WO2022105529A1 - 具有高温持久低各向异性的成形件、成形方法及成形粉末 - Google Patents

具有高温持久低各向异性的成形件、成形方法及成形粉末 Download PDF

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WO2022105529A1
WO2022105529A1 PCT/CN2021/125368 CN2021125368W WO2022105529A1 WO 2022105529 A1 WO2022105529 A1 WO 2022105529A1 CN 2021125368 W CN2021125368 W CN 2021125368W WO 2022105529 A1 WO2022105529 A1 WO 2022105529A1
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forming
path
anisotropy
high temperature
forming method
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PCT/CN2021/125368
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English (en)
French (fr)
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侯慧鹏
雷力明
常斐
付俊
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中国航发上海商用航空发动机制造有限责任公司
中国航发商用航空发动机有限责任公司
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Priority to US18/001,531 priority Critical patent/US20230243022A1/en
Priority to EP21893677.1A priority patent/EP4257715A1/en
Publication of WO2022105529A1 publication Critical patent/WO2022105529A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • B22F1/0003—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • 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
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • 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
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/64—Treatment of workpieces or articles after build-up by thermal means
    • 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
    • B33Y10/00—Processes of additive manufacturing
    • 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
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • 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
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention relates to the field of additive manufacturing, in particular to a shaped part, a forming method and a forming powder with high temperature, durability and low anisotropy.
  • Nickel-based superalloys are widely used in the aerospace field.
  • the alloys are mainly composed of Ni, Co, Cr, W and other elements, and have strong oxidation resistance and corrosion resistance in high temperature environments.
  • Additive manufacturing technology is predicted to be one of the key technologies that may trigger the "third industrial revolution". Compared with traditional processing technology, it has the advantages of high material utilization, high design freedom, high forming accuracy and surface quality. So many advantages.
  • additive manufacturing can be divided into two forms based on powder bed and material synchronous feeding.
  • the main technical principle of powder bed additive manufacturing is: the three-dimensional digital model of the part to be processed is layer by layer.
  • the forming process relies on the movement of the molten pool to achieve from point to line, from line to surface, and from surface to body. Due to this special process, the microstructure of the formed material in different directions has different characteristics, which in turn leads to anisotropy of mechanical properties. Anisotropy is a distinguishing feature of additive manufacturing processes.
  • the part has no significant directionality for the direction of force (that is, the direction of force is isotropic)
  • the anisotropy of the part material is as small as possible, and the direction of weaker strength is avoided to limit the overall strength and life of the part .
  • different positions of the parts have complex spatial orientations relative to the substrate, and the parts are often subjected to complex loads under actual service conditions. If anisotropy exists significantly in parts with complex structures, it will lead to increased differences in mechanical properties at different structural positions, which in turn will limit the service life and greatly increase the difficulty of part design and verification. Therefore, reducing the anisotropy of mechanical properties of additive manufacturing parts is of great significance for improving the engineering application level of additive manufacturing processes.
  • the high temperature endurance performance is one of the most basic and most important properties of nickel-based superalloys. How to reduce the anisotropy of the high temperature endurance performance of parts has also become an urgent problem to be solved.
  • An object of the present invention is to provide a forming powder for additively manufacturing a high temperature durable low anisotropy shaped part, which can form a high temperature durable low anisotropy shaped part.
  • Another object of the present invention is to provide a method for forming a low-anisotropy forming part with high temperature durability, using the above-mentioned forming powder for forming.
  • Yet another object of the present invention is to provide a molded article with high temperature and durable low anisotropy, which is molded by the aforementioned molding method.
  • the forming powder for additive manufacturing of high-temperature durable low-anisotropy shaped parts for achieving the above-mentioned purpose, in terms of mass percentage, is composed of the following chemical components:
  • the content of C is: 0.05% ⁇ C ⁇ 0.09%; the content of Si is: 0.07% ⁇ Si ⁇ 0.15%; wherein, 0.33 ⁇ C/ Si ⁇ 0.8.
  • the shaped powder is produced by gas atomization or rotating electrode atomization.
  • the shaped powder has a powder particle size of 15 ⁇ m to 150 ⁇ m.
  • the forming part with high-temperature durable low anisotropy is formed by an additive manufacturing process, and is characterized in that:
  • the forming powder used in the additive manufacturing process is the above-mentioned forming powder used for additive manufacturing of high-temperature durable low-anisotropy forming parts.
  • the additive manufacturing process is a laser selective melting forming process.
  • the forming method further comprises:
  • the forming method further comprises:
  • the forming method further comprises:
  • a formed part with high temperature and durable low anisotropy is produced by using the above-mentioned forming method for a formed part with high temperature and durable low anisotropy.
  • the forming powder of the present invention further optimizes the content of chemical elements that have an important influence on the high temperature persistent anisotropy, and stipulates that in terms of mass percentage, 0.03% ⁇ C ⁇ 0.09%, 0.0375% ⁇ Si ⁇ 0.15%, 0% ⁇ B ⁇ 0.002%, the ratio of the mass percentage of element C and element Si is 0.2 ⁇ C/Si ⁇ 1.0.
