CN110607473A - Transition metal carbonitride-based high-entropy metal ceramic and preparation method and application thereof - Google Patents
Transition metal carbonitride-based high-entropy metal ceramic and preparation method and application thereof Download PDFInfo
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- CN110607473A CN110607473A CN201910973986.3A CN201910973986A CN110607473A CN 110607473 A CN110607473 A CN 110607473A CN 201910973986 A CN201910973986 A CN 201910973986A CN 110607473 A CN110607473 A CN 110607473A
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- 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
- C22C29/04—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 carbonitrides
Abstract
The invention provides a transition metal carbonitride based high-entropy metal ceramic and a preparation method and application thereof, belonging to the field of high-entropy metal ceramic. The transition metal carbonitride-based high-entropy metal ceramic provided by the invention is obtained by sintering a mixture of a hard phase and a high-entropy alloy binding phase, wherein the hard phase is transition metal carbonitride-based high-entropy ceramic powder, and the binding phase is high-entropy alloy powder. The transition metal carbonitride-based high-entropy metal ceramic provided by the invention has the performances of high toughness, high hardness, high strength and the like, and the example results show that the fracture toughness of the transition metal carbonitride-based high-entropy metal ceramic prepared by the invention is 10.2-19.8 MPa-m1/2The high-temperature hardness is 22.0 to 29.9GPa, and the strength is 2100 to 3450 MPa. The invention provides a transition metal carbonitride baseThe preparation method of the high-entropy metal ceramic has the advantages of simple operation, easy popularization and the like.
Description
Technical Field
The invention relates to the field of high-entropy metal ceramics, in particular to transition metal carbonitride-based high-entropy metal ceramics and a preparation method and application thereof.
Background
Cermet is a composite material, is prepared by sintering metal and ceramic powder, has certain advantages of metal and ceramic, and is widely applied to the fields of mechanical manufacture, high-end cutters, wear resistance, corrosion resistance, high-temperature coatings, national defense equipment and the like.
Cermets can be classified into oxide-based cermets, carbide-based cermets, nitride-based cermets, boride-based cermets, silicide-based cermets, and the like, depending on the composition. In the common metal ceramic materials in the prior art, the ceramic material (namely hard phase) is TiC and/or WC, the metal (namely bonding phase) is Co and/or Ni, and the common metal ceramic materials have low mechanical properties, so that the wide application of the metal ceramic is limited.
Disclosure of Invention
In view of the above, the invention provides a transition metal carbonitride-based high-entropy metal ceramic and a preparation method and application thereof, and the transition metal carbonitride-based high-entropy metal ceramic provided by the invention has good mechanical properties and fracture toughness of 10.2-19.8 MPa-m1/2The high-temperature hardness is 22.0 to 29.9GPa, and the strength is 2100 to 3450 MPa.
The invention provides a transition metal carbonitride-based high-entropy metal ceramic, which is obtained by sintering a mixture of a hard phase and a binding phase, wherein the hard phase is transition metal carbonitride-based high-entropy ceramic powder, and the binding phase is high-entropy alloy powder;
the hard phase comprises a metal principal element and a non-metal principal element, wherein the metal principal element consists of five or more elements of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W; the nonmetal principal elements consist of C and N;
the binding phase is composed of five or more elements of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sc, Y, La, Ce, Pr, Er and Sm.
Preferably, the mass fraction of the binder phase in the mixture of the hard phase and the binder phase is 5-35%.
