CN114472904B - Preparation method of CuCrZr spherical powder for 3D printing - Google Patents
Preparation method of CuCrZr spherical powder for 3D printing Download PDFInfo
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- CN114472904B CN114472904B CN202210337932.XA CN202210337932A CN114472904B CN 114472904 B CN114472904 B CN 114472904B CN 202210337932 A CN202210337932 A CN 202210337932A CN 114472904 B CN114472904 B CN 114472904B
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/044—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by jet milling
Abstract
The invention discloses a preparation method of CuCrZr spherical powder for 3D printing, which comprises the following steps: s1, batching: preparing raw materials according to the requirements, wherein the raw materials comprise the following components in percentage by mass: 0.9 to 1.1 percent of metal chromium block, 0.04 to 0.05 percent of zirconia powder, 0.2 to 0.3 percent of zirconium oxychloride octahydrate and the balance of electrolytic copper plate; s2, primary vacuum melting; s3, secondary overweight smelting; s4, grinding into powder by airflow; and S5, post-processing. The CuCrZr spherical powder disclosed by the invention is good in sphericity and high in hardness, the material components meet requirements, and various requirements of SLM 3D printing can be met, so that the printed alloy material is high in density and uniform in structure, and further popularization and application are facilitated.
Description
Technical Field
The invention relates to the technical field of metal powder manufacturing, in particular to a preparation method of CuCrZr spherical powder for 3D printing.
Background
Pure copper and copper alloy are widely applied to the fields of electric power, heat dissipation, pipelines, decoration and the like due to the characteristics of excellent electric conductivity, heat conductivity, corrosion resistance, toughness and the like, and some copper alloy materials are widely applied to manufacturing aviation and aerospace engine combustor components due to good electric conductivity, heat conductivity and higher strength; however, as the demands of application ends on parts with complex structures increase, the traditional processing technology can not meet all the demands gradually;
The metal 3D printing technology can be used for manufacturing complex function integrated parts, the material utilization rate is high, a die is not needed, the advantages can be reflected in the field of copper metal manufacturing, for example, in the field of copper inductance coil manufacturing, the metal 3D printing technology can be used for replacing the traditional manufacturing process to directly manufacture complex inductance coils; the selective laser melting metal 3D printing technology (SLM) has the advantages of forming parts with complex structures, being high in material utilization rate, not needing a die and the like, and has great application potential in the aspect of preparing parts such as copper alloy heat exchangers, tail nozzles and the like with complex structures;
however, the alloy powder prepared by the traditional metal powder preparation process hardly meets the requirements of SLM 3D printing, the alloy powder obtained by the traditional processing process is often low in sphericity and more in microcrack and micro-void, so that the problem that a printed alloy workpiece is easy to crack and break and the like is easily caused, the expansion of cracks is promoted by the voids in an SLM forming part, and the mechanical property is remarkably reduced, so that the selection of the copper alloy spherical powder with good performance is the primary target of optimization of the 3D printing process;
the patent CN101628338B discloses an iron-copper alloy powder and a preparation method thereof, the iron-copper alloy powder prepared by the method is prepared by taking iron oxalate powder of industrial raw material grade and copper oxide powder of industrial raw material grade as raw materials and carrying out high-energy ball milling and hydrogen reduction, the Fisher particle size of the alloy powder is less than 1.0 mu m, and the oxygen content is less than or equal to 0.5 percent (wt); the alloy powder prepared by the method has finer grains, more excellent physical and chemical properties and low manufacturing cost; however, the alloy powder prepared by the method is difficult to apply to SLM 3D printing with high requirements on the powder.
