CN107900336A - A kind of method of laser 3D printing Fe base non-crystalline alloy compound material components - Google Patents
A kind of method of laser 3D printing Fe base non-crystalline alloy compound material components Download PDFInfo
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
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- B22—CASTING; POWDER METALLURGY
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
- B22F12/10—Auxiliary heating means
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Abstract
Description
技术领域technical field
本发明涉及合金增材制造技术领域，更具体地，涉及一种激光3D打印Fe基非晶合金复合材料构件的方法。The invention relates to the technical field of alloy additive manufacturing, and more specifically, to a method for laser 3D printing Fe-based amorphous alloy composite components.
背景技术Background technique
非晶态金属集众多优异性能于一身，如高强度、高硬度、耐磨以及耐腐蚀等。这些优异的性能使其在航空航天、汽车船舶、装甲防护、精密仪器、电力、能源、电子、生物医学等领域都存在广泛的应用前景。在所有的非晶合金体系中，Fe基非晶合金由于其低廉的成本，一直备受工程领域的关注。然而，目前通常采用的铜模铸造法制备出的Fe基非晶合金的尺寸仅为厘米级，严重地制约其工程化应用。另外，由于Fe基非晶合金存在严重的室温脆性问题，其在室温下难以进行机械加工，所以难以获得精密复杂的非晶态金属构件。因此，颠覆传统以铸造为主的制造工艺，从而无尺寸限制地制备具有复杂形状的Fe基非晶合金构件，是突破Fe基非晶合金工程化应用瓶颈的关键。Amorphous metals combine many excellent properties, such as high strength, high hardness, wear resistance and corrosion resistance. These excellent properties make it have broad application prospects in aerospace, automobile and ship, armor protection, precision instruments, electric power, energy, electronics, biomedicine and other fields. Among all amorphous alloy systems, Fe-based amorphous alloys have attracted much attention in the engineering field due to their low cost. However, the size of Fe-based amorphous alloys prepared by the copper mold casting method commonly used at present is only centimeter-level, which seriously restricts its engineering application. In addition, due to the serious room temperature brittleness of Fe-based amorphous alloys, it is difficult to machine at room temperature, so it is difficult to obtain sophisticated and complex amorphous metal components. Therefore, subverting the traditional casting-based manufacturing process to prepare Fe-based amorphous alloy components with complex shapes without size restrictions is the key to breaking through the bottleneck of Fe-based amorphous alloy engineering application.
激光3D打印技术属于快速成形技术的一种，与传统的切削等机械加工技术不同，该技术是一种以数字模型文件为基础的先进制造技术，其具有选材范围广、材料利用率高、低成本、精度高、周期短等优势。由于激光3D打印技术是一种逐点离散熔覆沉积的成型方法，其每点所受激光加热面积较小，熔池的热量可以迅速向基体扩散；如果熔池的冷却速率高于所打印金属材料形成非晶态所需的临界冷却速率，则熔体在冷凝的过程中不发生晶化，即获得非晶态；逐层沉积则可制备具有复杂形状、无尺寸限制的非晶态金属构件。然而，现有的利用激光3D打印技术成型的Fe基非晶合金复合材料都存在明显的裂纹。裂纹的存在严重地降低了Fe基非晶合金复合材料的优异力学性能，因此，如何抑制裂纹，是采用激光3D打印技术成型Fe基非晶合金复合材料构件的关键。Laser 3D printing technology is a kind of rapid prototyping technology. Different from traditional machining technologies such as cutting, this technology is an advanced manufacturing technology based on digital model files. It has a wide range of material selection, high material utilization, and low cost. Cost, high precision, short cycle and other advantages. Since laser 3D printing technology is a point-by-point discrete cladding deposition molding method, the area heated by the laser at each point is small, and the heat of the molten pool can quickly spread to the substrate; if the cooling rate of the molten pool is higher than that of the printed metal The critical cooling rate required for the material to form an amorphous state, the melt does not crystallize during the condensation process, that is, an amorphous state is obtained; layer-by-layer deposition can prepare amorphous metal components with complex shapes and no size restrictions . However, the existing Fe-based amorphous alloy composites formed by laser 3D printing technology have obvious cracks. The existence of cracks seriously reduces the excellent mechanical properties of Fe-based amorphous alloy composites. Therefore, how to suppress cracks is the key to using laser 3D printing technology to form Fe-based amorphous alloy composite components.
