CN118272686B - Hard alloy and preparation method thereof - Google Patents
Hard alloy and preparation method thereof Download PDFInfo
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- CN118272686B CN118272686B CN202410705626.6A CN202410705626A CN118272686B CN 118272686 B CN118272686 B CN 118272686B CN 202410705626 A CN202410705626 A CN 202410705626A CN 118272686 B CN118272686 B CN 118272686B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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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
- C22C29/067—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 comprising a particular metallic binder
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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
- C22C29/08—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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Abstract
The invention belongs to the technical field of powder metallurgy, and particularly relates to a hard alloy and a preparation method thereof, wherein the hard alloy comprises 75-95wt% of WC-Re hard phase and 5-25wt% of Co-Re binding phase as raw materials, so that the cooperative reinforcement of tungsten carbide and cobalt in the hard alloy is realized, the normal temperature and high temperature performances of the prepared hard alloy are cooperatively improved, the room temperature hardness is more than or equal to 1350HV, the room temperature toughness KIC is more than or equal to 25.0 (MPa.m 1/2), the room temperature bending strength is more than or equal to 4100MPa, and the high temperature (800 ℃) hardness is more than or equal to 1180HV.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a hard alloy and a preparation method thereof.
Background
The hard alloy is an alloy material prepared from hard compound of refractory metal and binding metal through a powder metallurgy process, and has a series of excellent properties of high hardness, wear resistance, good strength and toughness, heat resistance, corrosion resistance and the like, so that the hard alloy is widely applied to cutter materials. In particular cemented carbides have a high hardness and wear resistance, remain substantially unchanged even at temperatures of 500 ℃, and have a very high hardness at 1000 ℃ and are therefore often used for the manufacture of tools for cutting steel. The rapid development of aerospace, national defense and military industry and precision electronics industry brings forward the requirements of high speed, high precision and high efficiency for processing, and as is well known, the high-speed cutting naturally brings high temperature, so that the requirements on cutter materials are also more severe, and therefore, how to improve the high-temperature performance of the cutter materials is the research focus of the current material development.
The binding metal in the hard alloy is usually cobalt (Co), and cobalt can be used as the binding metal to ensure that the hard alloy has better sintering property and mechanical property, but the oxidation resistance and corrosion resistance of cobalt are poor, and solid solution strengthening of cobalt phase is always one of main directions for improving the comprehensive property research of the hard alloy. Re is a refractory rare metal, has excellent properties of high melting point, high strength, good shaping and the like, and is one of important constituent components of the high-temperature alloy. Rhenium (Re) is one of the elements that has the best effect of solid solution strengthening of nickel-base superalloys. But Re has relatively few applications in the cemented carbide industry. Studies show that partial noble metal can be dissolved in a solid to reduce dislocation energy of a W stacking layer, reduce grain boundary impedance of dislocation movement, enable W-Re alloy to easily form twin crystals in a deformation process, and simultaneously enable solid solution Co (Re, W, C) to have higher microhardness and elastic modulus than solid solution Co (W, C); rhenium may also reduce the stacking fault energy of the cobalt phase, promoting cobalt to hexagonal phase transition from the cubic phase. The addition of the modifier generally reduces the toughness performance of the alloy, improves the hardness of the material, and the finer the powder is, the more difficult the uniform distribution of the inhibitor is achieved, and the deviation of WC grains is easy to grow abnormally. The prior art aims at strengthening a binding phase, wherein the adding mode is mainly directly added with ball milling, the technical difficulty in the mode is mainly that the metal phase is uniformly and effectively dissolved in solid under the condition of low adding amount, has certain ductility, and is difficult to uniformly disperse under the ball milling mode, so that the performance of the alloy is influenced. At the same time, the addition of this mode can only play a role in improving the high-temperature softening resistance of the cobalt phase, and the increase of the content thereof leads to the reduction of the hardness of the alloy. In the prior art, mixing and stirring an aqueous solution of ammonium metatungstate and an aqueous solution of ammonium perrhenate, and then granulating by spraying to prepare precursor powder; calcining and reducing the precursor powder to obtain W-Re alloy powder; or preparing high-purity tungsten-rhenium alloy powder with uniform chemical components by using ammonium rhenate (ammonium perrhenate and ammonium perrhenate) and ammonium metatungstate as raw materials and adopting a spray drying pyrolysis method and a hydrogen reduction presintering method; or the W-Re alloy powder is prepared by combining a spray drying method with a later hydrogen reduction process, but the methods only improve the dispersion uniformity of rhenium in the alloy and still only improve the high-temperature softening resistance of cobalt.