Disclosure of Invention
Aiming at the existing problems, the invention provides a preparation method of CuCrZr spherical powder for 3D printing;
the technical scheme of the invention is as follows:
a preparation method of CuCrZr spherical powder for 3D printing comprises the following steps:
s1, batching: preparing raw materials according to the requirements, wherein the raw materials comprise the following components in percentage by mass: 0.9 to 1.1 percent of metal chromium block, 0.04 to 0.05 percent of zirconia powder, 0.2 to 0.3 percent of zirconium oxychloride octahydrate and the balance of electrolytic copper plate;
s2, primary vacuum melting: placing the prepared electrolytic copper plate into a crucible, vacuumizing, filling argon, heating the crucible to 1500-plus-1600 ℃ at the temperature rise speed of 200-plus-220 ℃/h, continuing to preserve heat for 30min after the electrolytic copper plate is completely melted, then adding a metal chromium block, heating the crucible to 1700-plus-1800 ℃ at the temperature rise speed of 140-plus-160 ℃/h, and completely melting the metal chromium block to obtain a copper-chromium alloy melt;
s3, secondary overweight smelting:
s3-1: preheating an overweight reaction vessel to 1350-1380 ℃, pouring a copper-chromium alloy melt, heating to 1850 ℃ at the temperature rise speed of 30-40 ℃/h under the protection of argon gas, simultaneously adding zirconia powder, then raising the gravity field to 6000-8000g at the weight rise speed of 220g/s of 180-8000 g, and keeping for 1-2 h;
S3-2: under the condition of keeping the gravity field unchanged, reducing the temperature to 1350-;
s3-3: removing the gravity field, and naturally cooling the overweight reaction container to room temperature to obtain a CuCrZr alloy cast ingot;
s4, airflow grinding:
s4-1: crushing the CuCrZr alloy cast ingot in a fully-sealed middle crusher for 3 hours to obtain CuCrZr alloy coarse powder with the particle size of less than 0.4 mm;
s4-2: placing the CuCrZr alloy coarse powder in an airflow mill, and performing airflow milling grinding by using high-purity nitrogen, wherein the airflow milling working medium pressure is 0.5-0.52MPa, the rotation speed of a sorting wheel is 3200-;
s5, post-processing: screening the CuCrZr alloy fine powder, screening the CuCrZr alloy fine powder with D50 being 40-80 mu m, putting the screened CuCrZr alloy fine powder in a magnetic field of 800kA/m, pressurizing for 1-2h, then carrying out cold isostatic pressing for 2h under the pressure of 200MPa, forming, and carrying out heat treatment and cooling to obtain CuCrZr spherical powder.
Further, the purity of the chromium metal block in the step S1 is 99.95-99.99%; ensuring that the added metal chromium block does not contain other impurities;
Further, the vacuum degree after the vacuum pumping in the step S2 is 0.5 Pa; the vacuum effect in the smelting process is ensured;
further, the zirconium oxychloride octahydrate is added in the step S3-2 in a dropwise manner, wherein the dropwise adding speed is 5-8 ml/S; the reasonable dropping speed is controlled to be beneficial to the stability of the reaction;
further, the velocity of removing the gravitational field in the step S3-3 is 100-120g/S, and the room temperature is 23-27 ℃; when the gravitational field is removed, the removal is not too fast, which can cause micro cracks to appear in the prepared CuCrZr spherical powder;
further, the purity of the high-purity nitrogen gas in the step S4-2 is 99.97-99.99%; the oxygen content in the process of milling by airflow grinding is reduced as much as possible;
further, the step of heat treatment in step S5 is: placing the CuCrZr alloy fine powder in a vacuum crucible, heating to 1200-1300 ℃ for vacuum sintering for 15-30min, then cooling to 850-890 ℃ at the cooling rate of 40-50 ℃/h, preserving the heat for 2h, and then cooling to 25-28 ℃ at the cooling rate of 120-140 ℃/h; the CuCrZr alloy powder has high saturation magnetization, uniform and adjustable powder granularity and good dispersibility through post-treatment;
further, the preparation method of the zirconia powder in step S1 is:
S1-1: mixing zircon concentrate powder, crystalline graphite, pyrolytic graphite and calcite in a proportion of 23: 6: 5: 2, putting the mixture into a grinder together to grind the mixture until the particle size is less than 0.5mm to obtain mixed powder;
s1-2: placing the ground mixed powder into an electric arc furnace, carrying out electric arc melting for 2-3h under the temperature condition of 2730-2750 ℃, and then carrying out quenching and cooling to 550-560 ℃ to obtain zirconium-rich crystals;
s1-3: calcining the zirconium-rich crystal in a crucible at the temperature of 1700-1800 ℃ for 2h to obtain zirconium oxide, cooling and crushing to obtain the zirconium oxide with the particle size of 0.05-0.2 mm;
furthermore, in the step S1-2, the quenching temperature reduction is performed by using liquid nitrogen, and the temperature reduction speed is 180-; the liquid nitrogen cooling promotes the crystal development, and the prepared zirconia has good stability.