  • mass percentages and ratios of C, Si, and B are controlled to be in the above ranges, the parts formed by using the above powders for additive manufacturing have lower permanent anisotropy at high temperature.
  • Figure 1 shows a schematic diagram of the longitudinal and transverse test specimens used for tensile testing
  • Figure 2 shows the horizontal-vertical comparison diagram of the high temperature durability performance of Examples 1-3 and Comparative Examples 1-3;
  • FIG. 3 is a comparison diagram of the difference obtained by subtracting the longitudinal high temperature endurance performance from the transverse high temperature endurance performance in the data measured in FIG. 2 .
  • Hastelloy X alloy in "Microstructure and Anisotropy of Tensile Properties of Hastelloy X Alloy by Selective Laser Melting” (Journal of Aeronautical Materials, 2018, 038(006): 50-56)
  • the composition was compared with the anisotropy of the forgings.
  • Xue Jiaqi et al. in "The Effect of Laser Selective Melting GH3536 Alloy Microstructure on Mechanical Properties” (Laser and Optoelectronics Progress, 2019, 56(14)), disclosed that under the conditions of additive process, different C and Si elements in different directions The strength of anisotropy shows that the influence of C element on anisotropy is significant, and the influence of Si element is not significant.
  • High temperature durability is an important mechanical property index of nickel-based superalloys in resisting high temperature and long-term load.
  • the present invention has anisotropy between the composition of the formed powder and the high temperature durability.
  • Anisotropy was further investigated to propose a shaping powder for additive manufacturing of low-anisotropy shaped parts with high temperature durability.
  • the high-temperature durability refers to the durability of the part when the temperature is > 500 degrees Celsius.
  • the nickel-based alloy forming powder is composed of the following chemical components in terms of mass percentage (wt-%):
  • the ratio of the mass percentage of element C and element Si satisfies 0.2 ⁇ C/Si ⁇ 1.0.
  • the influence of the content of carbon and silicon in the forming powder on the properties of the formed parts has been known.
  • the carbon content significantly affects the number of carbides in the grain and grain boundaries, and the grain size.
  • the effect of boundary carbide on grain size growth is more obvious.
  • the addition of silicon will form more crack sources, resulting in a decrease in tensile strength.
  • For boron it plays an important role in the mechanical properties of nickel-based superalloys, so nickel-based alloys usually contain trace amounts of boron.
  • the addition of boron element can improve the high temperature mechanical properties, improve the grain boundary morphology, and improve the processing properties of the alloy.
  • boron can enrich the re-grain boundary, fill the material vacancies and lattice defects, slow down the diffusion process of the grain boundary, and reduce the dislocation climbing speed, thereby strengthening the alloy.
  • Another theory is that boron on the grain boundary can inhibit the early aggregation of carbides, thereby delaying the generation of grain boundary cracks.
  • borides are easily formed at the grain boundaries, which may reduce the mechanical properties.
  • the nickel-based alloy forming powder of the present disclosure further optimizes the content of chemical elements that have an important influence on the high temperature persistent anisotropy, and stipulates that in terms of mass percentage, 0.03% ⁇ C ⁇ 0.09%, 0.0375% ⁇ Si ⁇ 0.15%, 0 % ⁇ B ⁇ 0.002%, the ratio of the mass percentage of element C and element Si is 0.2 ⁇ C/Si ⁇ 0.8.
  • mass percentages and ratios of C, Si, and B are controlled to be in the above ranges, the parts formed by using the above powders for additive manufacturing have lower permanent anisotropy at high temperature.
  • the high temperature durability anisotropy mentioned in this article is not directly related to the high temperature durability performance of the part, which refers to the anisotropy of the part durability performance of the formed part at a temperature > 500 degrees Celsius. That is, the difference between the longitudinal and transverse high temperature endurance performance tests of the parts in the same longitudinal direction as the forming direction and the transverse direction perpendicular to the forming direction. The following will further illustrate with specific embodiments.
  • the content of C is: 0.05% ⁇ C ⁇ 0.09%
  • the content of Si is: 0.07% ⁇ Si ⁇ 0.15%
  • the mass percentage of element C and element Si is The ratio of C/Si satisfies 0.33 ⁇ C/Si ⁇ 0.8, and the element content in the forming powder further satisfies the above three conditions at the same time, so as to further reduce the high-temperature persistent anisotropy of the parts formed after additive manufacturing by the above powder.
  • the nickel-based alloy powder is produced by gas atomization or rotary electrode atomization, so as to ensure that spherical powder with smooth surface can be obtained.
  • the nickel-based alloy powder can also be produced by other suitable methods.
  • the nickel-based alloy powder has a powder particle size of 15 ⁇ m to 150 ⁇ m. In some embodiments, different particle size ranges are selected according to different types of additive manufacturing processes.
  • Another aspect of the present invention provides a method for forming a shaped part with high temperature durability and low anisotropy, which adopts the nickel-based alloy powder as in one or more of the foregoing embodiments, and is formed by an additive manufacturing process with high temperature durability and low anisotropy.
