Double-phase high-entropy ceramic reinforced nickel-based composite material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of nickel-based composite material preparation, in particular to a double-phase high-entropy ceramic reinforced nickel-based composite material with the extremely high elongation rate and a preparation method and application of the double-phase high-entropy ceramic reinforced nickel-based composite material. TiO2 powder, Ta2O5 powder, Nb2O5 powder, ZrO2 powder, WO3 powder, V2O5 powder, HfO2 powder, MoO3 powder and C powder are used as raw materials, the molar ratio of all the material powder is controlled to be 2: 2: 1: 2: 2: 1: 1: 2: 47 in sequence, the sintering temperature is controlled to be 1550 DEG C or above, and under the synergistic effect of a proper amount of calcined powder and matrix powder and printing parameters, a printed product with extremely high ductility and high mechanical strength is obtained. The composition is reasonable in design, the preparation process is simple and controllable, the obtained product is excellent in performance, and large-scale industrial application is facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of nickel-based composite material preparation, and more specifically to a dual-phase high-entropy ceramic reinforced nickel-based composite material and a preparation method and application thereof. Background Art

[0002] Nickel-based alloys have been widely developed and have proven to be attractive in various industrial applications, such as turbine blades and engine components. Since they maintain excellent mechanical properties at high temperatures, a combination of high mechanical properties and excellent machinability is urgently needed. Nickel-based superalloys are characterized by high strength and excellent oxidation resistance and creep resistance at high temperatures up to 700°C, making them potential candidates for the production of gas turbines, jet engines and nuclear reactors. However, in the traditional processing of nickel-based alloys, there are usually problems such as low part precision and high processing difficulty. Additive manufacturing technology can achieve integrated molding of complex structural parts with short production cycle. Therefore, additive manufacturing technology provides an effective processing method for the processing of complex components of nickel-based superalloys.

[0003] In addition, with the rapid development of high-end technology industries including aircraft and nuclear industries, most nickel-based high-temperature alloy parts are currently difficult to meet high-temperature performance requirements. Ceramic particle reinforced nickel-based composites have the advantages of high specific strength, specific modulus, high temperature resistance, small thermal expansion coefficient, wear resistance, corrosion resistance, and good dimensional stability. However, traditional ceramic particles such as TiC, WC, SiC and other reinforced nickel-based composites have the problem of mismatch between strength and plasticity.

[0004] Therefore, the present invention designs a new dual-phase high-entropy ceramic reinforcement phase. By introducing the reinforcement phase, a dual-phase high-entropy ceramic reinforced nickel-based composite material is prepared using additive manufacturing technology, thereby effectively solving the problem of strength-plasticity mismatch of current ceramic particle reinforced nickel-based composite materials. Summary of the invention

[0005] Aiming at the strength-plasticity mismatch problem existing in ceramic particle reinforced nickel-based composite materials, the present invention designs a dual-phase high-entropy ceramic reinforced nickel-based composite material and develops a preparation method matching the dual-phase high-entropy ceramic reinforced nickel-based composite material.

[0006] The present invention discloses a dual-phase high-entropy ceramic reinforced nickel-based composite material. The dual-phase high-entropy ceramic reinforced nickel-based composite material is prepared by an additive manufacturing process and consists of a dual-phase high-entropy ceramic and a metal matrix. The dual-phase high-entropy ceramic contains (Ti, Ta, Nb, W, V, Mo) (C, N) phase and (Ti, Ta, Nb, Zr, Hf) (C, N) phase. The metal matrix is ​​a nickel-based high-temperature alloy. The mass ratio of the dual-phase high-entropy ceramic to the nickel-based high-temperature alloy is 1-5:98-95, preferably 1.5-2.5:98.5-97.5.

[0007] In the present invention, the dual-phase high-entropy ceramic phase contains (Ti, Ta, Nb, W, V, Mo) (C, N) phase and (Ti, Ta, Nb, Zr, Hf) (C, N) phase, which can play the role of regulating the morphology of the precipitation phase; the mass ratio of the dual-phase high-entropy ceramic phase and the nickel-based high-temperature alloy is controlled to be: 1~5:98~95, preferably 1.5~2.5:98.5~97.5, to ensure that the nickel-based high-temperature alloy has high strength and high elongation.

[0008] Preferably, the ceramic phase is a dual-phase high entropy ceramic; the raw material used in its preparation is TiO 2 Pink, Ta 2 O 5 Pink, Nb 2 O 5 Powder, ZrO 2 Pink, WO 3 Pink, V 2 O 5 Powder, HfO 2 Powder, MoO 3 powder, C powder, and TiO 2 Pink, Ta 2 O 5 Pink, Nb 2 O 5 Powder, ZrO 2 Pink, WO 3 Pink, V 2 O 5 Powder, HfO 2 Powder, MoO 3 The molar ratio of A powder and C powder is 2:1:1:2:2:1:2:2:47.

[0009] In the present invention, the molar ratio of each material is controlled to be 2:2:1:2:2:1:1:2:47 in order to control the molar ratio of each element. In the present invention, a large amount of C powder is used to not only play a reducing role but also form a proper amount of carbide at a special temperature.