Preferably, the preparation method of the hard phase comprises the following three parallel methods:
(i) mixing an oxide corresponding to a metal principal element and a carbon source, and then sequentially carrying out high-energy ball milling and heat treatment, wherein the heat treatment is carried out in a nitrogen atmosphere to obtain transition metal carbonitride high-entropy ceramic powder;
or, (ii) mixing the salt corresponding to the metal principal component, the carbon source and water, and then sequentially concentrating and drying to obtain precursor powder; then carrying out heat treatment on the precursor powder, wherein the heat treatment is carried out in a nitrogen atmosphere to obtain transition metal carbonitride high-entropy ceramic powder;
or (iii) mixing the salt corresponding to the metal principal element, a carbon source and water, carrying out hydrothermal reaction, and then carrying out heat treatment on the hydrothermal reaction product, wherein the heat treatment is carried out in a nitrogen atmosphere, so as to obtain the transition metal carbonitride high-entropy ceramic powder.
Preferably, the heat treatment temperature in the (i), (ii) and (iii) is 1400-1800 ℃ independently, and the heat treatment time is 0.5-4 h independently.
Preferably, the temperature of the hydrothermal reaction in the step (iii) is 160-240 ℃ and the time is 4-16 h.
The invention also provides a preparation method of the transition metal carbonitride-based high-entropy cermet in the technical scheme, which comprises the following steps:
and sequentially carrying out ball-milling mixing, granulating, pressing, sintering and cooling treatment on the hard phase and the binding phase to obtain the transition metal carbonitride-based high-entropy metal ceramic.
Preferably, the ball-milling mixing ball-material ratio is 4-12: 1, the ball-milling medium is absolute ethyl alcohol and/or acetone, and the ball-milling mixing time is 24-72 hours.
Preferably, the sintering temperature is 1350-1500 ℃, and the sintering time is 0.5-4 h.
Preferably, the pressing pressure is 150-250 MPa, and the pressing time is 10-30 s.
The invention also provides application of the transition metal carbonitride-based high-entropy metal ceramic in the technical scheme or the transition metal carbonitride-based high-entropy metal ceramic prepared by the method in the technical scheme in a ceramic cutter.
The invention provides a transition metal carbonitride-based high-entropy metal ceramic, which is obtained by sintering a mixture of a hard phase and a binding phase, wherein the hard phase is transition metal carbonitride-based high-entropy ceramic powder, and the binding phase is high-entropy alloy powder; the hard phase comprises a metal principal element and a non-metal principal element, wherein the metal principal element consists of five or more elements of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W; the nonmetal principal elements consist of C and N; the binding phase is composed of five or more elements of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sc, Y, La, Ce, Pr, Er and Sm. In the invention, the hard phase and the bonding phase both have a plurality of metal element main elements (the number of the main elements is more than or equal to 5) and the atomic ratios of the main elements are similar, so that the hard phase and the bonding phase both have extremely high chemical disorder degree (namely extremely high configuration entropy), thereby having excellent mechanical properties; in addition, each main element often carries respective special properties, such as Hf, Ta and the like which can improve red hardness, Cr which can improve corrosion resistance, V and Cu which can improve toughness, W which can obviously improve interface wettability, rare earth elements which can purify and strengthen an interface and the like. The example results show that the fracture toughness of the transition metal carbonitride-based high-entropy metal ceramic provided by the invention is 10.2-19.8 MPa-m1/2The high-temperature hardness is 22.0 to 29.9GPa, and the strength is 2100 to 3450 MPa.
The invention also provides a preparation method of the transition metal carbonitride-based high-entropy metal ceramic, which is simple to operate and easy to popularize.
Detailed Description
The invention provides a transition metal carbonitride-based high-entropy metal ceramic, which is obtained by sintering a mixture of a hard phase and a binding phase, wherein the hard phase is transition metal carbonitride-based high-entropy ceramic powder, and the binding phase is high-entropy alloy powder.
In the present invention, the hard phase includes a metal principal element and a non-metal principal element, the metal principal element being composed of five or more elements of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, and W; the non-metal main element consists of C and N.
In the present invention, the binder phase is composed of five or more elements of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sc, Y, La, Ce, Pr, Er, and Sm.
In the present invention, the crystal structure of the hard phase is preferably a face-centered cubic structure or/and a body-centered cubic structure formed by nesting metallic elements and non-metallic elements.
