磨罐内温度过高和MWCNTs纤维结构损伤，球磨时设备运行模式选用间隔式，每运行15min后暂停空冷5min。该球磨过程要求在惰性气体保护下进行，以防止铝基粉末在球磨过程中被氧化或污染。Preferably, in step (1), the ball mill adopts a QM series planetary ball mill, the ball-to-material ratio is 2:1, the ball-milling speed is 150-300rpm, and the ball-milling time is 3-6h. In order to prevent the high temperature in the ball milling tank and the damage to the MWCNTs fiber structure, the operation mode of the equipment during ball milling was selected as the interval type, and the air cooling was suspended for 5 minutes after every 15 minutes of operation. The ball milling process requires the protection of inert gas to prevent the aluminum-based powder from being oxidized or contaminated during the ball milling process.
优选地，步骤(3)中，使用SLM-150型选区激光熔化设备，该设备主要包括YLR-500型光纤激光器、激光成形室、自动铺粉系统、保护气氛装置、计算机控制电路系统以及冷却循环系统。在成形前将经喷砂处理的铝合金基板固定在选区激光熔化成形设备工作台上并进行调平，然后通过密封装置将成形腔密封、抽真空并通入惰性气体保护气氛。典型选区激光熔化成形过程如下：(a)铺粉装置将待加工粉末均匀铺放在成形基板上，激光束根据预先设计好的扫描路径对切片区域逐层进行扫描，使粉末层发生快速熔化/凝固，从而获得待成形零件的第一个二维平面；(b)计算机控制系统使成形基板下降一个粉层厚度，而供粉缸活塞上升一个粉层厚度，铺粉装置重新铺设一层待加工粉末，高能激光束根据切片信息完成第二层粉末扫描以获得待成形零件的第二个二维平面；(c)重复(b)步骤，待加工粉体逐层成形直至待成形零件加工完毕。Preferably, in step (3), use SLM-150 type selective laser melting equipment, which mainly includes YLR-500 type fiber laser, laser forming chamber, automatic powder spreading system, protective atmosphere device, computer control circuit system and cooling cycle system. Before forming, the sandblasted aluminum alloy substrate is fixed on the workbench of the selective laser melting forming equipment and leveled, and then the forming cavity is sealed by a sealing device, evacuated and introduced into an inert gas protective atmosphere. The typical selective laser melting forming process is as follows: (a) The powder spreading device evenly spreads the powder to be processed on the forming substrate, and the laser beam scans the slicing area layer by layer according to the pre-designed scanning path, so that the powder layer rapidly melts/ solidification, thereby obtaining the first two-dimensional plane of the part to be formed; (b) the computer control system lowers the forming substrate by one powder layer thickness, while the piston of the powder supply cylinder rises by one powder layer thickness, and the powder spreading device re-lays a layer to be processed powder, the high-energy laser beam scans the second layer of powder according to the slicing information to obtain the second two-dimensional plane of the part to be formed; (c) repeat step (b), the powder to be processed is formed layer by layer until the part to be formed is processed.
优选地，选区激光熔化成形设备采用的激光功率为250～400W，激光扫描速度为400～1000mm/s，扫描间距为60μm，铺粉厚度为30μm，采用分区岛状扫描策略，上述激光参数经工艺优化后确定。Preferably, the laser power used by the selective laser melting and forming equipment is 250-400W, the laser scanning speed is 400-1000mm/s, the scanning distance is 60μm, and the powder thickness is 30μm, and the partitioned island scanning strategy is adopted. Confirmed after optimization.
优选地，步骤(4)中，热处理设备采用的时效温度为300～375℃，保温时间为3～6h。Preferably, in step (4), the aging temperature used by the heat treatment equipment is 300-375° C., and the holding time is 3-6 h.
通过热处理工艺和多壁碳纳米管添加量调控Al4C3纳米增强相的原位生成含量，改善增强相与基体之间的界面结合，提高材料的成形质量，并作为异质形核点，促进Al3Sc、Al3Zr纳米增强相的大量析出，最终起到提升材料综合力学性能的作用。具有菱方晶体结构Al4C3纳米增强相可与铝基体紧密结合，具有面心立方晶体结构的Al3Sc和Al3Zr与铝基体可形成良好的共格界面关系，且热处理工艺可释放增强相与基体间热膨胀系数差异产生的残余应力。因此，纳米多相增强相析出会显著提升铝基复合材料的综合力学性能。The in-situ generation content of Al4 C3 nano-reinforced phase is regulated by the heat treatment process and the addition amount of multi-walled carbon nanotubes, so as to improve the interface bonding between the reinforced phase and the matrix, improve the forming quality of the material, and act as a heterogeneous nucleation point, It promotes the precipitation of Al3 Sc and Al3 Zr nano-enhanced phases, and finally plays a role in improving the comprehensive mechanical properties of the material. The Al4 C3 nano-enhanced phase with rhombohedral crystal structure can be closely combined with the aluminum matrix, and the Al3 Sc and Al3 Zr with face-centered cubic crystal structure can form a good coherent interface relationship with the aluminum matrix, and the heat treatment process can release Residual stresses due to differences in thermal expansion coefficients between the reinforcing phase and the matrix. Therefore, the precipitation of nano-heterogeneous reinforced phases can significantly improve the comprehensive mechanical properties of aluminum matrix composites.
以上参数为最佳参数，可根据铝基复合材料组织及性能特点，合理选择、适当添加铝基复合材料增强相，并采用与前沿的选区激光熔化技术兼热处理工艺相结合的制备方法，可有效调整陶瓷增强相的含量、形貌、尺寸和分布状态，成功制备出成形质量好、综合性能优异的铝基复合材料。The above parameters are the best parameters. According to the microstructure and performance characteristics of the aluminum matrix composite material, the reinforcement phase of the aluminum matrix composite material can be reasonably selected and appropriately added, and the preparation method combined with the cutting-edge selective laser melting technology and heat treatment process can be used effectively. By adjusting the content, morphology, size and distribution of the ceramic reinforcing phase, an aluminum matrix composite material with good forming quality and excellent comprehensive properties was successfully prepared.