发明内容Contents of the invention
本发明的目的在于克服现有技术存在的上述缺陷，提供一种激光3D打印Fe基非晶合金复合材料构件的方法，通过在Fe基非晶合金粉末中增加硬度比Fe基非晶合金粉末小的晶体金属粉末，使Fe基非晶合金在成型过程中产生的应力被较软晶体吸收，从而避免裂纹的产生。The purpose of the present invention is to overcome the above-mentioned defects existing in the prior art, and to provide a method for laser 3D printing of Fe-based amorphous alloy composite components, by increasing the hardness in Fe-based amorphous alloy powder which is smaller than that of Fe-based amorphous alloy powder The crystalline metal powder makes the stress generated by the Fe-based amorphous alloy during the forming process be absorbed by the softer crystal, thereby avoiding the generation of cracks.
为实现上述目的，本发明的技术方案如下：To achieve the above object, the technical scheme of the present invention is as follows:
一种激光3D打印Fe基非晶合金复合材料构件的方法，其特征在于，将粒径为1～500μm的Fe基非晶合金粉末和粒径为1～500μm、硬度比所述Fe基非晶合金粉末小的晶体金属粉末混合均匀，利用激光3D打印机在激光功率100W～2500W、扫描速度100mm/min～600mm/min、激光光斑直径1mm～6mm、搭接率为15％～50％、打印层厚0.005mm～2mm、打印环境氧浓度低于50ppm、基板预热温度0～800℃的条件下逐层打印Fe基非晶合金复合材料构件。A method for laser 3D printing Fe-based amorphous alloy composite material components, characterized in that Fe-based amorphous alloy powder with a particle size of 1-500 μm is mixed with Fe-based amorphous alloy powder with a particle size of 1-500 μm and a hardness higher than that of the Fe-based amorphous alloy Small alloy powder and crystal metal powder are mixed evenly. Using a laser 3D printer, the laser power is 100W-2500W, the scanning speed is 100mm/min-600mm/min, the laser spot diameter is 1mm-6mm, and the overlap rate is 15%-50%. Fe-based amorphous alloy composite components are printed layer by layer under the conditions of a thickness of 0.005 mm to 2 mm, an oxygen concentration of the printing environment lower than 50 ppm, and a substrate preheating temperature of 0 to 800 ° C.
进一步地，所述激光3D打印机为同轴送粉激光3D打印机，所述Fe基非晶合金粉末和所述晶体金属粉末分别放置在同轴送粉激光3D打印机的送粉器的两个送粉桶中。Further, the laser 3D printer is a coaxial powder-feeding laser 3D printer, and the Fe-based amorphous alloy powder and the crystalline metal powder are respectively placed in the two powder-feeding parts of the powder-feeding laser 3D printer. in the barrel.
进一步地，所述两个送粉桶的送粉率之比等于所述Fe基非晶合金粉末与所述晶体金属粉末的质量比，所述两个送粉桶的送粉率为0～30g/min。Further, the ratio of the powder feeding rate of the two powder feeding barrels is equal to the mass ratio of the Fe-based amorphous alloy powder to the crystalline metal powder, and the powder feeding rate of the two powder feeding barrels is 0-30g /min.
进一步地，还包括将逐层打印的Fe基非晶合金复合材料构件在惰性气体保护和温度300℃～800℃下退火，时间2h～12h。Further, it also includes annealing the layer-by-layer printed Fe-based amorphous alloy composite member under the protection of an inert gas at a temperature of 300° C. to 800° C. for 2 hours to 12 hours.
进一步地，所述晶体金属粉末为纯铁粉末、或316L不锈钢粉末、或304不锈钢粉末、或纯铜粉末、或铜合金粉末。Further, the crystalline metal powder is pure iron powder, or 316L stainless steel powder, or 304 stainless steel powder, or pure copper powder, or copper alloy powder.