Disclosure of Invention
In order to solve the problems in the prior art, the main purpose of the invention is to provide a hard alloy and a preparation method thereof, wherein uniform solid solution strengthening is realized on a binding phase under the condition of low-content noble metal additives, and the normal temperature and high temperature performances of the prepared hard alloy are synergistically improved, so that the hard alloy has good mechanical properties.
In order to solve the technical problems, according to one aspect of the present invention, the following technical solutions are provided:
The preparation method of the hard alloy comprises the following steps:
S1, preparing a Co-Re binding phase;
s2, preparation of WC-Re hard phase: firstly, preparing W-Re alloy powder, mixing the W-Re alloy powder with carbon powder, and carbonizing to obtain WC-Re hard phase;
And S3, taking a Co-Re binding phase and a WC-Re hard phase according to the composition of the hard alloy, adding a proper amount of forming agent, performing wet ball milling, drying and granulating to obtain a hard alloy mixture, and performing compression molding, degreasing, vacuum and pressure sintering on the hard alloy mixture, wherein the pressure of the pressure sintering is 5-6 MPa, the sintering temperature is 1400-1500 ℃, and the sintering time is 30-90 min, so that the hard alloy is obtained.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S1, re of the Co-Re binding phase is 1-15wt% of Co.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S2, re of the WC-Re hard phase is 0.01-2wt% of WC.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S3, 75-95wt% of WC-Re hard phase and 5-25wt% of Co-Re binding phase are taken according to mass percentage.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S1, mixing and stirring an aqueous solution of cobalt oxalate and an aqueous solution of ammonium perrhenate, then performing spray granulation to obtain precursor powder, and sending the precursor powder into a reduction furnace for reducing with reverse hydrogen at 1100-1300 ℃ to obtain a Co-Re binding phase.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S2, liquid-liquid doping is carried out on ammonium metatungstate and ammonium perrhenate solution, then spray ball milling is carried out, homogeneously doped composite powder is prepared, then calcination is carried out at 700-800 ℃ to prepare tungsten oxide and ammonium perrhenate, and then hydrogen is introduced for reduction, so that homogeneously doped W-Re alloy powder is prepared.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S2, the tungsten oxide and ammonium perrhenate solution are uniformly mixed in a solid-liquid doping mode, then dried, and reduced at a low temperature in a hydrogen atmosphere to prepare the homogeneously doped W-Re alloy powder.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S2, the tungsten powder and the ammonium perrhenate solution are uniformly mixed in a solid-liquid doping mode and then dried, so that the W-Re alloy powder is prepared.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S2, high-temperature solid solution is carried out on the W-Re alloy powder before carbonization, so that the W-Re alloy solid solution powder is prepared.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S2, the carbon quantity required by the tungsten powder to be completely carbonized into tungsten carbide is weighed, and the tungsten powder and the W-Re alloy powder are mixed and compacted for carbonization; carbonizing at 1380-1450 ℃, and then crushing and grading to obtain WC-Re powder with the required size fraction; and then carbonizing at a high temperature of 1700-2000 ℃ again in a loose state, and crushing and grading again to obtain the WC-Re hard phase.
