CN112191854A - Hard alloy powder for 3D printing and application thereof - Google Patents
Hard alloy powder for 3D printing and application thereof Download PDFInfo
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- CN112191854A CN112191854A CN202010575189.2A CN202010575189A CN112191854A CN 112191854 A CN112191854 A CN 112191854A CN 202010575189 A CN202010575189 A CN 202010575189A CN 112191854 A CN112191854 A CN 112191854A
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
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- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
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- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/10—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on titanium carbide
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- 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
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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Abstract
The invention provides hard alloy powder for 3D printing and application thereof, and relates to the technical field of metal ceramic composite materials, wherein the hard alloy powder is prepared by the following steps: 1) ball-milling the raw materials to obtain slurry; 2) after ball milling, spray drying and granulation are adopted to obtain a mixture; 3) flatly paving the granulated mixture in a vacuum sintering furnace and performing presintering to obtain well-bonded composite powder; 4) crushing and sieving the composite powder; this method yields cemented carbide powder that can be used for 3D printing. Compared with the prior art, the method for preparing the hard alloy powder by adopting the pre-sintering method has the advantages of low cost, simple and controllable operation, good fluidity and the like, and is suitable for powder feeding forming methods such as laser melting deposition and the like in 3D printing after crushing and sieving. The invention well bonds the transition metal powder and the refractory metal carbide powder together, is easier to print and form, has good and stable performance of the formed product, and can be used for large-scale production.
Description
Technical Field
The invention relates to the field of metal ceramics and additive manufacturing, in particular to hard alloy powder for 3D printing and application thereof.
Background
The laser melting deposition additive manufacturing technology is characterized in that high-energy laser beams emitted by a laser are used as a heat source, powder blown out by a powder feeder is melted, and a control system enables a substrate and a laser processing head to keep moving relatively to realize layered deposition and rapid forming of metal parts.
The laser melting deposition additive manufacturing technology can manufacture parts with complex structures on the same equipment without the clamping of a traditional cutter due to higher laser energy density, so that the forming technology is suitable for more material types compared with other additive manufacturing technologies. The laser melting solidification process can be regarded as a rapid solidification process, under the solidification condition, a solid-liquid interface is far deviated from the equilibrium solidification condition, a non-equilibrium supersaturated solid solution and a uniform and fine metallographic structure can be obtained, and the microstructure and the performance of a formed sample are obviously different from those of the traditional processing method.
The hard alloy has good hardness, wear resistance and corrosion resistance, is widely applied to the fields of metal cutting processing, mine excavation, oil drilling, national defense and military industry and the like, and is known as 'industrial teeth'. The traditional forming mode of the hard alloy mainly adopts powder metallurgy pressing or sintering forming after extrusion, but the complex structure or lattice structure parts are difficult to prepare due to the limitation of a die and forming conditions. Compared with the traditional forming mode, the 3D printing technology is not limited by a mould, can manufacture parts with complex structures, can be applied to various material systems and the like, and enables the production of hard alloy parts with complex structures to be possible.
Chinese patents No. cn201310470047.x and CN201810909559.4 disclose a method for preparing metal powder for 3D printing, and the common preparation method is mainly to prepare the required spheroidal or spherical powder by melting metal or powder and then atomizing. The method is suitable for alloy powder below 2000 ℃, and the refractory metal carbides (such as WC, TaC and TiC) in the hard alloy powder have the melting points above 2000 ℃, so that the method is not suitable for preparing the hard alloy powder.
Plasma spheroidization is not suitable for preparing hard alloy powder in large quantity in industry because of expensive equipment, complex operation and high technical requirement, especially for refractory metal carbide.
The existing technology is that powder or cast ingot is melted and then made into powder, and the carbide of refractory metals such as titanium, tantalum, tungsten and the like has high melting point, so that a large amount of hard alloy powder suitable for laser melting deposition forming cannot be prepared to a great extent, and therefore, the preparation method capable of preparing the carbide powder of the refractory metals with the characteristics of good fluidity, easiness in forming, low porosity and the like is urgently needed.