从上述技术方案可以看出，本发明通过在Fe基非晶合金粉末中增加硬度比Fe基非晶合金粉末小的晶体金属粉末，使Fe基非晶合金在成型过程中产生的应力被较软晶体吸收，即使不使用退火步骤，仍能使得到的Fe基非晶合金复合材料构件组织致密可控、力学性能适配、具有较高的强度和较好的塑性。同时，本发明克服水淬法和铜模铸造法成型Fe基非晶合金复合材料尺寸较小和形状简单的缺点，解决了Fe基非晶合金复合材料难以机械加工的难题，且具有节省原料，效率高等优点，在航空航天、汽车船舶、装甲防护、精密仪器、电力、能源等领域都具有巨大的应用前景。As can be seen from the above-mentioned technical scheme, the present invention makes the stress produced in the forming process of the Fe-based amorphous alloy be softened by adding a crystalline metal powder whose hardness is smaller than that of the Fe-based amorphous alloy powder in the Fe-based amorphous alloy powder. Crystal absorption, even without an annealing step, can still make the obtained Fe-based amorphous alloy composite structure dense and controllable, with suitable mechanical properties, high strength and good plasticity. Simultaneously, the present invention overcomes the disadvantages of small size and simple shape of the Fe-based amorphous alloy composite material formed by the water quenching method and the copper mold casting method, solves the difficult problem that the Fe-based amorphous alloy composite material is difficult to machine, and has the advantages of saving raw materials, With the advantages of high efficiency, it has great application prospects in aerospace, automobile and ship, armor protection, precision instruments, electric power, energy and other fields.
附图说明Description of drawings
图1是实施例一得到的单层打印的Fe基非晶合金复合材料的宏观形貌图；Fig. 1 is the macroscopic topography figure of the Fe-based amorphous alloy composite material of single-layer printing that embodiment one obtains;
图2是实施例二得到的Fe基非晶合金复合材料的宏观形貌图。Fig. 2 is a macroscopic view of the Fe-based amorphous alloy composite material obtained in Example 2.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。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劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. example. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
本发明通过将粒径为1～500μm的Fe基非晶合金粉末和粒径为1～500μm、硬度比所述Fe基非晶合金粉末小的晶体金属粉末混合均匀，利用激光3D打印机在激光功率100W～2500W、扫描速度100mm/min～600mm/min、激光光斑直径1mm～6mm、搭接率为15％～50％、打印层厚0.005mm～2mm、打印环境氧浓度低于50ppm、基板预热温度0～800℃的条件下逐层打印Fe基非晶合金复合材料构件，将逐层打印的Fe基非晶合金复合材料构件在惰性气体保护和温度300℃～800℃下退火，时间2h～12h。硬度比所述Fe基非晶合金粉末小的晶体金属粉末在合金从熔融态到凝固态的过程中吸收了多余的应力，避免Fe基非晶合金在凝固过程中出现的能够产生裂纹的应力集中，从而避免裂纹产生，使Fe基非晶合金复合材料构件组织致密可控、力学性能适配、具有较高的强度和较好的塑性。In the present invention, the Fe-based amorphous alloy powder with a particle size of 1-500 μm and the crystalline metal powder with a particle size of 1-500 μm and a hardness smaller than the Fe-based amorphous alloy powder are evenly mixed, and a laser 3D printer is used at a laser power 100W～2500W, scanning speed 100mm/min～600mm/min, laser spot diameter 1mm～6mm, overlap rate 15%～50%, printing layer thickness 0.005mm～2mm, printing environment oxygen concentration lower than 50ppm, substrate preheating Print Fe-based amorphous alloy composite components layer by layer at a temperature of 0-800°C, and anneal the Fe-based amorphous alloy composite components printed layer by layer under the protection of an inert gas at a temperature of 300°C-800°C for 2 hours to 12h. The crystalline metal powder with a hardness smaller than that of the Fe-based amorphous alloy powder absorbs excess stress in the process of the alloy from the molten state to the solidified state, and avoids the stress concentration that can cause cracks in the Fe-based amorphous alloy during the solidification process , so as to avoid cracks, so that the structure of the Fe-based amorphous alloy composite component is dense and controllable, the mechanical properties are suitable, and it has high strength and good plasticity.
硬度比所述Fe基非晶合金粉末小的晶体金属粉末可以选择为纯铁粉末、或316L不锈钢粉末、或304不锈钢粉末、或纯铜粉末、或铜合金粉末等。The crystalline metal powder whose hardness is smaller than the Fe-based amorphous alloy powder can be selected as pure iron powder, or 316L stainless steel powder, or 304 stainless steel powder, or pure copper powder, or copper alloy powder.
