CN111321313A - Preparation method of high-hardness tungsten-based alloy material - Google Patents
Preparation method of high-hardness tungsten-based alloy material Download PDFInfo
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Abstract
The preparation method of the high-hardness tungsten-based alloy material comprises the steps of ball milling treatment, laser sintering, secondary sintering and sample post-treatment, and further comprises a deoxidation treatment step, wherein the deoxidation treatment step is to place powder subjected to ball milling treatment in a vacuum glove box, set the temperature to 80-90 ℃, introduce argon, keep the pressure of the argon at 0.100-0.105 Mpa and keep the time for 2-2.5 hours. The invention can be used for preparing small parts by one-step molding, the agglomeration phenomenon can not occur, the surface of the final product is uniform, the poor products such as pits, air holes and the like can not occur, loose blocks can not occur, the material is uniform, the structure is compact, the cracking phenomenon can not occur even under larger stress, the product density is good and is more than 99%, the product hardness is high, and the melting point is as high as 3450 ℃.
Description
The invention is a divisional application of patent application No. 201910026643.6 entitled "a preparation method of tungsten-tantalum-rhenium alloy with high hardness".
Technical Field
The invention relates to a preparation method of a high-hardness tungsten-based metal alloy material.
Background
The tungsten metal is a metal material with the highest melting point, the melting point of the tungsten metal reaches 3410 ℃, but the tungsten metal has poor toughness and shock resistance and cannot meet the requirements of vibration places such as automobiles and vibration equipment, rhenium and tantalum are metals with the second and fourth highest melting points respectively, the melting points of the tungsten metal reach 3180 ℃ and 2996 ℃, the two metals have high melting points and are obviously superior to tungsten in toughness and shock resistance, but the tungsten-tantalum-rhenium alloy is very bitter and difficult to sinter, generally, a raw material for preparing the tungsten-tantalum-rhenium alloy is powder, and the tungsten-tantalum-rhenium alloy is prepared by multiple processes such as mixing, smelting, pressure forming, catalytic degreasing or solvent degreasing, vertical sintering and the like, the preparation process is very complex, the energy consumption is high, and the environment is polluted3And 96 × 30 × 660mm3The weights are 14 kg and 33 kg, respectively, and the sintering power thereof needs 600 kW. The size of the tungsten rod is required to be the same as that of the vertical melting sintering method developed by Liquanwang and the like of Beijing non-ferrous metal research institute
The sintering power is 100 kW. Therefore, the traditional vertical sintering method for producing tungsten and tungsten alloy requires large sample size and high energy consumption. The existing preparation method of the tungsten-tantalum-rhenium alloy mainly has the defects of complex preparation process, high energy consumption, great environmental pollution, incapability of preparing small parts at one time, easy agglomeration in the preparation process, easy pit formation due to severe shrinkage, easy cracking due to too large stress, easy generation of pores and loose blocks in the final product, and easy oxidation of tungsten to causePoor confidentiality, uneven components, influence on mechanical properties and other technical problems need to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a high-hardness tungsten-based alloy material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a high-hardness tungsten-based alloy material comprises the steps of raw material ball milling treatment, laser sintering, secondary sintering and sample post-treatment, and is characterized in that after the raw material ball milling treatment and before the laser sintering, a deoxidation treatment step is required, wherein in the deoxidation treatment step, powder after the ball milling treatment is placed in a vacuum glove box, the temperature is set to 80-90 ℃, argon is introduced, the argon pressure is kept to be 0.100-0.105 MPa, the holding time is 2-2.5 hours, the treatment is finished, and the material is sealed for later use. The raw material ball milling treatment comprises the steps of placing tungsten powder, tantalum powder and rhenium powder in a ball mill, adding absolute ethyl alcohol as a process control preparation, carrying out ball milling for 24-28 hours, cleaning for 2 times by using the absolute ethyl alcohol after the ball milling is finished, separating in a centrifugal machine after the cleaning is finished, placing collected powder in a vacuum drying box after the centrifugation is finished, setting the drying temperature to be 60-70 ℃, drying for 8-12 hours, placing in an agate mortar for grinding for 28-32 minutes after the drying is finished, and placing in a drying bottle for later use after the grinding is finished. The sample post-treatment is to perform linear cutting on the laser sintering sample and then perform stress relief annealing; and the annealing is to heat the sample to 600 ℃ at a heating rate of 8-12 ℃/min within 50-60 min, then to preserve heat for 30-40 min, to heat to 900 ℃ at a heating rate of 6-8 ℃/min within 45-50 min, then to preserve heat for 60min, and finally to cool along with the furnace, thus obtaining the material.
