CN113981333A - High-entropy-enhancement amorphous alloy composite material and preparation method thereof - Google Patents
High-entropy-enhancement amorphous alloy composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
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- 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]
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention belongs to the technical field of composite materials and preparation thereof, and relates to a high-entropy-enhancement amorphous alloy composite material and a preparation method thereof, wherein the preparation method comprises the following steps: the composite material consists of a Cr-Fe-Ni-Ta-Mo-V high-entropy alloy phase reinforced Co-Fe-Ta-La-B amorphous alloy matrix, wherein the volume of a high-entropy phase accounts for 0.1-1% of the total volume of the composite material, and the size of the high-entropy alloy reinforced phase is 30-80 mu m; the amorphous alloy matrix comprises the following components in atomic percentage: 15-25% of Fe, 2-10% of Ta, 11-17% of La, 15-25% of B and the balance of Co; the high-entropy alloy reinforcing phase comprises the following components in percentage by atom: 15-25% of Fe, 10-20% of Ni, 15-25% of Ta, 7-16% of Mo, 10-20% of V and the balance of Cr; the block high-entropy reinforced amorphous alloy composite material is finally obtained by adopting a laser additive manufacturing technology, and the plasticity and the toughness of the composite material can be enhanced.
Description
Technical Field
The invention belongs to the technical field of composite materials and preparation thereof, and relates to a high-entropy-enhancement amorphous alloy composite material and a preparation method thereof.
Background
Compared with the traditional block crystalline material, the block amorphous alloy has high breaking strength and yield strength, high hardness, high specific strength and high elastic limit, and can be used as a high-performance structural material. But the defect in the united states is that the macroscopic plasticity, especially the tensile plasticity of the amorphous alloy is poor, and the amorphous alloy is always the bottleneck of being used as an excellent structural material. The plasticity of amorphous alloys is improved by developing novel amorphous alloy components with high plastic deformation capacity, adding a second phase into an amorphous alloy matrix, performing surface treatment and the like. For example, finding amorphous alloy compositions with high poisson's ratio that produce more shear bands during deformation is one way to improve the plasticity of amorphous alloys. However, when the components and compositions of the alloy are changed, the plastic deformability of the alloy is also changed accordingly. Meanwhile, the amorphous forming ability of the alloy is also in close relation with the components of the alloy, so that the alloy with high amorphous forming ability is difficult to find and has high plastic deformation ability. Therefore, the problem of plasticity of amorphous alloys cannot be completely solved by developing alloys with large poisson's ratio.
Because the amorphous alloy does not have defects in crystals, a second phase is added into an amorphous matrix by an external addition method to prevent the instability expansion of the shear band, so that the method is a better method for improving the plasticity of the amorphous alloy. Designing a material with high thermodynamic stability and high plasticity as a reinforcing phase, which is one of key technologies for effectively improving the plasticity of the amorphous alloy; meanwhile, a proper preparation method is adopted, and a second phase is added into the amorphous alloy, so that the enhanced phase particles are uniformly distributed in the amorphous alloy matrix and form good combination with the matrix.
High entropy alloys are a class of disordered alloys discovered in recent years based on the search for bulk amorphous alloys. The most typical structure is a multi-component super solid solution, the solid solution strengthening effect is extremely strong, and the crystal lattice distortion exists. The unique crystal structure enables the high-entropy alloy to have excellent performance which cannot be compared with some traditional alloys. The current research result shows that the fracture toughness of the high-entropy alloy is obviously superior to that of other alloys. More importantly, the high mixed entropy effect is more prominent under the high temperature condition, so that the Gibbs free energy of an alloy system can be better reduced, the structure and the performance of the high entropy alloy are more stable at high temperature, and the high entropy alloy has high-temperature strength and excellent thermal stability, high-temperature oxidation resistance and high-temperature softening resistance. The excellent performance enables the high-entropy alloy to be very suitable for being used as a second reinforcing phase added in the amorphous alloy, and the plasticity of the amorphous alloy is improved.
Disclosure of Invention
The purpose of the invention is: the high-entropy strengthening amorphous alloy composite material is prepared by adding high-entropy alloy particles serving as a strengthening phase into an amorphous alloy matrix and adopting a laser material increase manufacturing technology, and finally, the high-entropy strengthening amorphous alloy composite material of a high-strength high-plasticity block is obtained.