为了避免Fe基非晶合金粉末和晶体金属粉末间由于密度相差较大产生的分层、混合不均匀的现象，进而导致激光加工点处合金粉末不均匀，影响最终的合金构件的质量，可以采用同轴送粉激光3D打印机，将Fe基非晶合金粉末和晶体金属粉末分别放置在同轴送粉激光3D打印机的送粉器的两个送粉桶中，通过真空或惰性气体送粉同时送粉，两种粉末在送粉过程中汇合并混合均匀，可以使到达激光加工点处的粉末具有很好的均匀性。通过调整两个送粉桶的送粉量，调整输送到激光加工点处的粉末中Fe基非晶合金粉末和晶体金属粉末的质量比。In order to avoid the phenomenon of delamination and uneven mixing between Fe-based amorphous alloy powder and crystalline metal powder due to the large density difference, which will lead to uneven alloy powder at the laser processing point and affect the quality of the final alloy component, you can use Coaxial powder feeding laser 3D printer, place Fe-based amorphous alloy powder and crystalline metal powder in the two powder feeding barrels of the powder feeding device of the coaxial powder feeding laser 3D printer respectively, and feed the powder simultaneously through vacuum or inert gas. Powder, the two powders are combined and mixed evenly during the powder feeding process, which can make the powder reaching the laser processing point have good uniformity. By adjusting the powder feeding volume of the two powder feeding barrels, the mass ratio of the Fe-based amorphous alloy powder and the crystalline metal powder in the powder delivered to the laser processing point is adjusted.
实施例一Embodiment one
采用同轴送粉激光3D打印机成型Fe37.5Cr27.5C12B13Mo10非晶合金构件。将粒径分别为1～500μm的的Fe37.5Cr27.5C12B13Mo10非晶合金粉末和304不锈钢粉末分别放置在同轴送粉激光3D打印机的送粉器的两个送粉桶内。The Fe 37.5 Cr 27.5 C 12 B 13 Mo 10 amorphous alloy component was formed by a coaxial powder feeding laser 3D printer. The Fe 37.5 Cr 27.5 C 12 B 13 Mo 10 amorphous alloy powder and 304 stainless steel powder with a particle size of 1-500 μm were respectively placed in the two powder feeding barrels of the powder feeder of the coaxial powder feeding laser 3D printer.
通过调整两个送粉桶的送粉量，调整输送到激光加工点处的粉末中Fe37.5Cr27.5C12B13Mo10非晶合金粉末和304不锈钢粉末的质量比。在本实施例中，Fe37.5Cr27.5C12B13Mo10非晶合金粉末和304不锈钢粉末的质量比为1:1。两个送粉桶的送粉率可以设定为0～30g/min。两个送粉桶的送粉率之比等于Fe基非晶合金粉末与304不锈钢粉末的质量比。By adjusting the powder feeding volume of the two powder feeding barrels, the mass ratio of Fe 37.5 Cr 27.5 C 12 B 13 Mo 10 amorphous alloy powder and 304 stainless steel powder in the powder delivered to the laser processing point is adjusted. In this embodiment, the mass ratio of Fe 37.5 Cr 27.5 C 12 B 13 Mo 10 amorphous alloy powder to 304 stainless steel powder is 1:1. The powder feeding rate of the two powder feeding barrels can be set from 0 to 30g/min. The ratio of the powder feeding rates of the two powder feeding barrels is equal to the mass ratio of the Fe-based amorphous alloy powder to the 304 stainless steel powder.
利用计算机构建三维实体模型，设置沿Z向生成每层厚度为0.5mm的层状模型以及各层扫描路径程序。A three-dimensional solid model is constructed using a computer, and a layered model with a thickness of 0.5 mm per layer and a program for scanning paths of each layer are set along the Z direction.
激光3D打印的工艺参数设定：激光功率1500W、扫描速度300mm/min、激光光斑直径4mm、搭接率为30％、打印层厚0.5mm、打印环境氧浓度低于50ppm、基板预热温度25℃。Laser 3D printing process parameter setting: laser power 1500W, scanning speed 300mm/min, laser spot diameter 4mm, overlap rate 30%, printing layer thickness 0.5mm, printing environment oxygen concentration lower than 50ppm, substrate preheating temperature 25 ℃.