Disclosure of Invention
According to the invention, the method for preparing the hard alloy powder for 3D printing with high efficiency by using the modes of ball milling, pre-sintering and mechanical crushing is tried for the first time; meanwhile, the invention also provides a printing process matched with the powder. According to the process developed by the invention, when products of the same batch are prepared, the fluctuation range of the hardness and the friction coefficient of the obtained products is smaller.
The invention relates to hard alloy powder for 3D printing, which is prepared by the following steps: distributing and taking binder phase powder and hard phase powder according to a design group; mixing uniformly; presintering under the vacuum atmosphere at the temperature of 1100-1500 ℃; and after pre-sintering, crushing and sieving to obtain hard alloy powder for 3D printing, wherein the pressure is controlled to be 1-2MPa during pressure pre-sintering.
As a preferred process; the invention relates to hard alloy powder for 3D printing, which is prepared by the following steps:
1) preparing raw materials: preparing refractory carbide powder and transition metal powder into mixed powder according to the mass ratio of 7-9:1-3, wherein the grain sizes of the refractory carbide powder and the transition metal powder are both 0.8-12 mu m;
2) ball-milling powder: grinding balls and mixed powder are mixed according to the mass ratio of 3-8: 1, putting the mixture into a ball mill, adding a dispersing agent according to the proportion that the dispersing agent accounts for 1-3% of the mixed powder, and adding a ball milling dispersing medium according to the proportion that 1L of the mixed powder is 1000-2500 g; ball milling; obtaining slurry after ball milling, wherein the ball milling time is 24-48 hours and the speed is 60-150 r/min;
3) and (3) granulation: feeding the slurry after wet grinding into a spray tower for drying and granulating to obtain a mixture, wherein the spray pressure is 1-1.5 MPa;
4) pre-sintering: spreading the mixture after ball milling, drying and granulation in a vacuum sintering furnace, and performing vacuum pressurization and pre-sintering to obtain composite powder; the specific sintering process comprises the following steps: applying a pressure of 1-2MPa to the mixture; then, heating the temperature in the furnace to 1350-1500 ℃ at 3-10 ℃/min, preferably 5 ℃/min from room temperature, and preserving the temperature for at least 60 min; cooling to 1100-1200 ℃, keeping the temperature for at least 30min, cooling to 150-300 ℃, releasing the pressure, and continuously cooling to room temperature; discharging to obtain composite powder;
5) crushing: crushing the composite powder by using a mechanical method after pre-sintering, wherein the particle size after crushing is within the range of 50-200 mu m;
6) sieving: and sequentially sieving the crushed composite powder by using 100-mesh and 200-mesh sieves, and taking the powder of 100-200 meshes as the hard alloy powder for laser melting deposition 3D printing.
As a preferred process; the invention provides a cemented carbide powder for 3D printing, which has D10 of more than 40 μm and D90 of less than 190 μm.
As a preferred process; according to the hard alloy powder for 3D printing, the average particle size range of the hard alloy powder for 3D printing is 75-150 micrometers.
As a preferred process; the invention relates to hard alloy powder for 3D printing, wherein the hard phase powder is selected from at least one of TiC and WC, the binder phase powder contains at least one element of Co and Ni, and the valence state of the element in the binder phase is 0 valence.
Preferably, in the step 1), 10 to 12 weight percent of Co and/or Ni powder and 88 to 90 weight percent of WC and/or TiC powder are weighed according to the weight percentage of the two powders.
Preferably, the grain size of WC or TiC ranges from 0.8 to 2 μm, and the grain size of Co or Ni ranges from 1 to 12 μm.
As a preferred process; the invention relates to hard alloy powder for 3D printing, wherein the ball milling mode is at least one of vibration milling, rolling ball milling or stirring ball milling. In the invention, the ball milling finishes the primary crushing of the powder and eliminates the hollowness in the powder while finishing the uniform mixing. In the invention and the sintering process, a pressure of 1-2MPa is applied to the mixture, then the temperature in the furnace is increased to 1350-1500 ℃ from room temperature at 3-10 ℃/min, preferably 5 ℃/min, and the temperature is kept for at least 60 min; cooling to 1100-1200 ℃, and keeping the temperature for at least 30 min; the aim is to further eliminate the hollow structure in the powder to complete the primary crushing of the powder and eliminate the hollowness in the powder.