  • Anisotropic shaped parts which adopts the nickel-based alloy powder as in one or more of the foregoing embodiments, and is formed by an additive manufacturing process with high temperature durability and low anisotropy.
  • the additive manufacturing process is a selective laser melting process (SLM).
  • SLM selective laser melting process
  • the additive manufacturing process may also be a laser melting deposition process (LMD).
  • the forming part formed by additive manufacturing is a blank part, and the forming method further includes performing stress relief annealing treatment on the forming part to further reduce its high temperature persistent anisotropy.
  • the forming part further includes performing wire cutting processing on the forming part to remove burrs on the surface of the part and further improve the forming quality of the outer surface of the part.
  • the forming part is further subjected to hot isostatic pressing, so as to further reduce the difference in the transverse and longitudinal structure of the part, thereby reducing its high temperature persistent anisotropy .
  • Yet another method of the present invention is to provide a high temperature durable low anisotropy shaped part produced by one or more of the aforementioned forming methods.
  • the following examples further illustrate that the nickel-based alloy powder-formed parts have lower high temperature persistent anisotropy.
  • Table 1 shows the chemical element compositions (in mass percent) of Examples 1-4 and Comparative Examples 1-3:
  • the above-mentioned powders of Examples 1-4 and Comparative Examples 1-3 were formed by laser selective melting using EOS M280 equipment.
  • the forming parameters are as follows: the layer thickness is 20 ⁇ m, the laser scanning power is 180 W, and the rotation angle between layers is 67° (which can avoid the generation of lateral anisotropy).
  • a longitudinal sample 1 and a transverse sample 2 as shown in FIG. 1 were formed for Examples 1-4 and Comparative Examples 1-3, respectively. Among them, both the longitudinal sample 1 and the transverse sample 2 are formed in the forming direction a.
  • the longitudinal sample 1 is subjected to a near-high temperature durability performance test in the first direction y that is the same as the forming direction a
  • the transverse sample 2 is subjected to a near-high temperature durability performance test in the second direction x perpendicular to the forming direction a
  • Figure 2 shows the horizontal-longitudinal comparison of the high temperature endurance strength of Examples 1-4 and Comparative Examples 1-3
  • Figure 3 is the difference obtained by subtracting the longitudinal high temperature endurance performance from the transverse high temperature endurance performance in the data measured in Figure 2 .
  • Example 1 of the formed part obtained by forming the formed powder provided by the present invention the transverse high temperature durability (average value of three groups) at a temperature of 815° C. and a tensile force of 105 MPa is 23.2 h, the longitudinal high temperature endurance life (average value of three groups) is 24.6h, and the difference between the longitudinal high temperature endurance life and the transverse high temperature endurance life is 1.4h.
  • the transverse high temperature endurance performance (average value of three groups) of Example 2 at a temperature of 815°C and a tensile force of 105MPa is 38.6h
  • the longitudinal high temperature endurance life (average value of three groups) is 37.9h
  • the longitudinal high temperature endurance life and the transverse high temperature endurance life The difference between them is -0.7h.
  • the transverse high temperature endurance performance (average value of three groups) of Example 3 at a temperature of 815°C and a tensile force of 105MPa is 21.7h
  • the longitudinal high temperature endurance life (average value of three groups) is 23.1h
  • the longitudinal high temperature endurance life and the transverse high temperature endurance life The difference between them is 1.4h.
  • the transverse high temperature endurance performance (average value of three groups) of Example 4 at a temperature of 815°C and a tensile force of 105MPa is 23.1h
  • the longitudinal high temperature endurance life (average value of three groups) is 25.4h
  • the longitudinal high temperature endurance life and the transverse high temperature endurance life The difference between them is 2.3h.
  • the transverse high temperature endurance performance (average of three groups) of Comparative Example 2 at a temperature of 815 ° C and a tensile force of 105 MPa is 33.0h
  • the longitudinal high temperature endurance (average of three groups) is 91.9h
  • the longitudinal high temperature endurance life and the transverse high temperature endurance life The difference between them is 58.9h.
  • the transverse high temperature endurance performance (average value of three groups) of Comparative Example 3 at a temperature of 815°C and a tensile force of 105MPa is 29.9h
  • the longitudinal high temperature endurance life (average value of three groups) is 37.0h
  • the longitudinal high temperature endurance life and the transverse high temperature endurance life The difference between them is 7.1h.
  • the formed parts formed by the forming powder provided by the present invention have a significantly reduced difference in the transverse and longitudinal durability life at high temperature, and the anisotropy of the high temperature durability performance has been significantly reduced. Parts that have significant directionality and are used at high temperatures.

