Nickel-based alloy containing stacking fault and gamma' phase composite structure and preparation method thereof
Technical Field
The invention relates to the technical field of nano-structure metal materials, in particular to a nickel-based alloy containing a high-strength high-thermal-stability laminated structure and a gamma' phase composite structure and a preparation method thereof.
Background
The nickel-based alloy has good oxidation resistance and certain corrosion resistance, and is widely applied to the industrial fields of aerospace, mechanical manufacturing and the like. The nickel base alloy has larger grains in the initial structure and lower strength. Therefore, in order to improve the strength of the nickel-based alloy, material scientists have made several centuries of effort to provide methods such as solid solution strengthening, second phase strengthening and plastic deformation strengthening. The strength of the alloy can be obviously improved by using a solid solution strengthening method and a second phase strengthening method, but the physical and chemical properties of the material are changed by adding alloy elements.
In addition, by plastic deformation, defects (e.g., grain boundaries, dislocations) can be introduced into the material to increase its strength, which does not change the chemical composition of the material as compared to solution treatment and second phase strengthening, but the resulting material is generally less plastic and thermally stable. The documents Sun Y, Xu S, Shann A. effects of influencing on microstructure and mechanical properties of nano-grained Ni-based alloy by means of rolling of nano-scale Materials Science & Engineering A,2015,641: 181-. However, after the cold-rolled nanocrystalline nickel-based alloy is annealed at 700 ℃ and 800 ℃ for 1 hour, the average size of nanocrystalline grains is 90nm and 200nm, and the nanocrystalline grains grow obviously, which proves that the nanocrystalline nickel-based alloy has poor thermal stability.
The Liu X C, Zhang H W, Lu K, Strain-induced ultra and ultrastable blanrelated structured in nickel [ J ] Science,2013,342(6156) 337-340, Liu Xiaochun et al, by surface mechanical milling treatment to introduce high shear deformation into pure nickel, to prepare a novel nano lamellar structure. The thickness of the lamellar is between 5nm and 50nm, the hardness is as high as 6.4GPa, the coarsening temperature of the lamellar structure is 506 ℃, and is 40 ℃ higher than that of steady-state ultrafine crystal nickel (466 ℃). The nano lamellar structure prepared by the method improves the strength and the thermal stability of the material to a certain extent, but the improvement range is lower.
The gradient structure which is currently in great interest can also enable the metal material to obtain good strength and stability. By performing shot blasting or the like on the surface of the rod-shaped metal, a gradient structure is obtained in which the core coarse crystals gradually transition to the surface layer nanocrystals. The structure realizes that the yield strength of the coarse-grain pure copper material is improved by 2 times, and meanwhile, the plasticity and the stability of the coarse-grain pure copper material are hardly lost. And the mechanical properties of the metal material can be adjusted by changing the volume percentage of the gradient layer, but as the percentage of the gradient layer increases, the strength increases but the plasticity and thermal stability decreases. Therefore, although this method improves the strength of the metal material, it is difficult to maintain good plasticity and thermal stability when the metal material attains high strength.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a nickel-based alloy containing a composite structure of a stacking fault and a gamma 'phase and a preparation method thereof, wherein the nickel-based alloy has high strength and high thermal stability through the composite structure of the stacking fault and the gamma' phase.
The technical solution for realizing the purpose of the invention is as follows:
the tissue structure of the surface layer of the nickel-based alloy is a composite structure of the stacking faults and the gamma ' phase, the stacking faults are high-density stacking faults, and a high-density stacking fault intersecting structure is arranged in the gamma ' phase to form the composite structure of the stacking faults and the gamma ' phase, so that the nickel-based alloy has high strength and high thermal stability.
Furthermore, the dislocation space in the composite structure of the stacking faults and the gamma ' phase is distributed between 5nm and 25nm, the size of the gamma ' phase is distributed between 30 nm and 80nm, and the thickness of the composite structure of the stacking faults and the gamma ' phase on the surface layer of the nickel-based alloy is 100-200 mu m.