In the present invention, the amounts of the species of different metals in the metal main elements of the hard phase are preferably the same or similar; the chemical formula of the hard phase is preferably: (Ti)aVbCrcZrdNbeMofHfgTahWi)(CxNy) Wherein a + b + c + d + e + f + g + h + i is 1, and at least 5 values of a to i are more than 0; x + y is 1, and x and y are both greater than 0; further preferred is any one of the following chemical formulae:
(Ti0.2V0.2Zr0.2Nb0.2Ta0.2)(C0.5N0.5)；
(Ti1/9V1/9Cr1/9Zr1/9Nb1/9Mo1/9Hf1/9Ta1/9W1/9)(C0.3N0.7)；
(Ti0.2V0.2Cr0.2Mo0.2W0.2)(C0.6N0.4)；
(Zr0.2Nb0.2Mo0.2Ta0.2W0.2)(C0.1N0.9)；
(Ti0.2V0.2Zr0.2Nb0.2Mo0.2)(C0.9N0.1)；
(Ti0.2V0.2Zr0.2Nb0.2Mo0.2)(C0.1N0.9)；
(Ti1/8V1/8Cr1/8Zr1/8Nb1/8Mo1/8Hf1/8Ta1/8)(C0.3N0.7)；
(V1/7Cr1/7Zr1/7Nb1/7Mo1/7Hf1/7Ta1/7)(C0.5N0.5)；
(Ti1/6Cr1/6Zr1/6Mo1/6Ta1/6W1/6)(C0.8N0.2)。
in the invention, after the hard phase and the binder phase are sintered, the hard phase (the transition metal carbonitride high-entropy ceramic) forms solid solution with certain concentration in the binder phase due to the 'dissolution-precipitation' phenomenon of the hard phase, so that the binder phase of the transition metal carbonitride-based high-entropy ceramic also comprises certain hard phase ceramic components besides metal components. In the invention, after the bonding phase is subjected to sintering treatment, the crystal structure of the bonding phase is a face-centered cubic structure or/and a body-centered cubic structure with highly disordered solid solution among main elements. In the present invention, the amounts of the species of different metals in the metal main elements of the binder phase are preferably the same or similar.
In the present invention, the preparation method of the hard phase comprises the following three parallel methods:
(i) mixing an oxide corresponding to a metal principal element and a carbon source, and then sequentially carrying out high-energy ball milling and heat treatment, wherein the heat treatment is carried out in a nitrogen atmosphere to obtain transition metal carbonitride high-entropy ceramic powder;
or, (ii) mixing the salt corresponding to the metal principal component, the carbon source and water, and then sequentially concentrating and drying to obtain precursor powder; then carrying out heat treatment on the precursor powder, wherein the heat treatment is carried out in a nitrogen atmosphere to obtain transition metal carbonitride high-entropy ceramic powder;
or (iii) mixing the salt corresponding to the metal principal element, a carbon source and water, carrying out hydrothermal reaction, and then carrying out heat treatment on the hydrothermal reaction product, wherein the heat treatment is carried out in a nitrogen atmosphere, so as to obtain the transition metal carbonitride high-entropy ceramic powder.
In the invention, when the hard phase is prepared by the method (i), the oxide corresponding to the metal principal component and the carbon source are mixed, and then high-energy ball milling and heat treatment are sequentially carried out to obtain the transition metal carbonitride high-entropy ceramic powder.