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Abstract

一种用于增材制造具有高温持久低各向异性成形件的成形粉末、具有高温持久低各向异性的成形件以及成形件的成形方法。用于增材制造具有高温持久低各向异性成形件的成形粉末，以质量百分比计，由以下化学成分组成：0.03%≤C≤0.09%、20.50%≤Cr≤23.00%、0.50≤Co≤2.50%、8.00%≤Mo≤10.00%、0.20 %≤W≤1.00%、17.00%≤Fe≤20.00%、0%<B<0.002%、0%≤Mn≤1.00%、0.0375%≤Si≤0.15%、0%≤O≤0.02%、0%≤N≤0.015 %、余量的Ni以及不可避免的杂质；其中，0.2≤C/Si≤1.0。

Description

具有高温持久低各向异性的成形件、成形方法及成形粉末 技术领域
本发明涉及增材制造领域，尤其涉及一种具有高温持久低各向异性的成形件、成形方法及成形粉末。
背景技术
镍基高温合金在航空航天领域应用广泛，合金主要成为为Ni、Co、Cr、W等元素，在高温环境中拥有较强的抗氧化能力和耐腐蚀性。增材制造(Additive Manufacturing)技术被预测为可能引发“第三次工业革命”的关键技术之一，相比于传统加工工艺，具有材料利用率高、设计自由度高、成形精度高、表面质量好等多重优势。根据原材料的送给形式不同，增材制造可分为基于粉末床和材料同步送进两种形式，其中粉末床式增材制造的主要技术原理为：将待加工的零件三维数字模型进行逐层分割，输入到成形设备中；将基板固定在成形平台上，并进行调平，利用铺粉机构(通常为刮板或粉辊)进行单层铺粉，利用一束或多束激光/电子束，对铺放好的单层粉末进行选区熔化，实现由点到线，由线到面的成形过程；待一层成形完后成形平台下降一定高度，进行下一层铺粉及选区熔化成形，最终实现了由面到体的成形过程，由此获得最终零件，特别适合于航空航天等高附加值行业。
由于增材制造技术成形过程依靠熔池的移动实现由点到线、由线到面、由面到体。由于这一特殊的过程，导致了在不同方向上成形材料的显微组织具有不同特征，进而导致了力学性能的各向异性。各向异性是增材制造工艺显著特征。
当零件对于受力方向不存在显著的方向性时(即受力方向为各向同性)，则希望零件材料的各向异性越小越好，避免强度较弱的方向限制零件整体的强度和寿命。特别是在利用增材制造成形具有异形复杂薄壁结构零件时，零件不同位置相对于基板具有复杂的空间取向，零件在实际服役条件下往往会受到复杂的载荷作用。如果各向异性显著存在于具有复杂结构的零件当中，会导致力学性能在不同结构位置的差异增大，进而导致了服役寿命受到限制，且零件设计和考核验证 难度也大幅增加。因此，降低增材制造制件的力学性能各向异性对于提升增材制造工艺的工程化应用水平具有重要的意义。
其中，高温持久性能是镍基高温合金最基础最为重要的性能之一，如何降低零件高温持久性能的各向异性也成为目前亟需解决的问题。
发明内容
本发明的一个目的在于提供一种用于增材制造具有高温持久低各向异性成形件的成形粉末，能够成形具有高温持久低各向异性的成形件。
本发明的另一个目的在于提供一种具有高温持久低各向异性成形件的成形方法，采用前述成形粉末进行成形。
本发明的又一个目的在于提供一种具有高温持久低各向异性的成形件，采用前述成形方法进行成形。
为实现前述一个目的的用于增材制造具有高温持久低各向异性成形件的成形粉末，以质量百分比计，由以下化学成分组成：
0.03％≤C≤0.09％、20.50％≤Cr≤23.00％、0.50≤Co≤2.50％、8.00％≤Mo≤10.00％、0.20％≤W≤1.00％、17.00％≤Fe≤20.00％、0％＜B＜0.002％、0％≤Mn≤1.00％、0.0375％≤Si≤0.15％、0％≤O≤0.02％、0％≤N≤0.015％、余量的Ni以及不可避免的杂质；
其中，0.2≤C/Si≤1.0。
在一个或多个实施方式中，以质量百分比计：所述C的含量为：0.05％≤C≤0.09％；所述Si的含量为：0.07％≤Si≤0.15％；其中，0.33≤C/Si≤0.8。
在一个或多个实施方式中，所述成形粉末通过气雾化或旋转电极雾化制成。
在一个或多个实施方式中，所述成形粉末的粉末粒度大小为15μm至150μm。
为实现前述另一目的的具有高温持久低各向异性成形件的成形方法，通过增材制造工艺成形所述具有高温持久低各向异性的成形件，其特征在于：
所述增材制造工艺采用的成形粉末为如前所述的用于增材制造具有高温持久低各向异性成形件的成形粉末。
在一个或多个实施方式中，所述增材制造工艺为激光选区熔化成形工艺。
在一个或多个实施方式中，所述成形方法还包括：
对成形件进行去应力退火处理。
在一个或多个实施方式中，在所述去应力退火处理后，所述成形方法还包括：
对成形件进行线切割处理。