有益效果：Beneficial effects:
1、本发明中多壁碳纳米管/铝-硅-钪-锆-锰合金材料受到激光辐照发生熔化形成熔池时，较大的多壁碳纳米管部分与铝基体发生原位反应生成Al4C3增强相，而较小的陶瓷相完全反应。多壁碳纳米管的加入细化了晶粒尺寸，使得部分柱状晶趋于等轴化倾向，等轴晶区区间增大。在随后的非平衡凝固和快速冷却的过程中，铝合金中会固溶大量的Sc、Zr元素，经过后续的热处理，未反应的多壁碳纳米管完全转化为高强度的Al4C3纳米增强相，改善了增强相与基体间的界面结合，提高材料的成形质量，并作为异质形核点，促进Al3Sc、Al3Zr纳米增强相在其周围大量析出，最终提升铝基复合材料的综合力学性能。1. In the present invention, when the multi-walled carbon nanotube/aluminum-silicon-scandium-zirconium-manganese alloy material is melted by laser irradiation to form a molten pool, the larger part of the multi-walled carbon nanotube and the aluminum matrix react in situ to generate The Al4 C3 reinforces the phase, while the smaller ceramic phase reacts completely. The addition of multi-walled carbon nanotubes refines the grain size, which makes some columnar crystals tend to be equiaxed, and the equiaxed crystal region increases. During the subsequent non-equilibrium solidification and rapid cooling process, a large amount of Sc and Zr elements will be dissolved in the aluminum alloy. After subsequent heat treatment, the unreacted multi-walled carbon nanotubes are completely transformed into high-strength Al4 C3 nanometers. The reinforcement phase improves the interface between the reinforcement phase and the matrix, improves the forming quality of the material, and acts as a heterogeneous nucleation point to promote the precipitation of Al3 Sc and Al3 Zr nano-reinforced phases around it, and finally improve the aluminum matrix composite. Comprehensive mechanical properties of materials.
2本发明中以铝-硅-钪-锆-锰合金粉末以及纳米级多壁碳纳米管为原料，将粉末混合后置于QM系列行星式球磨机中进行球磨混粉，通过球磨工艺最终获得陶瓷增强相分布均匀、流动性能良好、激光吸收率高且适用于选区激光熔化成形的复合粉体，该工艺操作简单并节约成本。采用选区激光熔化技术兼热处理工艺制备纳米多相增强铝基复合材料不仅缩短生产周期，提高产品生产效率，而且几乎无需后续机加工处理即可成形具有复杂几何形状的零件。选区激光熔化成形时熔池的冷却速度极高，可达103～108K/s，有效避免传统加工工艺中纳米颗粒团聚、晶粒粗化特征，提高零件的力学性能。2 In the present invention, aluminum-silicon-scandium-zirconium-manganese alloy powder and nanoscale multi-walled carbon nanotubes are used as raw materials, the powders are mixed and then placed in a QM series planetary ball mill for ball milling and powder mixing, and ceramics are finally obtained through the ball milling process. The enhanced phase distribution is uniform, the flow performance is good, the laser absorption rate is high, and the composite powder is suitable for selective laser melting and forming, and the process is simple and cost-saving. The preparation of nano-multiphase reinforced aluminum matrix composites by selective laser melting technology and heat treatment process not only shortens the production cycle, improves product production efficiency, but also can form parts with complex geometric shapes almost without subsequent machining. The cooling rate of the molten pool during selective laser melting and forming is extremely high, reaching 103 to 108 K/s, which effectively avoids the agglomeration of nanoparticles and coarsening of grains in the traditional processing technology, and improves the mechanical properties of the parts.
3、本发明可通过改变激光功率、激光扫描速度来调整激光能量密度，随着粉床激光能量输入变化，激光与粉床作用形成的熔池热力学和动力学特性也发生改变，通过合理选取激光工艺参数，调整激光能量输入，减少球化效应、孔隙等冶金缺陷产生，获得高成形质量纳米多相增强铝-硅-钪-锆-锰复合材料。3. The present invention can adjust the laser energy density by changing the laser power and the laser scanning speed. With the change of the laser energy input of the powder bed, the thermodynamic and dynamic characteristics of the molten pool formed by the action of the laser and the powder bed also change. Process parameters, adjust the laser energy input, reduce the generation of metallurgical defects such as spheroidization effect and porosity, and obtain nano-multiphase reinforced aluminum-silicon-scandium-zirconium-manganese composite materials with high forming quality.
4、本发明通过改变时效工艺参数(时效温度、保温时间)来调控选区激光熔化技术成形纳米多相增强铝基复合材料中多相纳米增强相的析出与分布，改善增强相和基体之间的界面结合，获得高强度高承载纳米多相增强铝-硅-钪-锆-锰复合材料。4. The present invention regulates the precipitation and distribution of the multi-phase nano-reinforced phase in the nano-multi-phase reinforced aluminum matrix composite material formed by the selective laser melting technology by changing the aging process parameters (aging temperature, holding time), and improves the reinforced phase and the matrix. Interface bonding to obtain high-strength and high-load bearing nano-multiphase reinforced aluminum-silicon-scandium-zirconium-manganese composites.
附图说明Description of drawings
下面结合附图和具体实施方式对本发明做更进一步的具体说明，本发明的上述和/或其他方面的优点将会变得更加清楚。The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the above-mentioned and/or other aspects of the present invention will become clearer.
图1位实施例1制备的多壁碳纳米管/铝-硅-钪-锆-锰复合材料试样的光学图像。Figure 1 is an optical image of the multi-walled carbon nanotube/aluminum-silicon-scandium-zirconium-manganese composite sample prepared in Example 1.
图2为实施例1制备的多壁碳纳米管/铝-硅-钪-锆-锰复合材料试样中多相陶瓷分布示意图及其界面TEM照片。2 is a schematic diagram of the distribution of multi-phase ceramics in the multi-walled carbon nanotube/aluminum-silicon-scandium-zirconium-manganese composite sample prepared in Example 1 and its interface TEM photograph.