Further, the nickel-base alloy has the following composition in atomic percent (at.%): 46.50-48.50% of Ni, 22.94-25.14% of Co, 14.36-15.46% of Cr, 5.10-6.20% of Al, 4.05-4.97% of Ti, 1.82-2.70% of Mo, 0.24-0.34% of W, 0.50-0.62% of Fe, 0.02-0.05% of Zr, 0.07-0.11% of C and 0.06-0.07% of B.
The method for preparing the nickel-based alloy comprises the following specific steps:
(1) carrying out solution treatment on the nickel-based alloy to obtain the nickel-based alloy with a high-density gamma' phase strengthened gamma matrix structure;
(2) the surface mechanical rolling treatment is utilized to process the nickel-based alloy with the high-density gamma 'phase strengthened gamma matrix structure, and a high-density fault intersected structure is obtained on the surface layer of the nickel-based alloy, wherein the fault structure destroys the gamma' phase L12An ordering structure;
(3) the nickel base alloy in the step (2) is aged, and gamma' phase L12And recovering the ordered structure again to finally obtain the nickel-based alloy containing the composite structure of the stacking fault and the gamma' phase.
Further, the surface mechanical rolling treatment adopts a surface mechanical rolling treatment system, the surface mechanical rolling treatment system comprises a treatment cutter and a cooling system, the treatment cutter is used for carrying out mechanical rolling treatment on the surface layer of the nickel-based alloy, and the cooling system is used for reducing the temperature of the surface of the sample in the mechanical rolling treatment.
Further, the cutter head part of the processing cutter is a hard alloy ball, the hard alloy ball is made of WC-Co alloy, and the diameter of the hard alloy ball is 4-10 mm; the cooling system is cooled in a liquid nitrogen atmosphere.
Further, the shape of the nickel-based alloy is a rod, and the mechanical surface rolling treatment specifically comprises the following steps: the rod-shaped nickel-based alloy rotates along the self axial direction, a hard alloy ball of the processing cutter is in contact with the surface of the nickel-based alloy and pressed into the nickel-based alloy to a certain depth, the processing cutter is fed and moves from one end of the workpiece to the other end along the surface of the rod-shaped nickel-based alloy, and one pass processing is completed; after the above process is repeated for a plurality of times, a plastic deformation layer is formed on the surface of the nickel-based alloy; the depth of the hard alloy ball pressed into the surface of the nickel-based alloy is determined according to the thickness of the composite structure surface layer of the stacking fault and the gamma' phase of the nickel-based alloy to be processed.
Further, the diameter of the rod-shaped nickel-based alloy is 8-15mm, the rotating speed of the rod-shaped nickel-based alloy in the axial direction is 100-800r/min, the feeding speed of the treatment cutter along the axial direction of the rod-shaped nickel-based alloy is 40-80mm/min, the pressing depth of the hard alloy ball on the surface of the nickel-based alloy in each treatment pass is 20-80 mu m, and the processing pass is 1-10.
Further, the aging treatment in the step (3) adopts a box-type electric furnace, and specifically comprises the following steps: and (3) heating the box type electric furnace to a preset aging temperature, then putting the nickel-based alloy subjected to surface treatment into the furnace, preserving heat, taking out the sample, and naturally cooling the sample in the air.
Further, the aging temperature is 600-800 ℃, and the heat preservation time is 25-100 h.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the invention utilizes the method of combining the surface mechanical rolling treatment and the aging treatment to obtain a composite structure of the stacking fault and the gamma' phase on the surface of the nickel-based alloy, wherein the surface mechanical rolling treatment is used for obtaining a high-density stacking fault intersecting structure on the surface of the nickel-based alloy, the strengthening mechanism can be explained by using Hall-Petch relation, and the strength of the nickel-based alloy is obviously improved because the spacing of the stacking fault is only a few nanometers. And the gamma 'phase of the ordered structure is restored through aging treatment, so that the resistance of the stacking fault movement is further increased, and the strength and the thermal stability of the nickel-based alloy are remarkably improved through the composite structure of the stacking fault and the gamma' phase.
