CN112695238A - Vanadium-titanium composite binder phase hard alloy and preparation method thereof - Google Patents
Vanadium-titanium composite binder phase hard alloy and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 106
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 105
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- 239000011230 binding agent Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims abstract description 20
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
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- 238000000498 ball milling Methods 0.000 claims description 29
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention belongs to the technical field of alloy, and particularly relates to a vanadium-titanium composite binder phase hard alloy and a preparation method thereof. The vanadium-titanium composite binding phase hard alloy provided by the invention comprises the following components in percentage by mass in the vanadium-titanium composite binding phase hard alloy: 84.12-94.28% of tungsten carbide, 4.76-14.88% of vanadium-titanium composite binder phase and 0.6-1% of vanadium carbide; the vanadium-titanium composite binding phase comprises the following elements in percentage by mass: 80.23-90.25% of cobalt, 5.91-11.88% of vanadium and 3.84-7.89% of titanium. The vanadium-titanium composite binding phase is beneficial to forming a gamma + gamma' phase coherent microstructure by element compounding, improving the strength and hardness of the vanadium-titanium composite binding phase hard alloy and improving the toughness.
Description
Technical Field
The invention belongs to the technical field of alloy, and particularly relates to a vanadium-titanium composite binder phase hard alloy and a preparation method thereof.
Background
The hard alloy is an alloy material prepared from a hard compound of refractory metal and bonding metal through a powder metallurgy process, has the advantages of high carbide melting point and good ductility of the bonding metal, has the characteristics of high strength and hardness, good wear resistance and corrosion resistance and good chemical stability, and is widely applied to the field of metal cutting tools. The traditional hard alloy uses hard compound WC of refractory metal as main phase, which contributes to hardness, strength and wear resistance of the hard alloy, and uses transition metals Fe, Co or Ni as binding phase to bind the hard phases together, which contributes to toughness of the hard alloy.
This relationship between the composition of the hard compounds of the refractory metals and the binder metal results in certain contradictory properties of cemented carbides: when the content of the metal in the binding phase is less (less than or equal to 6 percent), the hardness of the hard alloy is increased but the fracture toughness is reduced; on the contrary, when the content of the metal in the binder phase is too high (not less than 15%), the fracture toughness of the hard alloy is improved, but the hardness and the wear resistance are obviously reduced. The hardness of the prior art "wear resistant alloys" of both the A-Structure Properties and the hardness of the alloy "A-Structure Properties", the hardness of the alloy "A-Structure Properties" and "hardness of the alloy" of the prior art "of the composition of the Materials in the characterized Metals of the composites in the technology,2001 (1780)", "Fang Z.Corning Z.correction of transition growth of the composition of the alloy of WC-Co with hardness. International Journal of the composition of the alloy Metals and Hard Metals 2005,23(2): 119-.
Disclosure of Invention
In view of the above, the present invention provides a vanadium-titanium composite binder phase cemented carbide, which has the characteristics of fine crystal grains, high strength and hardness, and excellent toughness.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a vanadium-titanium composite binder phase hard alloy, which comprises the following components in percentage by mass in the vanadium-titanium composite binder phase hard alloy:
84.12 to 94.28 percent of tungsten carbide,
4.76 to 14.88 percent of vanadium-titanium composite binder phase,
0.6-1% of vanadium carbide;
the vanadium-titanium composite binding phase comprises the following elements in percentage by mass:
80.23-90.25% of cobalt, 5.91-11.88% of vanadium and 3.84-7.89% of titanium.
Preferably, the particle size of the tungsten carbide is 100-300 nm; the particle size of the vanadium carbide is 2-5 mu m.
Preferably, the particle size of the vanadium-titanium composite binder phase is 1-40 μm.