图3为实施例2制备的多壁碳纳米管/铝-硅-钪-锆-锰复合材料试样的光学图像。FIG. 3 is an optical image of the multi-walled carbon nanotube/aluminum-silicon-scandium-zirconium-manganese composite material sample prepared in Example 2. FIG.
图4为实施例3制备的多壁碳纳米管铝-硅-钪-锆-锰复合材料试样的光学图像。FIG. 4 is an optical image of the multi-walled carbon nanotube aluminum-silicon-scandium-zirconium-manganese composite material sample prepared in Example 3. FIG.
图5为对比例1制备的多壁碳纳米管/铝-硅-钪-锆-锰复合材料试样的光学图像。FIG. 5 is an optical image of the multi-walled carbon nanotube/aluminum-silicon-scandium-zirconium-manganese composite sample prepared in Comparative Example 1. FIG.
图6为对比例3制备的多壁碳纳米管铝-硅-钪-锆-锰复合材料试样的光学图像。FIG. 6 is an optical image of the multi-walled carbon nanotube aluminum-silicon-scandium-zirconium-manganese composite sample prepared in Comparative Example 3. FIG.
具体实施方式Detailed ways
根据下述实施例，可以更好地理解本发明。The present invention can be better understood from the following examples.
以下实施例中，所使用的铝-硅-钪-锆-锰合金粉末中硅含量为1.3wt.％，钪含量0.66wt.％，锆含量0.42wt.％，锰含量为0.49wt.％，余量为Al，平均粒径为38.8μm，纯度大于99.0％，粉末流动性70s/50g。In the following examples, the aluminum-silicon-scandium-zirconium-manganese alloy powder used has a silicon content of 1.3wt.%, a scandium content of 0.66wt.%, a zirconium content of 0.42wt.%, and a manganese content of 0.49wt.%, The balance is Al, the average particle size is 38.8 μm, the purity is more than 99.0%, and the powder flowability is 70s/50g.
所使用的多壁碳纳米管粉末平均外径为30nm，平均长度为30μm。The multi-walled carbon nanotube powder used had an average outer diameter of 30 nm and an average length of 30 μm.
实施例1Example 1
(1)将1.0wt.％多壁碳纳米管粉末(占复合材料总质量的百分比)与铝-硅-钪-锆-锰合金粉末混合，进行球磨混粉制备1.0wt.％多壁碳纳米管/铝-硅-钪-锆-锰复合粉体。采用QM系列行星式球磨机内进行球磨混粉操作，该过程采用陶瓷罐，球磨介质为直径6mm、8mm和10mm的陶瓷磨球。球磨工艺参数设定为：球料比为2:1，球磨转速为200rpm，球磨时间为6h。同时为防止球磨罐内温度过高，造成多壁碳纳米管纤维结构损伤，球磨时设备运行模式选用间隔式，即设备每运行15min后暂停空冷5min。该球磨过程要求在氩气保护下进行，以防止球磨过程中铝基粉末被氧化或污染。(1) Mix 1.0 wt.% multi-walled carbon nanotube powder (as a percentage of the total mass of the composite material) with aluminum-silicon-scandium-zirconium-manganese alloy powder, and perform ball milling to prepare 1.0 wt.% multi-walled carbon nanotubes Tube/aluminum-silicon-scandium-zirconium-manganese composite powder. The QM series planetary ball mill is used for ball milling and powder mixing operation. The process uses a ceramic tank, and the ball milling medium is ceramic grinding balls with diameters of 6mm, 8mm and 10mm. The ball milling process parameters are set as: the ratio of ball to material is 2:1, the ball milling speed is 200rpm, and the ball milling time is 6h. At the same time, in order to prevent the damage of the multi-wall carbon nanotube fiber structure due to the high temperature in the ball milling tank, the operation mode of the equipment during ball milling is the interval type, that is, the air cooling is suspended for 5 minutes after every 15 minutes of operation of the equipment. The ball milling process requires argon protection to prevent the aluminum-based powder from being oxidized or contaminated during the ball milling process.
(2)目标零件建模及切片处理(2) Modeling and slicing of target parts
在计算机中使用Soildworks软件建立目标零件的三维实体几何模型，然后利用Magics软件对三维实体模型进行分层切片和扫描路径规划，将三维实体离散成一系列二维数据，将此数据保存并导入选区激光熔化成形设备中。其中激光工艺参数设定为：激光功率为300W，激光扫描速度为600mm/s，扫描间距为60μm，铺粉厚度为30μm，采用分区岛状扫描策略，相邻层的激光扫描方向旋转角度为37°。Use Soildworks software in the computer to establish a 3D solid geometric model of the target part, and then use Magics software to perform layered slicing and scanning path planning for the 3D solid model, discretize the 3D solid into a series of 2D data, save this data and import it into the selection laser melting and forming equipment. The laser process parameters are set as follows: the laser power is 300W, the laser scanning speed is 600mm/s, the scanning spacing is 60μm, the powder thickness is 30μm, the partitioned island scanning strategy is adopted, and the rotation angle of the laser scanning direction of the adjacent layers is 37 μm. °.