(2) The method is characterized in that a laminated fault and gamma ' phase composite structure is prepared in the nickel-based alloy through surface mechanical rolling treatment and aging treatment, and deformation process parameters are easy to control in the surface mechanical rolling treatment process, so that the thickness of a laminated fault and gamma ' phase composite structure area can be controlled by combining the characteristics of a base material and optimizing various parameters, cutter parameters and the like in the surface mechanical treatment process, and high strength and high thermal stability of the laminated fault and gamma ' phase composite structure area can be still maintained when a thin deformation layer is prepared on the surface of the nickel-based alloy.
(3) The surface mechanical rolling treatment method of the invention prepares a composite structure of the stacking fault and the gamma' phase with a certain thickness on the surface layer of the nickel-based alloy, which is different from a uniform structure material prepared by the traditional method. The invention improves the strength and the thermal stability of the nickel-based alloy by only changing the microstructure on the premise of not changing the chemical components of the material. And the aging treatment can flexibly change the aging temperature and time, and is easy to control the size of the gamma' phase, thereby ensuring that the performance of the nickel-based alloy reaches the optimum.
The present invention is described in further detail below with reference to the attached drawing figures.
Drawings
Fig. 1 is a high-resolution transmission electron microscope image of a composite structure of a stacking fault and a γ' phase in the nickel-based alloy in example 1.
Fig. 2 is a high-resolution transmission electron microscope image of a composite structure of a stacking fault and a γ' phase in the nickel-based alloy in example 2.
Fig. 3 is a high-resolution transmission electron microscope image of a composite structure of a stacking fault and a γ' phase in the nickel-based alloy in example 3.
FIG. 4 is a comparison of the micro-hardness of the nickel-base alloys of examples 1, 2, and 3 and the micro-hardness of the prior art nickel-base alloy.
Detailed Description
Nickel base with composite structure containing stacking fault and gamma' phaseThe preparation method of the alloy has the advantages that the composite structure of the stacking fault and the gamma' phase has high strength and high thermal stability. Firstly, the nickel-based alloy is subjected to solution treatment to obtain a high-density gamma' phase strengthened gamma matrix structure. Then mechanically rolling the surface of the high-density gamma '-phase strengthened nickel-based alloy to obtain a high-density fault intersected structure on the surface layer, wherein the fault intersected structure breaks the gamma' -phase L12Ordering the structure, then carrying out aging treatment on the nickel-based alloy, wherein the gamma' phase is L12And the ordered structure is restored again, and finally a structure with the composite of the stacking fault and the gamma' phase is obtained, and the structure remarkably improves the strength and the thermal stability of the nickel-based alloy.
The dislocation space of the composite structure of the stacking faults and the gamma 'phase is distributed in the range of 5-25nm, and the size of the gamma' phase is distributed in the range of 30-80 nm.
When the nickel-based alloy is subjected to surface plastic deformation by adopting surface mechanical rolling treatment, the surface mechanical rolling treatment system comprises a treatment cutter and a cooling system. The tool bit part of the tool is a hard alloy ball which is made of WC-Co alloy, and the diameter of the hard alloy ball is 4-10 mm. And the cooling treatment process adopts liquid nitrogen atmosphere cooling to reduce the temperature rise of the surface of the sample in the treatment process. For the low-layer fault energy nickel-based alloy, the surface mechanical rolling treatment process does not need cooling, and the room temperature is kept.
The surface mechanical rolling treatment process comprises the following steps: firstly, cutting the nickel-based alloy into a rod shape by utilizing linear cutting, enabling the rod-shaped nickel-based alloy to rotate along the self axial direction, enabling a hard alloy ball of a processing cutter to be in contact with the surface of the nickel-based alloy and pressed into the surface of the nickel-based alloy to a certain depth, and then moving from one end of a workpiece to the other end along the surface of a nickel-based alloy rotating piece to finish one pass processing; after the above process is repeated for a plurality of times, a plastic deformation layer is formed on the surface of the nickel-based alloy; the diameter of the rod-shaped nickel-based alloy is 8-15mm, the rotating speed of the nickel-based alloy rotating member is 800-800 r/min, the feeding speed of the processing cutter along the axial direction of the nickel-based alloy rotating member is 40-80mm/min, the pressing depth of the hard alloy ball cutter head on the surface of the nickel-based alloy in each processing pass is 20-80 mu m, and the processing pass is 1-10.