The invention relates to application of hard alloy powder for 3D printing, which is used for preparing a hard alloy product through laser melting deposition 3D printing.
The application of the hard alloy powder for 3D printing is characterized in that the laser scanning speed in the 3D printing process is 500-800 mm/min, and the laser power is 600-800W.
The invention relates to 3D printingUse of cemented carbide powders in which the hardness difference at the points is 150HV or less0.3. The fluctuation range of the friction coefficient in the same batch of products is less than 0.16.
Compared with the prior art, the invention adopts a pre-sintering powder preparation method to obtain the hard alloy powder, particularly the hard alloy powder with different particle sizes is obtained by controlling the temperature rise time and temperature of each stage in the pre-sintering process, and simultaneously the two powders are bonded together through liquid phase sintering, so that the hard alloy powder suitable for laser melting deposition can be obtained at low cost, has good fluidity in the printing process, can effectively avoid the generation of hollowness and cracks, and improves the quality of products and the stability of the performance of the products.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a graph showing the particle size distribution of cemented carbide powder prepared in example 1 of the present invention;
fig. 2 is an SEM photograph of the cemented carbide powder prepared in example 1 of the present invention.
Fig. 3 is a picture of a sample of the cemented carbide powder prepared in example 1 of the present invention after being formed by a laser melting deposition 3D printing technique.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely explained below with reference to the drawings in the embodiments of the present invention. The following examples are only some examples of the present invention, and not all examples. Other examples obtained by the preparation method of the present invention based on the examples of the present invention belong to the protection scope of the present invention.
The powder in the step 1) has no morphology requirement, and can be regular or irregular. In order to reduce the cost, the invention adopts irregular powder, and the purity is more than 99.99 percent.
In the present invention, the raw powder is preferably a mixed powder of WC and Co or a mixed powder of TiC and Ni.
In the present invention, the ball milling treatment method in step 1) is preferably vibration milling, stirring ball milling and rolling ball milling, more preferably stirring ball milling, and most preferably wet stirring ball milling. In the present invention, the grinding media are preferably cemented carbide balls similar to the mixed powder in order not to introduce other metal impurities. The diameter of the hard alloy ball is selected to be smaller as the average particle size of the powder is smaller, and the diameter of the hard alloy ball is also smaller, so that the friction and impact action between the powder and the hard alloy ball during ball milling are increased. In the invention, the diameter of the hard alloy ball is preferably 1-6 mm, more preferably 1-3 mm, and good grinding effect can be realized. In the present invention, the dispersion medium for the wet agitation ball milling is preferably an organic solvent, more preferably an alcohol-based organic solvent, and most preferably alcohol.
In the present invention, the stirring speed of the wet stirring ball mill is preferably 60 to 150 rpm, more preferably 80 to 120 rpm, and finally preferably 95 rpm. The speed is too slow, the powder cannot be ground, the speed is too fast, and the powder is easy to be abraded to a greater extent due to higher hardness of the powder. In the invention, the ball milling time is preferably 24-48 hours, so that the powder can be uniformly mixed, more preferably 24-36 hours, and most preferably 32-36 hours. In the invention, the ball milling time is not short enough, the proportion is not high enough because Co powder or Ni powder mainly plays a role of binding in the sintering process and the printing process, and the mass of the transition metal powder is preferably 10-20% of the mixed powder, and most preferably 10-12%. Therefore, the two powders need to be uniformly mixed for a long time, and the powder agglomeration in the sintering and printing processes can be effectively avoided.
In the invention, a dispersing agent is required to be added before or during ball milling, and after the dispersing agent is added, the prepared mixture has better fluidity and lower oxygen content. The dispersant is preferably one or two of polyethylene glycol, polyethylene and polypropylene, and accounts for 1-3% of the total weight of the mixed powder.
In the invention, the granulation mode in the step 4) is preferably a spray drying granulation mode, and the produced mixture has better fluidity and more uniform granularity, and is suitable for mass production. The spraying pressure is preferably 1 to 1.5MPa, more preferably 1 to 1.3 MPa.