The invention has the beneficial effects that:
(1) the CuCrZr spherical powder disclosed by the invention is good in sphericity and high in hardness, the material components meet requirements, and various requirements of SLM 3D printing can be met, so that the printed alloy material is high in density and uniform in structure, and further popularization and application are facilitated;
(2) according to the preparation method of the CuCrZr spherical powder ball, the CuCrZr spherical powder ball is smelted in an overweight state by introducing a secondary supergravity smelting method, so that the diffusion and mass transfer processes among particles are enhanced, the prepared powder has better dispersibility, the surface of the powder is complete and compact, and the generation of micropores and microcracks is avoided, so that the strength performance of a 3D printing alloy part is improved;
(3) According to the preparation method of the CuCrZr spherical powder ball, trace zirconia powder is added in the smelting process, the preparation process of the zirconia powder is optimized, liquid nitrogen cooling promotes the growth of zirconia crystals, and through the characteristics of high strength, high toughness, high surface finish, no toxicity, corrosion resistance and stable chemical performance of the zirconia powder, the zirconium oxychloride octahydrate and the copper-chromium alloy are added for co-sintering, so that the performance advantages of all components are integrated, and no impurity element is introduced;
(4) the preparation method of the CuCrZr spherical powder ball has the advantages of high refining efficiency by using airflow grinding, uniform and adjustable prepared powder granularity, good dispersibility, large saturation magnetization by pressurizing in a magnetic field, and good stability and reliability along with the change of temperature and environment.
Drawings
FIG. 1 is a process flow diagram of a preparation method of the present invention;
FIG. 2 is a gold phase diagram of an alloy material obtained by SLM 3D printing of the CuCrZr spherical powder prepared by the preparation method in the embodiment 1 of the invention.
Detailed Description
Example 1
A preparation method of CuCrZr spherical powder for 3D printing comprises the following steps:
s1, batching: preparing raw materials according to the requirements, wherein the raw materials comprise the following components in percentage by mass: 1% of metal chromium block, 0.045% of zirconia powder, 0.25% of octahydrate zirconium oxychloride with the mass concentration of 20%, and the balance of electrolytic copper plate, wherein the purity of the metal chromium block is 99.97%;
The preparation method of the zirconium oxide powder comprises the following steps:
s1-1: mixing zircon concentrate powder, crystalline flake graphite, pyrolytic graphite and calcite in a proportion of 23: 6: 5: 2, putting the mixture into a grinder together to grind the mixture until the particle size is less than 0.5mm to obtain mixed powder;
s1-2: placing the ground mixed powder into an electric arc furnace, carrying out electric arc melting for 2.5h at the temperature of 2740 ℃, then carrying out quenching and cooling to 555 ℃, cooling by using liquid nitrogen at the quenching and cooling speed of 190 ℃/h to obtain zirconium-rich crystals;
s1-3: putting the zirconium-rich crystal into a crucible, calcining for 2h at 1750 ℃ to obtain zirconium oxide, cooling, and crushing to obtain the zirconium oxide with the particle size of 0.1 mm;
s2, primary vacuum melting: putting the prepared electrolytic copper plate into a crucible, vacuumizing to 0.5Pa, filling argon, heating the crucible to 1550 ℃ at the heating rate of 210 ℃/h, continuing to preserve heat for 30min after the electrolytic copper plate is completely melted, then adding a metal chromium block, heating the crucible to 1750 ℃ at the heating rate of 150 ℃/h, and completely melting the metal chromium block to obtain a copper-chromium alloy melt;
s3, secondary overweight smelting:
s3-1: preheating an overweight reaction vessel to 1360 ℃, pouring a copper-chromium alloy melt, heating to 1840 ℃ at a heating rate of 34 ℃/h under the protection of argon gas, simultaneously adding zirconia powder, then increasing the gravity field to 7000g at a weighting rate of 200g/s, and keeping for 1.5 h;
