CN115652122B - Hard alloy and preparation process thereof - Google Patents
Hard alloy and preparation process thereof Download PDFInfo
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- CN115652122B CN115652122B CN202211227237.4A CN202211227237A CN115652122B CN 115652122 B CN115652122 B CN 115652122B CN 202211227237 A CN202211227237 A CN 202211227237A CN 115652122 B CN115652122 B CN 115652122B
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Abstract
The invention provides a hard alloy and a preparation process thereof, comprising the following steps: the carbon-based carrier formed by loading vanadium and chromium with biochar is mixed with graphene, WC and Co to form a mixed material; and ball milling, granulating, forming and sintering the mixture material to obtain the hard alloy. The hard alloy provided by the invention effectively improves the equipartition of the grain inhibitor in the hard alloy, and also realizes the control of grain growth in the hard alloy; the process of the invention is convenient to operate and easy to realize amplified production.
Description
Technical Field
The invention relates to a hard alloy material, in particular to a hard alloy and a preparation process thereof.
Background
Cemented carbide is known as industrial tooth, and for common cemented carbide, the content of WC needs to be increased in order to improve the hardness, wear resistance and corrosion resistance of the product; if the strength, toughness and processability of the product are improved, the Co content is increased, which results in a contradiction between the improvement of hardness and strength.
Research results show that when the WC grain size in the alloy is submicron, the hardness, strength, toughness and wear resistance of the alloy are all improved along with the refinement of the WC grain, and the lower the temperature required for achieving complete densification is; as the superfine grain hard alloy with WC grain size of only 0.2-0.5 mu m, the alloy strength can be obviously improved to obtain the double high characteristic on the premise of improving the hardness; compared with common hard alloy with the same components, the superfine grain hard alloy has the hardness increased by more than 2 (HRA) and the bending strength increased by 600-800 MPa. In addition, compared with the common hard alloy, the superfine hard alloy has the characteristics of high heat conductivity, strong corrosion resistance and the like, so that the superfine hard alloy has wide application in the fields of micro drills, metal material cutters, medical instruments, precision molds and the like in the electronic industry, and is deeply focused by the hard alloy industry.
However, the biggest difficulty in producing ultra-fine WC cemented carbide is to suppress the growth of WC grains during sintering. To achieve the purpose of inhibiting the growth of crystal grains, small amounts of VC and Cr are added into the alloy 3 C 2 Isomorphous inhibitors are currently one of the most effective methods. The common grain inhibitor is added during ball milling to control the growth of WC grains. If the addition amount of the crystal grains is small, the crystal grains are difficult to uniformly mix, and the growth of the crystal grains is difficult to inhibit during sintering; if the addition amount of the crystal grains is large, the crystal grain growth inhibitor can obstruct the densification process of alloy sintering, so that the alloy performance is poor.
Disclosure of Invention
The invention is used for solving the technical problem that the existing grain inhibitor is difficult to inhibit the growth of grains.
Based on the technical problems, the invention is realized by the following technical scheme:
in particular, the method comprises the steps of,
the invention provides a preparation process of hard alloy, which comprises the following steps:
the carbon-based carrier formed by loading vanadium and chromium with biochar is mixed with graphene, WC and Co to form a mixed material;
and ball milling, granulating, forming and sintering the mixture material to obtain the hard alloy.
The invention takes the biochar loaded with vanadium and chromium as the carbon-based carrier, and the biochar has the characteristics of controllable shape and easy dispersion, so that the carbon-based carrier is further dispersed in the ball milling process of WC and Co. Meanwhile, the graphene is added, and the characteristics of high hardness and high toughness of the graphene can be utilized by adding the graphene, so that the graphene can be fully exerted; meanwhile, the interface limiting performance of the two-dimensional lamellar in the graphene can be used for controlling the size of the biochar, and the obtained carbon-based carrier is small in size under the synergistic effect; and the carbonization of the carbon-based carrier is realized in the subsequent sintering process, so that the sizes of vanadium carbide and chromium carbide can be reduced, and the characteristics of the obtained vanadium carbide and chromium carbide are further improved by the nano reinforcing effect of the graphene. The obtained grain inhibitors of vanadium carbide and chromium carbide can improve the uniformity of the grain inhibitors in the hard alloy and realize the control of grain growth in the hard alloy.