In the invention, the sintering mode in the step 5) is preferably vacuum sintering and hydrogen sintering, more preferably vacuum sintering, and under the negative pressure state, the wettability of the bonding phase relative to the hard phase is improved, so that the obtained hard alloy powder after sintering can be more compact. In the present invention, the method of vacuum sintering the powder is preferably:
and flatly paving the ball-milled powder on a quartz substrate, heating to a sintering temperature, preserving heat, and then depressurizing, cooling and releasing pressure.
In the present invention, the high-temperature sintering is preferably performed under vacuum or under inert gas protection. In the present invention, the initial pressurization temperature is preferably 300 to 500 ℃, more preferably 350 to 450 ℃, and most preferably 400 ℃. In the invention, the heating rate is 4-6 ℃/min, and the most preferable is 5 ℃/min.
In the invention, the high temperature liquid phase sintering temperature is preferably 1350-1500 ℃, more preferably 1400-1450 ℃, and most preferably 1400-1420 ℃. In the invention, the high-temperature heat preservation time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours. In the invention, the heat preservation condition at high temperature is preferably carried out under vacuum, and the vacuum condition is preferably 1-3 MPa.
In the invention, the temperature reduction and heat preservation temperature is preferably 1000-1300 ℃, and more preferably 1100-1200 ℃. The heat preservation time is preferably 50-70 minutes, and more preferably 55-65 minutes.
In the invention, in the step 4), the powder crushing mode is preferably a mechanical crushing mode, the agglomerated powder is crushed and dispersed, and the rotating speed is preferably 1300-2000 r/min. In the invention, in order to obtain the hard alloy powder with the particle size of 75-150 microns, the crushed powder is firstly sieved by a 100-mesh sieve, then the powder below the 100-mesh sieve is sieved by a 200-mesh sieve, and the hard alloy powder above the 200-mesh sieve is taken to obtain the hard alloy powder with the particle size of 75-150 microns.
The invention provides a hard alloy product, which is obtained by taking the mixed powder as the raw material to prepare hard alloy powder and performing laser melting deposition forming on the hard alloy powder. The invention provides a low-cost preparation method of hard alloy powder for 3D printing, wherein the forming mode is mainly a laser melting deposition forming mode. The hard alloy powder prepared by the method provided by the invention has good bonding with the hard phase, good fluidity, is especially suitable for laser melting deposition raw materials, and the formed hard alloy product has good performance (especially uniform hardness distribution). The method for preparing the hard alloy powder provided by the invention has the advantages of common equipment, low powder production cost, high working efficiency and batch production.
The raw materials used in the following examples of the present invention are commercially available, so the laser fused deposition modeling powder obtained by the method is low in cost.
Example 1
Selecting powder with WC and Co content of more than 99.98%, mixing the powder according to the weight ratio of WC to Co of 90 to 10, wherein the mass ratio of wet grinding balls to mixed powder is 7:1, the grinding medium is alcohol, the ratio of the alcohol to the mixed powder is 1L to 2kg, carrying out ball milling for 32 hours, and adding polyethylene glycol accounting for 2% of the total weight of the raw materials during ball milling. After being subjected to spray drying and granulation, the slurry after ball milling is spread in a vacuum sintering furnace with the pressure of 1.5MPa, is subjected to heat preservation for 2 hours at the temperature of 1420 ℃ and then is cooled, is subjected to heat preservation for 57 minutes at the temperature of 1120 ℃, is cooled to the room temperature in the vacuum sintering furnace, and then is crushed by utilizing an airflow crushing mode. And (3) sieving the crushed powder with a 100-mesh sieve, then sieving the powder below the 100-mesh sieve with a 200-mesh sieve, and taking the hard alloy powder above the 200-mesh sieve to obtain the hard alloy powder with the particle size of 75-150 microns.