The mass ratio of the tungsten powder to the tantalum powder to the rhenium powder is 95:3:2, and the addition amount of the absolute ethyl alcohol of the process control preparation is 20-25% of the total mass of the tungsten powder, the tantalum powder and the rhenium powder; the using amount of absolute ethyl alcohol for cleaning is 10-15 times of the total mass of tungsten powder, tantalum powder and rhenium powder, the tungsten powder needs to be sieved by a 500-mesh sieve, the tantalum powder needs to be sieved by a 500-mesh sieve, the rhenium powder needs to be sieved by a 400-mesh sieve, and the ball-to-material ratio in the ball milling process is 10: 1.
The laserSintering, placing the deoxidized mixed powder in a powder feeder of an automatic laser sintering operation platform, and setting a laser spot to be 5 × 4mm2Square light spots, wherein the laser scanning speed is 2mm/s, the single stroke of a laser head is 100-150 mm, the line spacing is 3-4 mm, the single-layer reciprocating times are 2-10, the layer spacing is 0.5-1 mm, and the number of powder laying layers is 2-10; the laser sintering is a composite forming method combining sintering and cladding, a laser head reciprocates once in each stroke, the stroke moving process is a sintering process, the return stroke is a cladding process, the power of the laser sintering process is set to be 1.8-2 kW, and the power of the cladding process is set to be 2.6-2.8 kW.
The laser sintering process needs to be protected by continuously introducing argon, the purity of the argon is 99.999%, the pressure of the argon is 0.100-0.105 MPa, the flow is 8-10L/min, and the laser head needs to be cooled by introducing circulating water.
The invention has the following beneficial effects:
the preparation method of the high-hardness tungsten-based alloy material can be used for preparing small parts through one-step molding, the agglomeration phenomenon cannot occur, the surface of the final product is uniform, poor products such as pits and air holes cannot occur, loose blocks cannot occur, the material is uniform, the structure is compact, the cracking phenomenon cannot occur even under large stress, the product density is good and is more than 99 percent, the product hardness is high and can reach 870.7, the toughness is good, the melting point is high and can reach more than 3450 ℃, the preparation process is simple and feasible, energy is saved, environment is protected, parts with simple shapes can be directly prepared, the average grain size of product grains is 3.4 mu m, the grain size distribution is uniform and is close to isometric crystals, the density is uniform, and the average density is 19.2g/cm3And is worthy of market popularization and application.
Drawings
FIG. 1 is a scanning electron microscope image of the powder of the mixed tungsten-tantalum-rhenium alloy of the invention.
Figure 2 is an EDS energy spectrum of a tungsten-tantalum-rhenium alloy of the present invention.
FIG. 3 is a drawing of a sample of a tungsten-tantalum-rhenium alloy of the present invention obtained by wire cutting after laser sintering.
FIG. 4 is a microstructure of W-Ta-Re alloy obtained by scanning electron microscopy according to the present invention.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-described disclosure.