S3-2: under the condition of keeping the gravity field unchanged, reducing the temperature to 1400 ℃ at the cooling speed of 35 ℃/h, simultaneously adding zirconium oxychloride octahydrate, dropwise adding zirconium oxychloride octahydrate at the dropping speed of 6ml/s, and keeping for 0.75 h;
s3-3: removing the gravity field at the speed of 110g/s, and naturally cooling the overweight reaction container to room temperature, wherein the room temperature is 25 ℃, so as to obtain a CuCrZr alloy cast ingot;
s4, airflow grinding:
s4-1: crushing the CuCrZr alloy cast ingot in a fully-sealed middle crusher for 3 hours, wherein the fully-sealed middle crusher is a commercially-available CJMR-150X type middle crusher, and CuCrZr alloy coarse powder with the particle size of less than 0.4mm is obtained;
s4-2: placing the CuCrZr alloy coarse powder into an airflow mill, and performing airflow milling grinding by using high-purity nitrogen gas, wherein the airflow mill is a commercial QLM-2C airflow mill pulverizer, the purity of the high-purity nitrogen gas is 99.98%, the working pressure of the airflow mill is 0.51MPa, the rotating speed of a sorting wheel is 3300r/min, and the CuCrZr alloy coarse powder is ground for 110min at the airflow speed of 265m/s to obtain CuCrZr alloy fine powder;
s5, post-processing: screening the CuCrZr alloy fine powder, screening the CuCrZr alloy fine powder with D50 being 50-60 mu m, putting the screened CuCrZr alloy fine powder in a magnetic field of 800kA/m for pressurizing for 1.5h, then carrying out cold isostatic pressing for 2h under the pressure condition of 200MPa for molding, and then carrying out heat treatment and cooling to obtain CuCrZr spherical powder, wherein the heat treatment step is as follows: placing the CuCrZr alloy fine powder into a vacuum crucible, heating to 1250 ℃, vacuum sintering for 20min, then cooling to 870 ℃ at a cooling rate of 45 ℃/h, preserving heat for 2h, and then cooling to 26 ℃ at a cooling rate of 130 ℃/h.
Example 2
The present embodiment is different from embodiment 1 in that: the ingredients in the step S1 have different ingredient ratios;
s1, batching: preparing raw materials according to the requirements, wherein the raw materials comprise the following components in percentage by mass: 0.9 percent of metal chromium block, 0.04 percent of zirconia powder, 0.2 percent of zirconium oxychloride octahydrate with the mass concentration of 20 percent, and the balance of electrolytic copper plate, wherein the purity of the metal chromium block is 99.95 percent.
Example 3
The present embodiment is different from embodiment 1 in that: the ingredients in the step S1 have different ingredient ratios;
s1, batching: preparing raw materials according to the requirements, wherein the raw materials comprise the following components in percentage by mass: 1.1 percent of metal chromium block, 0.05 percent of zirconia powder, 0.3 percent of octahydrate dichloro zirconia with the mass concentration of 20 percent, and the balance of electrolytic copper plate, wherein the purity of the metal chromium block is 99.99 percent.
Example 4
The present embodiment is different from embodiment 1 in that: the preparation method parameters of the zirconium oxide powder are different;
the preparation method of the zirconium oxide powder comprises the following steps:
s1-1: mixing zircon concentrate powder, crystalline flake graphite, pyrolytic graphite and calcite in a proportion of 23: 6: 5: 2, putting the mixture into a grinder together to grind the mixture until the particle size is less than 0.5mm to obtain mixed powder;
s1-2: placing the ground mixed powder into an electric arc furnace, carrying out electric arc melting for 2h at the temperature of 2730 ℃, then carrying out quenching and cooling to 550 ℃, and carrying out quenching and cooling by using liquid nitrogen at the cooling speed of 180 ℃/h to obtain a zirconium-rich crystal;
S1-3: and putting the zirconium-rich crystal into a crucible, calcining for 2 hours at the temperature of 1700 ℃ to obtain zirconium oxide, cooling, and crushing to obtain the zirconium oxide with the particle size of 0.05 mm.