In the invention, the oxide corresponding to the metal principal element preferably comprises one or more of titanium dioxide, vanadium pentoxide, vanadium trioxide, chromium trioxide, zirconium dioxide, niobium pentoxide, molybdenum trioxide, molybdenum dioxide, hafnium dioxide, tantalum pentoxide and tungsten trioxide; the carbon source preferably comprises one or more of carbon powder, graphite and carbon black; the rotation speed of the high-energy ball mill is preferably 200-1200 rpm, more preferably 400-1000 rpm, and even more preferably 600-800 rpm; the high-energy ball milling time is preferably 1-20 h, more preferably 2-18 h, and even more preferably 5-15 h; the ball-to-material ratio of the high-energy ball milling is preferably 5-10: 1, and more preferably 6-8: 1. In the high-energy ball milling treatment process, the materials are violently collided, so that certain energy is stored in the crystal lattices of the raw materials, the raw materials are activated and are more easily reduced and nitrided by subsequent carbothermic, and the subsequent thermal reaction temperature is favorably reduced.
After the high-energy ball milling is finished, the high-energy ball milling method carries out heat treatment on the material obtained by the high-energy ball milling to obtain the transition metal carbonitride high-entropy ceramic powder. In the invention, the heat treatment is preferably carried out under flowing nitrogen, the flow rate of the nitrogen is preferably 0.2-2L/min, and the temperature of the heat treatment is preferably 1400-1800 ℃, and more preferably 1500-1700 ℃; the time of the heat treatment is preferably 0.5 to 4 hours, more preferably 1 to 3 hours, and even more preferably 1.5 to 2.5 hours. In the heat treatment process, the raw materials are subjected to carbothermic reduction nitridation reaction to generate the transition metal carbonitride high-entropy ceramic powder. After the heat treatment is finished, the invention preferably carries out cooling, crushing and sieving treatment in sequence; the temperature after cooling is preferably room temperature, the aperture or mesh number of the screen for sieving treatment is preferably 100 to 300 meshes, more preferably 200 meshes, and the undersize is collected. The invention preferably carries out crushing and sieving treatment, which is beneficial to the uniform grain size of the ceramic powder.
In the invention, when the transition metal carbonitride high-entropy ceramic powder is prepared by the method (ii), the salt corresponding to the metal main element, the carbon source and water are mixed, and then concentration and drying treatment are sequentially carried out to obtain precursor powder; and then carrying out heat treatment on the precursor powder to obtain the transition metal carbonitride high-entropy ceramic powder.
In the present invention, the salt corresponding to the metal main element preferably comprises one or more of ammonium metavanadate, metatitanic acid, ammonium chromate, zirconium oxychloride, ammonium niobium oxalate, ammonium molybdate, tantalic acid, hafnium hydroxide and ammonium metatungstate; the carbon source preferably comprises one or more of starch, glucose, carbon powder, graphite and carbon black; the invention has no special requirement on the dosage of water, and can fully dissolve and disperse the salt and the carbon source corresponding to the metal principal element.
And after mixing, sequentially concentrating and drying the mixed material liquid obtained by mixing to obtain precursor powder. In the invention, the concentration temperature is preferably 120-180 ℃, the concentration time is preferably 20-60 min, and the invention preferably performs stirring treatment simultaneously in the concentration process, so that the uniformity of materials is ensured, and the concentration evaporation speed is accelerated; the drying is preferably spray drying, and the nozzle temperature of the spray drying is preferably 150-200 ℃. In the drying treatment process, besides moisture removal, the method also promotes the mixed material liquid to gradually form microcrystals, provides crystal nuclei for the subsequent carbothermic reduction nitridation reaction, and is favorable for reducing the reaction temperature.
After precursor powder is obtained, the invention carries out heat treatment on the precursor powder to obtain the transition metal carbonitride high-entropy ceramic powder. In the invention, the heat treatment is preferably carried out under flowing nitrogen, the flow rate of the nitrogen is preferably 0.2-2L/min, and the temperature of the heat treatment is preferably 1400-1800 ℃, and more preferably 1500-1700 ℃; the time of the heat treatment is preferably 0.5 to 4 hours, more preferably 1 to 3 hours, and even more preferably 1.5 to 2.5 hours. In the heat treatment process, the raw materials are subjected to carbothermic reduction nitridation reaction to generate the transition metal carbonitride high-entropy ceramic powder.