[0010] In the present invention, TiO 2 Powder particle size ≤1.5μm; Ta 2 O 5 Powder particle size ≤1.5μm; Nb 2 O 5 Powder particle size ≤1.5μm; ZrO 2 Powder particle size ≤1.5μm; WO 3 Powder particle size ≤1.5μm; V 2 O 5 Powder particle size ≤1.0μm; HfO 2 Powder particle size ≤2.0μm; MoO 3The particle size of the powder ≤ 2.0 μm; the particle size of the C powder ≤ 0.3 μm.

[0011] The present invention relates to a method for preparing a dual-phase high-entropy ceramic reinforced nickel-based composite material, wherein the dual-phase high-entropy ceramic particles are prepared by the following process: Step 1 TiO 2 powder: Ta 2 O 5 powder: Nb 2 O 5 powder: ZrO 2 powder: WO 3 powder: V 2 O 5 powder: HfO 2 powder: MoO 3 The powders of C powder and the above-mentioned powders are taken in a molar ratio of 2:2:1:2:2:1:1:2:47. The weighed material powders are poured into the ball mill tank in sequence, and then grinding balls are added to the ball mill tank according to a ball-to-material mass ratio of 5:1; then anhydrous ethanol is poured into the ball mill tank as the ball milling medium. Finally, the anhydrous ethanol should submerge the grinding balls and the mixed powder, and the liquid level height is 0.4 - 0.6 of the tank height, preferably 0.48 - 0.52; the ball mill tank is fully sealed and placed in a planetary ball mill, and rotated at a speed of 200 r / min for 24 h in a manner of forward rotation for 30 min, interval of 10 min, reverse rotation for 30 min, interval of 10 min; After the ball milling is completed, the mixed powder slurry and the grinding balls are separated by a funnel, and the residual raw materials on the ball mill tank, grinding balls and funnel are repeatedly rinsed with anhydrous ethanol to obtain a mixed powder slurry completely separated from the grinding balls; The obtained slurry is poured into a spherical flask through a funnel, and then the spherical flask containing the mixed powder slurry is installed on a rotary evaporator. After rotary evaporation, the mixed powder is placed in a drying oven at 90 °C for drying for 20 - 24 h. The dried mixed powder is sieved through a 100-mesh sieve at least 2 times, and the undersize is taken to obtain a uniform mixed powder with consistent particle size.

[0012] Step 2 The mixed powder is sintered at a sintering temperature of 1550 °C and above, preferably 1590 - 1650 °C, more preferably 1600 °C, and held for at least 90 min, preferably held for 110 - 130 min, and then furnace cooled. Nitrogen is introduced during sintering; the sintered particles are ground, and after grinding, they are sieved through a 280-mesh sieve, and the dual-phase high-entropy ceramic powder after sieving is taken as one of the raw materials for printing; Pour the weighed nickel-based high-temperature alloy powder and dual-phase high-entropy ceramic powder into the ball mill in turn, and then add grinding balls into the ball mill according to the ball-to-material mass ratio of 5:1; fully seal the ball mill and put it into a planetary ball mill and rotate it at a speed of 200r / min for 20min to make it evenly mixed. Before printing, a three-dimensional model is created on the computer according to the shape of the part; the model is sliced ​​into layers using slicing software and imported into the additive manufacturing system; through the CNC system, a focused high-energy laser beam is used to scan the composite powder layer by layer according to the prescribed scanning route, and the layers are stacked until a three-dimensional part is formed.

[0013] The high-temperature tensile properties (650°C) of the printed product are as follows: the ultimate tensile strength is 805±12.71MPa, the yield strength is 506.39±11.43MPa, and the elongation is 40.87%.

[0014] Principles and advantages The present invention uses TiO 2 Pink, Ta 2 O 5 Pink, Nb 2 O 5 Powder, ZrO 2 Pink, WO 3 Pink, V 2 O 5 Powder, HfO 2 Powder, MoO 3 Powder and C powder are used as raw materials for sintering, and the sintering temperature is controlled at above 1550℃ to obtain dual-phase high-entropy ceramic powder. Under the synergistic effect of appropriate dual-phase high-entropy ceramic and nickel-based high-temperature alloy powder and printing parameters, a printed product with extremely high elongation and high mechanical strength is obtained. The optimized solution of the present invention has, for the first time, surpassed the pure printed nickel-based high-temperature alloy in three aspects: tensile strength, elongation, and hardness. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 XRD diagrams of the samples corresponding to Example 1, Example 2, and Comparative Example 1 of the present invention and the dual-phase high entropy ceramic powder; Figure 2 is a SEM image of the dual-phase high entropy ceramic powder of the present invention; Figure 3 This is a SEM image of the mixed powder in Example 1 of the present invention; Figure 4 This is a comparison chart of the high temperature tensile test results of Examples 1 and 2 of the present invention and Comparative Example 1; Figure 5 The figure is a comparison chart of the hardness of the products obtained in Examples 1 and 2 of the present invention and Comparative Example 1.