在一个或多个实施方式中，在所述线切割处理后，所述成形方法还包括：
对成形件进行热等静压处理。
为实现前述又一目的的具有高温持久低各向异性的成形件，采用如前所述的具有高温持久低各向异性成形件的成形方法制成。
本发明的进步效果包括以下之一或组合：
本发明的成形粉末进一步优化了对高温持久各向异性起重要影响的化学元素成分含量，规定了以质量百分比计，0.03％≤C≤0.09％，0.0375％≤Si≤0.15％，0％＜B＜0.002％，元素C以及元素Si质量百分数的比值为0.2≤C/Si≤1.0。在控制C、Si以及B的质量百分比以及比值分别在于上述区间时，采用上述粉末进行增材制造后所成形的零件具有较低的高温持久各向异性。
附图概述
本发明的具体特征、性能由以下的实施例及其附图进一步给出。
图1示出了用于进行拉伸试验用的纵向试样以及横向试样的示意图；
图2示出了实施例1-3以及对照例1-3的高温持久性能横-纵向对比图；
图3为图2中所测数据中纵向高温持久性能减去横向高温持久性能所得到的差值对比图。
本发明的最佳实施方式
本申请使用了特定词语来描述本申请的实施例，如“一个实施例”、“一实施例”、和/或“一些实施例”意指与本申请至少一个实施例相关的某一特征、结构或特点。因此，应强调并注意的是，本说明书中在不同位置两次或多次提及的“一实施例”或“一个实施例”并不一定是指同一实施例。此外，本申请的一个或多个实施例中的某些特征、结构或特点可以进行适当的组合。另外，使用“第一”、“第二”等词语来限定零部件，仅仅是为了便于对相应零部件进行区别，如没有另行声明，上述词语并没有特殊含义，因此也不能理解为对本申请保护范围的限制。
现有文献中已有对于成形粉末成分对于增材制造成形件的各向成形性能影响的讨论。如魏菁等人在《Hastelloy-X粉末成分对激光选区熔化成形各向成形性能的影响》(中国激光，2018，045(012)：135-141)对比了使用粒度为15～45μm的两个批次Hastelloy-X金属粉末的各向异性，其中公开了C、Si两个元素对各向异性的影响。张永志等人在《激光选区熔化Hastelloy X合金的显微组织与拉伸性能的各向异性》(航空材料学报，2018，038(006)：50-56)中，公布了一种Hastelloy X合金的成分，并和锻件的各向异性进行了对比。薛珈琪等人在《激光选区熔化GH3536合金组织对力学性能的影响》(激光与光电子学进展，2019，56(14))中，公开了在增材工艺条件下，不同C、Si元素的各向异性强弱，确定了C元素对各向异性的影响显著，Si元素影响不显著。另有多项镍基合金相关专利，通过控制元素成分达到降低裂纹密度，改善裂纹敏感性。在公开号为CN105828983A的专利文献中，公开一种降低裂纹密度的镍基高温合金。在公开号为CN106513660A的专利文献中公开了一种镍基合金成分，通过控制多种元素的含量：20.5-23.0Cr、17.0-20.0Fe、8.0-10.0Mo、0.50-2.50Co、0.20-1.00W、0.04-0.10C、0-0.5Si、0-0.5Mn、0-0.008B，以及元素间含量比值C/B＞5，提升了高温拉伸塑性，降低了裂纹敏感性。在公开号为US20180073106A的专利文献中确定了8.0-8.5Cr，9.0-9.5Co，0.4-0.6Mo，9.3-9.7W，2.9-3.6Ta，4.9-5.6Al，0.2-1.0Ti等元素，在不牺牲强度的情况下，减少裂纹倾向。在公开号为CN107486555A的专利文献中公开一种镍基合金C/Hf＞1.55，0.01％＜C＜0.2％，起到降低裂纹敏感性的目的。
高温持久是镍基高温合金在抵抗高温长时载荷的重要力学性能指标，为进一步优化降低增材制造成形镍基合金高温持久性能的各向异性，本发明对成形粉末的成分与高温持久各向异性进行了进一步研究，提出了一种用于增材制造具有高温持久低各向异性成形件的成形粉末。其中，高温持久性能是指零件在温度为＞500摄氏度时的持久性能。
本镍基合金成形粉末以质量百分比(wt-％)计，由以下化学成分组成：
0.03％≤C≤0.09％、20.50％≤Cr≤23.00％、0.50≤Co≤2.50％、8.00％≤Mo≤10.00％、0.20％≤W≤1.00％、17.00％≤Fe≤20.00％、0％＜B＜0.002％、0％≤Mn≤1.00％、0.0375％≤Si≤0.15％、0％≤O≤0.02％、0％≤N≤0.015％、余 量的Ni以及不可避免的杂质；
其中，元素C以及元素Si质量百分数的比值满足0.2≤C/Si≤1.0。