Example 5
The present embodiment is different from embodiment 1 in that: the preparation method parameters of the zirconium oxide powder are different;
the preparation method of the zirconium oxide powder comprises the following steps:
s1-1: mixing zircon concentrate powder, crystalline flake graphite, pyrolytic graphite and calcite in a proportion of 23: 6: 5: 2, putting the mixture into a grinder together to grind the mixture until the particle size is less than 0.5mm to obtain mixed powder;
s1-2: placing the ground mixed powder into an electric arc furnace, carrying out electric arc melting for 2h at the temperature of 2750 ℃, then carrying out quenching and cooling to 560 ℃, and carrying out quenching and cooling by using liquid nitrogen at the cooling speed of 200 ℃/h to obtain zirconium-rich crystals;
s1-3: and calcining the zirconium-rich crystal in a crucible at the temperature of 1800 ℃ for 2 hours to obtain zirconium oxide, cooling, and crushing to obtain the zirconium oxide with the particle size of 0.2 mm.
Example 6
The present embodiment is different from embodiment 1 in that: the parameters of the primary vacuum melting in the step S2 are different;
s2, primary vacuum melting: and putting the prepared electrolytic copper plate into a crucible, vacuumizing to 0.5Pa, filling argon, heating the crucible to 1500 ℃ at the heating rate of 200 ℃/h, keeping the temperature for 30min after the electrolytic copper plate is completely melted, adding a metal chromium block, heating the crucible to 1700 ℃ at the heating rate of 140 ℃/h, and completely melting the metal chromium block to obtain the copper-chromium alloy melt.
Example 7
The present embodiment is different from embodiment 1 in that: the parameters of the primary vacuum melting in the step S2 are different;
s2, primary vacuum melting: and putting the prepared electrolytic copper plate into a crucible, vacuumizing to 0.5Pa, filling argon, heating the crucible to 1600 ℃ at the heating rate of 220 ℃/h, keeping the temperature for 30min after the electrolytic copper plate is completely melted, adding a metal chromium block, heating the crucible to 1800 ℃ at the heating rate of 160 ℃/h, and completely melting the metal chromium block to obtain the copper-chromium alloy melt.
Example 8
The present embodiment is different from embodiment 1 in that: step S3, parameters of the secondary overweight smelting are different;
s3, secondary overweight smelting:
s3-1: preheating an overweight reaction container to 1350 ℃, pouring a copper-chromium alloy melt, heating to 1830 ℃ at a heating rate of 30 ℃/h under the protection of argon, simultaneously adding zirconia powder, then increasing a gravity field to 6000g at a weighting rate of 180g/s, and keeping for 1 h;
s3-2: under the condition of keeping the gravity field unchanged, reducing the temperature to 1350 ℃ at the cooling speed of 30 ℃/h, simultaneously adding zirconium oxychloride octahydrate, dropwise adding zirconium oxychloride octahydrate at the dropping speed of 5ml/s, and keeping for 0.5 h;
S3-3: and removing the gravity field at the speed of 100g/s, and naturally cooling the overweight reaction container to room temperature of 23 ℃ to obtain the CuCrZr alloy cast ingot.
Example 9
The present embodiment is different from embodiment 1 in that: step S3, parameters of the secondary overweight smelting are different;
s3, secondary overweight smelting:
s3-1: preheating an overweight reaction vessel to 1380 ℃, pouring a copper-chromium alloy melt, heating to 1850 ℃ at a heating rate of 40 ℃/h under the protection of argon gas, simultaneously adding zirconia powder, then increasing a gravity field to 8000g at a weighting rate of 220g/s, and keeping for 2 h;
s3-2: under the condition of keeping the gravity field unchanged, reducing the temperature to 1450 ℃ at the cooling speed of 40 ℃/h, simultaneously adding zirconium oxychloride octahydrate, dropwise adding zirconium oxychloride octahydrate at the dropwise adding speed of 8ml/s, and keeping for 1 h;
s3-3: and removing the gravity field at the speed of 120g/s, and naturally cooling the overweight reaction container to room temperature, wherein the room temperature is 27 ℃, so as to obtain the CuCrZr alloy cast ingot.