As a preferable scheme of the method for preparing the cemented carbide, the invention comprises the following steps: in the step S3, 0.5-0.7wt% of an inhibitor is also added during wet ball milling, wherein the inhibitor is VC or Cr 2C3.
In order to solve the above technical problems, according to another aspect of the present invention, the following technical solutions are provided:
The hard alloy is prepared by the preparation method, and has room temperature hardness of more than or equal to 1355HV, room temperature toughness KIC of more than or equal to 25.0 (MPa.m 1/2), room temperature bending strength of more than or equal to 4100MPa and high temperature (800 ℃) hardness of more than or equal to 1190HV.
The beneficial effects of the invention are as follows:
The invention provides a hard alloy and a preparation method thereof, wherein the hard alloy comprises 75-95wt% of WC-Re hard phase and 5-25wt% of Co-Re binding phase as raw materials, so that the cooperative reinforcement of tungsten carbide and cobalt in the hard alloy is realized, the normal temperature and high temperature performances of the prepared hard alloy are cooperatively improved, the room temperature hardness is more than or equal to 1350HV, the room temperature toughness KIC is more than or equal to 25.0 (MPa.m 1/2), the room temperature bending strength is more than or equal to 4100MPa, and the high temperature (800 ℃) hardness is more than or equal to 1180HV.
Detailed Description
The following description will be made clearly and fully with reference to the technical solutions in the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to one aspect of the invention, the invention provides the following technical scheme:
The preparation method of the hard alloy comprises the following steps:
S1, preparing a Co-Re binding phase;
s2, preparation of WC-Re hard phase: firstly, preparing W-Re alloy powder, mixing the W-Re alloy powder with carbon powder, and carbonizing to obtain WC-Re hard phase;
S3, taking a Co-Re binding phase and a WC-Re hard phase according to the composition of the hard alloy, adding a proper amount of a forming agent (for example, 2wt percent), wherein the forming agent can be 48-56# paraffin or at least one of PEG 1000-10000), carrying out wet ball milling, drying and granulating to obtain a hard alloy mixture, carrying out compression molding, degreasing, vacuum-pressure sintering on the hard alloy mixture, wherein the pressure of the pressure sintering is 5-6 MPa, the sintering temperature is 1400-1500 ℃, and the sintering time is 30-90 min, so as to obtain the hard alloy.
Preferably, in the step S1, an aqueous solution of cobalt oxalate and an aqueous solution of ammonium perrhenate are mixed and stirred, and then spray granulation is performed to obtain precursor powder, and the precursor powder is sent into a reducing furnace to be reduced at 1100-1300 ℃ by reverse hydrogen, so as to obtain a Co-Re binding phase.
Preferably, in the step S1, re of the co—re binder phase is 1 to 15wt% of Co. More preferably, the Re of the Co-Re binder phase is 5 to 15wt% of Co.
Preferably, in the step S2, re of the WC-Re hard phase is 0.01 to 2wt% of WC. Further preferably, re of the WC-Re hard phase is 0.01-1wt% of WC.
Preferably, in the step S3, 75-95wt% of WC-Re hard phase and 5-25wt% of Co-Re binder phase are taken according to mass percentage.
Preferably, in the step S2, the method for preparing the W-Re alloy powder may be:
Carrying out liquid-liquid doping on ammonium metatungstate and ammonium perrhenate solution, then carrying out spray ball milling to obtain homogeneously doped composite powder, then calcining at 600-800 ℃ to obtain tungsten oxide and rhenium oxide, and then introducing hydrogen for reduction to obtain homogeneously doped W-Re alloy powder;
or uniformly mixing tungsten oxide and ammonium perrhenate solution in a solid-liquid doping mode, drying, and reducing at a low temperature in a hydrogen atmosphere to prepare homogeneously doped W-Re alloy powder;
or uniformly mixing tungsten powder and ammonium perrhenate solution in a solid-liquid doping mode, and drying to obtain the W-Re alloy powder.