现有技术中已有对于碳元素以及硅元素在成形粉末中的含量对于成形件性能的影响，其中，如背景技术文献中所公开的碳含量显著影响晶内和晶界的碳化物数量，晶界碳化物对晶粒尺寸长大的抑制作用更明显。而添加硅元素会形成更多的裂纹源，导致拉伸强度降低。对于硼元素，对于镍基高温合金的力学性能发挥重要作用，因此通常镍基合金都要含有微量的硼元素。加入硼元素可以改善高温力学性能，改善晶界形态，提高合金的加工性能。关于硼元素的强化机理，一种理论研究认为，硼元素可以富集再晶界，填满材料空位和晶格缺陷，减慢晶界的扩散过程，降低位错攀移速度，从而强化合金。另外一种理论认为晶界上的硼元素可以抑制碳化物的早期聚集，从而延缓晶界裂纹产生。但加入过多硼元素时，容易在晶界形成硼化物，可能降低力学性能。
虽然现有技术中已有对于碳元素、硅元素以及硼元素在成形粉末中含量对于成形件中裂纹的生成机理以及零件的拉伸强度之间影响的讨论，然而现有技术中缺乏对于高温持久各向异性起重要影响的化学元素的研究。
本公开的镍基合金成形粉末进一步优化了对高温持久各向异性起重要影响的化学元素成分含量，规定了以质量百分比计，0.03％≤C≤0.09％，0.0375％≤Si≤0.15％，0％＜B＜0.002％，元素C以及元素Si质量百分数的比值为0.2≤C/Si≤0.8。在控制C、Si以及B的质量百分比以及比值分别在于上述区间时，采用上述粉末进行增材制造后所成形的零件具有较低的高温持久各向异性。
可以理解的是，本文中提及的高温持久各向异性，与零件高温持久性能的高低并无直接关联，其是指成形件在温度＞500摄氏度下，零件持久性能的各向异性。即对零件以与成形方向相同的纵向以及与成形方向垂直的横向，分别对零件进行纵向-横向高温持久性能测试后得到的差值。后文中将以具体的实施例来进一步阐述。
进一步地，在一个优选的实施方式中，以质量百分比计，C的含量为：0.05％≤C≤0.09％，Si的含量为：0.07％≤Si≤0.15％，同时元素C以及元素Si质量百分数的比值满足0.33≤C/Si≤0.8，成形粉末中的元素含量进一步同时满足以上三个 条件，以进一步降低通过上述粉末进行增材制造后所成形的零件的高温持久各向异性。
在本镍基合金粉末的一个或多个实施方式中，镍基合金粉末是通过气雾化或旋转电极雾化制成，从而保证能够得到表面光滑的球形粉末。在其他一些实施方式中，镍基合金粉末也可以采用其他合适的方法制成。
在本镍基合金粉末的一个或多个实施方式中，镍基合金粉末的粉末粒度大小为15μm至150μm。在一些实施方式中，是根据不同的增材制造工艺种类选择不同的粒度范围。
本发明的另一个方面提供了一种具有高温持久低各向异性成形件的成形方法，其采用如前述一个或多个实施方式中的镍基合金粉末，通过增材制造工艺成形具有高温持久低各向异性的成形件。
在本成形方法的一个实施方式中，增材制造工艺为激光选区熔化成形工艺(SLM)。其中，在一些不同的实施方式中，增材制造工艺也可以是如激光熔化沉积工艺(LMD)。
在本成形方法的一个实施方式中，通过增材制造成形的成形件为毛坯件，本成形方法还包括对成形件进行去应力退火处理，以进一步降低其高温持久各向异性。
在本成形方法的一个实施方式中，在对成形件进行去应力退火处理后，还包括对成形件进行线切割处理，以去除零件表面毛刺，对零件外表面的成形质量进行进一步提升。
在本成形方法的一个实施方式中，在对成形件进行线切割处理后，还包括对成形件进行热等静压处理，以进一步降低零件的横纵向组织差异，从而降低其高温持久各向异性。
本发明的又一个方法在于提供了一种具有高温持久低各向异性的成形件，其通过如前所述一个或多个试试方式中的成形方法制成。
如下通过实施例进一步阐述本镍基合金粉末成形的零件具有较低的高温持久各向异性。
实施例：
本实施例中，设置了4组实施例以及3组对照例，其中实施例1-4的成形粉末采用本镍基合金粉末，其中的实施例1-3采用前述优选实施方式中的镍基合金粉末，对照例1中C元素的质量百分数以及C/S、对照例2中Si元素的质量百分数以及C/S、对照例3中B元素的质量百分数以及C/S分别超出本发明所述元素范围。
表一中示出了实施例1-4以及对照例1-3的化学元素组成(以质量百分比计)：
元素 实施例1 对照例1 实施例2 对照例2 实施例3 对照例3 实施例4
C 0.065 0.12 0.064 0.05 0.055 0.082 0.055
Cr 21.582 21.72 21.266 21.35 21.338 21.55 21.31
Co 1.577 1.45 1.561 1.58 1.522 1.64 1.51
Mo 8.983 8.85 9.325 9.15 9.114 9.11 9.07
W 0.653 0.58 0.808 0.62 0.584 0.62 0.59
Fe 18.785 18.51 18.606 18.57 18.648 18.53 18.65
B 0.001 ＜0.001 0.002 ＜0.002 0.001 0.003 0.001
Mn 0.033 0.012 0.011 0.006 0.015 0.014 0.015
Si 0.127 0.059 0.112 0.37 0.074 0.075 0.056