Example 10
The present embodiment is different from embodiment 1 in that: step S4, the parameters of airflow grinding are different;
s4, airflow grinding:
S4-1: crushing the CuCrZr alloy cast ingot for 3 hours in a fully-sealed medium crusher which is a commercially-available CJMR-150X type medium crusher to obtain CuCrZr alloy coarse powder with the particle size of less than 0.4 mm;
s4-2: and (2) placing the CuCrZr alloy coarse powder into an air flow mill, carrying out air flow milling grinding by using high-purity nitrogen gas, wherein the air flow mill is a commercial QLM-2C air flow mill pulverizer, the purity of the high-purity nitrogen gas is 99.97%, the working pressure of the air flow mill is 0.5MPa, the rotating speed of a sorting wheel is 3200r/min, and grinding for 100min at the air flow speed of 260m/s to obtain the CuCrZr alloy fine powder.
Example 11
The present embodiment is different from embodiment 1 in that: step S4, the parameters of airflow grinding are different;
s4, airflow grinding:
s4-1: crushing the CuCrZr alloy cast ingot in a fully-sealed middle crusher for 3 hours, wherein the fully-sealed middle crusher is a commercially-available CJMR-150X type middle crusher, and CuCrZr alloy coarse powder with the particle size of less than 0.4mm is obtained;
s4-2: and (2) placing the CuCrZr alloy coarse powder into an air flow mill, carrying out air flow milling grinding by using high-purity nitrogen gas, wherein the air flow mill is a commercial QLM-2C air flow mill pulverizer, the purity of the high-purity nitrogen gas is 99.99%, the working pressure of the air flow mill is 0.52MPa, the rotating speed of a sorting wheel is 3400r/min, and grinding for 120min at the air flow speed of 270m/s to obtain the CuCrZr alloy fine powder.
Example 12
The present embodiment is different from embodiment 1 in that: the post-processing parameters of step S5 are different;
s5, post-processing: screening the CuCrZr alloy fine powder, screening the CuCrZr alloy fine powder with D50 being 40-60 mu m, putting the screened CuCrZr alloy fine powder in a magnetic field of 800kA/m for pressurizing for 1h, then carrying out cold isostatic pressing for 2h under the pressure of 200MPa for molding, and then carrying out heat treatment and cooling to obtain CuCrZr spherical powder, wherein the heat treatment step is as follows: placing the CuCrZr alloy fine powder into a vacuum crucible, heating to 1200 ℃, sintering in vacuum for 15min, then cooling to 850 ℃ at a cooling rate of 40 ℃/h, preserving heat for 2h, and then cooling to 25 ℃ at a cooling rate of 120 ℃/h.
Example 13
The present embodiment is different from embodiment 1 in that: the post-processing parameters of step S5 are different;
s5, post-processing: screening the CuCrZr alloy fine powder, screening the CuCrZr alloy fine powder with D50 being 60-80 mu m, putting the screened CuCrZr alloy fine powder in a magnetic field of 800kA/m for pressurizing for 2h, then carrying out cold isostatic pressing for 2h under the pressure of 200MPa for molding, and carrying out heat treatment and cooling to obtain CuCrZr spherical powder, wherein the heat treatment step is as follows: placing the CuCrZr alloy fine powder in a vacuum crucible, heating to 1300 ℃, vacuum sintering for 30min, then cooling to 890 ℃ at a cooling rate of 50 ℃/h, preserving heat for 2h, and then cooling to 28 ℃ at a cooling rate of 140 ℃/h.