In order to solve the technical problem, the technical scheme of the invention is as follows:
on the one hand, the high-entropy enhancement amorphous alloy composite material is composed of a Cr-Fe-Ni-Ta-Mo-V high-entropy alloy phase enhanced Co-Fe-Ta-La-B amorphous alloy matrix, wherein the volume of a high-entropy phase accounts for 0.1-1% of the total volume of the composite material, and the size of the high-entropy alloy enhanced phase is 30-80 mu m;
the amorphous alloy matrix comprises the following components in atomic percentage: 15-25% of Fe, 2-10% of Ta, 11-17% of La, 15-25% of B and the balance of Co; the high-entropy alloy reinforcing phase comprises the following components in percentage by atom: 15-25% of Fe, 10-20% of Ni, 15-25% of Ta, 7-16% of Mo, 10-20% of V and the balance of Cr.
Further, the amorphous alloy matrix comprises the following components in atomic percentage: 16-22% of Fe, 4-8% of Ta, 12-15% of La, 17-23% of B and the balance of Co. The high-entropy alloy reinforcing phase comprises the following components in percentage by atom: 16-19% of Fe, 12-17% of Ni, 16-23% of Ta, 9-15% of Mo, 11-16% of V and the balance of Cr.
The volume fraction of the high-entropy alloy reinforcing phase in the amorphous alloy matrix is 0.2-0.8%, and the size of the high-entropy alloy reinforcing phase is 40-70 μm. In the preferable scheme, the volume fraction of the high-entropy alloy reinforcing phase in the amorphous alloy matrix is 0.3-0.5%, and the size of the high-entropy alloy reinforcing phase is 50-60 mu m.
On the other hand, the preparation method adopts a laser powder feeding additive manufacturing technology to prepare the amorphous alloy composite material on the substrate, and adopts a double-channel mode to feed powder.
The double-channel mode specifically comprises the following steps:
respectively loading amorphous alloy powder and high-melting-point and high-entropy alloy powder with high toughness into a double-channel powder feeding device in laser additive manufacturing equipment, and adjusting the powder feeding amount and the powder carrier flow rate of each channel in the double-channel powder feeding device of the laser additive manufacturing equipment to enable the volume ratio of a reinforcing phase in the composite material obtained by additive manufacturing to meet requirements, wherein the powder feeding amount of a powder feeding channel in which the high-entropy alloy powder is located is 500-1000 rpm, the powder carrier flow rate is 3-6L/min, the powder feeding amount of a powder feeding channel in which the amorphous alloy powder is located is 2200-3600 rpm, and the powder carrier flow rate is 6-9L/min. .
The principle of the invention is that the designed Cr-Fe-Ni-Ta-Mo-V high-entropy alloy reinforcing phase has similar density and thermal expansion coefficient with the Co-Fe-Ta-La-B amorphous alloy matrix, and the Cr-Fe-Ni-Ta-Mo-V high-entropy alloy has higher physical chemistry and thermal stability, not only can form good physical chemistry compatibility with the Co-Fe-Ta-La-B amorphous alloy, but also can continuously keep excellent reinforcing effect in a high-temperature environment.
Cr-Fe-Ni-Ta-Mo-V high-entropy alloy reinforcing phase particles existing in a Co-Fe-Ta-La-B amorphous alloy matrix can prevent the slippage of a shear band of the Co-Fe-Ta-La-B amorphous alloy in a stressed state, so that more shear bands are generated in other areas in the alloy, and the plasticity is obviously improved; meanwhile, the Cr-Fe-Ni-Ta-Mo-V high-entropy particles can also greatly reduce the speed of reducing the viscosity near a deformation region, remarkably weaken the conditions of shear softening and shear band slippage instability, prolong the failure time of fracture and further improve the plasticity of the Co-Fe-Ta-La-B amorphous alloy.
The melting point of the Cr-Fe-Ni-Ta-Mo-V high-entropy alloy is 1950-2300 ℃ which is higher than the melting point of the Co-Fe-Ta-La-B amorphous alloy by 1300-1700 ℃, the amorphous alloy powder is melted and deposited on the substrate to form the amorphous alloy by controlling the laser additive manufacturing process parameters, and the high-entropy alloy powder is not melted so as to be reserved and uniformly distributed in the amorphous alloy matrix in the process of solidifying the amorphous alloy melt, so that the three-dimensional forming of the amorphous alloy composite material is finally realized.
The invention has the beneficial effects that:
1. by adding the high-entropy reinforcing phase into the amorphous alloy, the composite material has high strength and high plasticity, and the brittleness of the amorphous alloy is improved. The designed Cr-Fe-Ni-Ta-Mo-V high-entropy alloy and the Co-Fe-Ta-La-B amorphous alloy have good physical and chemical compatibility, and can form a second phase reinforced amorphous alloy composite material with stable thermodynamics.