启动打印程序，激光束按照预置的扫描路径完成第一层截面图形打印，激光打印头上升一打印层厚高度，开始第二层截面图形打印，上述过程循环进行，得到Fe基非晶合金复合材料构件。Start the printing program, the laser beam completes the printing of the cross-sectional graphics of the first layer according to the preset scanning path, the laser printing head rises to the height of the printing layer thickness, and starts printing the cross-sectional graphics of the second layer. The above process is repeated to obtain Fe-based amorphous alloy composite Material components.
图1是按照上述条件得到的单层打印的Fe基非晶合金复合材料的宏观形貌图。如图所示，所得构件表面质地均匀，没有明显的裂纹等缺陷。和现有技术相比，304不锈钢粉末的加入在未执行退火步骤时，未有明显的裂纹等缺陷产生，已经表现了优异的力学性能。Figure 1 is a macroscopic view of the Fe-based amorphous alloy composite material printed in a single layer according to the above conditions. As shown in the figure, the surface texture of the obtained component is uniform without obvious defects such as cracks. Compared with the prior art, when the annealing step is not performed, the addition of 304 stainless steel powder has no obvious defects such as cracks, and has already shown excellent mechanical properties.
实施例二Embodiment two
将粒径为1～500μm的Fe37.5Cr27.5C12B13Mo10非晶合金粉末和纯铜粉末分别放置在同轴送粉激光3D打印机送粉器的两个送粉桶内。The Fe 37.5 Cr 27.5 C 12 B 13 Mo 10 amorphous alloy powder and pure copper powder with a particle size of 1-500 μm were respectively placed in two powder feeding barrels of the coaxial powder feeding laser 3D printer powder feeder.
通过调整送粉桶的送粉量，调整输送到激光加工点处的粉末中Fe37.5Cr27.5C12B13Mo10非晶合金粉末和纯铜粉末的质量比为1:1。By adjusting the powder feeding volume of the powder feeding barrel, the mass ratio of Fe 37.5 Cr 27.5 C 12 B 13 Mo 10 amorphous alloy powder and pure copper powder in the powder delivered to the laser processing point is adjusted to be 1:1.
打印机基板为厚度为20mm，材质为45号钢。The substrate of the printer is 20mm thick and made of No. 45 steel.
利用导热硅胶将基板紧密粘贴到导热铜板上。Use heat-conducting silicone to stick the substrate tightly to the heat-conducting copper plate.
导热铜板内部接通温度为室温的循环流动水。The inside of the heat-conducting copper plate is connected with circulating water at room temperature.
利用计算机构建三维实体模型，设置沿Z向生成每层厚度为0.5mm的层状模型以及各层扫描路径程序。A three-dimensional solid model is constructed using a computer, and a layered model with a thickness of 0.5 mm per layer and a program for scanning paths of each layer are set along the Z direction.
激光3D打印的工艺参数：激光功率1500W，扫描速度300mm/min，激光光斑直径4mm，搭接率30％，打印环境氧浓度低于50ppm。Process parameters of laser 3D printing: laser power 1500W, scanning speed 300mm/min, laser spot diameter 4mm, overlap rate 30%, printing environment oxygen concentration lower than 50ppm.
启动打印程序，激光束按照预置的扫描路径完成第一层截面图形打印，激光打印头上升0.5mm，开始第二层截面图形打印，上述过程循环进行，最终得到Fe基非晶合金复合材料构件。Start the printing program, the laser beam completes the printing of the cross-sectional graphics of the first layer according to the preset scanning path, the laser printing head rises by 0.5mm, and starts printing the cross-sectional graphics of the second layer, the above process is repeated, and finally Fe-based amorphous alloy composite components are obtained .
将得到的Fe基非晶合金复合材料构件5移到加热炉中，炉内有N2气体保护，温度500℃，退火处理时间2h，完成Fe基非晶合金复合材料构件5的制备。The obtained Fe-based amorphous alloy composite component 5 was moved to a heating furnace with N 2 gas protection in the furnace, the temperature was 500°C, and the annealing treatment time was 2h, and the preparation of the Fe-based amorphous alloy composite component 5 was completed.
图2是按照上述条件得到的Fe基非晶合金复合材料的宏观形貌图。由此图可见，Fe基非晶合金复合材料构件表面质地均匀，没有明显的裂纹等缺陷。Fig. 2 is a macroscopic view of the Fe-based amorphous alloy composite material obtained according to the above conditions. It can be seen from this figure that the surface texture of the Fe-based amorphous alloy composite component is uniform, and there are no obvious defects such as cracks.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.
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