The technical scheme of the invention has at least the following advantages and beneficial effects:
the hard alloy provided by the invention effectively improves the uniformity of the grain inhibitor in the hard alloy, and also realizes the control of grain growth in the hard alloy. Meanwhile, the process provided by the invention is convenient to operate and easy to realize amplified production.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a hard alloy and a preparation process thereof.
Specifically, the method comprises the following steps:
the method is characterized in that a carbon-based carrier formed by loading vanadium and chromium with biochar is mixed with graphene, WC and Co to form a mixture material;
and ball milling, granulating, forming and sintering the mixture material to obtain the hard alloy.
In the invention, the raw materials of the hard alloy comprise, by weight, 0.5-10% of a carbon-based carrier, 75-90% of WC, 3-15% of Co and 0.5-2% of graphene.
In the invention, the average thickness of the graphene is less than 3nm, and the sheet size is less than 5 mu m.
In the invention, the carbon-based carrier is obtained by loading vanadium and chromium with biochar, filtering and drying. The biochar is obtained by sintering biomass. In particular, the method comprises the steps of,
in the process of obtaining the biochar by sintering the biomass, the biomass needs to be subjected to activation treatment, and the biomass is selected from straw.
The method comprises the specific operation steps of dissolving vanadium salt and chromium salt in water to form a salt solution, simultaneously dispersing biomass in the salt solution through ultrasonic treatment to obtain a treatment solution, carrying out oscillating treatment on the treatment solution for 20-48 h, and then filtering, drying and roasting to obtain the carbon-based carrier.
In the foregoing, the vanadium salt is derived from at least one of vanadium chloride and vanadium nitrate; the chromium salt is derived from at least one of chromium chloride and chromium nitrate. The concentration of vanadium ions in the treatment liquid is 0.5 to 1.5mol/L, preferably 0.8 to 1.2mol/L, and more preferably 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, and 1.2mol/L may be selected independently. The concentration of chromium ions in the treatment solution is 0.5 to 1.5mol/L, preferably 0.8 to 1.2mol/L, and more preferably 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, and 1.2mol/L may be selected independently.
In the foregoing, the drying is performed by using a vacuum drying box.
In the foregoing, the roasting parameters are 150-200 ℃ and the time is 3-6 h.
In the foregoing, the biochar in the treatment fluid is impregnated to exchange balance in the shaking process. The oscillation is a batch oscillator.
In the invention, the ball milling can be performed by vibration ball milling, rolling ball milling and the like. The ball milling process is carried out at a rotating speed of 150-300 r/min for 2-5 h, and the ball milling medium is absolute ethyl alcohol.
In the invention, a forming agent is added in the granulating process, the forming agent is paraffin, and the addition amount of the paraffin accounts for 1-5% of the mass of the mixture.
In the invention, the sintering process parameters are that the sintering temperature is 1300-1550 ℃.
< example >
Example 1
The preparation process of the hard alloy comprises the following steps:
(1) Preparation of carbon-based Carrier
Straw is taken as biomass, and after sulfuric acid activation treatment, the biomass is carbonized through conventional hydrothermal or pyrolysis to obtain biochar;
mixing 0.1mol/L chromium chloride solution and 0.1mol/L vanadium chloride solution according to the volume ratio of 1:1, adding biochar, and performing ultrasonic dispersion to obtain a dispersion liquid; and then the dispersion is carried out for 20 to 48 hours by using an intermittent oscillator, so that the biochar is immersed to exchange balance. After the completion, the carbon-based carrier is obtained through the roasting treatment of filtering and vacuum drying box treatment and roasting at 180 ℃ for 5 hours.
(2) Preparation of cemented carbide
Weighing 8.5% of carbon-based carrier, 85% of WC, 5% of Co and 1.5% of graphene according to weight percentage, premixing, and performing ball milling treatment with absolute ethyl alcohol as a medium at a rotating speed of 200r/min for 3 hours to obtain a mixture material; sieving and drying; then adding 1.5% of paraffin into the mixture, removing paraffin at 400 ℃ after molding treatment, heating to 1400 ℃ for vacuum sintering, wherein the sintering pressure is 4-5 MPa, and the heat preservation time is 1.5h.
The carbide obtained by the process has the advantages of uniform microstructure, no abnormal growth of crystal grains and 3760MPa of flexural strength, and the WC grain size is 0.35 mu m.