The invention also provides a preparation method of the vanadium-titanium composite binder phase hard alloy, which comprises the following steps:
mixing vanadium-titanium composite binder phase raw materials, and sequentially smelting and cooling to obtain a composite binder phase alloy ingot;
remelting and atomizing the composite bonding phase alloy ingot to obtain composite bonding phase alloy powder;
mixing the composite binder phase alloy powder, tungsten carbide and vanadium carbide, and sequentially carrying out wet ball milling and drying to obtain hard alloy powder;
and performing discharge plasma sintering on the hard alloy powder to obtain the vanadium-titanium composite binding phase hard alloy.
Preferably, the smelting temperature is 1500-2000 ℃.
Preferably, the particle size of the composite binder phase alloy powder is 1-40 μm.
Preferably, the ball-to-material ratio of the wet ball milling is (4-6): 1, the ball milling medium is ethanol; the ball milling speed is 200-300 rpm, and the ball milling time is 24-48 h.
Preferably, the drying temperature is 50-100 ℃, and the drying time is 6-24 h.
Preferably, the conditions of the spark plasma sintering include: the rated power of the equipment for spark plasma sintering is 80-120 kW, the sintering temperature is 1200-1400 ℃, and the heat preservation time is 10-30 min; the sintering pressure is 30-60 MPa.
Preferably, the sintering temperature is obtained by raising the temperature; the temperature rise rate is 50-100 ℃/min.
The invention provides a vanadium-titanium composite binder phase hard alloy, which comprises the following components in percentage by mass in the vanadium-titanium composite binder phase hard alloy: 84.12-94.28% of tungsten carbide, 4.76-14.88% of vanadium-titanium composite binder phase and 0.6-1% of vanadium carbide; the vanadium-titanium composite binding phase comprises the following elements in percentage by mass: 80.23-90.25% of cobalt, 5.91-11.88% of vanadium and 3.84-7.89% of titanium. According to the invention, a Co-V-Ti ternary alloy is used for replacing a traditional pure Co binding phase, and the Co-V-Ti ternary alloy is a Co-based high-temperature alloy, so that a coherent microstructure of gamma + gamma 'phase is formed, an ordered gamma' phase with fine grain size is formed, and further the vanadium-titanium composite binding phase in the hard alloy has the properties of Co-V-Ti, namely high strength, hardness and good toughness, so that compared with the traditional hard alloy using pure Co as the binding phase, the vanadium-titanium composite binding phase hard alloy provided by the invention has more excellent mechanical properties and toughness such as bending strength.
The test result of the embodiment shows that the Vickers hardness HV of the vanadium-titanium composite binding phase hard alloy provided by the invention301761-2286 kg/mm2The hardness is high; the transverse breaking strength is 513-1455 MPa, and the bending strength is high; the fracture toughness is 8.6-11.43 MPa.m1/2The toughness is excellent; the density is 13.32 to 14.26g/cm3And the density is moderate.
The invention also provides a preparation method of the vanadium-titanium composite binder phase hard alloy, which comprises the following steps: mixing vanadium-titanium composite binder phase raw materials, and sequentially smelting and cooling to obtain a composite binder phase alloy ingot; remelting and atomizing the composite bonding phase alloy ingot to obtain composite bonding phase alloy powder; mixing the composite binder phase alloy powder, tungsten carbide and vanadium carbide, and sequentially carrying out wet ball milling and drying to obtain hard alloy powder; and performing discharge plasma sintering on the hard alloy powder to obtain the vanadium-titanium composite binding phase hard alloy. According to the invention, the vanadium-titanium composite binder phase raw material is smelted, so that the components of the composite binder phase alloy ingot are uniform, and the composite binder phase alloy powder obtained by atomizing is favorable to have the same components, so that the defect of non-uniform components of the raw material powder generated by directly performing mechanical alloying in the traditional hard alloy preparation process is avoided; then, the composite binder phase alloy powder, tungsten carbide and vanadium carbide are mixed and subjected to wet ball milling, so that the uniformity of the particle size of the powder is improved, and the uniformity of the components of a sintered product is improved; the discharge plasma sintering is adopted, so that the growth of tungsten carbide crystal grains is favorably inhibited, fine hard alloy crystal grains are obtained, and the toughness of the composite bonding phase hard alloy is improved.