(3)选区激光熔化成形过程(3) Selective laser melting forming process
将步骤(1)中制得的多壁碳纳米管/铝-硅-钪-锆-锰复合粉体用于选区激光熔化成形。采用SLM-150型选区激光熔化设备，该系统主要包括YLR-500型光纤激光器、激光成形室、自动铺粉系统、保护气氛装置、计算机控制电路系统以及冷却循环系统。在成形前将经喷砂处理的铝合金基板固定在选区激光熔化成形设备工作台上并进行调平，然后通过密封装置将成形腔密封、抽真空并通入氩气保护气氛(Ar纯度为99.999％，出口压力为30mbar)，保证成形室内的O2含量低于10ppm。典型选区激光熔化成形过程如下：(a)铺粉装置将待加工粉末均匀铺放在成形基板上，激光束根据预先设计好的扫描路径对切片区域逐行进行扫描，使粉层发生快速熔融-固化，从而获得零件的第一个二维平面；(b)计算机控制系统使成形基板下降一个粉层厚度，相反地，使供粉缸活塞上升一个粉层厚度，铺粉装置重新铺设一层待加工粉末，激光束根据切片信息完成第二粉末层扫描以获得零件的第二个二维平面；(c)重复(b)步骤，待加工粉体逐层成形直至零件加工完毕。The multi-walled carbon nanotube/aluminum-silicon-scandium-zirconium-manganese composite powder prepared in step (1) is used for selective laser melting forming. SLM-150 type selective laser melting equipment is used, the system mainly includes YLR-500 type fiber laser, laser forming chamber, automatic powder spreading system, protective atmosphere device, computer control circuit system and cooling circulation system. Before forming, the sandblasted aluminum alloy substrate is fixed on the table of the selective laser melting forming equipment and leveled, and then the forming cavity is sealed by a sealing device, evacuated and introduced into an argon protective atmosphere (the purity of Ar is 99.999 %, the outlet pressure is 30mbar), to ensure that theO2 content in the forming chamber is less than 10ppm. The typical selective laser melting forming process is as follows: (a) The powder spreading device evenly spreads the powder to be processed on the forming substrate, and the laser beam scans the slicing area line by line according to the pre-designed scanning path, so that the powder layer rapidly melts- Solidification, thereby obtaining the first two-dimensional plane of the part; (b) the computer control system lowers the forming substrate by one powder layer thickness, on the contrary, makes the piston of the powder supply cylinder rise one powder layer thickness, and the powder spreading device re-lays a layer to be prepared. To process the powder, the laser beam scans the second powder layer according to the slicing information to obtain the second two-dimensional plane of the part; (c) Step (b) is repeated, and the powder to be processed is formed layer by layer until the part is processed.
(4)待冷却后，将成形基板从设备内取出，利用线切割工艺将零件与基板分离，获得纳米多相增强铝基复合材料三维实体零件，后续经过325℃/6h时效处理，最终获得高强度高承载纳米多相增强铝基复合材料试样。(4) After cooling, the formed substrate is taken out from the equipment, and the parts are separated from the substrate by a wire cutting process to obtain a three-dimensional solid part of nano-multiphase reinforced aluminum matrix composite material. High-strength load-bearing nano-multiphase reinforced aluminum matrix composite samples.
按照标准金相试样制备方法对纳米多相增强铝基复合材料块体试样打磨、抛光及腐蚀处理。该选区激光熔化过程兼热处理工艺制备的高致密纳米多相增强铝-硅-钪-锆-锰复合材料试样无裂纹生成，纳米陶瓷增强颗粒均匀分布在基体中，其显微组织的光学图像，如图1所示。对实施例1制备的试样进行TEM分析，见图2。从图中可见，Al4C3纳米增强相均匀分布在基体中，且与基体间紧密结合，周围析出大量的Al3Sc、Al3Zr纳米颗粒，这说明Al4C3在铝合金基体中形成稳定的界面结构，减小了界面应力集中，提高了成形质量，并作为异质形核点，促进Al3Sc、Al3Zr纳米增强相在其周围大量析出，从而起到提升材料综合力学性能的作用。According to the standard metallographic sample preparation method, the nano-multiphase reinforced aluminum matrix composite bulk sample was ground, polished and etched. The high-density nano-heterogeneous reinforced aluminum-silicon-scandium-zirconium-manganese composite sample prepared by this selective laser melting process and heat treatment process has no cracks, and the nano-ceramic reinforcing particles are uniformly distributed in the matrix. The optical image of its microstructure ,As shown in Figure 1. TEM analysis was performed on the sample prepared in Example 1, as shown in FIG. 2 . It can be seen from the figure that the Al4 C3 nano-enhancing phase is uniformly distributed in the matrix, and is closely combined with the matrix, and a large number of Al3 Sc and Al3 Zr nanoparticles are precipitated around it, which indicates that Al4 C3 is in the aluminum alloy matrix. It forms a stable interface structure, reduces the interface stress concentration, improves the forming quality, and acts as a heterogeneous nucleation point to promote the precipitation of Al3 Sc and Al3 Zr nano-enhanced phases around it, thereby improving the comprehensive mechanics of the material. effect of performance.
将获得的纳米多相增强铝-硅-钪-锆-锰复合材料试样进行室温拉伸和纳米硬度测试，其拉伸强度和弹性模量分别可达562MPa和98GPa，相较于铝合金(铝合金的拉伸强度和弹性模量为517MPa和80GPa)分别提升了8.7％和22.5％，具有高强度与高承载性能于一体。The obtained nano-multiphase reinforced aluminum-silicon-scandium-zirconium-manganese composite samples were subjected to room temperature tensile and nano-hardness tests, and their tensile strength and elastic modulus could reach 562MPa and 98GPa, respectively. The tensile strength and elastic modulus of the aluminum alloy are 517MPa and 80GPa), which are increased by 8.7% and 22.5%, respectively, with high strength and high load-bearing performance.