After the heat treatment is finished, the invention preferably carries out cooling, crushing and sieving treatment in sequence; the temperature after cooling is preferably room temperature, the aperture or mesh number of the screen for sieving treatment is preferably 100 to 300 meshes, more preferably 200 meshes, and the undersize is collected. The invention preferably carries out crushing and sieving treatment, which is beneficial to the uniform grain size of the ceramic powder.
In the invention, when the transition metal carbonitride high-entropy ceramic powder is prepared by the method (iii), the salt corresponding to the metal principal element, the carbon source and water are mixed and then subjected to hydrothermal reaction, and then the hydrothermal reaction product is subjected to heat treatment to obtain the transition metal carbonitride high-entropy ceramic powder.
In the present invention, the salt corresponding to the metal main element preferably comprises one or more of ammonium metavanadate, metatitanic acid, ammonium chromate, zirconium oxychloride, ammonium niobium oxalate, ammonium molybdate, tantalic acid, hafnium hydroxide and ammonium metatungstate; the carbon source preferably comprises one or more of starch, glucose, carbon powder, graphite and carbon black; the invention has no special requirement on the dosage of water, and can fully dissolve and disperse the salt and the carbon source corresponding to the metal principal element.
After the mixing is finished, the invention carries out hydrothermal reaction on the mixed material liquid obtained by mixing. In the invention, the temperature of the hydrothermal reaction is preferably 160-240 ℃, more preferably 180-220 ℃, and more preferably 200-220 ℃; the time of the hydrothermal reaction is preferably 4-16 h, more preferably 5-15 h, and even more preferably 8-13 h. In the hydrothermal reaction process, the components can be uniformly mixed at an atomic level, and then are gradually decomposed and crystallized to form uniformly mixed fine precipitates.
After the hydrothermal reaction is finished, the hydrothermal reaction system is preferably filtered, solids are collected, and then the solids are sequentially washed and dried to obtain a hydrothermal reaction product. In the invention, the washing solvent is preferably water, the drying temperature is preferably 60-80 ℃, and the drying time is preferably 4-8 h.
After the hydrothermal reaction product is obtained, the invention carries out heat treatment on the hydrothermal reaction product to obtain the transition metal carbonitride high-entropy ceramic powder. In the invention, the heat treatment is preferably carried out under flowing nitrogen, the flow rate of the nitrogen is preferably 0.2-2L/min, and the temperature of the heat treatment is preferably 1400-1800 ℃, and more preferably 1500-1700 ℃; the time of the heat treatment is preferably 0.5 to 4 hours, more preferably 1 to 3 hours, and even more preferably 1.5 to 2.5 hours. In the heat treatment process, the raw materials are subjected to carbothermic reduction nitridation reaction to generate the transition metal carbonitride high-entropy ceramic powder.
After the heat treatment is finished, the invention preferably carries out cooling, crushing and sieving treatment in sequence; the temperature after cooling is preferably room temperature, the aperture or mesh number of the screen for sieving treatment is preferably 100 to 300 meshes, more preferably 200 meshes, and the undersize is collected. The invention preferably carries out crushing and sieving treatment, which is beneficial to the uniform grain size of the ceramic powder.
In the mixture of the hard phase and the binder phase of the present invention, the mass fraction of the binder phase is preferably 5% to 35%, more preferably 10% to 30%, and still more preferably 15% to 25%.
The invention also provides a preparation method of the transition metal carbonitride-based high-entropy cermet in the technical scheme, which comprises the following steps:
and sequentially carrying out ball-milling mixing, granulating, pressing, sintering and cooling treatment on the hard phase and the binding phase to obtain the transition metal carbonitride-based high-entropy metal ceramic.