Drawings
FIG. 1 is an SEM image of composite binder phase alloy powder of example 1;
FIG. 2 is an SEM photograph of the cemented carbide powder of example 1;
fig. 3 is an SEM image of the vanadium-titanium composite binder phase cemented carbide obtained in example 1.
Detailed Description
The invention provides a vanadium-titanium composite binder phase hard alloy, which comprises the following components in percentage by mass in the vanadium-titanium composite binder phase hard alloy:
84.12 to 94.28 percent of tungsten carbide,
4.76 to 14.88 percent of vanadium-titanium composite binder phase,
0.6-1% of vanadium carbide;
the vanadium-titanium composite binding phase comprises the following elements in percentage by mass:
80.23-90.25% of cobalt, 5.91-11.88% of vanadium and 3.84-7.89% of titanium.
In the invention, the vanadium-titanium composite binder phase hard alloy comprises 84.12-94.28% of tungsten carbide, preferably 84.5-94%, more preferably 85-93.5%, and even more preferably 85.2-93% by mass percentage in the vanadium-titanium composite binder phase hard alloy. In the invention, the particle size of the tungsten carbide is preferably 100 to 300nm, more preferably 150 to 250nm, and most preferably 200 nm. In the invention, the tungsten carbide is taken as a hard compound of refractory metal, which is beneficial to improving the hardness and the strength of the composite binding phase hard alloy.
In the invention, the vanadium-titanium composite binder phase hard alloy comprises 4.76-14.88% of vanadium-titanium composite binder phase by mass percentage, preferably 5-14.5%, more preferably 5.5-14%, and even more preferably 6-13.5%. In the invention, the particle size of the vanadium-titanium composite binder phase is preferably 1-40 μm, more preferably 2-38 μm, and still more preferably 3-35 μm.
In the invention, the vanadium-titanium composite binder phase comprises, by mass percentage, 80.23-90.25% of cobalt, preferably 80.5-90%, more preferably 82-89.5%, and even more preferably 83-89%. In the invention, the cobalt can be combined with vanadium and titanium, so that the vanadium-titanium composite binding phase forms a gamma + gamma' phase coherent microstructure, which is beneficial to improving the strength and hardness of the vanadium-titanium composite binding phase hard alloy and improving the toughness of the hard alloy.
In the invention, the vanadium-titanium composite binder phase comprises 5.91-11.88% of vanadium by mass percentage, preferably 6-11.5% of vanadium by mass percentage, more preferably 6.5-11% of vanadium by mass percentage, and even more preferably 7-10.5% of vanadium by mass percentage. In the invention, the vanadium can be combined with cobalt and titanium, so that the vanadium-titanium composite binding phase forms a gamma + gamma' phase coherent microstructure, which is beneficial to improving the strength and hardness of the vanadium-titanium composite binding phase hard alloy and improving the toughness of the hard alloy.
In the invention, the vanadium-titanium composite binder phase comprises 3.84-7.89% of titanium, preferably 4-7.5%, more preferably 4.5-7%, and even more preferably 5-6.5% of titanium by mass percentage in the vanadium-titanium composite binder phase. In the invention, the titanium can be combined with cobalt and vanadium, so that the vanadium-titanium composite binding phase forms a gamma + gamma' phase coherent microstructure, which is beneficial to improving the strength and hardness of the vanadium-titanium composite binding phase hard alloy and improving the toughness of the hard alloy.