O 0.008 0.01 0.009 0.02 0.01 0.02 0.009
N 0.006 0.006 0.006 0.01 0.007 0.01 0.007
C/Si 0.51 2.03 0.57 0.14 0.74 1.09 0.996
Ni 余量 余量 余量 余量 余量 余量 余量
表一
对上述实施例1-4以及对照例1-3粉末采用EOS M280设备进行激光选区熔化成形。成形参数为：层厚20μm，激光扫描功率180W，层间旋转角度为67°(可避免横向各向异性产生)。分别对实施例1-4以及对照例1-3成形如图1中所示出的纵向试样1以及横向试样2。其中，纵向试样1以及横向试样2均以成形方向a进行成形。
成形过程结束后进行后处理，依次完成去应力退火、线切割、热等静压步骤，按照标准开展室温高温持久性能测试。具体地，对纵向试样1进行以与成形方向a相同的第一方向y近高温持久性能测试，对横向试样2进行以与成形方向a垂直的第二方向x近高温持久性能测试，如图2示出了实施例1-4以及对照例1-3的高 温持久强度横-纵向对比，图3为图2中所测数据中横向高温持久性能减去纵向高温持久性能所得到的差值。
具体地，参照图2以及图3可得，通过本发明提供的成形粉末成形得到的成形件实施例1，在温度815℃、拉力为105MPa下的横向高温持久性能(三组平均值)为23.2h，纵向高温持久寿命(三组平均值)为24.6h，纵向高温持久寿命与横向高温持久寿命之间的差值为1.4h。
实施例2在温度815℃、拉力为105MPa下的横向高温持久性能(三组平均值)为38.6h，纵向高温持久寿命(三组平均值)为37.9h，纵向高温持久寿命与横向高温持久寿命之间的差值为-0.7h。
实施例3在温度815℃、拉力为105MPa下的横向高温持久性能(三组平均值)为21.7h，纵向高温持久寿命(三组平均值)为23.1h，纵向高温持久寿命与横向高温持久寿命之间的差值为1.4h。
实施例4在温度815℃、拉力为105MPa下的横向高温持久性能(三组平均值)为23.1h，纵向高温持久寿命(三组平均值)为25.4h，纵向高温持久寿命与横向高温持久寿命之间的差值为2.3h。
对照例1，在温度815℃、拉力为105MPa下的横向高温持久性能(三组平均值)为11.3h，纵向高温持久寿命(三组平均值)为36.8h，纵向高温持久寿命与横向高温持久寿命之间的差值为25.6h。
对照例2在温度815℃、拉力为105MPa下的横向高温持久性能(三组平均值)为33.0h，纵向高温持久寿命(三组平均值)为91.9h，纵向高温持久寿命与横向高温持久寿命之间的差值为58.9h。
对照例3在温度815℃、拉力为105MPa下的横向高温持久性能(三组平均值)为29.9h，纵向高温持久寿命(三组平均值)为37.0h，纵向高温持久寿命与横向高温持久寿命之间的差值为7.1h。
经上述对比可知，通过本发明提供的成形粉末成形得到的成形件，高温下横向与纵向持久寿命差异显著缩小，高温持久性能的各向异性得到了显著的降低，尤其适用于制造受力方向不存在显著的方向性、且在高温工况下使用的零件。
本发明虽然以较佳实施例公开如上，但其并不是用来限定本发明，任何本领 域技术人员在不脱离本发明的精神和范围内，都可以做出可能的变动和修改。因此，凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何修改、等同变化及修饰，均落入本发明权利要求所界定的保护范围之内。

Claims (20)

  1. [援引加入(细则20.6) 03.12.2021]
    一种用于增材制造具有高温持久低各向异性成形件的成形粉末，其特征在于，以质量百分比计，由以下化学成分组成：
    0.03％≤C≤0.09％、20.50％≤Cr≤23.00％、0.50≤Co≤2.50％、8.00％≤Mo≤10.00％、0.20％≤W≤1.00％、17.00％≤Fe≤20.00％、0％<B<0.002％、0％≤Mn≤1.00％、0.0375％≤Si≤0.15％、0％≤O≤0.02％、0％≤N≤0.015％、余量的Ni以及不可避免的杂质；
    其中，0.2≤C/Si≤1.0。
  2. [援引加入(细则20.6) 03.12.2021]
    如权利要求1所述的用于增材制造具有高温持久低各向异性成形件的成形粉末，其特征在于，以质量百分比计：
    所述C的含量为：0.05％≤C≤0.09％；
    所述Si的含量为：0.07％≤Si≤0.15％；
    其中，0.33≤C/Si≤0.8。
  3. [援引加入(细则20.6) 03.12.2021]
    如权利要求1所述的用于增材制造具有高温持久低各向异性成形件的成形粉末，其特征在于，所述成形粉末通过气雾化或旋转电极雾化制成。
  4. [援引加入(细则20.6) 03.12.2021]