Preferably, in the step S2, the W-Re alloy powder is further subjected to high-temperature solid solution before carbonization, so as to obtain the W-Re alloy solid solution powder.
Preferably, in the step S2, the carbon amount required by the tungsten powder to be completely carbonized into tungsten carbide is weighed, mixed with the W-Re alloy powder, compacted and carbonized; the carbonization is carried out in two steps: carbonizing at 1380-1450 ℃, and then crushing and grading to obtain WC-Re powder with the required size fraction; and then carbonizing at a high temperature of 1700-2000 ℃ again in a loose state, and crushing and grading again to obtain the WC-Re hard phase. The first step of carbonization realizes complete carbonization of tungsten powder, and the second step of carbonization realizes high-temperature solid solution of rhenium in tungsten carbide; in order to prevent the abnormal growth of tungsten carbide powder in the high-temperature carbonization process, VC or Cr 2C3 can be added in the high-temperature carbonization process.
Preferably, in the step S3, 0.5-0.7wt% of an inhibitor is further added during wet ball milling, and the inhibitor is VC or Cr 2C3.
According to another aspect of the invention, the invention provides the following technical scheme:
the hard alloy is prepared by the preparation method, and the room temperature hardness of the hard alloy is more than or equal to 1350HV, the room temperature toughness KIC is more than or equal to 25.0 (MPa.m 1/2), the room temperature bending strength is more than or equal to 4100MPa, and the high temperature (800 ℃) hardness is more than or equal to 1180HV.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
The preparation method of the hard alloy comprises the following steps:
S1, preparation of Co-Re binding phase: according to the composition of the Co-Re binding phase, mixing and stirring an aqueous solution of cobalt oxalate and an aqueous solution of ammonium perrhenate, then preparing precursor powder through spray granulation, and sending the precursor powder into a reduction furnace to be subjected to reverse hydrogen reduction at 1200 ℃ for 1.5 hours to prepare the Co-Re binding phase;
s2, preparation of WC-Re hard phase: carrying out liquid-liquid doping on ammonium metatungstate and ammonium perrhenate solution, then carrying out spray ball milling to obtain homogeneously doped composite powder, then calcining at 700 ℃ for 1.5H to obtain tungsten oxide and rhenium oxide, and then introducing hydrogen (800 ℃ and H 2 flow of 52m 3/H) for reduction to obtain homogeneously doped W-Re alloy powder; and (3) carrying out high-temperature solid solution on the W-Re alloy powder in a vacuum furnace, wherein the temperature is 1200 ℃ and the time is 2h. According to the composition of WC-Re hard phase, weighing the carbon quantity required by completely carbonizing tungsten powder into tungsten carbide, mixing the tungsten powder with W-Re alloy powder, compacting, carbonizing for 2.5 hours at 1400 ℃ in a molybdenum wire furnace under the hydrogen atmosphere, and then crushing and grading to obtain WC-Re powder with the required size fraction; then, carbonizing again at 1700 ℃ in a loose state in a vacuum furnace at high temperature, and crushing and grading again to obtain WC-Re hard phase;
S3, according to the composition of the hard alloy, 88.8 weight percent of WC-Re hard phase (Re of the WC-Re hard phase is 1 weight percent of WC), 10.6 weight percent of Co-Re bonding phase (Re of the Co-Re bonding phase is 6 weight percent of Co), 0.6 weight percent of Cr 2C3 and 2 weight percent of paraffin wax are added as a forming agent, wet ball milling is carried out (alcohol is taken as a ball milling medium, the ball material ratio is 6:1, the ball milling time is 32 h), then drying and granulating are carried out, hard alloy mixture is obtained, and the hard alloy mixture is subjected to compression molding, degreasing, vacuum and pressure sintering, the pressure of pressure sintering is 6MPa, the sintering temperature is 1400 ℃, and the sintering time is 60min, so that the hard alloy is obtained.