According to the invention, the Co-V-Ti ternary alloy is used for replacing the traditional pure Co binder phase to serve as the vanadium-titanium composite binder phase, the provided Co-V-Ti ternary alloy is a Co-based high-temperature alloy, the formation of a gamma + gamma 'phase coherent microstructure is facilitated, and an ordered gamma' phase with fine grain size is formed, so that the vanadium-titanium composite binder phase in the vanadium-titanium composite binder phase hard alloy has the performance of Co-V-Ti which is a Co-based high-temperature alloy, namely high strength, hardness and good toughness.
In the invention, the vanadium-titanium composite binder phase hard alloy comprises 0.6-1% of vanadium carbide, preferably 0.65-0.95%, more preferably 0.7-0.9%, and even more preferably 0.75-0.85% by mass of the vanadium-titanium composite binder phase hard alloy. In the invention, the particle size of the vanadium carbide is preferably 2-5 μm, and more preferably 2.5-4.5 μm. In the invention, the vanadium carbide is beneficial to inhibiting the growth of vanadium-titanium composite binding phase hard alloy crystal grains.
The invention also provides a preparation method of the vanadium-titanium composite binder phase hard alloy, which comprises the following steps:
mixing vanadium-titanium composite binder phase raw materials, and sequentially smelting and cooling to obtain a composite binder phase alloy ingot;
remelting and atomizing the composite bonding phase alloy ingot to obtain composite bonding phase alloy powder;
mixing the composite binder phase alloy powder, tungsten carbide and vanadium carbide, and sequentially carrying out wet ball milling and drying to obtain hard alloy powder;
and performing discharge plasma sintering on the hard alloy powder to obtain the vanadium-titanium composite binding phase hard alloy.
The vanadium-titanium composite binder phase raw materials are mixed, and smelting and cooling are sequentially carried out to obtain the composite binder phase alloy ingot.
In the invention, the vanadium-titanium composite binder phase raw material is subject to the element composition and proportion of the vanadium-titanium composite binder phase. In the invention, the purity of the vanadium-titanium composite binding phase raw material is preferably more than or equal to 99.99%. In the present invention, the source of the vanadium-titanium composite binder phase raw material is not particularly limited, and commercially available raw materials known to those skilled in the art may be used.
In the invention, the smelting temperature is preferably 1500-2000 ℃, more preferably 1550-1950 ℃, and further preferably 1600-1900 ℃; the smelting time is based on the condition that liquid alloy melt is obtained by smelting. In the present invention, the melting facility is preferably an induction melting furnace, more preferably a high-frequency induction melting furnace. In the present invention, the degree of vacuum in the melting apparatus is preferably 6X 10-3Pa。
Before smelting, oxide skin on the surface of the vanadium-titanium composite binding phase raw material is preferably removed; the method for removing the oxide scale on the surface of the vanadium-titanium composite binder phase raw material is not particularly limited, and the removing method known to those skilled in the art can be adopted, specifically, grinding is carried out.
In the present invention, the cooling is preferably furnace cooling.
After cooling, the alloy ingot obtained by cooling is preferably polished by the invention to remove an oxide layer on the surface of the alloy ingot. The present invention is not particularly limited to the polishing, and polishing known to those skilled in the art may be used. In the present invention, the grinding apparatus is preferably a grinder.
After obtaining the composite bonding phase alloy ingot, the invention remelts and atomizes the composite bonding phase alloy ingot to obtain the composite bonding phase alloy powder.
In the present invention, the equipment for remelting and atomizing is preferably an ultrasonic atomizing furnace. In the invention, the remelting temperature is preferably 1500-2000 ℃, more preferably 1550-1950 ℃, and still more preferably 1600-1900 ℃; said remeltingThe time of melting is based on obtaining liquid alloy melt. In the present invention, the remelting is preferably carried out under protective atmosphere conditions; the gas of the protective atmosphere is preferably argon. In the invention, the method for forming the protective atmosphere is preferably to introduce protective atmosphere gas into the remelting device after vacuumizing the remelting device; the degree of vacuum after evacuation is preferably 6X 10-3Pa; the pressure after the protective atmosphere gas is introduced is preferably 1 to 1.2atm, and more preferably 1.05 to 1.15 atm.