    如权利要求1所述的用于增材制造具有高温持久低各向异性成形件的成形粉末，其特征在于，所述成形粉末的粉末粒度大小为15μm至150μm。
  5. [援引加入(细则20.6) 03.12.2021]
    一种具有高温持久低各向异性成形件的成形方法，通过增材制造工艺成形所述具有高温持久低各向异性的成形件，其特征在于：
    所述增材制造工艺采用的成形粉末为如权利要求1至4中任一项所述的用于增材制造具有高温持久低各向异性成形件的成形粉末。
  6. [援引加入(细则20.6) 03.12.2021]
    如权利要求5所述的具有高温持久低各向异性成形件的成形方法，其特征在于，所述增材制造工艺为激光选区熔化成形工艺。
  7. [援引加入(细则20.6) 03.12.2021]
    如权利要求5所述的具有高温持久低各向异性成形件的成形方法，其特征在于，所述成形方法还包括：
    对成形件进行去应力退火处理。
  8. [援引加入(细则20.6) 03.12.2021]
    如权利要求7所述的具有高温持久低各向异性成形件的成形方法，其特征 在于，在所述去应力退火处理后，所述成形方法还包括：
    对成形件进行线切割处理。
  9. [援引加入(细则20.6) 03.12.2021]
    如权利要求8所述的具有高温持久低各向异性成形件的成形方法，其特征在于，在所述线切割处理后，所述成形方法还包括：
    对成形件进行热等静压处理。
  10. [援引加入(细则20.6) 03.12.2021]
    一种具有高温持久低各向异性的成形件，其特征在于，采用如权利要求5至9中任一项所述的具有高温持久低各向异性成形件的成形方法制成。
  11. 一种带悬臂结构成形件的成形方法，用于成形带悬臂结构的成形件，所述悬臂结构与成形件的激光熔化沉积方向垂直，且下方呈悬空状态；
    其特征在于，所述成形方法包括：
    获得待成形零件的模型，所述模型具有至少一个悬臂结构；
    为所述悬臂结构添加至少一个倾斜支撑部，所述倾斜支撑部支撑于所述悬臂结构呈悬空部分的下方，具有至少一个倾斜面，所述倾斜面具有倾角，所述倾角为所述倾斜面与成形基板之间的呈锐角的夹角；
    对所述模型沿垂直于沉积方向分层切片处理成为若干成形层；
    对每一所述成形层进行扫描路径规划，规划后的所述扫描路径包括内填充扫描路径以及位于所述内填充扫描路径外周的边框扫描路径；
    其中，对于构成所述倾斜面的多个成形层中，至少一个待成形层具有突出于已成形层的悬空区域以及非悬空区域，所述边框扫描路径由第一路径以及第二路径组成，所述第一路径对应所述非悬空区域，所述第二路径对应所述悬空区域；
    根据倾角大小对所述第一路径设定第一制备工艺参数，以及对所述第二路径设定第二制备工艺参数；
    采用激光熔化沉积工艺，根据已设定的所述制备工艺参数逐层打印，以成形带悬臂结构的成形件；
    其中，所述第一制备工艺参数中的能量密度小于所述第二制备工艺参数中的能量密度。
  12. 如权利要求1所述的带悬臂结构成形件的成形方法，其特征在于，还包括：
    对所述内填充扫描路径设定第三制备工艺参数；
    其中，所述第三制备工艺参数中的能量密度小于所述第一制备工艺参数中的能量密度。
  13. 如权利要求2所述的带悬臂结构成形件的成形方法，其特征在于，通过调 节制备工艺参数中的激光功率和/或扫描速率以获得不同大小的所述能量密度。
  14. 如权利要求1所述的带悬臂结构成形件的成形方法，其特征在于，所述成形方法还包括：
    对所述成形件进行去支撑处理，以得到所述带悬臂结构的成形件。
  15. 如权利要求1所述的带悬臂结构成形件的成形方法，其特征在于：
    成形时，对所述第一路径以及所述第二路径连续打印。
  16. 如权利要求1所述的带悬臂结构成形件的成形方法，其特征在于，
    相邻两成形层中，所述内填充扫描路径之间具有90°夹角。
  17. 如权利要求1所述的带悬臂结构成形件的成形方法，其特征在于，所述路径规划还包括：
    规划所述第二路径沿所述第一路径延伸的延伸路径；
    规划所述第二路径与所述内填充扫描路径之间的距离；
    其中，对所述延伸路径设定第二制备工艺参数。
  18. 如权利要求1所述的带悬臂结构成形件的成形方法，其特征在于，所述路径规划还包括：
    规划所述第二路径朝向所述内填充扫描路径的偏置距离。
  19. 如权利要求1所述的带悬臂结构成形件的成形方法，其特征在于，在所述对所述模型进行分层切片处理之前，所述成形方法还包括：
    对所述模型进行余量添加处理。
  20. 一种带悬臂结构的成形件，其特征在于，采用如权利要求1至9中任一项所述的带悬臂结构成形件的成形方法成形。
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