[0016] from Figure 1 It can be seen that the phase composition of the dual-phase high-entropy ceramic powder is (Ti, Ta, Nb, W, V, Mo) (C, N) and (Ti, Ta, Nb, Zr, Hf) (C, N), and the addition of dual-phase high-entropy ceramics has no obvious effect on the phase composition of the nickel-based high-temperature alloy.

[0017] from Figure 3 It can be seen that the dual-phase high entropy ceramic powder is evenly attached to the surface of the nickel-based high-temperature alloy powder.

[0018] from Figure 4 It can be seen that while the strength of Example 1 is improved, the plasticity is not reduced.

[0019] from Figure 5 It can be seen that the hardness of Example 1 is greatly improved. DETAILED DESCRIPTION

[0020] The present invention is further described in detail below in conjunction with specific embodiments.

[0021] Comparative Example 1 Step 1: Create a 3D model on the computer according to the shape of the part; slice the model into layers using slicing software and import it into the additive manufacturing system; use the CNC system to scan the nickel-based high-temperature alloy powder layer by layer according to the determined scanning route using a focused high-energy laser beam, and stack them layer by layer until a 3D part is formed; Step 2: The nickel-based alloy specimen formed by directed energy deposition has the following process parameters selected through preliminary process optimization: laser power 420 W, scanning speed 300 mm / min, scanning spacing 0.6 mm, laser spot 3 mm, and interlayer angle: 90°.

[0022] The mechanical properties of the printed products are as follows: The ultimate tensile strength at high temperature (650°C) is 759.09±4.96MPa, the yield strength is 485.96±2.44MPa, the elongation is 38.86%, and the hardness is 297.68±11.25HV 0.5 .

[0023] Comparative Example 2 Step 1: TiO 2 Powder (particle size ≤ 1.50 μm), Ta 2 O 5 Powder (particle size ≤ 1.10 μm), Nb 2 O 5 Powder (particle size ≤ 1.20 μm), ZrO 2 Powder (particle size ≤ 1.35 μm), WO 3 Powder (particle size ≤ 1.25 μm), V 2 O 5Powder (particle size ≤ 1.0 μm), HfO 2 Powder (particle size ≤ 2.0 μm), MoO 3 A powder (particle size ≤ 2.0 μm) and C powder (particle size ≤ 0.3 μm) are ball-milled to obtain a mixed powder; Step 2: TiO 2 Pink, Ta 2 O 5 Pink, Nb 2 O 5 Powder, ZrO 2 Pink, WO 3 Pink, V 2 O 5 Powder, HfO 2 Powder, MoO 3 The molar ratios of A powder and C powder are 2:2:1:2:2:1:1:2:47; Step 3: Pour the weighed powder into the ball mill in turn, and then add grinding balls into the ball mill according to the ball-to-powder mass ratio of 5:1; Step 4: Then slowly pour an appropriate amount of anhydrous ethanol into the ball mill as the ball milling medium. The anhydrous ethanol should eventually submerge the grinding balls and mixed powders, and the height of the liquid level should be about 0.5 of the tank body. Step 5: Seal the ball mill jar fully, put it into the planetary ball mill, and rotate it at 200r / min for 24h in the following manner: forward rotation for 30min, interval for 10min, reverse rotation for 30min, interval for 10min; Step 6: After the ball milling is completed, the mixed powder slurry and the grinding balls are separated by a funnel, and the residual raw materials on the ball mill, the grinding balls and the funnel are repeatedly rinsed with anhydrous ethanol to obtain a mixed powder slurry completely separated from the grinding balls; Step 7: The obtained slurry flows into a spherical bottle through a funnel, and then the spherical bottle containing the mixed powder slurry is installed on a rotary evaporator for rotary evaporation; Step 8: Place the mixed powder in a drying oven at 90°C and dry for 24 hours; Step 9: Sieve the dried mixed powder through a 200-mesh sieve three times to obtain a uniform mixed powder with a consistent particle size; Step 10: Place the mixed powder in a tube furnace for sintering at a temperature of 1400° C., keep the temperature for 2 hours, and then cool to room temperature in the furnace; Step 11: Grind the synthesized powder with an agate mortar, and then sieve it with a 280-mesh sieve to obtain a uniform dual-phase high-entropy ceramic powder with a consistent particle size; Step 12: Using dual-phase high-entropy ceramic powder as raw material A and nickel-based high-temperature alloy powder as raw material B; weighing raw material A: raw material B at a mass ratio of 2:98; then mixing raw material A and raw material B and drying for 12 hours to obtain a composite powder with uniformly distributed dual-phase high-entropy ceramic particles; Step 13: Building a three-dimensional model on a computer according to the shape of the part; using slicing software to slice the model into layers and importing it into an additive manufacturing system; using a numerical control system, using a focused high-energy laser beam to reciprocately scan the uniformly mixed powder in step (12) layer by layer according to a prescribed scanning route, and stacking layers until a three-dimensional part is formed; Step 14: The process parameters of the dual-phase high-entropy ceramic reinforced nickel-based composite material sample formed by directed energy deposition were selected through preliminary process optimization as follows: laser power 420 W, scanning speed 300 mm / min, scanning spacing 0.6 mm, laser spot 3 mm, and interlayer angle 90°.