In the invention, the gas sprayed from the atomizing nozzle in the atomization process is preferably argon gas; the discharge pressure of the atomizing nozzle is preferably 5 to 10MPa, and more preferably 6 to 9 MPa. In the invention, the particle size of the composite binder phase alloy powder is preferably 1-40 μm, and more preferably 2-38 μm.
After the composite binder phase alloy powder is obtained, the composite binder phase alloy powder, tungsten carbide and vanadium carbide are mixed, and wet ball milling and drying are sequentially carried out to obtain the hard alloy powder.
In the invention, the ball-to-material ratio of the wet ball milling is preferably (4-6): 1, more preferably (4.5 to 5.5): 1, and preferably (4.7-5.3): 1. in the present invention, the ball milling medium in the wet ball milling is preferably ethanol. In the present invention, the purity of the ethanol is preferably analytical grade. In the invention, the ball milling speed of the wet ball milling is preferably 200-300 rpm, more preferably 220-280 rpm, and further preferably 230-270 rpm; the ball milling time is preferably 24-48 h, more preferably 26-46 h, and further preferably 30-45 h. In the present invention, the apparatus for wet ball milling is preferably a ball mill, more preferably a planetary ball mill.
In the invention, the drying temperature is preferably 50-100 ℃, more preferably 60-90 ℃, and further preferably 70-85 ℃; the time is preferably 6 to 24 hours, more preferably 8 to 22 hours, and still more preferably 10 to 20 hours. In the present invention, the drying apparatus is preferably a drying oven, more preferably a vacuum drying oven.
After drying, the material obtained by drying is preferably sieved, and the sieved material is taken for subsequent spark plasma sintering. In the invention, the mesh number of the screen for sieving is preferably 100-300 meshes, more preferably 120-280 meshes, and further preferably 150-250 meshes.
After obtaining the hard alloy powder, the invention carries out spark plasma sintering on the hard alloy powder to obtain the vanadium-titanium composite binding phase hard alloy.
In the invention, the rated power of the equipment for spark plasma sintering in the spark plasma sintering is preferably 80-120 kW, more preferably 90-110 kW, and most preferably 100 kW. In the invention, the sintering temperature in the spark plasma sintering is preferably 1200-1400 ℃, more preferably 1220-1380 ℃, and further preferably 1250-1350 ℃; the heat preservation time is preferably 10-30 min, and more preferably 15-25 min. In the present invention, the sintering temperature is preferably obtained by raising the temperature; the heating rate is preferably 50-100 ℃/min, more preferably 55-95 ℃/min, and still more preferably 60-90 ℃/min. In the present invention, the sintering pressure in the spark plasma sintering is preferably 30 to 60MPa, more preferably 35 to 55MPa, and still more preferably 40 to 50 MPa. In the present invention, the apparatus for spark plasma sintering is preferably a spark plasma sintering furnace.
After spark plasma sintering, the invention preferably cools the obtained sintered product to obtain the composite binder phase hard alloy. In the present invention, the cooling is preferably furnace cooling.