实施例2Example 2
(1)将0.5wt.％多壁碳纳米管粉末(占复合材料总质量的百分比)与铝-硅-钪-锆-锰合金粉末混合，进行球磨混粉制备0.5wt.％多壁碳纳米管/铝-硅-钪-锆-锰复合粉体。采用QM系列行星式球磨机内进行球磨混粉操作，该过程采用陶瓷罐，球磨介质为直径6mm、8mm和10mm的陶瓷磨球。球磨工艺参数设定为：球料比为2:1，球磨转速为250rpm，球磨时间为5h。同时为防止球磨罐内温度过高，造成多壁碳纳米管纤维结构损伤，球磨时设备运行模式选用间隔式，即设备每运行15min后暂停空冷5min。该球磨过程要求在氩气保护下进行，以防止球磨过程中铝基粉末被氧化或污染。(1) Mix 0.5wt.% multi-walled carbon nanotube powder (as a percentage of the total mass of the composite material) with aluminum-silicon-scandium-zirconium-manganese alloy powder, and perform ball milling to prepare 0.5wt.% multi-walled carbon nanotubes Tube/aluminum-silicon-scandium-zirconium-manganese composite powder. The QM series planetary ball mill is used for ball milling and powder mixing operation. The process uses a ceramic tank, and the ball milling medium is ceramic grinding balls with diameters of 6mm, 8mm and 10mm. The parameters of the ball milling process are set as follows: the ball-to-material ratio is 2:1, the ball-milling speed is 250rpm, and the ball-milling time is 5h. At the same time, in order to prevent the damage of the multi-wall carbon nanotube fiber structure due to the high temperature in the ball milling tank, the operation mode of the equipment during ball milling is the interval type, that is, the air cooling is suspended for 5 minutes after every 15 minutes of operation of the equipment. The ball milling process requires argon protection to prevent the aluminum-based powder from being oxidized or contaminated during the ball milling process.
(2)目标零件建模及切片处理(2) Modeling and slicing of target parts
在计算机中使用Soildworks软件建立目标零件的三维实体几何模型，然后利用Magics软件对三维实体模型进行分层切片和扫描路径规划，将三维实体离散成一系列二维数据，将此数据保存并导入选区激光熔化成形设备中。其中激光工艺参数设定为：激光功率为350W，激光扫描速度为800mm/s，扫描间距为60μm，铺粉厚度为30μm，采用分区岛状扫描策略，相邻层的激光扫描方向旋转角度为37°。Use Soildworks software in the computer to establish a 3D solid geometric model of the target part, and then use Magics software to perform layered slicing and scanning path planning for the 3D solid model, discretize the 3D solid into a series of 2D data, save this data and import it into the selection laser melting and forming equipment. The laser process parameters are set as follows: the laser power is 350W, the laser scanning speed is 800mm/s, the scanning spacing is 60μm, the powder thickness is 30μm, the partitioned island scanning strategy is adopted, and the rotation angle of the laser scanning direction of the adjacent layers is 37 μm. °.
(3)选区激光熔化成形过程(3) Selective laser melting forming process
将步骤(1)中制得的MWCNTs/铝-硅-钪-锆-锰复合粉体用于选区激光熔化成形。采用SLM-150型选区激光熔化设备，该系统主要包括YLR-500型光纤激光器、激光成形室、自动铺粉系统、保护气氛装置、计算机控制电路系统以及冷却循环系统。在成形前将经喷砂处理的铝合金基板固定在选区激光熔化成形设备工作台上并进行调平，然后通过密封装置将成形腔密封、抽真空并通入氩气保护气氛(Ar纯度为99.999％，出口压力为30mbar)，保证成形室内的O2含量低于10ppm。典型选区激光熔化成形过程如下：(a)铺粉装置将待加工粉末均匀铺放在成形基板上，激光束根据预先设计好的扫描路径对切片区域逐行进行扫描，使粉层发生快速熔融-固化，从而获得零件的第一个二维平面；(b)计算机控制系统使成形基板下降一个粉层厚度，相反地，使供粉缸活塞上升一个粉层厚度，铺粉装置重新铺设一层待加工粉末，激光束根据切片信息完成第二粉末层扫描以获得零件的第二个二维平面；(c)重复(b)步骤，待加工粉体逐层成形直至零件加工完毕。The MWCNTs/aluminum-silicon-scandium-zirconium-manganese composite powder prepared in step (1) is used for selective laser melting forming. SLM-150 type selective laser melting equipment is used, the system mainly includes YLR-500 type fiber laser, laser forming chamber, automatic powder spreading system, protective atmosphere device, computer control circuit system and cooling circulation system. Before forming, the sandblasted aluminum alloy substrate is fixed on the table of the selective laser melting forming equipment and leveled, and then the forming cavity is sealed by a sealing device, evacuated and introduced into an argon protective atmosphere (the purity of Ar is 99.999 %, the outlet pressure is 30mbar), to ensure that theO2 content in the forming chamber is less than 10ppm. The typical selective laser melting forming process is as follows: (a) The powder spreading device evenly spreads the powder to be processed on the forming substrate, and the laser beam scans the slicing area line by line according to the pre-designed scanning path, so that the powder layer rapidly melts- Solidification, thereby obtaining the first two-dimensional plane of the part; (b) the computer control system lowers the forming substrate by one powder layer thickness, on the contrary, makes the piston of the powder supply cylinder rise one powder layer thickness, and the powder spreading device re-lays a layer to be prepared. To process the powder, the laser beam scans the second powder layer according to the slicing information to obtain the second two-dimensional plane of the part; (c) Step (b) is repeated, and the powder to be processed is formed layer by layer until the part is processed.
(4)待冷却后，将成形基板从设备内取出，利用线切割工艺将零件与基板分离，获得纳米多相增强铝基复合材料三维实体零件，后续经过350℃/5h时效处理，最终获得高强度高承载纳米多相增强铝基复合材料试样。(4) After cooling, the formed substrate is taken out from the equipment, and the parts are separated from the substrate by the wire cutting process to obtain a three-dimensional solid part of nano-multiphase reinforced aluminum matrix composite material. High-strength load-bearing nano-multiphase reinforced aluminum matrix composite samples.
按照标准金相试样制备方法对纳米多相增强铝基复合材料块体试样打磨、抛光及腐蚀处理。该选区激光熔化过程兼热处理工艺制备的高致密纳米多相增强铝-硅-钪-锆-锰复合材料试样无裂纹生成，Al4C3纳米增强相均匀分布在基体中，且与基体间紧密结合，周围析出的Al3Sc、Al3Zr纳米颗粒含量略有降低，其显微组织的光学图像，如图3所示。According to the standard metallographic sample preparation method, the nano-multiphase reinforced aluminum matrix composite bulk sample was ground, polished and etched. The high-density nano-multiphase reinforced aluminum-silicon-scandium-zirconium-manganese composite samples prepared by this selective laser melting process and heat treatment process have no cracks, and the Al4 C3 nano-reinforced phase is uniformly distributed in the matrix, and there is no gap between the Al 4 C 3 and the matrix. Closely combined, the content of Al3 Sc and Al3 Zr nanoparticles precipitated around is slightly reduced, and the optical image of the microstructure is shown in Figure 3.