[0024] After the product is printed, it can barely take shape, but the mechanical properties cannot be tested.

[0025] Comparative Example 3 Step 1: TiO 2 Powder (particle size ≤ 1.50 μm), Ta 2 O 5 Powder (particle size ≤ 1.10 μm), Nb 2 O 5 Powder (particle size ≤ 1.20 μm), ZrO 2 Powder (particle size ≤ 1.35 μm), WO 3 Powder (particle size ≤ 1.25 μm), V 2 O 5 Powder (particle size ≤ 1.0 μm), HfO 2 Powder (particle size ≤ 2.0 μm), MoO 3 A powder (particle size ≤ 2.0 μm) and C powder (particle size ≤ 0.3 μm) are ball-milled to obtain a mixed powder; Step 2: TiO 2 Pink, Ta 2 O 5 Pink, Nb 2 O 5 Powder, ZrO 2 Pink, WO 3 Pink, V 2 O 5 Powder, HfO 2 Powder, MoO 3 The molar ratios of A powder and C powder are 2:2:1:2:2:1:1:2:47; Step 3: Pour the weighed powder into the ball mill in turn, and then add grinding balls into the ball mill according to the ball-to-powder mass ratio of 5:1; Step 4: Then slowly pour an appropriate amount of anhydrous ethanol into the ball mill as the ball milling medium. The anhydrous ethanol should eventually submerge the grinding balls and mixed powders, and the height of the liquid level should be about 0.5 of the tank body. Step 5: Seal the ball mill jar fully, put it into the planetary ball mill, and rotate it at 200r / min for 24h in the following manner: forward rotation for 30min, interval for 10min, reverse rotation for 30min, interval for 10min; Step 6: After the ball milling is completed, the mixed powder slurry and the grinding balls are separated by a funnel, and the residual raw materials on the ball mill, the grinding balls and the funnel are repeatedly rinsed with anhydrous ethanol to obtain a mixed powder slurry completely separated from the grinding balls; Step 7: The obtained slurry flows into a spherical bottle through a funnel, and then the spherical bottle containing the mixed powder slurry is installed on a rotary evaporator for rotary evaporation; Step 8: Place the mixed powder in a drying oven at 90°C and dry for 24 hours; Step 9: Sieve the dried mixed powder through a 200-mesh sieve three times to obtain a uniform mixed powder with a consistent particle size; Step 10: Place the mixed powder in a tube furnace for sintering at a temperature of 1500° C., keep the temperature for 2 hours, and then cool to room temperature in the furnace; Step 11: Grind the synthesized powder with an agate mortar, and then sieve it with a 280-mesh sieve to obtain a uniform dual-phase high-entropy ceramic powder with a consistent particle size; Step 12: Using dual-phase high-entropy ceramic powder as raw material A and nickel-based high-temperature alloy powder as raw material B; weighing raw material A: raw material B at a mass ratio of 2:98; then mixing raw material A and raw material B and drying for 12 hours to obtain a composite powder with uniformly distributed dual-phase high-entropy ceramic particles; Step 13: Building a three-dimensional model on a computer according to the shape of the part; using slicing software to slice the model into layers and importing it into an additive manufacturing system; using a numerical control system, using a focused high-energy laser beam to reciprocately scan the uniformly mixed powder in step (12) layer by layer according to a prescribed scanning route, and stacking layers until a three-dimensional part is formed; Step 14: The process parameters of the dual-phase high-entropy ceramic reinforced nickel-based composite material sample formed by directed energy deposition were selected through preliminary process optimization as follows: laser power 420 W, scanning speed 300 mm / min, scanning spacing 0.6 mm, laser spot 3 mm, and interlayer angle 90°.

[0026] After the product is printed, it can barely take shape, but the mechanical properties cannot be tested.