In order to further illustrate the present invention, the following will describe a vanadium-titanium composite binder phase cemented carbide and a method for preparing the same in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The vanadium-titanium composite binding phase hard alloy is designed to comprise the following components: WC-5 (Co)85.28-V8.88-Ti5.84) (ii) a The preparation method comprises the following steps:
will be pureCobalt, vanadium and titanium with the degree of more than or equal to 99.99 percent are respectively taken and mixed according to the mass percent of 85.28 percent, 8.88 percent and 5.84 percent, and the mixture is heated at 2000 ℃ and the vacuum degree of 6 multiplied by 10-3Carrying out high-frequency induction melting on Pa until the Pa is molten, and cooling along with the furnace to obtain a composite bonding phase alloy ingot; placing the obtained composite bonding phase alloy ingot in a crucible of an ultrasonic atomization furnace, and vacuumizing the furnace chamber to 6 multiplied by 10-3Pa, filling argon gas of 0.5atm, remelting at 1800 ℃ to obtain an alloy solution, and atomizing the obtained alloy solution by adopting argon gas under the pressure of a 7MPa nozzle to obtain composite bonding phase alloy powder with the particle size of 10 mu m;
taking and mixing the obtained composite binder alloy powder, tungsten carbide and vanadium carbide according to the mass percentages of 4.96%, 94.24% and 0.8%, respectively, taking analytically pure ethanol as a ball-milling liquid medium, and mixing the materials according to the ball-material ratio of 6: 1. carrying out wet ball milling for 48h at the rotating speed of 280rpm, drying the obtained wet grinding material in a vacuum drying oven at 70 ℃ for 24h, sieving the dried material with a 150-mesh sieve, and taking the undersize material as hard alloy powder;
and heating the obtained hard alloy powder to 1350 ℃ at the speed of 80 ℃/min, preserving heat under the condition of 40MPa, then performing discharge plasma sintering for 10min (the vacuum degree of the plasma sintering furnace is less than or equal to 5Pa) in a discharge plasma sintering furnace with the rated power of 100kW, the pressure of 60MPa and the temperature of 1350 ℃, and cooling along with the furnace to obtain the vanadium-titanium composite binder phase hard alloy.
Scanning electron microscopy tests were performed on the composite binder phase alloy powder of example 1 and the resulting SEM image is shown in fig. 1. As can be seen from FIG. 1, the composite binder phase alloy powder is in the form of spherical particles with a size of 5-20 μm.
Scanning electron microscopy tests were performed on the cemented carbide powder of example 1 and the resulting SEM image is shown in figure 2. As can be seen from FIG. 2, the hard alloy powder has a uniform and fine structure and an average grain size of 200 nm.
Scanning electron microscopy tests are carried out on the vanadium-titanium composite binder phase cemented carbide obtained in example 1, and the SEM image is shown in figure 3. As can be seen from FIG. 3, the vanadium-titanium composite binder phase cemented carbide has uniform structure and fine grains, the grain structure of the cemented carbide does not grow larger than that of powder, and the average grain size of WC is 210 nm.
Example 2
The vanadium-titanium composite binding phase hard alloy is designed to comprise the following components: WC-8 (Co)85.28-V8.88-Ti5.84) (ii) a The preparation method comprises the following steps:
cobalt, vanadium and titanium with the purity of more than or equal to 99.99 percent are respectively taken and mixed according to the mass percentage of 85.28 percent, 8.88 percent and 5.84 percent, and the mixture is heated at 1900 ℃ and the vacuum degree of 6 multiplied by 10-3Carrying out high-frequency induction melting on Pa until the Pa is molten, and cooling along with the furnace to obtain a composite bonding phase alloy ingot; placing the obtained composite bonding phase alloy ingot in a crucible of an ultrasonic atomization furnace, and vacuumizing the furnace chamber to 6 multiplied by 10-3Pa, filling argon gas of 0.5atm, remelting at 1800 ℃ to obtain an alloy solution, and atomizing the obtained alloy solution by adopting argon gas under the pressure of a 7MPa nozzle to obtain composite bonding phase alloy powder with the particle size of 10 mu m;
taking and mixing the obtained composite binder alloy powder, tungsten carbide and vanadium carbide according to the mass percentages of 7.94%, 91.26% and 0.8%, respectively, taking analytically pure ethanol as a ball-milling liquid medium, and mixing the materials according to the ball-material ratio of 4: 1. performing wet ball milling for 24 hours at the rotating speed of 300rpm, drying the obtained wet grinding material in a vacuum drying oven at the temperature of 50 ℃ for 24 hours, sieving the dried material by a 150-mesh sieve, and taking undersize materials as hard alloy powder;
and (3) heating the obtained hard alloy powder to 1250 ℃ at the speed of 80 ℃/min, preserving heat under the condition of 30MPa, then performing discharge plasma sintering for 30min in a discharge plasma sintering furnace with the rated power of 100kW, the pressure of 60MPa and the temperature of 1250 ℃ (the vacuum degree of the discharge plasma sintering furnace is less than or equal to 5Pa), and cooling along with the furnace to obtain the vanadium-titanium composite binding phase hard alloy.