Example 2
The preparation method of the hard alloy comprises the following steps:
S1, preparation of Co-Re binding phase: according to the composition of the Co-Re binding phase, mixing and stirring an aqueous solution of cobalt oxalate and an aqueous solution of ammonium perrhenate, then preparing precursor powder through spray granulation, and sending the precursor powder into a reduction furnace to be subjected to reverse hydrogen reduction at 1200 ℃ for 1.5 hours to prepare the Co-Re binding phase;
S2, preparing WC-Re hard phase, selecting proper amount of tungsten oxide and ammonium perrhenate solid-liquid doping according to weight requirements, ball milling, mixing, drying to obtain powder, and then introducing hydrogen (800 ℃ C., H 2 flow is 52m 3/H) for reduction to obtain homogeneously doped W-Re alloy powder; and (3) carrying out high-temperature solid solution on the W-Re alloy powder in a vacuum furnace, wherein the temperature is 1200 ℃ and the time is 2h. According to the composition of WC-Re hard phase, weighing the carbon quantity required by completely carbonizing tungsten powder into tungsten carbide, mixing the tungsten powder with W-Re alloy powder, compacting, carbonizing for 2.5 hours at 1400 ℃ in a molybdenum wire furnace under the hydrogen atmosphere, and then crushing and grading to obtain WC-Re powder with the required size fraction; then, carbonizing again at 1700 ℃ in a loose state in a vacuum furnace at high temperature, and crushing and grading again to obtain WC-Re hard phase;
S3, according to the composition of the hard alloy, 88.8 weight percent of WC-Re hard phase (Re of the WC-Re hard phase is 1 weight percent of WC), 10.6 weight percent of Co-Re bonding phase (Re of the Co-Re bonding phase is 6 weight percent of Co), 0.6 weight percent of Cr 2C3 and 2 weight percent of paraffin wax are added as a forming agent, wet ball milling is carried out (alcohol is taken as a ball milling medium, the ball material ratio is 6:1, the ball milling time is 32 h), then drying and granulating are carried out, hard alloy mixture is obtained, and the hard alloy mixture is subjected to compression molding, degreasing, vacuum and pressure sintering, the pressure of pressure sintering is 6MPa, the sintering temperature is 1400 ℃, and the sintering time is 60min, so that the hard alloy is obtained.
Example 3
A preparation method of hard alloy, which comprises 0.6wt% of Cr 2C3. The method comprises the following steps:
S1, preparation of Co-Re binding phase: according to the composition of the Co-Re binding phase, mixing and stirring an aqueous solution of cobalt oxalate and an aqueous solution of ammonium perrhenate, then preparing precursor powder through spray granulation, and sending the precursor powder into a reduction furnace to be subjected to reverse hydrogen reduction at 1200 ℃ for 1.5 hours to prepare the Co-Re binding phase;
S2, preparing WC-Re hard phase, selecting proper amount of tungsten powder and ammonium perrhenate solution according to weight requirements, uniformly mixing by adopting a solid-liquid doping mode, and drying to prepare homogeneously doped W-Re alloy powder; and (3) carrying out high-temperature solid solution on the W-Re alloy powder in a vacuum furnace, wherein the temperature is 1200 ℃ and the time is 2h. According to the composition of WC-Re hard phase, weighing the carbon quantity required by completely carbonizing tungsten powder into tungsten carbide, mixing the tungsten powder with W-Re alloy powder, compacting, carbonizing for 2.5 hours at 1400 ℃ in a molybdenum wire furnace under the hydrogen atmosphere, and then crushing and grading to obtain WC-Re powder with the required size fraction; then, carbonizing again at 1700 ℃ in a loose state in a vacuum furnace at high temperature, and crushing and grading again to obtain WC-Re hard phase;
S3, according to the composition of the hard alloy, 88.8 weight percent of WC-Re hard phase (Re of the WC-Re hard phase is 1 weight percent of WC), 10.6 weight percent of Co-Re bonding phase (Re of the Co-Re bonding phase is 6 weight percent of Co), 0.6 weight percent of Cr 2C3 and 2 weight percent of paraffin wax are added as a forming agent, wet ball milling is carried out (alcohol is taken as a ball milling medium, the ball material ratio is 6:1, the ball milling time is 32 h), then drying and granulating are carried out, hard alloy mixture is obtained, and the hard alloy mixture is subjected to compression molding, degreasing, vacuum and pressure sintering, the pressure of pressure sintering is 6MPa, the sintering temperature is 1400 ℃, and the sintering time is 60min, so that the hard alloy is obtained.