Embodiment 1 a method for preparing a high-hardness tungsten-based alloy material, comprising the steps of:
(1) raw material treatment
The mixed material comprises the following components in percentage by mass: tantalum powder: rhenium powder 95:3:2 (total batch 50 g). The particle diameters of the three powders are respectively: rhenium powder is 500 meshes, tungsten powder is 500 meshes, and tantalum powder is 400 meshes. The inner lining of the ball milling tank is made of ceramic materials, ceramic balls with the diameter of 10mm are used as milling balls, the ball material ratio is 10:1, the process control agent is 23% absolute ethyl alcohol, and the ball milling time is 36 hours. The raw materials are washed twice by using absolute ethyl alcohol after ball milling, 650g of absolute ethyl alcohol is used for washing each time, then the raw materials are placed in a centrifuge, the centrifugal speed is set to be 1500 r/min, the centrifugal time is set to be 2 minutes for separation, the washed powder is dried in a vacuum drying oven, the temperature is set to be 65 ℃, and the drying time is 10 hours. The dried powder was ground with an agate mortar for 30min, and the obtained powder was placed in a drying bottle for later use, and the prepared powder was as shown in fig. 1. And (3) placing the powder subjected to ball milling treatment in a vacuum glove box, setting the temperature to 85 ℃, introducing argon, keeping the pressure of the argon at 0.103MPa for 2 hours, finishing the treatment, and sealing for later use.
(2) Laser sintering process parameter setting
Placing the deoxidized mixed powder in a powder feeder of an automatic laser sintering operation platform, and setting a laser spot to be 5 × 4mm2Square light spots, wherein the laser scanning speed is 2mm/s, the single stroke of a laser head is 130mm, the line spacing is 3.5mm, the single-layer reciprocating frequency is 8, the layer spacing is 0.7mm, and the number of powder laying layers is 8; the laser sintering is a composite forming method combining sintering and cladding, the laser head reciprocates once in each stroke, the stroke going process is a sintering process, the return stroke is a cladding process, and the laser deviceSetting the power of the sintering process at 1.8-2 kW, and setting the power of the cladding process at 2.6-2.8 kW; the purity of the argon is 99.999 percent, the pressure of the argon is 0.103MPa, the flow is 9L/min, and circulating water is introduced into the laser head for cooling treatment. And repeating the laser sintering process to obtain the second sintering.
(3) Sample post-treatment
Cutting the laser sintering sample into 6 × 6 × 3mm3As shown in fig. 3. Then, stress relief annealing is performed to relieve residual stress. And the annealing is to heat the sample to 600 ℃ within 55min at a heating rate of 10 ℃/min, then to preserve heat for 35min, to heat to 900 ℃ within 48min at a heating rate of 7 ℃/min, then to preserve heat for 60min, and finally to cool along with the furnace.
The sample obtained in example 1 was subjected to the observation of the texture, the density test and the hardness test, and the results of the tests are shown in fig. 4, table 1 and table 2, respectively. FIG. 4 shows the grain structure of the sample observed by scanning electron microscope, and the obtained sample has an average grain size of 3.4 μm and a uniform grain size distribution, which is close to equiaxed grains. The density of the sample was measured 10 times under the same conditions, and the average density of the sample was found to be 19.20g/cm as shown in Table 13. The samples were subjected to microhardness testing, and 10 random tests were performed on the polished surface of the sample, and the average was taken, as shown in table 1, to give an average vickers hardness of 870.7.
TABLE 1 mean Density test values
| Serial number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | Mean value of |
| g/cm3 | 19.21 | 19.20 | 19.21 | 19.19 | 19.20 | 19.21 | 19.20 | 19.19 | 19.20 | 19.21 | 19.20 |
TABLE 2 Vickers hardness test values
| Serial number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | Mean value of |
| HV | 871 | 865 | 880 | 882 | 876 | 887 | 863 | 878 | 856 | 849 | 870.7 |
Experiment 1: the product obtained in example 1 was subjected to density measurement
Electronic balanceMeasuring the mass m of the sample to be measured1(ii) a And then filling a proper amount of water into the measuring cylinder (the proper amount means that the object can be completely immersed and cannot exceed the maximum scale of the measuring cylinder), placing the measuring cylinder on an electronic balance, and returning the electronic balance to zero. Tying the object with filament (with negligible volume when put into water), slowly sliding down along the measuring cylinder wall until completely immersed, and reading the mass number m2(ii) a The density of the object can be found by using a density formula: ρ ═ m1ρWater (W)/m2。
The product of example 1 was determined to be 99.5% dense.