2. The Cr-Fe-Ni-Ta-Mo-V high-entropy alloy reinforced phase particles can effectively prevent the slippage of a shear band of the Co-Fe-Ta-La-B amorphous alloy in a stressed state, reduce the speed of viscosity reduction near a deformation region and obviously improve the plasticity of the Co-Fe-Ta-La-B amorphous alloy.
3. The method can realize the three-dimensional complex shape forming of the high-entropy reinforced amorphous alloy composite material, improve the related processes of amorphous alloy preparation, processing and treatment, and realize the shape-constraint-free net forming of the amorphous alloy.
Detailed Description
The process of the present invention is described in detail below with reference to specific examples.
The preparation method of the high-entropy strengthening amorphous alloy composite material comprises the following steps:
(1) the laser additive manufacturing equipment is provided with 6000W fiber laser, a five-axis linkage numerical control machine tool and a double-channel synchronous powder feeding device.
(2) According to the design scheme of the composite material, the adopted amorphous alloy matrix comprises the following components in percentage by atom: 38 to 42 percent of Co, 18 to 20 percent of Fe, 5 to 6 percent of Ta, 13 to 15 percent of La and 20 to 23 percent of B, and the granularity of the powder is 53 to 106 mu m. The adopted high-entropy alloy reinforcing phase comprises the following components in percentage by atom: 20 to 24 percent of Cr, 16 to 17 percent of Fe, 12 to 15 percent of Ni, 20 to 23 percent of Ta, 12 to 15 percent of Mo and 13 to 16 percent of V, and the powder granularity is 40 to 70 mu m.
(3) And respectively filling Cr-Fe-Ni-Ta-Mo-V high-entropy alloy powder and Co-Fe-Ta-La-B amorphous alloy powder into a double-channel powder feeding device of laser additive manufacturing equipment.
(4) A laser additive manufacturing test was performed using a GH3536 sheet material as a substrate. And adjusting the powder feeding amount and the powder carrier flow rate of the laser equipment (the powder feeding amount of a powder feeding channel in which the high-entropy alloy powder is positioned is 500-1000 rpm, the powder carrier flow rate is 3-6L/min, the powder feeding amount of a powder feeding channel in which the amorphous alloy powder is positioned is 2200-3600 rpm, and the powder carrier flow rate is 6-9L/min), so that the volume fraction of the high-entropy reinforcing phase in the composite material reaches a design value. The adopted laser process parameters are as follows: the laser power is 900W, the scanning speed is 600mm/min, the diameter of a light spot is 2.0mm, and the flow of protective gas is 30L/min.
In the following examples, the high entropy strengthening amorphous alloy composite material system used comprises the following components:
the Co-Fe-Ta-La-B amorphous alloy comprises the following components in atomic percentage: 38 to 42 percent of Co, 18 to 20 percent of Fe, 5 to 6 percent of Ta, 13 to 15 percent of La and 20 to 23 percent of B.
The Cr-Fe-Ni-Ta-Mo-V high-entropy alloy reinforcing phase comprises the following components in percentage by atom: 20 to 24 percent of Cr, 16 to 17 percent of Fe, 12 to 15 percent of Ni, 20 to 23 percent of Ta, 12 to 15 percent of Mo and 13 to 16 percent of V.
The following examples discuss the enhancement effect of different volume fractions and sizes of the high entropy enhancing phase based on the above composition.
Example 1:
the volume fraction of the high-entropy reinforcing phase in the composite material is 0.8%, and the size of the high-entropy alloy reinforcing phase is 40 mu m.
Example 2:
the volume fraction of the high-entropy reinforcing phase in the composite material is 0.5 percent, and the size of the high-entropy alloy reinforcing phase is 50 mu m.
Example 3:
the volume fraction of the high-entropy reinforcing phase in the composite material is 0.3 percent, and the size of the high-entropy alloy reinforcing phase is 60 mu m.
Example 4:
the volume fraction of the high-entropy reinforcing phase in the composite material is 0.2 percent, and the size of the high-entropy alloy reinforcing phase is 70 mu m.
The performance results of the embodiment of the invention are compared with the performance of the Co-Fe-Ta-La-B amorphous alloy without adding the high-entropy reinforcing phase, and the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the room temperature compression plasticity and fracture toughness of the reinforced amorphous alloy are greatly improved.