Comparative example 1
The difference from example 1 is that the cemented carbide component is WC-10Co-0.6Cr 3C2, and no rhenium is added. According to the composition of the hard alloy, adding tungsten carbide, cobalt powder and Cr 2C3 in proportion, adding 2wt% of paraffin as a forming agent, performing wet ball milling (alcohol is used as a ball milling medium, the ball material ratio is 6:1, and the ball milling time is 32 h), drying and granulating to obtain a hard alloy mixture, performing compression molding, degreasing, vacuum and pressure sintering on the hard alloy mixture, wherein the pressure of the pressure sintering is 6MPa, the sintering temperature is 1400 ℃, and the sintering time is 60min, so as to obtain the hard alloy.
Comparative example 2
The difference from example 1 is that the raw materials used were tungsten carbide, cobalt powder, rhenium powder and chromium carbide powder, and all the raw materials were added by ball milling. According to the composition of the hard alloy, tungsten carbide, cobalt powder, rhenium powder and Cr 2C3 are taken, 2wt% of paraffin is added as a forming agent, wet ball milling is carried out (alcohol is taken as a ball milling medium, the ball material ratio is 6:1, the ball milling time is 32 h), then drying and granulating are carried out, and the hard alloy mixture is subjected to compression molding, degreasing, vacuum and pressure sintering, the pressure of the pressure sintering is 6MPa, the sintering temperature is 1400 ℃, and the sintering time is 60min, so that the hard alloy is obtained.
Comparative example 3
The preparation method of the hard alloy comprises the following steps:
S1, preparation of WC-Re hard phase: carrying out liquid-liquid doping on ammonium metatungstate and ammonium perrhenate solution, then carrying out spray ball milling to obtain homogeneously doped composite powder, then calcining at 700 ℃ for 1.5H to obtain tungsten oxide and rhenium oxide, and then introducing hydrogen (800 ℃ and H 2 flow of 52m 3/H) for reduction to obtain homogeneously doped W-Re alloy powder; and (3) carrying out high-temperature solid solution on the W-Re alloy powder in a vacuum furnace, wherein the temperature is 1200 ℃ and the time is 2h. According to the composition of WC-Re hard phase, weighing the carbon quantity required by completely carbonizing tungsten powder into tungsten carbide, mixing the tungsten powder with W-Re alloy powder, compacting, carbonizing for 2.5 hours at 1400 ℃ in a molybdenum wire furnace under the hydrogen atmosphere, and then crushing and grading to obtain WC-Re powder with the required size fraction; then, carbonizing again at 1700 ℃ in a loose state in a vacuum furnace at high temperature, and crushing and grading again to obtain WC-Re hard phase.
S2, according to the composition of the hard alloy, 88.8 weight percent of WC-Re hard phase (Re of the WC-Re hard phase is 1 weight percent of WC), 10.6 weight percent of cobalt powder, 0.6 weight percent of Cr 2C3 and 2 weight percent of paraffin are added as a forming agent, wet ball milling is carried out (alcohol is used as a ball milling medium, the ball material ratio is 6:1, the ball milling time is 32 h), then the hard alloy mixture is obtained through drying and granulating, and the hard alloy mixture is subjected to compression molding, degreasing, vacuum and pressure sintering, wherein the pressure of the pressure sintering is 6MPa, the sintering temperature is 1400 ℃, and the sintering time is 60min, so that the hard alloy is obtained.