Experiment 2: the product obtained in example 1 was subjected to melting point measurement
The highest temperature of a sample during laser sintering is obtained by combining an ST200-F type Bluetooth infrared thermometer produced by the Xian infrared detection instrument Co.
TABLE 3 actual temperature measurement of samples during laser sintering
| Serial number | 1 | 2 | 3 | 4 | 5 | Mean value of |
| Temperature (. degree.C.) | 3451 | 3463 | 3455 | 3449 | 3461 | 3456 |
Embodiment 2 a method for preparing a high-hardness tungsten-based alloy material, comprising the steps of:
(1) raw material treatment
The mixed material comprises the following components in percentage by mass: tantalum powder: rhenium powder 95:3:2 (total batch 50 g). The particle diameters of the three powders are respectively: rhenium powder is 500 meshes, tungsten powder is 500 meshes, and tantalum powder is 400 meshes. The inner lining of the ball milling tank is made of ceramic materials, ceramic balls with the diameter of 10mm are used as milling balls, the ball material ratio is 10:1, the process control agent is 25% absolute ethyl alcohol, and the ball milling time is 48 hours. The raw materials are washed twice by absolute ethyl alcohol after ball milling, 750g of absolute ethyl alcohol is used for washing each time, then the raw materials are placed in a centrifuge, the centrifugal speed is set to 2000 r/min, the centrifugal time is set to 2 minutes for separation, the washed powder is dried in a vacuum drying oven, the temperature is set to 70 ℃, and the drying time is set to 8 hours. The dried powder was ground with an agate mortar for 32min, and the obtained powder was placed in a drying bottle for later use, and the prepared powder was as shown in fig. 1. And (3) placing the powder subjected to ball milling treatment in a vacuum glove box, setting the temperature to 90 ℃, introducing argon, keeping the pressure of the argon at 0.105MPa for 2.5 hours, finishing the treatment, and sealing for later use.
(2) Laser sintering process parameter setting
Placing the deoxidized mixed powder in a powder feeder of an automatic laser sintering operation platform, and setting a laser spot to be 5 × 4mm2Square light spots, the laser scanning speed of 2mm/s, the single stroke of a laser head of 150mm, the line spacing of 4mm, the single-layer reciprocating times of 10, the layer spacing of 1mm and the number of powder laying layers of 10; the laser sintering is a composite forming method combining sintering and cladding, a laser head reciprocates once in each stroke, the stroke is a sintering process, the return stroke is a cladding process, the power of the laser sintering process is set to be 1.8-2 kW, and the power of the cladding process is set to be 2.6-2.8kW; the purity of the argon is 99.999 percent, the pressure of the argon is 0.105MPa, the flow is 10L/min, and circulating water is introduced into the laser head for cooling treatment. And repeating the laser sintering process to obtain the second sintering.
(3) Sample post-treatment
Cutting the laser sintering sample into 6 × 5 × 4mm3Then stress relief annealing is performed to relieve residual stress. The annealing is to heat the sample to 600 ℃ within 60min at a heating rate of 10 ℃/min, then to preserve heat for 40min, to heat to 900 ℃ within 50min at a heating rate of 6 ℃/min, then to preserve heat for 60min, and finally to cool along with the furnace.
The experiment of the sample in the embodiment 2 is carried out according to the method in the embodiment 1, and the result shows that the product has the advantages of uniform surface, no pits, no air holes, uniform product material, compact structure, 99.3% of compactness, no cracking phenomenon, good product compactness, high hardness, good toughness, high melting point which can reach more than 3450 ℃, uniform grain size distribution, nearly isometric crystal and uniform density.