The aging treatment process comprises the following steps: and (3) heating the box type electric furnace to a preset aging temperature, then putting the nickel-based alloy subjected to surface treatment into the furnace, preserving heat for a certain time, taking out the sample, and naturally cooling the sample in the air.
The aging time is as follows: 25-100h, aging temperature: 600 ℃ and 800 ℃.
The nickel-based alloy with the composite structure of the stacking fault and the gamma' phase has the following properties: the micro hardness of the alloy is 1.2-1.8 times of that of the nickel-based alloy before surface treatment, and the structure coarsening temperature is 30-80 ℃ higher than that of the nanocrystalline nickel-based alloy.
Example 1
The nickel-based alloy containing the composite structure of the stacking fault and the gamma 'phase is obtained by utilizing surface mechanical rolling treatment and aging treatment, and the composite structure of the stacking fault and the gamma' phase has high strength and high thermal stability. The chemical elements in the nickel-based alloy are measured in atomic percent (at.%): 46.50-48.50% of Ni; 22.94 to 25.14 percent of Co; 14.36 to 15.46 percent of Cr; al: 5.10-6.20%; 4.05 to 4.97 percent of Ti; 1.82-2.70% of Mo; w: 0.24-0.34%; fe: 0.50-0.62%; 0.02-0.05% of Zr; 0.07-0.11% of C; 0.06-0.07% of B.
The surface mechanical rolling treatment parameters are as follows: the diameter of the rod-shaped nickel-based alloy is 11mm, the rotating speed is 600r/min, the processing cutter head is a WC-Co hard alloy ball with the diameter of 8mm, the feeding speed is 40mm/min, the pressing depth of the hard alloy ball cutter head on the surface of the nickel-based alloy in each processing pass is 20 mu m, and the processing pass is 3. The aging treatment parameters are as follows: the aging temperature is 700 ℃, and the aging time is 50 h.
The thickness of the composite structure of the surface layer stacking fault and the gamma ' phase of the nickel-based alloy obtained in the example is 150 μm, wherein the spacing of the stacking fault is 10nm, the size of the gamma ' phase is 38nm, the number of the nickel-based alloy in the example is #1, as shown in a transmission electron microscope image of the stacking fault-gamma ' phase structure in the nickel-based alloy in fig. 1, the microhardness of the structure is 6.98 GPa. The structure obviously improves the strength and the thermal stability of the nickel-based alloy.
Example 2
The difference from the embodiment 1 is that:
the nickel-based alloy with the composite structure of the stacking fault and the gamma 'phase is obtained by utilizing surface mechanical rolling treatment and aging treatment, and the composite structure of the stacking fault and the gamma' phase has high strength and high thermal stability. The chemical elements in the nickel-based alloy are the same as those in example 1. The surface mechanical rolling treatment parameters are as follows: the diameter of the rod-shaped nickel-based alloy is 11mm, the rotating speed is 600r/min, the processing cutter head is a WC-Co hard alloy ball with the diameter of 8mm, the feeding speed is 40mm/min, the pressing depth of the hard alloy ball cutter head on the surface of the nickel-based alloy in each processing pass is 20 mu m, and the processing pass is 3. The aging treatment parameters are as follows: the aging temperature is 780 ℃ and the aging time is 50 h.
The thickness of the composite structure of the surface layer stacking fault and the gamma ' phase of the nickel-based alloy obtained in the example is 150 μm, wherein the spacing of the stacking fault is 18nm, the size of the gamma ' phase is 65nm, the number of the nickel-based alloy in the example is #2, as shown in fig. 2, the transmission electron microscope image of the structure of the stacking fault-gamma ' phase in the nickel-based alloy is shown, and the microhardness of the structure is 6.26 GPa. The structure obviously improves the strength and the thermal stability of the nickel-based alloy.