Comparative example 4
The preparation method of the hard alloy comprises the following steps:
S1, preparation of Co-Re binding phase: according to the composition of the Co-Re binding phase, mixing and stirring an aqueous solution of cobalt oxalate and an aqueous solution of ammonium perrhenate, then preparing precursor powder through spray granulation, and sending the precursor powder into a reduction furnace to be subjected to reverse hydrogen reduction at 1200 ℃ for 1.5 hours to prepare the Co-Re binding phase;
S2, according to the composition of the hard alloy, taking 87.9 weight percent of tungsten carbide powder, 0.9 weight percent of rhenium powder and 10.6 weight percent of Co-Re binding phase (Re of Co-Re binding phase is 6 weight percent of Co), adding 0.6 weight percent of Cr 2C3, adding 2 weight percent of paraffin as a forming agent, performing wet ball milling (taking alcohol as a ball milling medium, wherein the ball material ratio is 6:1, and the ball milling time is 32 h), drying and granulating to obtain a hard alloy mixture, and performing compression molding, degreasing, vacuum and pressure sintering on the hard alloy mixture, wherein the pressure of pressure sintering is 6MPa, the sintering temperature is 1400 ℃, and the sintering time is 60min to obtain the hard alloy.
Comparative example 5
The preparation method of the hard alloy comprises the following steps:
S1, preparation of Co-Re binding phase: according to the composition of the Co-Re binding phase, mixing and stirring an aqueous solution of cobalt oxalate and an aqueous solution of ammonium perrhenate, then preparing precursor powder through spray granulation, and sending the precursor powder into a reduction furnace to be subjected to reverse hydrogen reduction at 1200 ℃ for 1.5 hours to prepare the Co-Re binding phase;
s2, preparation of WC-Re hard phase: carrying out liquid-liquid doping on ammonium metatungstate and ammonium perrhenate solution, then carrying out spray ball milling to obtain homogeneously doped composite powder, then calcining at 700 ℃ for 1.5H to obtain tungsten oxide and rhenium oxide, and then introducing hydrogen (800 ℃ and H 2 flow of 52m 3/H) for reduction to obtain homogeneously doped W-Re alloy powder; and (3) carrying out high-temperature solid solution on the W-Re alloy powder in a vacuum furnace, wherein the temperature is 1200 ℃ and the time is 2h. According to the composition of WC-Re hard phase, weighing the carbon quantity required by completely carbonizing tungsten powder into tungsten carbide, mixing the tungsten powder with W-Re alloy powder, compacting, carbonizing for 2.5 hours at 1400 ℃ in a molybdenum wire furnace under the hydrogen atmosphere, and then crushing and grading to obtain WC-Re powder with the required size fraction;
S3, according to the composition of the hard alloy, 88.8 weight percent of WC-Re hard phase (Re of the WC-Re hard phase is 1 weight percent of WC), 10.6 weight percent of Co-Re bonding phase (Re of the Co-Re bonding phase is 6 weight percent of Co), 0.6 weight percent of Cr 2C3 and 2 weight percent of paraffin wax are added as a forming agent, wet ball milling is carried out (alcohol is taken as a ball milling medium, the ball material ratio is 6:1, the ball milling time is 32 h), then drying and granulating are carried out, hard alloy mixture is obtained, and the hard alloy mixture is subjected to compression molding, degreasing, vacuum and pressure sintering, the pressure of pressure sintering is 6MPa, the sintering temperature is 1400 ℃, and the sintering time is 60min, so that the hard alloy is obtained.
The properties of the cemented carbides prepared in each of the examples and comparative examples were tested and the results are shown in table 1.