Embodiment 3 a method for preparing a high-hardness tungsten-based alloy material, comprising the steps of:
(1) raw material treatment
The mixed material comprises the following components in percentage by mass: tantalum powder: rhenium powder 95:3:2 (total batch 50 g). The particle diameters of the three powders are respectively: rhenium powder is 500 meshes, tungsten powder is 500 meshes, and tantalum powder is 400 meshes. The inner lining of the ball milling tank is made of ceramic materials, ceramic balls with the diameter of 10mm are used as milling balls, the ball material ratio is 10:1, the process control agent is 20% absolute ethyl alcohol, and the ball milling time is 24 hours. The raw materials are washed twice by absolute ethyl alcohol after ball milling, 500g of absolute ethyl alcohol is used for washing each time, then the raw materials are placed in a centrifuge, the centrifugal speed is set to be 1000 r/min, the centrifugal time is 2 minutes for separation, the washed powder is dried in a vacuum drying oven, the temperature is set to be 60 ℃, and the drying time is 12 hours. The dried powder was ground with an agate mortar for 32min, and the obtained powder was placed in a drying bottle for later use, and the prepared powder was as shown in fig. 1. And (3) placing the powder subjected to ball milling treatment in a vacuum glove box, setting the temperature to 90 ℃, introducing argon, keeping the pressure of the argon at 0.100MPa for 2.5 hours, finishing the treatment, and sealing for later use.
(2) Laser sintering process parameter setting
Placing the deoxidized mixed powder in a powder feeder of an automatic laser sintering operation platform, and setting a laser spot to be 5 × 4mm2Square light spots, the laser scanning speed of 2mm/s, the single stroke of a laser head of 100mm, the line spacing of 3mm, the single-layer reciprocating times of 2, the layer spacing of 1mm and the number of powder laying layers of 10; the laser sintering is a composite forming method combining sintering and cladding, a laser head reciprocates once in each stroke, the stroke is a sintering process, the return stroke is a cladding process, the power of the laser sintering process is set to be 1.8-2 kW, and the power of the cladding process is set to be 2.6-2.8 kW; the purity of the argon is 99.999 percent, the pressure of the argon is 0.100MPa, the flow is 8L/min, and circulating water is introduced into the laser head for cooling treatment. And repeating the laser sintering process to obtain the second sintering.
(3) Sample post-treatment
Cutting the laser sintering sample into 6 × 7 × 2mm3Of a small sample. Then, stress relief annealing is performed to relieve residual stress. And the annealing is to heat the sample to 600 ℃ within 50min at a heating rate of 12 ℃/min, then to keep the temperature within 30min, then to heat the sample to 900 ℃ within 50min at a heating rate of 8 ℃/min, then to keep the temperature for 60min, and finally to cool the sample along with the furnace.
The experiment of the sample in the embodiment 3 is carried out according to the method in the embodiment 1, and the result shows that the product has the advantages of uniform surface, no pits, no air holes, uniform product material, compact structure, density of 99.1%, no cracking phenomenon, good product density, high hardness, good toughness, high melting point which can reach more than 3450 ℃, uniform grain size distribution, approximate equiaxed crystal and uniform density.