将获得的纳米多相增强铝-硅-钪-锆-锰复合材料试样进行室温拉伸和纳米硬度测试，其拉伸强度和弹性模量分别可达545MPa和94GPa，相较于铝合金(铝合金的拉伸强度和弹性模量为517MPa和80GPa)分别提升了5.4％和17.5％，具有高强度与高承载性能于一体。The obtained nano-multiphase reinforced aluminum-silicon-scandium-zirconium-manganese composite samples were subjected to room temperature tensile and nano-hardness tests, and their tensile strength and elastic modulus could reach 545MPa and 94GPa, respectively, compared with aluminum alloy ( The tensile strength and elastic modulus of the aluminum alloy are 517MPa and 80GPa), which are increased by 5.4% and 17.5%, respectively, with high strength and high load-bearing performance.
实施例3Example 3
(1)将0.1wt.％多壁碳纳米管纤维粉末(占复合材料总质量的百分比)与铝-硅-钪-锆-锰合金粉末混合，进行球磨混粉制备0.1wt.％多壁碳纳米管/铝-硅-钪-锆-锰复合粉体。采用QM系列行星式球磨机内进行球磨混粉操作，该过程采用陶瓷罐，球磨介质为直径6mm、8mm和10mm的陶瓷磨球。球磨工艺参数设定为：球料比为2:1，球磨转速为300rpm，球磨时间为4h。同时为防止球磨罐内温度过高，造成多壁碳纳米管纤维结构损伤，球磨时设备运行模式选用间隔式，即设备每运行15min后暂停空冷5min。该球磨过程要求在氩气保护下进行，以防止球磨过程中铝基粉末被氧化或污染。(1) Mix 0.1 wt.% multi-wall carbon nanotube fiber powder (as a percentage of the total mass of the composite material) with aluminum-silicon-scandium-zirconium-manganese alloy powder, and perform ball milling to prepare 0.1 wt. % multi-wall carbon Nanotube/aluminum-silicon-scandium-zirconium-manganese composite powder. The QM series planetary ball mill is used for ball milling and powder mixing operation. The process uses a ceramic tank, and the ball milling medium is ceramic grinding balls with diameters of 6mm, 8mm and 10mm. The ball milling process parameters are set as: the ratio of ball to material is 2:1, the ball milling speed is 300rpm, and the ball milling time is 4h. At the same time, in order to prevent the damage of the multi-wall carbon nanotube fiber structure due to the high temperature in the ball milling tank, the operation mode of the equipment during ball milling is the interval type, that is, the air cooling is suspended for 5 minutes after every 15 minutes of operation of the equipment. The ball milling process requires argon protection to prevent the aluminum-based powder from being oxidized or contaminated during the ball milling process.
(2)目标零件建模及切片处理(2) Modeling and slicing of target parts
在计算机中使用Soildworks软件建立目标零件的三维实体几何模型，然后利用Magics软件对三维实体模型进行分层切片和扫描路径规划，将三维实体离散成一系列二维数据，将此数据保存并导入选区激光熔化成形设备中。其中激光工艺参数设定为：激光功率为400W，激光扫描速度为1000mm/s，扫描间距为60μm，铺粉厚度为30μm，采用分区岛状扫描策略，相邻层的激光扫描方向旋转角度为37°。Use Soildworks software in the computer to establish a 3D solid geometric model of the target part, and then use Magics software to perform layered slicing and scanning path planning for the 3D solid model, discretize the 3D solid into a series of 2D data, save this data and import it into the selection laser melting and forming equipment. The laser process parameters are set as follows: the laser power is 400W, the laser scanning speed is 1000mm/s, the scanning spacing is 60μm, the powder thickness is 30μm, the partitioned island scanning strategy is adopted, and the rotation angle of the laser scanning direction of the adjacent layers is 37 μm. °.
(3)选区激光熔化成形过程(3) Selective laser melting forming process
将步骤(1)中制得的MWCNTs/铝-硅-钪-锆-锰复合粉体用于选区激光熔化成形。采用SLM-150型选区激光熔化设备，该系统主要包括YLR-500型光纤激光器、激光成形室、自动铺粉系统、保护气氛装置、计算机控制电路系统以及冷却循环系统。在成形前将经喷砂处理的铝合金基板固定在选区激光熔化成形设备工作台上并进行调平，然后通过密封装置将成形腔密封、抽真空并通入氩气保护气氛(Ar纯度为99.999％，出口压力为30mbar)，保证成形室内的O2含量低于10ppm。典型选区激光熔化成形过程如下：(a)铺粉装置将待加工粉末均匀铺放在成形基板上，激光束根据预先设计好的扫描路径对切片区域逐行进行扫描，使粉层发生快速熔融-固化，从而获得零件的第一个二维平面；(b)计算机控制系统使成形基板下降一个粉层厚度，相反地，使供粉缸活塞上升一个粉层厚度，铺粉装置重新铺设一层待加工粉末，激光束根据切片信息完成第二粉末层扫描以获得零件的第二个二维平面；(c)重复(b)步骤，待加工粉体逐层成形直至零件加工完毕。The MWCNTs/aluminum-silicon-scandium-zirconium-manganese composite powder prepared in step (1) is used for selective laser melting forming. SLM-150 type selective laser melting equipment is used, the system mainly includes YLR-500 type fiber laser, laser forming chamber, automatic powder spreading system, protective atmosphere device, computer control circuit system and cooling circulation system. Before forming, the sandblasted aluminum alloy substrate is fixed on the table of the selective laser melting forming equipment and leveled, and then the forming cavity is sealed by a sealing device, evacuated and introduced into an argon protective atmosphere (the purity of Ar is 99.999 %, the outlet pressure is 30mbar), to ensure that theO2 content in the forming chamber is less than 10ppm. The typical selective laser melting forming process is as follows: (a) The powder spreading device evenly spreads the powder to be processed on the forming substrate, and the laser beam scans the slicing area line by line according to the pre-designed scanning path, so that the powder layer rapidly melts- Solidification, thereby obtaining the first two-dimensional plane of the part; (b) the computer control system lowers the forming substrate by one powder layer thickness, on the contrary, makes the piston of the powder supply cylinder rise one powder layer thickness, and the powder spreading device re-lays a layer to be prepared. To process the powder, the laser beam scans the second powder layer according to the slicing information to obtain the second two-dimensional plane of the part; (c) Step (b) is repeated, and the powder to be processed is formed layer by layer until the part is processed.