[0027] Example 1 Step 1: TiO 2 Powder (particle size ≤ 1.50 μm), Ta2 O 5 Powder (particle size ≤ 1.10 μm), Nb 2 O 5 Powder (particle size ≤ 1.20 μm), ZrO 2 Powder (particle size ≤ 1.35 μm), WO 3 Powder (particle size ≤ 1.25 μm), V 2 O 5 Powder (particle size ≤ 1.0 μm), HfO 2 Powder (particle size ≤ 2.0 μm), MoO 3 A powder (particle size ≤ 2.0 μm) and C powder (particle size ≤ 0.3 μm) are ball-milled to obtain a mixed powder; Step 2: TiO 2 Pink, Ta 2 O 5 Pink, Nb 2 O 5 Powder, ZrO 2 Pink, WO 3 Pink, V 2 O 5 Powder, HfO 2 Powder, MoO 3 The molar ratios of A powder and C powder are 2:2:1:2:2:1:1:2:47; Step 3: Pour the weighed powder into the ball mill in turn, and then add grinding balls into the ball mill according to the ball-to-powder mass ratio of 5:1; Step 4: Then slowly pour an appropriate amount of anhydrous ethanol into the ball mill as the ball milling medium. The anhydrous ethanol should eventually submerge the grinding balls and mixed powders, and the height of the liquid level should be about 0.5 of the tank body. Step 5: Seal the ball mill jar fully, put it into the planetary ball mill, and rotate it at 200r / min for 24h in the following manner: forward rotation for 30min, interval for 10min, reverse rotation for 30min, interval for 10min; Step 6: After the ball milling is completed, the mixed powder slurry and the grinding balls are separated by a funnel, and the residual raw materials on the ball mill, the grinding balls and the funnel are repeatedly rinsed with anhydrous ethanol to obtain a mixed powder slurry completely separated from the grinding balls; Step 7: The obtained slurry flows into a spherical bottle through a funnel, and then the spherical bottle containing the mixed powder slurry is installed on a rotary evaporator for rotary evaporation; Step 8: Place the mixed powder in a drying oven at 90°C and dry for 24 hours; Step 9: Sieve the dried mixed powder through a 200-mesh sieve three times to obtain a uniform mixed powder with a consistent particle size; Step 10: Place the mixed powder in a tube furnace for sintering at a temperature of 1600° C., keep the temperature for 2 hours, and then cool to room temperature in the furnace; Step 11: Grind the synthesized powder with an agate mortar, and then sieve it with a 280-mesh sieve to obtain a uniform dual-phase high-entropy ceramic powder with a consistent particle size; Step 12: Using dual-phase high-entropy ceramic powder as raw material A and nickel-based high-temperature alloy powder as raw material B; weighing raw material A: raw material B at a mass ratio of 2:98; then mixing raw material A and raw material B and drying for 12 hours to obtain a composite powder with uniformly distributed dual-phase high-entropy ceramic particles; Step 13: Building a three-dimensional model on a computer according to the shape of the part; using slicing software to slice the model into layers and importing it into an additive manufacturing system; using a numerical control system, using a focused high-energy laser beam to reciprocately scan the uniformly mixed powder in step (12) layer by layer according to a prescribed scanning route, and stacking layers until a three-dimensional part is formed; Step 14: The process parameters of the dual-phase high-entropy ceramic reinforced nickel-based composite material sample formed by directed energy deposition were selected through preliminary process optimization as follows: laser power 420 W, scanning speed 300 mm / min, scanning spacing 0.6 mm, laser spot 3 mm, and interlayer angle 90°.

[0028] The mechanical properties of the printed product are as follows: The ultimate tensile strength at high temperature (650°C) is 805.15±12.71Mpa, the yield strength is 506.39±11.43Mpa, the elongation is 40.87%, and the hardness is 358.74±7.99HV 0.5 .

[0029] Comparative Example 4 Step 1: TiO 2 Powder (particle size ≤ 1.50 μm), Ta 2 O 5 Powder (particle size ≤ 1.10 μm), Nb 2 O 5 Powder (particle size ≤ 1.20 μm), ZrO 2 Powder (particle size ≤ 1.35 μm), WO 3 Powder (particle size ≤ 1.25 μm), V 2 O 5 Powder (particle size ≤ 1.0 μm), HfO 2 Powder (particle size ≤ 2.0 μm), MoO 3 A powder (particle size ≤ 2.0 μm) and C powder (particle size ≤ 0.3 μm) are ball-milled to obtain a mixed powder; Step 2: TiO 2 Pink, Ta 2 O5 Pink, Nb 2 O 5 Powder, ZrO 2 Pink, WO 3 Pink, V 2 O 5 Powder, HfO 2 Powder, MoO 3 The molar ratios of A powder and C powder are 2:2:1:2:2:1:1:2:47; Step 3: Pour the weighed powder into the ball mill in turn, and then add grinding balls into the ball mill according to the ball-to-powder mass ratio of 5:1; Step 4: Then slowly pour an appropriate amount of anhydrous ethanol into the ball mill as the ball milling medium. The anhydrous ethanol should eventually submerge the grinding balls and mixed powders, and the height of the liquid level should be about 0.5 of the tank body. Step 5: Seal the ball mill jar fully, put it into the planetary ball mill, and rotate it at 200r / min for 24h in the following manner: forward rotation for 30min, interval for 10min, reverse rotation for 30min, interval for 10min; Step 6: After the ball milling is completed, the mixed powder slurry and the grinding balls are separated by a funnel, and the residual raw materials on the ball mill, the grinding balls and the funnel are repeatedly rinsed with anhydrous ethanol to obtain a mixed powder slurry completely separated from the grinding balls; Step 7: The obtained slurry flows into a spherical bottle through a funnel, and then the spherical bottle containing the mixed powder slurry is installed on a rotary evaporator for rotary evaporation; Step 8: Place the mixed powder in a drying oven at 90°C and dry for 24 hours; Step 9: Sieve the dried mixed powder through a 200-mesh sieve three times to obtain a uniform mixed powder with a consistent particle size; Step 10: Place the mixed powder in a tube furnace for sintering at a temperature of 1400° C., keep the temperature for 2 hours, and then cool to room temperature in the furnace; Step 11: Grind the synthesized powder with an agate mortar, and then sieve it with a 280-mesh sieve to obtain a uniform dual-phase high-entropy ceramic powder with a consistent particle size; Step 12: Using dual-phase high-entropy ceramic powder as raw material A and nickel-based high-temperature alloy powder as raw material B; weighing raw material A: raw material B at a mass ratio of 5:95; then mixing raw material A and raw material B and drying for 12 hours to obtain a composite powder with uniformly distributed dual-phase high-entropy ceramic particles; Step 13: Building a three-dimensional model on a computer according to the shape of the part; using slicing software to slice the model into layers and importing it into an additive manufacturing system; using a numerical control system, using a focused high-energy laser beam to reciprocately scan the uniformly mixed powder in step (12) layer by layer according to a prescribed scanning route, and stacking layers until a three-dimensional part is formed; Step 14: The process parameters of the dual-phase high-entropy ceramic reinforced nickel-based composite material sample formed by directed energy deposition were selected through preliminary process optimization as follows: laser power 420 W, scanning speed 300 mm / min, scanning spacing 0.6 mm, laser spot 3 mm, and interlayer angle 90°.