The hard alloy is formed by utilizing a laser melting deposition additive manufacturing technology, wherein the fixed process parameters comprise the lap joint rate (50%), the diameter of a light spot (phi 2mm), the rotating speed of a powder disc (0.4r/min) and the thickness of a powder layer (0.2 mm). The laser scanning speed is 600mm/min, and the laser power is 700W. The mechanical property test result of the formed hard alloy is as follows: the hardness is 1320 +/-72 HV0.3(i.e., the minimum hardness at the test point is 1248 HV)0.3A maximum hardness of 1392HV0.3(ii) a I.e. a hardness fluctuation of 144HV0.3(ii) a The number of the test points is 20), the friction coefficient is 0.5 +/-0.05, i.e. the fluctuation of the friction coefficient was 0.1.
Example 2
Selecting powder with TiC and Ni content of more than 99.98%, mixing the powder according to the weight ratio of TiC to Ni of 88:12, wherein the mass ratio of wet grinding balls to mixed powder is 6:1, the grinding medium is alcohol, the ratio of the alcohol to the mixed powder is 1L to 2kg, carrying out ball milling for 34 hours, and adding polyethylene glycol accounting for 2% of the total weight of the raw materials during ball milling. After being subjected to spray drying and granulation, the slurry after ball milling is spread in a vacuum sintering furnace with the pressure of 1.5MPa, is subjected to heat preservation for 2 hours at the temperature of 1420 ℃ and then is cooled, is subjected to heat preservation for 60 minutes at the temperature of 1150 ℃, is cooled to the room temperature in the vacuum sintering furnace, and then is crushed by utilizing an airflow crushing mode. And (3) sieving the crushed powder with a 100-mesh sieve, then sieving the powder below the 100-mesh sieve with a 200-mesh sieve, and taking the hard alloy powder above the 200-mesh sieve to obtain the hard alloy powder with the particle size of 75-150 microns.
The hard alloy is formed by utilizing a laser melting deposition additive manufacturing technology, wherein the fixed process parameters comprise the lap joint rate (50%), the diameter of a light spot (phi 2mm), the rotating speed of a powder disc (0.4r/min) and the thickness of a powder layer (0.2 mm). The laser scanning speed is 500mm/min, and the laser power is 600W. The mechanical property test result of the formed hard alloy is as follows: the hardness is 1200 +/-67 HV0.3(i.e., the minimum hardness at the test point is 1134HV0.3A maximum hardness of 1267HV0.3I.e. fluctuation in hardness of 134HV0.3(ii) a The number of test points is 20), the friction coefficient is 0.6 +/-0.07, namely the fluctuation of the friction coefficient is 0.14.
Example 3
Selecting powder with WC and Co content of more than 99.98%, mixing the powder according to the weight ratio of WC to Co of 88 to 12, wherein the mass ratio of wet grinding balls to mixed powder is 8:1, the grinding medium is alcohol, the ratio of the alcohol to the mixed powder is 1L to 2kg, carrying out ball milling for 34 hours, and adding polyethylene glycol accounting for 2% of the total weight of the raw materials during ball milling. After being subjected to spray drying and granulation, the slurry after ball milling is spread in a vacuum sintering furnace with the pressure of 1.5MPa, is subjected to heat preservation for 2 hours at the temperature of 1420 ℃ and then is cooled, is subjected to heat preservation for 60 minutes at the temperature of 1150 ℃, is cooled to the room temperature in the vacuum sintering furnace, and then is crushed by utilizing an airflow crushing mode. And (3) sieving the crushed powder with a 100-mesh sieve, then sieving the powder below the 100-mesh sieve with a 200-mesh sieve, and taking the hard alloy powder above the 200-mesh sieve to obtain the hard alloy powder with the particle size of 75-150 microns.
The hard alloy is formed by utilizing a laser melting deposition additive manufacturing technology, wherein the fixed process parameters comprise the lap joint rate (50%), the diameter of a light spot (phi 2mm), the rotating speed of a powder disc (0.4r/min) and the thickness of a powder layer (0.2 mm). The laser scanning speed is 650mm/min, and the laser power is 600W. The mechanical property test result of the formed hard alloy is as follows: hardness of 1150 +/-55 HV0.3(i.e., the minimum hardness at the test point is 1134HV0.3A maximum hardness of 1267HV0.3I.e. a fluctuation in hardness of 110HV0.3(ii) a The number of test points is 20), the friction coefficient is 0.5 +/-0.08, namely the fluctuation of the friction coefficient is 0.16.