Example 3
The difference from the embodiment 1 is that:
the nickel-based alloy with the composite structure of the stacking fault and the gamma 'phase is obtained by utilizing surface mechanical rolling treatment and aging treatment, and the composite structure of the stacking fault and the gamma' phase has high strength and high thermal stability. The chemical elements in the nickel-based alloy are the same as those in example 1. The surface mechanical rolling treatment parameters are as follows: the diameter of the rod-shaped nickel-based alloy is 11mm, the rotating speed is 600r/min, the processing tool bit is a WC-Co hard alloy ball with the diameter of 8mm, the feeding speed is 40mm/min, the pressing depth of the hard alloy ball tool bit on the surface of the nickel-based alloy in each processing pass is 20 mu m, and the processing pass is 1. The aging treatment parameters are as follows: the aging temperature is 700 ℃, and the aging time is 50 h.
The thickness of the composite structure of the surface layer stacking fault and the gamma ' phase of the nickel-based alloy obtained in the example is 100 μm, wherein the spacing of the stacking fault is 25nm, the size of the gamma ' phase is 50nm, the number of the nickel-based alloy in the example is #3, as shown in a transmission electron microscope image of the stacking fault-gamma ' phase structure in the nickel-based alloy, the microhardness of the structure is 6.02 GPa. The structure obviously improves the strength and the thermal stability of the nickel-based alloy.
Comparative example 1
The document Shankar M R, Rao B C, Chandrasekar S, et al, thermally stable nanostructured materials from crystalline plastic Ni-based alloys [ J ] ScriptA materials, 2008,58(8): 675) 678, et al, said M.ravi Shankar et al, prepared nanocrystalline Inconel 718 alloy using SPD (polycrystalline plastic deformation) process, with grain size of around 100 nm. The microhardness of the material is about 5.4 GPa. The nanocrystalline Inconel 718 alloy is subjected to aging treatment of heat preservation at 600 ℃ for 6 hours to achieve the micro hardness of 6.2GPa, and is subjected to aging treatment at 700 ℃ for 36 hours to achieve the micro hardness of only 5.4 GPa. The nanocrystalline nickel-based alloy prepared by the method has high strength, but the thermal stability is poor.
Comparative example 2
The nanocrystalline nickel-based alloy is prepared by Shanghai university Mono-Aidang and the like through a cold rolling process, the average grain size of the nanocrystalline is 50nm, the microhardness is 4.80GPa, the average grain size of the nanocrystalline is 90nm after the nanocrystalline nickel-based alloy is annealed at 700 ℃ for 1h, the microhardness reaches 6.10GPa, and the average grain size of the nanocrystalline is 200nm and the microhardness reaches 4.85GPa after the nanocrystalline nickel-based alloy is annealed at 800 ℃ for 1 h. The nanocrystalline nickel-based alloy prepared by the cold rolling process has high strength, but poor thermal stability.
Comparative example 3
Takizawa Y, Otsuka K, Masuda T, et al, High-string Rate Superplastic of Inconel 718 through gain Steel reference by High-Pressure Torque Tosion [ J ]. Materials Science & Engineering A,2015, it is mentioned that Yoichi Takizawa et al, by treating an Inconel 718 nickel-based alloy with High Pressure Torsion at room temperature up to 6GPa, reduced the Grain size to the nanoscale after treatment. The microhardness of the material is about 5.45 GPa. Compared with a coarse-grain nickel-based alloy, the nano-crystal nickel-based alloy prepared by high-pressure torsion treatment Inconel 718 has the advantage that the hardness is improved to some extent, but the hardness is not improved to a great extent.
The result shows that the composite structure of the stacking fault and the gamma 'phase is prepared on the surface of the nickel-based alloy by applying surface plastic processing and then performing medium-high temperature aging treatment, wherein the spacing of the stacking fault is distributed in the range of 5-25nm, and the size of the gamma' phase is distributed in the range of 30-80 nm. The nickel-based alloy prepared by the invention is insulated for 50h at the temperature of 600-800 ℃, and the micro-hardness is between 6.10 and 7.00 GPa. The nickel-based alloy prepared by the invention has ultrahigh strength and thermal stability.