(4)待冷却后，将成形基板从设备内取出，利用线切割工艺将零件与基板分离，获得多相陶瓷增强铝基复合材料三维实体零件，后续经过375℃/4h时效处理，最终获得高强度高承载纳米多相增强铝基复合材料试样。(4) After cooling, the formed substrate is taken out from the equipment, and the parts are separated from the substrate by a wire cutting process to obtain a three-dimensional solid part of multi-phase ceramic reinforced aluminum matrix composite material. High-strength load-bearing nano-multiphase reinforced aluminum matrix composite samples.
按照标准金相试样制备方法对纳米多相增强铝基复合材料块体试样打磨、抛光及腐蚀处理。该选区激光熔化过程兼热处理工艺制备的高致密纳米多相增强铝-硅-钪-锆-锰复合材料试样无裂纹生成，Al4C3纳米增强相均匀分布在基体中，且与基体间紧密结合，周围析出的Al3Sc、Al3Zr纳米颗粒含量明显减少，其显微组织的光镜OM图像，如图4所示。According to the standard metallographic sample preparation method, the nano-multiphase reinforced aluminum matrix composite bulk sample was ground, polished and etched. The high-density nano-multiphase reinforced aluminum-silicon-scandium-zirconium-manganese composite samples prepared by this selective laser melting process and heat treatment process have no cracks, and the Al4 C3 nano-reinforced phase is uniformly distributed in the matrix, and there is no gap between the Al 4 C 3 and the matrix. Tightly combined, the content of Al3 Sc and Al3 Zr nanoparticles precipitated around is significantly reduced, and the optical microscope OM image of its microstructure is shown in Figure 4.
将获得的纳米多相增强铝-硅-钪-锆-锰复合材料试样进行室温拉伸和纳米硬度测试，其拉伸强度和弹性模量可达538MPa和91GPa，相较于铝合金(铝合金的拉伸强度和弹性模量为517MPa和80GPa)分别提升了4.1％和13.8％，具有高强度与高承载性能于一体。The obtained nano-multiphase reinforced aluminum-silicon-scandium-zirconium-manganese composite samples were subjected to room temperature tensile and nano-hardness tests, and their tensile strength and elastic modulus could reach 538MPa and 91GPa, compared with aluminum alloys (aluminum alloys). The tensile strength and elastic modulus of the alloy are 517MPa and 80GPa), which are increased by 4.1% and 13.8%, respectively, with high strength and high load-bearing performance.
对比例1Comparative Example 1
本对比例与实施例1步骤相同，区别在于步骤(1)中，未以MWCNTs粉末为增强相原料来球磨工艺制备复合粉体，而选用1.0wt.％Al4C3纳米陶瓷和铝-硅-钪-锆-锰粉末为原料，球磨制备复合粉体，并进行选区激光熔化成形，后续经过325℃/6h时效处理，其显微组织如图5所示。对比图1和图5可发现，对比例1直接添加Al4C3陶瓷制备纳米多相增强铝基复合材料显微组织中Al4C3纳米增强相分布不均匀，与基体界面结合力偏低，在激光成形样品中产生孔隙等冶金缺陷，降低铝基复合材料的成形质量，且周围析出的Al3Sc、Al3Zr纳米增强相颗粒较少。对比例1直接添加Al4C3陶瓷制备的纳米多相增强铝-硅-钪-锆-锰复合材料试样拉伸强度和弹性模量为491MPa和74GPa，相比较实施例1原位反应制备的纳米多相增强铝基复合材料，拉伸强度和弹性模量降低明显。This comparative example is the same as Example 1, except that in step (1), the MWCNTs powder is not used as the reinforcing phase raw material to prepare the composite powder by ball milling, but 1.0wt.% Al4 C3 nano-ceramic and aluminum-silicon are selected. - The scandium-zirconium-manganese powder was used as the raw material, and the composite powder was prepared by ball milling, and then subjected to selective laser melting and forming, followed by aging treatment at 325°C/6h, and its microstructure is shown in Figure 5. Comparing Fig. 1 and Fig. 5, it can be found that the Al4 C3 nano-reinforced phase distribution is uneven in the microstructure of the nano-multiphase reinforced aluminum matrix composite prepared by directly adding Al4 C3 ceramics in Comparative Example 1, and the bonding force with the matrix interface is low. , metallurgical defects such as pores are generated in the laser forming samples, which reduces the forming quality of the aluminum matrix composites, and there are less Al3 Sc and Al3 Zr nano-reinforced phase particles precipitated around them. Comparative Example 1 The tensile strength and elastic modulus of the nano-heterogeneous reinforced aluminum-silicon-scandium-zirconium-manganese composite material prepared by directly adding Al4 C3 ceramics are 491MPa and 74GPa, compared with the in-situ reaction preparation of Comparative Example 1 The tensile strength and elastic modulus of the nano-heterogeneous reinforced aluminum matrix composites decreased significantly.