Comparative example 1
Selecting powder with WC and Co content of more than 99.98%, mixing the powder according to the weight ratio of WC to Co of 88 to 12, wherein the mass ratio of wet grinding balls to mixed powder is 8:1, the grinding medium is alcohol, the ratio of the alcohol to the mixed powder is 1L to 2kg, carrying out ball milling for 34 hours, and adding polyethylene glycol accounting for 2% of the total weight of the raw materials during ball milling. And (4) after the ball-milled slurry is subjected to spray drying, crushing the powder by using an airflow crushing mode. And (3) sieving the crushed powder with a 100-mesh sieve, then sieving the powder below the 100-mesh sieve with a 200-mesh sieve, and taking the hard alloy powder above the 200-mesh sieve to obtain the hard alloy powder with the particle size of 75-150 microns.
The hard alloy is formed by utilizing a laser melting deposition additive manufacturing technology, wherein the fixed process parameters comprise the lap joint rate (50%), the diameter of a light spot (phi 2mm), the rotating speed of a powder disc (0.4r/min) and the thickness of a powder layer (0.2 mm). The laser scanning speed is 600mm/min, and the laser power is 650W. The hardness of the obtained product is 980 +/-140 HV0.3(i.e., minimum hardness at test point 840 HV)0.3The maximum hardness is 1120HV0.3, i.e., the fluctuation in hardness is 280HV0.3(ii) a The number of the measuring points is 20). Microhardness tests on the same deposit gave considerably different values. Because the powder is not sintered and the laser focus temperature is too high, the decomposition speed of polyethylene glycol is higher than that of the Co phase for liquid phase migration, so that pores and defects are formed, the hardness is reduced, and the hardness distribution is not uniform; the coefficient of friction was 0.5. + -. 0.1, i.e. the fluctuation of the coefficient of friction was 0.2.
Comparative example 2
Selecting powder with WC and Co content of more than 99.98%, mixing the powder according to the weight ratio of WC to Co of 88 to 12, wherein the mass ratio of wet grinding balls to mixed powder is 8:1, the grinding medium is alcohol, the ratio of the alcohol to the mixed powder is 1L to 2kg, carrying out ball milling for 34 hours, and adding polyethylene glycol accounting for 2% of the total weight of the raw materials during ball milling. After being subjected to spray drying and granulation, the slurry after ball milling is spread in a vacuum sintering furnace with the pressure of 5MPa, is cooled after being kept at the temperature of 1420 ℃ for 2 hours, is kept at the temperature of 1150 ℃ for 60 minutes, is cooled to the room temperature in the vacuum sintering furnace, and is crushed by an airflow crushing mode. And (3) sieving the crushed powder with a 100-mesh sieve, then sieving the powder below the 100-mesh sieve with a 200-mesh sieve, and taking the hard alloy powder above the 200-mesh sieve to obtain the hard alloy powder with the particle size of 75-150 microns.
The hard alloy is formed by utilizing a laser melting deposition additive manufacturing technology, wherein the fixed process parameters comprise the lap joint rate (50%), the diameter of a light spot (phi 2mm), the rotating speed of a powder disc (0.4r/min) and the thickness of a powder layer (0.2 mm). The laser scanning speed is 600mm/min, and the laser power is 650W. The hardness of the obtained product is 1120 +/-110 HV0.3(i.e., the minimum hardness at the test point is 1010 HV)0.3Maximum hardness of 1230HV0.3I.e. a fluctuation in hardness of 220HV0.3(ii) a The number of the measuring points is 20), the porosity of the powder is too large due to too large pressure intensity during sintering, so that microcracks are generated during laser melting deposition to reduce microhardness, and the microhardness values have more phase difference and are distributed unevenly; the coefficient of friction was 0.5 ± 0.2, i.e., the fluctuation of the coefficient of friction was 0.4, and the coefficient of friction was unstable due to the generation of microcracks caused by stress concentration.