Experimental example 1
The CuCrZr spherical powder prepared by the preparation method in the embodiments 1-3 is applied to SLM 3D printing, the strength performance of the printed alloy material is tested, and meanwhile, compared with CuCrZr powder obtained by a conventional melting method (comparative example 1), the SLM 3D printing method comprises the following steps: paving powder, printing by using a 400W laser, scanning at a speed of 10m/s, a spot diameter of 100 mu m, a layer thickness of 60 mu m, and protecting by argon gas to obtain an alloy material with mechanical properties shown in Table 1;
TABLE 1 mechanical Properties of alloy materials of examples 1-3 and comparative example 1
| Examples | Density% | Tensile strength MPa | Yield strength MPa |
| Example 1 | 99.4 | 392 | 365 |
| Example 2 | 99.1 | 388 | 361 |
| Example 3 | 99.5 | 393 | 366 |
| Comparative example 1 | 98.7 | 376 | 349 |
As can be seen from the data in Table 1, the alloy material obtained by SLM 3D printing of the CuCrZr spherical powder prepared by the preparation method disclosed by the invention is superior to that of comparative example 1 in the performances of density, tensile strength and yield strength, and the preparation method disclosed by the invention can enable the CuCrZr spherical powder to be more compact and have fewer surface cracks, so that the mechanical property of the 3D printed alloy material is improved; comparing with examples 1-3, it can be seen that the charge ratios of 3 different metal elements in 3 groups of examples can achieve better mechanical properties, and the mechanical properties of the CuCrZr spherical powder prepared from the chromium block with the highest purity in example 3 after 3D printing are optimal.
Experimental example 2
Applying the CuCrZr spherical powder prepared by the preparation method in the embodiments 1, 8 and 9 of the invention to SLM 3D printing, testing the strength performance of the printed alloy material, and comparing with the comparative example 2, wherein the comparative example 2 does not use the secondary overweight smelting of the invention, the rest steps are the same as the embodiment 1, the SLM 3D printing method is the same as the embodiment 1, and the mechanical properties of the obtained alloy material are shown in Table 2;
TABLE 2 mechanical Properties of alloy materials of examples 1, 8, 9 and comparative example 2
| Examples | Hardness HBW | Tensile strength MPa | Yield strength MPa |
| Example 1 | 87 | 392 | 365 |
| Example 8 | 85 | 387 | 364 |
| Example 9 | 86 | 391 | 365 |
| Comparative example 2 | 79 | 379 | 343 |
As can be seen from the data in Table 2, compared with the comparative example 2, the alloy materials in the examples 1, 8 and 9 have obvious improvement on the mechanical properties, particularly the hardness, and the tensile strength and the yield strength are improved in a small range, so that the hardness of the prepared CuCrZr spherical powder and the hardness of the 3D printing material can be effectively improved by the secondary overweight smelting of the invention.
Experimental example 3
Applying the CuCrZr spherical powder prepared by the preparation method in the embodiments 1, 12 and 13 of the invention to SLM 3D printing, testing the strength performance of the printed alloy material, and comparing with the comparative example 3, wherein the comparative example 3 does not use the post-treatment of the invention, the rest steps are the same as the embodiment 1, the SLM 3D printing method is the same as the embodiment 1, and the mechanical properties of the obtained alloy material are shown in Table 3;
TABLE 3 mechanical Properties of alloy materials of examples 1, 12, 13 and comparative example 3
| Examples | Elongation percentage% | Tensile strength MPa | Yield strength MPa |
| Example 1 | 12.9 | 392 | 365 |
| Example 12 | 12.5 | 388 | 364 |
| Example 13 | 12.6 | 392 | 363 |
| Comparative example 3 | 12.1 | 390 | 362 |
As can be seen from the data in table 3, compared with comparative example 3, the elongation of the alloy materials in examples 1, 12 and 13 is significantly improved, which indicates that the post-treatment method of the present invention has a significant effect on the elongation of the alloy material obtained by 3D printing of the CuCrZr spherical powder, and the CuCrZr spherical powder obtained by the post-treatment parameters in example 1 has the best performance;
in addition, the parameters in examples 4-7, 10 and 11 are routine adjustments within the range given by the invention, and any group of the prepared CuCrZr spherical powder can achieve better performance.