In the present invention, the volume fraction and size of the Cr-Fe-Ni-Ta-Mo-V high entropy enhancing phase is critical. From the results of 4 examples, the volume fraction of the reinforcing phase is 0.2-0.8%, and the size is 40-70 μm, so that the plasticity and toughness of the composite material can be enhanced. However, when the volume fraction of the Cr-Fe-Ni-Ta-Mo-V high-entropy alloy reinforcing phase in the Co-Fe-Ta-La-B amorphous alloy matrix is 0.3-0.5%, and the size of the high-entropy reinforcing phase is 50-60 mu m, the reinforcing effect is optimal, and the amorphous alloy can be effectively prevented from slipping in a shear zone under a stress state, so that more shear zones can be generated in other areas. The volume fraction of the Cr-Fe-Ni-Ta-Mo-V phase is too small to achieve the enhancement effect; too large a volume fraction may affect the formation of amorphous phase and crystallize the matrix. Too large or too small a Cr-Fe-Ni-Ta-Mo-V phase size cannot match the size and slippage size of the Co-Fe-Ta-La-B amorphous alloy shear band, so that the shear band cannot be prevented from moving, and too large a size can reduce the amorphous forming capability.
Claims (8)
1. A high-entropy-strength amorphous alloy composite material is characterized in that: the composite material consists of a Cr-Fe-Ni-Ta-Mo-V high-entropy alloy phase reinforced Co-Fe-Ta-La-B amorphous alloy matrix, wherein the volume of a high-entropy phase accounts for 0.1-1% of the total volume of the composite material, and the size of the high-entropy alloy reinforced phase is 30-80 mu m;
the amorphous alloy matrix comprises the following components in atomic percentage: 15-25% of Fe, 2-10% of Ta, 11-17% of La, 15-25% of B and the balance of Co;
the high-entropy alloy reinforcing phase comprises the following components in percentage by atom: 15-25% of Fe, 10-20% of Ni, 15-25% of Ta, 7-16% of Mo, 10-20% of V and the balance of Cr.
2. The composite material of claim 1, wherein: the amorphous alloy matrix comprises the following components in atomic percentage: 16-22% of Fe, 4-8% of Ta, 12-15% of La, 17-23% of B and the balance of Co.
3. The composite material of claim 1, wherein: the high-entropy alloy reinforcing phase comprises the following components in percentage by atom: 16-19% of Fe, 12-17% of Ni, 16-23% of Ta, 9-15% of Mo, 11-16% of V and the balance of Cr.
4. The composite material of claim 1, wherein: the volume fraction of the high-entropy alloy reinforcing phase in the amorphous alloy matrix is 0.2-0.8%, and the size of the high-entropy alloy reinforcing phase is 40-70 μm.
5. The composite material of claim 1, wherein: the volume fraction of the high-entropy alloy reinforcing phase in the amorphous alloy matrix is 0.3-0.5%, and the size of the high-entropy alloy reinforcing phase is 50-60 mu m.
6. A method of making the composite of claim 1, wherein: the preparation method adopts a laser powder feeding additive manufacturing technology to prepare on the substrate, and adopts a double-channel mode to feed powder.
7. The method of claim 6, wherein: the double-channel mode specifically comprises the following steps:
amorphous alloy powder and high-melting-point and high-entropy alloy powder with high toughness are respectively loaded into a double-channel powder feeding device in laser additive manufacturing equipment, and the volume ratio of a reinforcing phase in a composite material obtained by additive manufacturing meets the requirement by adjusting the powder feeding amount and the powder carrier flow of each channel in the double-channel powder feeding device of the laser additive manufacturing equipment.
8. The method of claim 7, wherein: the powder feeding amount of the powder feeding channel where the high-entropy alloy powder is located is 500-1000 rpm, the flow rate of the powder carrier is 3-6L/min, the powder feeding amount of the powder feeding channel where the amorphous alloy powder is located is 2200-3600 rpm, and the flow rate of the powder carrier is 6-9L/min.
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| CN114807825A (en) * | 2022-04-13 | 2022-07-29 | 四川大学 | Preparation method of MCrAlY high-temperature-resistant coating |
| RU2806693C1 (en) * | 2023-05-25 | 2023-11-03 | Федеральное государственное бюджетное учреждение науки Институт металлургии и материаловедения им. А.А. Байкова Российской академии наук (ИМЕТ РАН) | Amorphous glass-metal reinforcing element for dispersed reinforcement of concrete |
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