In conclusion, the mechanical properties of the formed cemented carbide in example 1 are the best.
The foregoing is a further description of the specific details and instructional concepts of the invention in connection with the preferred embodiments, for the purpose of enabling those skilled in the art to understand the invention and to practice it accordingly. Suitable modifications or adaptations, and similar uses and properties, without departing from the spirit of the invention, are intended to be covered by the present invention.
Claims (9)
1. A cemented carbide powder for 3D printing, characterized in that it is prepared by the following steps: distributing and taking binder phase powder and hard phase powder according to a design group; mixing uniformly; presintering under the vacuum atmosphere at the temperature of 1100-1500 ℃; and after pre-sintering, crushing and sieving to obtain hard alloy powder for 3D printing, wherein the pressure is controlled to be 1-2MPa during pressure pre-sintering.
2. The cemented carbide powder for 3D printing according to claim 1, characterized in that: it is prepared by the following steps:
1) preparing raw materials: preparing refractory carbide powder and transition metal powder into mixed powder according to the mass ratio of 7-9:1-3, wherein the grain sizes of the refractory carbide powder and the transition metal powder are both 0.8-12 mu m;
2) ball-milling powder: grinding balls and mixed powder are mixed according to the mass ratio of 3-8: 1, placing the mixture into a ball mill, adding a dispersing agent according to the proportion that the dispersing agent accounts for 1-3% of the mixed powder, and adding a ball milling dispersion medium according to the proportion that 1L of mixed powder is prepared into 1000-2500g of mixed powder; ball milling; obtaining slurry after ball milling, wherein the ball milling time is 24-48 hours and the speed is 60-240 r/min;
3) and (3) granulation: feeding the slurry after wet grinding into a spray tower for drying and granulating to obtain a mixture, wherein the spray pressure is 1-1.5 MPa;
4) pre-sintering: spreading the mixture after ball milling, drying and granulation in a vacuum sintering furnace, and performing vacuum pressurization and pre-sintering to obtain composite powder; the specific sintering process comprises the following steps: applying a pressure of 1-2MPa to the mixture; then, heating the temperature in the furnace to 1350-1500 ℃ at 3-10 ℃/min, preferably 5 ℃/min from room temperature, and preserving the temperature for at least 60 min; cooling to 1100-1200 ℃, keeping the temperature for at least 30min, cooling to 150-300 ℃, releasing the pressure, and continuously cooling to room temperature; discharging to obtain composite powder;
5) crushing: crushing the composite powder by using a mechanical method after pre-sintering, wherein the particle size after crushing is within the range of 50-200 mu m;
6) sieving: and sequentially sieving the crushed composite powder by using 100-mesh and 200-mesh sieves, and taking the powder of 100-250 meshes as the hard alloy powder for 3D printing.
3. The cemented carbide powder for 3D printing according to claim 2, characterized in that: the cemented carbide powder for 3D printing has a D10 > 40 μm and a D90<190 μm.
4. The cemented carbide powder for 3D printing according to claim 1, characterized in that: the average particle size range of the hard alloy powder for 3D printing is 75-150 mu m.
5. The cemented carbide powder for 3D printing according to claim 1, characterized in that: the hard phase powder is at least one selected from TiC and WC, the binder phase powder contains at least one element of Co and Ni, and the valence state of the element in the binder phase is 0 valence.
6. The cemented carbide powder for 3D printing according to claim 1, characterized in that: the ball milling mode is at least one of vibration milling, rolling ball milling or stirring ball milling.
7. Use of a cemented carbide powder for 3D printing according to any of claims 1-6, characterized in that: the hard alloy product is prepared from the hard alloy powder for 3D printing through 3D printing.
8. Use of a cemented carbide powder for 3D printing according to claim 7, characterized in that: the laser scanning speed in the laser melting deposition 3D printing process is 500-800 mm/min, and the laser power is 600-800W.
9. Use of a cemented carbide powder for 3D printing according to claim 7, characterized in that: the hardness difference of points in the hard alloy product is less than or equal to 150HV0.3. The fluctuation range of the friction coefficient in the same batch of products is less than 0.16.
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