Claims (2)
1. A preparation method of a high-hardness tungsten-based alloy material is characterized by comprising the following steps: the method comprises the steps of ball milling tungsten powder, tantalum powder and rhenium powder raw materials, laser sintering, secondary sintering and sample post-processing according to the mass ratio of 95:3:2, and is characterized in that after the ball milling processing of the raw materials and before the laser sintering, a deoxidation processing step is needed, wherein the deoxidation processing step is to place the powder after the ball milling processing in a vacuum glove box, set the temperature to be about 80-90 ℃, introduce argon, keep the pressure of the argon at 0.100-0.105 MPa, keep the time for 2-2.5 hours, finish the processing and seal for later use; the post-processing of the sample is to perform linear cutting on the laser sintering sample, then perform stress relief annealing, wherein the annealing is to heat the sample to 600 ℃ in 50-60 min at a heating rate of 8-12 ℃/min, then preserve heat for 30-40 min, heat the sample to 900 ℃ in 45-50 min at a heating rate of 6-8 ℃/min, then preserve heat for 60min, and finally cool the sample along with the furnace;
the laser sintering is to place the deoxidized mixed powder in a powder feeder of an automatic laser sintering operation platform, and set a laser spot to be 5 × 4mm2Square light spots, wherein the laser scanning speed is 2mm/s, the single stroke of a laser head is 100-150 mm, the line spacing is 3-4 mm, the single-layer reciprocating times are 2-10, the layer spacing is 0.5-1 mm, and the number of powder laying layers is 2-10; the laser sintering is a composite forming method combining sintering and cladding, a laser head reciprocates once in each stroke, the stroke is a sintering process, the return stroke is a cladding process, the power of the laser sintering process is set to be 1.8-2 kW, and the power of the cladding process is set to be 2.6-2.8 kW; the secondary sintering is to repeat the laser sintering process again.
2. The preparation method of the high-hardness tungsten-based alloy material is characterized by comprising the following steps of:
(1) raw material treatment
The mixed material comprises the following components in percentage by mass: tantalum powder: rhenium powder = 95:3:2 (total amount of ingredients is 50g), and the particle sizes of the three powders are respectively as follows: rhenium powder is 500 meshes, tungsten powder is 500 meshes, and tantalum powder is 400 meshes; the inner lining of the ball milling tank is made of ceramic materials, ceramic balls with the diameter of 10mm are used as milling balls, the ball material ratio is 10:1, the process control agent is 23% absolute ethyl alcohol, and the ball milling time is 36 hours; after ball milling, the raw materials are washed twice by using absolute ethyl alcohol, 650g of absolute ethyl alcohol is used for washing each time, then the raw materials are placed in a centrifuge, the centrifugal speed is set to be 1500 revolutions per minute, the centrifugal time is 2 minutes for separation, the washed powder is dried in a vacuum drying oven, the temperature is set to be 65 ℃, and the drying time is 10 hours; grinding the dried powder for 30min by using an agate mortar, and placing the obtained powder in a drying bottle for later use; placing the powder subjected to ball milling treatment in a vacuum glove box, setting the temperature to 85 ℃, introducing argon, keeping the pressure of the argon at 0.103MPa for 2 hours, finishing the treatment, and sealing for later use;
(2) laser sintering
Placing the deoxidized mixed powder in a powder feeder of an automatic laser sintering operation platform, and setting a laser spot to be 5 × 4mm2Square light spots, wherein the laser scanning speed is 2mm/s, the single stroke of a laser head is 130mm, the line spacing is 3.5mm, the single-layer reciprocating frequency is 8, the layer spacing is 0.7mm, and the number of powder laying layers is 8; the laser sintering is a composite forming method combining sintering and cladding, a laser head reciprocates once in each stroke, the stroke is a sintering process, the return stroke is a cladding process, the power of the laser sintering process is set to be 1.8-2 kW, and the power of the cladding process is set to be 2.6-2.8 kW; the purity of the argon is 99.999 percent, the pressure of the argon is 0.103MPa, the flow is 9L/min, circulating water is introduced into the laser head for cooling treatment, and the laser sintering process is repeated to obtain the second sintering;
(3) sample post-treatment
Cutting the laser sintering sample into 6 × 6 × 3mm3The small sample of (2); and then carrying out stress relief annealing to eliminate residual stress, wherein the annealing is to heat the sample to 600 ℃ within 55min at a heating rate of 10 ℃/min, then preserving heat for 35min, then heating to 900 ℃ within 48min at a heating rate of 7 ℃/min, then preserving heat for 60min, and finally cooling along with the furnace to obtain the alloy material.
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