[0030] After the product is printed, it can barely take shape, but the mechanical properties cannot be tested.

[0031] Comparative Example 5 Step 1: TiO 2 Powder (particle size ≤ 1.50 μm), Ta 2 O 5 Powder (particle size ≤ 1.10 μm), Nb 2 O 5 Powder (particle size ≤ 1.20 μm), ZrO 2 Powder (particle size ≤ 1.35 μm), WO 3 Powder (particle size ≤ 1.25 μm), V 2 O 5 Powder (particle size ≤ 1.0 μm), HfO 2 Powder (particle size ≤ 2.0 μm), MoO 3 A powder (particle size ≤ 2.0 μm) and C powder (particle size ≤ 0.3 μm) are ball-milled to obtain a mixed powder; Step 2: TiO 2 Pink, Ta 2 O 5 Pink, Nb 2 O 5 Powder, ZrO 2 Pink, WO 3 Pink, V 2 O 5 Powder, HfO 2 Powder, MoO 3 The molar ratios of A powder and C powder are 2:2:1:2:2:1:1:2:47; Step 3: Pour the weighed powder into the ball mill in turn, and then add grinding balls into the ball mill according to the ball-to-powder mass ratio of 5:1; Step 4: Then slowly pour an appropriate amount of anhydrous ethanol into the ball mill as the ball milling medium. The anhydrous ethanol should eventually submerge the grinding balls and mixed powders, and the height of the liquid level should be about 0.5 of the tank body. Step 5: Seal the ball mill jar fully, put it into the planetary ball mill, and rotate it at 200r / min for 24h in the following manner: forward rotation for 30min, interval for 10min, reverse rotation for 30min, interval for 10min; Step 6: After the ball milling is completed, the mixed powder slurry and the grinding balls are separated by a funnel, and the residual raw materials on the ball mill, the grinding balls and the funnel are repeatedly rinsed with anhydrous ethanol to obtain a mixed powder slurry completely separated from the grinding balls; Step 7: The obtained slurry flows into a spherical bottle through a funnel, and then the spherical bottle containing the mixed powder slurry is installed on a rotary evaporator for rotary evaporation; Step 8: Place the mixed powder in a drying oven at 90°C and dry for 24 hours; Step 9: Sieve the dried mixed powder through a 200-mesh sieve three times to obtain a uniform mixed powder with a consistent particle size; Step 10: Place the mixed powder in a tube furnace for sintering at a temperature of 1500° C., keep the temperature for 2 hours, and then cool to room temperature in the furnace; Step 11: Grind the synthesized powder with an agate mortar, and then sieve it with a 280-mesh sieve to obtain a uniform dual-phase high-entropy ceramic powder with a consistent particle size; Step 12: Using dual-phase high-entropy ceramic powder as raw material A and nickel-based high-temperature alloy powder as raw material B; weighing raw material A: raw material B at a mass ratio of 5:95; then mixing raw material A and raw material B and drying for 12 hours to obtain a composite powder with uniformly distributed dual-phase high-entropy ceramic particles; Step 13: Building a three-dimensional model on a computer according to the shape of the part; using slicing software to slice the model into layers and importing it into an additive manufacturing system; using a numerical control system, using a focused high-energy laser beam to reciprocately scan the uniformly mixed powder in step (12) layer by layer according to a prescribed scanning route, and stacking layers until a three-dimensional part is formed; Step 14: The process parameters of the dual-phase high-entropy ceramic reinforced nickel-based composite material sample formed by directed energy deposition were selected through preliminary process optimization as follows: laser power 420 W, scanning speed 300 mm / min, scanning spacing 0.6 mm, laser spot 3 mm, and interlayer angle 90°.

[0032] After the product is printed, it can barely take shape, but the mechanical properties cannot be tested.