Example 3
The vanadium-titanium composite binding phase hard alloy is designed to comprise the following components: WC-10 (Co)85.28-V8.88-Ti5.84) (ii) a The preparation method comprises the following steps:
cobalt, vanadium and titanium with the purity of more than or equal to 99.99 percent are respectively taken and mixed according to the mass percentage of 85.28 percent, 8.88 percent and 5.84 percent, and the mixture is processed at 2000 ℃ and the vacuum degree of 6 multiplied by 10-3Pa is subjected to high-frequency induction melting to be molten, and the mixture is cooled along with the furnace to obtain composite bonding phaseGold ingots; placing the obtained composite bonding phase alloy ingot in a crucible of an ultrasonic atomization furnace, and vacuumizing the furnace chamber to 6 multiplied by 10-3Pa, filling argon gas of 0.5atm, remelting at 1800 ℃ to obtain an alloy solution, and atomizing the obtained alloy solution by adopting argon gas under the pressure of a 7MPa nozzle to obtain composite bonding phase alloy powder with the particle size of 10 mu m;
respectively taking the obtained composite binder alloy powder, tungsten carbide and vanadium carbide according to the mass percentages of 9.92%, 89.28% and 0.8%, mixing, taking analytically pure ethanol as a ball-milling liquid medium, and mixing the materials according to the ball-material ratio of 6: 1. performing wet ball milling for 48h at the rotating speed of 200rpm, drying the obtained wet grinding material in a vacuum drying oven at the temperature of 100 ℃ for 6h, sieving the dried material by using a 150-mesh sieve, and taking the undersize material as hard alloy powder;
heating the obtained hard alloy powder to 1300 ℃ at the speed of 80 ℃/min, preserving heat under the condition of 60MPa, then carrying out discharge plasma sintering for 10min (the vacuum degree of the discharge plasma sintering furnace is less than or equal to 5Pa) in a discharge plasma sintering furnace with the rated power of 100kW, the pressure of 60MPa and the temperature of 1300 ℃, and cooling along with the furnace to obtain the vanadium-titanium composite binding phase hard alloy.
Example 4
The vanadium-titanium composite binding phase hard alloy is designed to comprise the following components: WC-15 (Co)85.28-V8.88-Ti5.84) (ii) a The preparation method comprises the following steps:
cobalt, vanadium and titanium with the purity of more than or equal to 99.99 percent are respectively taken and mixed according to the mass percentage of 85.28 percent, 8.88 percent and 5.84 percent, and the mixture is processed at 2000 ℃ and the vacuum degree of 6 multiplied by 10-3Carrying out high-frequency induction melting on Pa until the Pa is molten, and cooling along with the furnace to obtain a composite bonding phase alloy ingot; placing the obtained composite bonding phase alloy ingot in a crucible of an ultrasonic atomization furnace, and vacuumizing the furnace chamber to 6 multiplied by 10-3Pa, filling argon gas of 0.5atm, remelting at 1800 ℃ to obtain an alloy solution, and atomizing the obtained alloy solution by adopting argon gas under the pressure of a 7MPa nozzle to obtain composite bonding phase alloy powder with the particle size of 10 mu m;
taking the obtained composite binder alloy powder, tungsten carbide and vanadium carbide according to the mass percentages of 14.88%, 84.32% and 0.8%, mixing, taking analytically pure ethanol as a ball-milling liquid medium, and mixing the materials according to the ball-material ratio of 6: 1. carrying out wet ball milling for 48h at the rotating speed of 280rpm, drying the obtained wet grinding material in a vacuum drying oven at 70 ℃ for 24h, sieving the dried material with a 150-mesh sieve, and taking the undersize material as hard alloy powder;
and heating the obtained hard alloy powder to 1350 ℃ at the speed of 80 ℃/min, preserving heat under the condition of 40MPa, then performing discharge plasma sintering for 10min in a discharge plasma sintering furnace with the rated power of 100kW, the pressure of 60MPa and the temperature of 1350 ℃ (the vacuum degree of the discharge plasma sintering furnace is less than or equal to 5Pa), and cooling along with the furnace to obtain the vanadium-titanium composite binding phase hard alloy.