Claims (8)
1. A preparation method of CuCrZr spherical powder for 3D printing is characterized by comprising the following steps:
s1, batching: preparing raw materials according to the requirements, wherein the raw materials comprise the following components in percentage by mass: 0.9 to 1.1 percent of metal chromium block, 0.04 to 0.05 percent of zirconia powder, 0.2 to 0.3 percent of zirconium oxychloride octahydrate and the balance of electrolytic copper plate;
s2, primary vacuum melting: placing the prepared electrolytic copper plate into a crucible, vacuumizing, filling argon, heating the crucible to 1500-plus-1600 ℃ at the temperature rise speed of 200-plus-220 ℃/h, continuing to preserve heat for 30min after the electrolytic copper plate is completely melted, then adding a metal chromium block, heating the crucible to 1700-plus-1800 ℃ at the temperature rise speed of 140-plus-160 ℃/h, and completely melting the metal chromium block to obtain a copper-chromium alloy melt;
S3, secondary overweight smelting:
s3-1: preheating an overweight reaction vessel to 1350-1380 ℃, pouring a copper-chromium alloy melt, heating to 1850 ℃ at the temperature rise speed of 30-40 ℃/h under the protection of argon gas, simultaneously adding zirconia powder, then raising the gravity field to 6000-8000g at the weight rise speed of 220g/s of 180-8000 g, and keeping for 1-2 h;
s3-2: under the condition of keeping the gravity field unchanged, reducing the temperature to 1350-;
s3-3: removing the gravity field, and naturally cooling the overweight reaction container to room temperature to obtain a CuCrZr alloy cast ingot;
s4, airflow grinding:
s4-1: crushing the CuCrZr alloy cast ingot in a fully-sealed middle crusher for 3 hours to obtain CuCrZr alloy coarse powder with the particle size of less than 0.4 mm;
s4-2: placing the CuCrZr alloy coarse powder in an airflow mill, and performing airflow milling grinding by using high-purity nitrogen, wherein the airflow milling working medium pressure is 0.5-0.52MPa, the rotation speed of a sorting wheel is 3200-;
s5, post-processing: screening the CuCrZr alloy fine powder, placing the screened CuCrZr alloy fine powder with D50 of 40-80 mu m in a magnetic field of 800kA/m, pressurizing for 1-2h, then carrying out cold isostatic pressing for 2h under the pressure of 200MPa, forming, and carrying out heat treatment and cooling to obtain the CuCrZr spherical powder.
2. The method for preparing the spherical powder of CuCrZr used for 3D printing according to claim 1, wherein the purity of the metal chromium block in the step S1 is 99.95-99.99%.
3. The method for preparing CuCrZr spherical powder for 3D printing according to claim 1, wherein the vacuum degree after vacuum pumping in step S2 is 0.5 Pa.
4. The method for preparing CuCrZr spherical powder for 3D printing as claimed in claim 1, wherein the gravity field removal rate in step S3-3 is 100-120g/S, and the room temperature is 23-27 ℃.
5. The method for preparing CuCrZr spherical powder for 3D printing according to claim 1, wherein the purity of high-purity nitrogen gas in step S4-2 is 99.97-99.99%.
6. The method for preparing CuCrZr spherical powder for 3D printing according to claim 1, wherein the step of heat treatment in step S5 is: placing the CuCrZr alloy fine powder in a vacuum crucible, heating to 1200-1300 ℃ for vacuum sintering for 15-30min, then cooling to 850-890 ℃ at a cooling rate of 40-50 ℃/h, preserving heat for 2h, and then cooling to 25-28 ℃ at a cooling rate of 120-140 ℃/h.
7. The method for preparing the spherical powder of CuCrZr for 3D printing according to claim 1, wherein the method for preparing the zirconia powder in step S1 comprises the following steps:
S1-1: mixing zircon concentrate powder, crystalline graphite, pyrolytic graphite and calcite in a proportion of 23: 6: 5: 2, putting the mixture into a grinder together to grind the mixture until the particle size is less than 0.5mm to obtain mixed powder;
s1-2: placing the ground mixed powder into an electric arc furnace, carrying out electric arc melting for 2-3h under the temperature condition of 2730-2750 ℃, and then carrying out quenching and cooling to 550-560 ℃ to obtain zirconium-rich crystals;
s1-3: the zirconium-rich crystal is placed in a crucible to be calcined for 2 hours at the temperature of 1700-1800 ℃ to obtain the zirconium oxide, and the zirconium oxide is cooled and then crushed to the grain diameter of 0.05-0.2 mm.
8. The method for preparing CuCrZr spherical powder for 3D printing as claimed in claim 7, wherein the quenching and temperature reduction in step S1-2 is performed by using liquid nitrogen, and the temperature reduction rate is 180-.
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