对比例2Comparative Example 2
本对比例的具体步骤与实施例1基本一致，不同之处在于：本对比例的步骤(2)和(3)中，采用热等静压法对制备的MWCNTs/铝-硅-钪-锆-锰复合粉体进行成形。本对比例中，成形的多相增强铝-硅-钪-锆-锰复合材料试样中纳米陶瓷颗粒分布不均匀，陶瓷颗粒与基体间发生部分反应，且两者之间界面结合不佳，导致该试样的力学性能严重下降。成形试样的拉伸强度和弹性模量为307MPa和67GPa，相比较实施例1中纳米多相增强铝基复合材料，拉伸强度和弹性模量大大降低。The specific steps of this comparative example are basically the same as those of Example 1, the difference is that: in steps (2) and (3) of this comparative example, the prepared MWCNTs/aluminum-silicon-scandium-zirconium was subjected to a hot isostatic pressing method. - Manganese composite powder is shaped. In this comparative example, the distribution of nano-ceramic particles in the formed multi-phase reinforced aluminum-silicon-scandium-zirconium-manganese composite sample is uneven, and a partial reaction occurs between the ceramic particles and the matrix, and the interface between the two is not well bonded. As a result, the mechanical properties of the sample were seriously degraded. The tensile strength and elastic modulus of the formed samples are 307MPa and 67GPa. Compared with the nano-multiphase reinforced aluminum matrix composite material in Example 1, the tensile strength and elastic modulus are greatly reduced.
对比例3Comparative Example 3
本对比例的具体步骤与实施例1基本一致，不同之处在于：本对比例的步骤(1)中，将5.0wt.％多壁碳纳米管(合金材料总质量的百分比)与铝-硅-钪-锆-锰合金粉末混合，进行球磨混粉制备5.0wt.％MWCNTs/铝-硅-钪-锆-锰复合粉体。本对比例中，高含量的碳纳米管易发生团聚现象，在激光成形样品中产生大量的孔隙及裂纹等冶金缺陷，显著降低铝基复合材料的成形质量。同时，后续的热处理过程中生成大量团聚的Al4C3相与基体间界面结合不佳，并作为裂纹的萌发点，导致成形试样发生严重变形、开裂现象，大大降低了综合力学性能，其显微组织的光镜OM图像，如图6所示。相比较实施例1中纳米多相增强铝基复合材料，拉伸强度和弹性模量大大降低。The specific steps of this comparative example are basically the same as those of Example 1, except that: in step (1) of this comparative example, 5.0 wt. -Mix scandium-zirconium-manganese alloy powders, and perform ball milling to prepare 5.0wt.% MWCNTs/aluminum-silicon-scandium-zirconium-manganese composite powders. In this comparative example, the high content of carbon nanotubes is prone to agglomeration, resulting in a large number of metallurgical defects such as pores and cracks in the laser formed sample, which significantly reduces the forming quality of the aluminum matrix composite. At the same time, in the subsequent heat treatment process, a large number of agglomerated Al4 C3 phases are not well combined with the interface between the matrix and act as the initiation point of cracks, resulting in severe deformation and cracking of the formed samples, which greatly reduces the comprehensive mechanical properties. The light microscope OM image of the microstructure is shown in Figure 6. Compared with the nano-heterogeneous reinforced aluminum matrix composite material in Example 1, the tensile strength and elastic modulus are greatly reduced.
由实施例1和对比例1～3可知，选区激光熔化技术兼热处理工艺制备纳米多相增强铝基复合材料试样的裂纹明显减少，成形质量显著改善，纳米增强相均匀分散，拉伸强度和弹性模量维持在较高水平，具有高强度与高承载性能于一体，力学性能得到优化，相对于铝合金的拉伸强度和弹性模量分别提升了4.1％～8.7％和13.8％～22.5％。这主要归因于多壁碳纳米管的加入细化了晶粒尺寸，促进了选区激光熔化成形过程中Sc、Zr元素的大量固溶，后续的热处理过程使得未完全反应的多壁碳纳米管全部转化为强承载Al4C3纳米增强相，并与铝基体之间形成了紧密结合的界面，且促进了与铝基体形成良好共格界面关系的纳米增强相Al3Sc和Al3Zr在其周围的大量析出。同时，与基体紧密结合且均匀分散的强承载Al4C3纳米增强相有效约束了时效过程中基体的热膨胀行为，释放了增强相与基体间因热膨胀系数差异产生的高残余应力。因此，纳米多相增强铝基复合材料的拉伸强度和弹性模量显著提高。From Example 1 and Comparative Examples 1 to 3, it can be seen that the cracks of the nano-multiphase reinforced aluminum matrix composite samples prepared by the selective laser melting technology and heat treatment process are significantly reduced, the forming quality is significantly improved, the nano-reinforced phase is uniformly dispersed, and the tensile strength and The elastic modulus is maintained at a high level, with high strength and high load-bearing performance, and the mechanical properties are optimized. Compared with aluminum alloys, the tensile strength and elastic modulus are increased by 4.1% to 8.7% and 13.8% to 22.5%. . This is mainly due to the fact that the addition of MWCNTs refines the grain size and promotes a large amount of solid solution of Sc and Zr elements during the selective laser melting forming process. The subsequent heat treatment process makes the incompletely reacted MWCNTs. All of them are transformed into strong supporting Al4 C3 nano-enhanced phase, and form a tightly bonded interface with the aluminum matrix, and the nano-enhanced phases Al3 Sc and Al3 Zr that promote the formation of a good coherent interface relationship with the aluminum matrix are in the A lot of precipitation around it. At the same time, the strong support Al4 C3 nano-reinforced phase, which is tightly combined with the matrix and uniformly dispersed, effectively constrains the thermal expansion behavior of the matrix during the aging process, and releases the high residual stress caused by the difference in thermal expansion coefficient between the reinforcement phase and the matrix. Therefore, the tensile strength and elastic modulus of nano-heterophase reinforced aluminum matrix composites are significantly improved.
本发明提供了一种纳米多相增强铝基复合材料及其制备方法的思路及方法，具体实现该技术方案的方法和途径很多，以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。The present invention provides an idea and method for a nano-multiphase reinforced aluminum matrix composite material and a preparation method thereof. There are many specific methods and approaches for realizing the technical solution. The above are only the preferred embodiments of the present invention. It should be pointed out that for For those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can also be made, and these improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented by existing technologies.
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