[0033] Example 2 Step 1: TiO 2 Powder (particle size ≤ 1.50 μm), Ta 2 O 5 Powder (particle size ≤ 1.10 μm), Nb 2 O 5 Powder (particle size ≤ 1.20 μm), ZrO 2 Powder (particle size ≤ 1.35 μm), WO 3 Powder (particle size ≤ 1.25 μm), V 2 O 5Powder (particle size ≤ 1.0 μm), HfO 2 Powder (particle size ≤ 2.0 μm), MoO 3 A powder (particle size ≤ 2.0 μm) and C powder (particle size ≤ 0.3 μm) are ball-milled to obtain a mixed powder; Step 2: TiO 2 Pink, Ta 2 O 5 Pink, Nb 2 O 5 Powder, ZrO 2 Pink, WO 3 Pink, V 2 O 5 Powder, HfO 2 Powder, MoO 3 The molar ratios of A powder and C powder are 2:2:1:2:2:1:1:2:47; Step 3: Pour the weighed powder into the ball mill in turn, and then add grinding balls into the ball mill according to the ball-to-powder mass ratio of 5:1; Step 4: Then slowly pour an appropriate amount of anhydrous ethanol into the ball mill as the ball milling medium. The anhydrous ethanol should eventually submerge the grinding balls and mixed powders, and the height of the liquid level should be about 0.5 of the tank body. Step 5: Seal the ball mill jar fully, put it into the planetary ball mill, and rotate it at 200r / min for 24h in the following manner: forward rotation for 30min, interval for 10min, reverse rotation for 30min, interval for 10min; Step 6: After the ball milling is completed, the mixed powder slurry and the grinding balls are separated by a funnel, and the residual raw materials on the ball mill, the grinding balls and the funnel are repeatedly rinsed with anhydrous ethanol to obtain a mixed powder slurry completely separated from the grinding balls; Step 7: The obtained slurry flows into a spherical bottle through a funnel, and then the spherical bottle containing the mixed powder slurry is installed on a rotary evaporator for rotary evaporation; Step 8: Place the mixed powder in a drying oven at 90°C and dry for 24 hours; Step 9: Sieve the dried mixed powder through a 200-mesh sieve three times to obtain a uniform mixed powder with a consistent particle size; Step 10: Place the mixed powder in a tube furnace for sintering at a temperature of 1600° C., keep the temperature for 2 hours, and then cool to room temperature in the furnace; Step 11: Grind the synthesized powder with an agate mortar, and then sieve it with a 280-mesh sieve to obtain a uniform dual-phase high-entropy ceramic powder with a consistent particle size; Step 12: Using dual-phase high-entropy ceramic powder as raw material A and nickel-based high-temperature alloy powder as raw material B; weighing raw material A: raw material B at a mass ratio of 5:95; then mixing raw material A and raw material B and drying for 12 hours to obtain a composite powder with uniformly distributed dual-phase high-entropy ceramic particles; Step 13: Building a three-dimensional model on a computer according to the shape of the part; using slicing software to slice the model into layers and importing it into an additive manufacturing system; using a numerical control system, using a focused high-energy laser beam to reciprocately scan the uniformly mixed powder in step (12) layer by layer according to a prescribed scanning route, and stacking layers until a three-dimensional part is formed; Step 14: The process parameters of the dual-phase high-entropy ceramic reinforced nickel-based composite material sample formed by directed energy deposition were selected through preliminary process optimization as follows: laser power 420 W, scanning speed 300 mm / min, scanning spacing 0.6 mm, laser spot 3 mm, and interlayer angle 90°.

[0034] The mechanical properties of the printed product are as follows: The ultimate tensile strength at high temperature (650°C) is 733.08±6.56Mpa, the yield strength is 475.46±7.62Mpa, the elongation is 30.86%, and the hardness is 267.86±5.69HV 0.5 .

[0035]

[0036] There are some records of adding ceramic particles to nickel-based high-temperature alloys in the prior art: adding 10% Ti2AlC, the elongation drops from 24.6% to 12.6% (Additive manufacturing of high-strength Inconel 718 alloy through the addition of Ti2AlC MAX particles).

[0037] By adding 2% SiC, the elongation decreases from 30.3% to 12.3% (Strengthening additively manufactured Inconel 718 through in-situ formation of nanocarbides and silicides).

[0038] By adding 1.5% TiC, the elongation decreases from 27.17% to 12.08% (Regulating strength and ductility of additively manufactured Inconel 718 alloy via adding nano-TiC and deep cryogenic treatment).

Claims

1. A dual-phase high entropy ceramic reinforced nickel-based composite material; characterized in that: It is prepared by an additive manufacturing process and consists of a ceramic phase and a metal matrix; the dual-phase high-entropy ceramic phase contains (Ti, Ta, Nb, W, V, Mo) (C, N) phase and (Ti, Ta, Nb, Zr, Hf) (C, N) phase; the metal matrix is ​​a nickel-based high-temperature alloy; the mass ratio of the high-entropy ceramic phase to the nickel-based high-temperature alloy is: 1~5:99~95.

2. A dual-phase high entropy ceramic reinforced nickel-based composite material according to claim 1; characterized in that: The mass ratio of high entropy ceramic phase and metal matrix is ​​1.5~2.5:98.5~97.

5.