Example 2
The preparation process of the hard alloy comprises the following steps:
(1) Preparation of carbon-based Carrier
Straw is taken as biomass, and after sulfuric acid activation treatment, the biomass is carbonized through conventional hydrothermal or pyrolysis to obtain biochar;
mixing 0.1mol/L chromium chloride solution and 0.1mol/L vanadium chloride solution according to the volume ratio of 1:2, adding biochar, and performing ultrasonic dispersion to obtain a dispersion liquid; and then the dispersion is carried out for 20 to 48 hours by using an intermittent oscillator, so that the biochar is immersed to exchange balance. After the completion, the carbon-based carrier is obtained through the roasting treatment of filtering and vacuum drying box treatment and roasting at 180 ℃ for 5 hours.
(2) Preparation of cemented carbide
Weighing 5% of carbon-based carrier, 88% of WC, 5% of Co and 2% of graphene according to weight percentage, premixing, and performing ball milling treatment with absolute ethyl alcohol as a medium at a rotating speed of 200r/min for 3 hours to obtain a mixture material; sieving and drying; then adding 1.5% of paraffin into the mixture, removing paraffin at 400 ℃ after molding treatment, heating to 1400 ℃ for vacuum sintering, wherein the sintering pressure is 4-5 MPa, and the heat preservation time is 1.5h.
The carbide obtained by the process has the advantages of uniform microstructure, no abnormal growth of crystal grains and 3720MPa of flexural strength, and the WC grain size is 0.4 mu m.
Example 3
The preparation process of the hard alloy comprises the following steps:
(1) Preparation of carbon-based Carrier
Straw is taken as biomass, and after sulfuric acid activation treatment, the biomass is carbonized through conventional hydrothermal or pyrolysis to obtain biochar;
mixing 0.1mol/L chromium chloride solution and 0.1mol/L vanadium chloride solution according to the volume ratio of 1:1, adding biochar, and performing ultrasonic dispersion to obtain a dispersion liquid; and then the dispersion is carried out for 20 to 48 hours by using an intermittent oscillator, so that the biochar is immersed to exchange balance. After the completion, the carbon-based carrier is obtained through the roasting treatment of filtering and vacuum drying box treatment and roasting at 180 ℃ for 5 hours.
(2) Preparation of cemented carbide
Weighing 4% of carbon-based carrier, 85% of WC, 9% of Co and 2% of graphene according to weight percentage, premixing, and performing ball milling treatment with absolute ethyl alcohol as a medium at a rotating speed of 200r/min for 3 hours to obtain a mixture material; sieving and drying; then adding 1.5% of paraffin into the mixture, removing paraffin at 400 ℃ after molding treatment, heating to 1350 ℃ after removal, and performing vacuum sintering at a sintering pressure of 4-5 MPa for 1.5h.
The carbide obtained by the process has the advantages of uniform microstructure, no abnormal growth of crystal grains, and flexural strength of 3680MPa, and the WC grain size is 0.5 mu m.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation process of the hard alloy is characterized by comprising the following steps of:
the carbon-based carrier formed by loading vanadium and chromium with biochar is mixed with graphene, WC and Co to form a mixed material;
ball milling, granulating, forming and sintering the mixture material to obtain hard alloy;
the hard alloy comprises, by weight, 0.5-10% of a carbon-based carrier, 75-90% of WC, 3-15% of Co and 0.5-2% of graphene.
2. The process for preparing cemented carbide according to claim 1, wherein the carbon-based carrier is obtained by loading vanadium and chromium with biochar, filtering, and drying.
3. The process for preparing a hard alloy according to claim 2, wherein the vanadium salt and the chromium salt are dissolved in water to form a salt solution, and simultaneously the biomass is dispersed in the salt solution by ultrasonic treatment to obtain a treatment solution, and the treatment solution is subjected to oscillation treatment, filtration, drying and roasting to obtain the carbon-based carrier.
4. A process for preparing a cemented carbide according to claim 3, wherein the vanadium salt is derived from at least one of vanadium chloride and vanadium nitrate; the chromium salt is derived from at least one of chromium chloride and chromium nitrate.
5. The process for preparing cemented carbide according to claim 4, wherein the concentration of vanadium ions is 0.5 to 1.5mol/L; the concentration of chromium ions is 0.5 to 1.5mol/L.
6. The process for preparing cemented carbide according to claim 3, wherein the firing parameters are 150-200 ℃ for 3-6 hours.
7. The process for preparing cemented carbide according to any one of claims 3 to 6, wherein the firing parameters are 150 to 200 ℃ for 3 to 6 hours.
8. Cemented carbide obtainable by the process according to any one of claims 1 to 6.
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