The vanadium-titanium composite binder phase cemented carbide obtained in examples 1 to 4 was tested, and the test methods and test results are shown in table 1.
Table 1 test methods and test results for composite binder phase cemented carbide obtained in examples 1 to 4
As can be seen from Table 1, the Vickers hardness HV of the vanadium-titanium composite binder phase cemented carbide provided by the invention301761-2286 kg/mm2The hardness is high; the transverse breaking strength is 513-1455 MPa, and the bending strength is high; the fracture toughness is 8.6-11.43 MPa.m1/2The toughness is excellent; the density is 13.32 to 14.26g/cm3And the density is moderate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The vanadium-titanium composite binder phase hard alloy comprises the following components in percentage by mass:
84.12 to 94.28 percent of tungsten carbide,
4.76 to 14.88 percent of vanadium-titanium composite binder phase,
0.6-1% of vanadium carbide;
the vanadium-titanium composite binding phase comprises the following elements in percentage by mass:
80.23-90.25% of cobalt, 5.91-11.88% of vanadium and 3.84-7.89% of titanium.
2. The vanadium-titanium composite binder phase cemented carbide according to claim 1, wherein the particle size of the tungsten carbide is 100 to 300 nm; the particle size of the vanadium carbide is 2-5 mu m.
3. The vanadium-titanium composite binder phase cemented carbide according to claim 1, wherein the particle size of the vanadium-titanium composite binder phase is 1 to 40 μm.
4. A method for preparing the vanadium-titanium composite binder phase hard alloy as defined in any one of claims 1 to 3, which comprises the following steps:
mixing vanadium-titanium composite binder phase raw materials, and sequentially smelting and cooling to obtain a composite binder phase alloy ingot;
remelting and atomizing the composite bonding phase alloy ingot to obtain composite bonding phase alloy powder;
mixing the composite binder phase alloy powder, tungsten carbide and vanadium carbide, and sequentially carrying out wet ball milling and drying to obtain hard alloy powder;
and performing discharge plasma sintering on the hard alloy powder to obtain the vanadium-titanium composite binding phase hard alloy.
5. The preparation method according to claim 4, wherein the temperature of the smelting is 1500-2000 ℃.
6. The production method according to claim 4, wherein the particle size of the composite binder phase alloy powder is 1 to 40 μm.
7. The preparation method according to claim 4, wherein the ball-to-material ratio of the wet ball milling is (4-6): 1, the ball milling medium is ethanol; the ball milling speed is 200-300 rpm, and the ball milling time is 24-48 h.
8. The method according to claim 4 or 7, wherein the drying is carried out at a temperature of 50 to 100 ℃ for 6 to 24 hours.
9. The method according to claim 4, wherein the conditions for spark plasma sintering include: the rated power of the equipment for spark plasma sintering is 80-120 kW, the sintering temperature is 1200-1400 ℃, and the heat preservation time is 10-30 min; the sintering pressure is 30-60 MPa.
10. The production method according to claim 4, wherein the sintering temperature is obtained by raising a temperature; the temperature rise rate is 50-100 ℃/min.
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