3. A dual-phase high entropy ceramic reinforced nickel-based composite material according to claim 1; characterized in that: The ceramic phase is a dual-phase high-entropy ceramic; the raw materials used in its preparation are TiO2 powder, Ta2O5 powder, Nb2O5 powder, ZrO2 powder, WO3 powder, V2O5 powder, HfO2 powder, MoO3 powder, and C powder, and the molar ratios of the material powders are 2:1:1:2:2:1:2:2:47 respectively.

4. A dual-phase high entropy ceramic reinforced nickel-based composite material according to claim 1; characterized in that: The particle size of TiO2 powder is ≤1.5μm; the particle size of Ta2O5 powder is ≤1.5μm; the particle size of Nb2O5 powder is ≤1.5μm; the particle size of ZrO2 powder is ≤1.5μm; the particle size of WO3 powder is ≤1.5μm; the particle size of V2O5 powder is ≤1.0μm; the particle size of HfO2 powder is ≤2.0μm; the particle size of MoO3 powder is ≤2.0μm; the particle size of C powder is ≤0.3μm.

5. A method for preparing a dual-phase high entropy ceramic reinforced nickel-based composite material according to any one of claims 1 to 4; characterized in that: The steps include: Step 1 Using dual-phase high entropy ceramic particles as raw material A and nickel-based high-temperature alloy powder as raw material B; according to the mass ratio, raw material A: raw material B = 2-5:98-95, preferably 1.5-2.5:98.5-97.5; preparing the raw materials; then placing raw material A and raw material B in a ball mill, mixing them evenly and drying them to obtain a composite powder; Step 2 The composite powder is used as raw material and the directed energy deposition forming process is adopted to print and prepare the product; during printing, the following controls are controlled: laser power 400~450W, preferably 415~425W, scanning speed 250~310mm / min, preferably 295~305mm / s, scanning spacing 0.6mm, laser spot 3mm, and interlayer angle 90°.

6. The method for preparing a dual-phase high entropy ceramic reinforced nickel-based composite material according to claim 5, characterized in that: In step 2, composite powder is used as raw material, and a directed energy deposition forming process is adopted to print and prepare the product; during printing, the following controls are controlled: laser power 415~425W, scanning speed 295~305mm / min, scanning spacing 0.6mm, laser spot 3mm, and interlayer angle 90°.

7. The method for preparing a dual-phase high entropy ceramic reinforced nickel-based composite material according to claim 5, characterized in that: The dual-phase high entropy ceramic particles are prepared by the following process: Step 1 TiO2 powder: Ta2O5 powder: Nb2O5 powder: ZrO2 powder: WO3 powder: V2O5 powder: HfO2 powder: MoO3 powder: C powder are prepared in a molar ratio of 2:2:1:2:2:1:1:2:47, and the prepared powders are poured into a ball mill in sequence, and then grinding balls are added to the ball mill according to a ball-to-material mass ratio of 5:1; then anhydrous ethanol is poured into the ball mill as a ball milling medium, and the anhydrous ethanol should eventually submerge the grinding balls and the mixed powder, and the height of the liquid level is 0.4-0.6 of the tank height, preferably 0.48-0.52; the ball mill is fully sealed, placed in a planetary ball mill, and mixed evenly; After the ball milling is completed, the mixed powder slurry and the grinding balls are separated by a funnel, and the residual raw materials on the ball mill, the grinding balls and the funnel are repeatedly rinsed with anhydrous ethanol to obtain the mixed powder slurry completely separated from the grinding balls; The obtained slurry flows into the spherical bottle through the funnel, and then the spherical bottle containing the mixed powder slurry is installed on the rotary evaporator. After rotary evaporation, the mixed powder is placed in a drying oven at 90°C for 20-24 hours. The dried mixed powder is sieved through a 100-mesh sieve at least twice, and the sieved material is taken to obtain a uniform mixed powder with consistent particle size; Step 2 The mixed powder is sintered at a sintering temperature of 1550°C or above, preferably 159-1650°C, and more preferably 1600°C. After keeping the temperature for at least 90 minutes, preferably 110-130 minutes, the mixed powder is cooled in the furnace and nitrogen is passed during sintering. After sintering, the mixed powder is ground and passed through a 280-mesh sieve. The sieved high-entropy ceramic powder is used as one of the raw materials for printing.

8. The method for preparing a dual-phase high-entropy ceramic reinforced nickel-based composite material according to claim 5, characterized in that: Pour the weighed nickel-based high-temperature alloy powder and dual-phase high-entropy ceramic powder into the ball mill in sequence, and then add grinding balls into the ball mill at a ball-to-material mass ratio of 5:1; fully seal the ball mill and put it into a planetary ball mill for uniform mixing; After ball milling, the mixed powder and the grinding balls were separated using a 100-mesh sieve to finally obtain a dual-phase high-entropy ceramic reinforced nickel-based composite powder.

9. The method for preparing a dual-phase high entropy ceramic reinforced nickel-based composite material according to claim 5, characterized in that: The properties of the printed product under high temperature tensile test are as follows: the ultimate tensile strength is 805±12.71MPa, the yield strength is 506.39±11.43MPa, and the elongation is 40.87%.

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