Table 1 properties of cemented carbides of examples and comparative examples
As can be seen from table 1, the cemented carbide of each embodiment of the present invention exhibits improved mechanical properties at normal temperature and improved hardness at high temperature. Comparative example 1 has lowest normal temperature mechanical properties and high temperature hardness because rare metal rhenium is not added; in comparative example 2, rare metal rhenium is added in a metal phase, and the phenomena of uneven dispersion and the like exist in the ball milling process, compared with comparative example 1, the performance difference at normal temperature is small, but the high-temperature hardness is obviously improved; in comparative examples 3 to 5, since the Co-Re binder phase or WC-Re hard phase was not prepared or the WC-Re hard phase was not carbonized at high temperature, both the normal temperature mechanical properties and the high temperature hardness were lower than those of examples.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (7)
1. The preparation method of the hard alloy is characterized by comprising the following steps:
S1, preparation of Co-Re binding phase: mixing and stirring an aqueous solution of cobalt oxalate and an aqueous solution of ammonium perrhenate, then performing spray granulation to obtain precursor powder, and sending the precursor powder into a reduction furnace to reduce with reverse hydrogen at 1100-1300 ℃ to obtain a Co-Re binding phase;
S2, preparation of WC-Re hard phase: firstly, preparing W-Re alloy powder, weighing the carbon quantity required by the tungsten powder to be completely carbonized into tungsten carbide, mixing the tungsten powder with the W-Re alloy powder, compacting the mixture, and carbonizing the mixture; carbonizing at 1380-1450 ℃, and then crushing and grading to obtain WC-Re powder with the required size fraction; then carbonizing at a high temperature of 1700-2000 ℃ again in a loose state, and crushing and grading again to obtain WC-Re hard phase;
S3, according to the composition of the hard alloy, taking 75-95wt% of WC-Re hard phase and 5-25wt% of Co-Re binding phase, adding a proper amount of forming agent, performing wet ball milling, drying and granulating to obtain a hard alloy mixture, performing compression molding, degreasing, vacuum and pressure sintering on the hard alloy mixture, wherein the pressure of the pressure sintering is 5-6 MPa, the sintering temperature is 1400-1500 ℃, and the sintering time is 30-90 min, so that the hard alloy is obtained;
The hardness of the hard alloy at room temperature is more than or equal to 1350HV, the toughness KIC at room temperature is more than or equal to 25.0 (MPa.m 1/2), the bending strength at room temperature is more than or equal to 4100MPa, and the hardness at 800 ℃ is more than or equal to 1180HV.
2. The method of producing cemented carbide according to claim 1, wherein Re of the Co-Re binder phase in step S1 is 1-15 wt% of Co.
3. The method of producing cemented carbide according to claim 1, wherein in step S2, re of WC-Re hard phase is 0.01-2 wt% of WC.
4. The method for preparing cemented carbide according to claim 1, wherein in step S2, the method for preparing the W-Re alloy powder comprises:
Carrying out liquid-liquid doping on ammonium metatungstate and ammonium perrhenate solution, then carrying out spray ball milling to obtain homogeneously doped composite powder, then calcining at 700-800 ℃ to obtain tungsten oxide and ammonium rhenate, and then introducing hydrogen for reduction to obtain homogeneously doped W-Re alloy powder;
or uniformly mixing tungsten oxide and ammonium perrhenate solution in a solid-liquid doping mode, drying, and reducing at a low temperature in a hydrogen atmosphere to prepare homogeneously doped W-Re alloy powder;
or uniformly mixing tungsten powder and ammonium perrhenate solution in a solid-liquid doping mode, and drying to obtain the W-Re alloy powder.
5. The method of producing cemented carbide according to claim 1, wherein in step S2, the W-Re alloy powder is further subjected to high-temperature solid solution before carbonization to produce a W-Re alloy solid solution powder.
6. The method for preparing cemented carbide according to claim 1, wherein in step S3, 0.5-0.7wt% of an inhibitor, VC or Cr 2C3, is added during wet ball milling.
7. A cemented carbide, characterized in that it is produced by the method for producing a cemented carbide according to any one of claims 1-6.
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