According to the invention, the hard phase and the binding phase are mixed by ball milling to obtain a mixture. In the invention, the ball-to-material ratio of the ball milling is preferably 4-12: 1, more preferably 5-10: 1, and more preferably 6-8: 1; the ball milling medium is preferably absolute ethyl alcohol and/or acetone, and the ball milling time is preferably 24-72 hours, more preferably 25-70 hours, and even more preferably 30-60 hours. The invention makes the hard phase and the binding phase fully and uniformly mixed by ball milling.
After the ball milling is finished, the ball milling mixture is sequentially granulated and pressed to obtain a pressed compact. In the invention, the particle size of the granules obtained by granulating is preferably 0.5-2 mm, and more preferably 1-1.5 mm; the pressing pressure is preferably 150-250 MPa; the pressing time is preferably 10s to 30 s. In the present invention, the compacting serves to preform the powder material.
And after the pressing is finished, sintering and cooling the pressed compact in sequence to obtain the transition metal carbonitride-based high-entropy metal ceramic. In the invention, the sintering temperature is preferably 1350-1500 ℃, more preferably 1400-1450 ℃, and the sintering time is preferably 0.5-4 h, more preferably 1-3 h. In the sintering treatment process, liquid phase sintering is generated between the hard phase powder and the bonding phase powder, atoms are continuously migrated, diffused, dissolved and separated out, and uniform arrangement and densification of the powder are realized. In the present invention, the cooling is preferably natural cooling, and the temperature after the cooling is preferably room temperature.
The invention also provides application of the transition metal carbonitride-based high-entropy metal ceramic in the technical scheme or the transition metal carbonitride-based high-entropy metal ceramic prepared by the method in the technical scheme in a ceramic cutter. In the invention, the ceramic cutter preferably comprises a cutter head for preparing a precision machining turning tool, a milling cutter, a PCB micro drill and a tunnel boring machine cutter head, a high-speed rail milling cutter, a wear-resistant roller and the like.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
(1) Preparation of hard phases
9.6g of titanium dioxide, 11g of vanadium pentoxide, 15g of zirconium dioxide, 16.3g of niobium pentoxide, 27.1g of tantalum pentoxide and 21g of carbon black are weighed and put into a ball milling tank, and high-energy ball milling is carried out for 10 hours under the conditions that the rotating speed is 500rpm and the ball-to-material ratio is 10: 1. Drying the ball-milled material in an oven at 75 deg.C for 4h, placing in a heat treatment furnace, heating to 1500 deg.C under flowing nitrogen (nitrogen flow: 1L/min), heat treating for 3h, cooling with the furnace, taking out, crushing, and sieving to obtain component (Ti)0.2V0.2Zr0.2Nb0.2Ta0.2)(C0.5N0.5) The transition metal carbonitride high entropy ceramic powder of (1) as a hard phase.
(2) Mixing and forming
Weighing 95g of the transition metal carbonitride high-entropy ceramic powder prepared in the step (1), 0.93g of Cr powder, 0.98g of Mn powder, 1.00g of Fe powder, 1.05g of Co powder and 1.05g of Ni powder, putting into a ball milling tank, wherein the ball-material ratio is 4:1, the ball milling medium is absolute ethyl alcohol, ball milling and mixing for 72h, taking out the mixture, putting into an oven, further drying for 8h at 60 ℃, then uniformly doping paraffin with the weight fraction of 1%, sieving and granulating, putting into a mold, and pressing into a preset shape by a press.
(3) Sintering
And (3) transferring the pressed compact prepared in the step (2) into a low-pressure sintering furnace, degumming and sintering, wherein the sintering temperature is 1350 ℃, and cooling along with the furnace after sintering and heat preservation for 4h to prepare the (Ti, V, Zr, Nb, Ta) (C, N) -CrMnFeCoNi transition metal carbonitride based high-entropy metal ceramic material.
Example 2
(1) Preparation of hard phases
Weighing 5.8g of titanium dioxide, 6.6g of vanadium pentoxide, 4.6g of chromium trioxide, 7.5g of zirconium dioxide, 8.1g of niobium pentoxide, 8.8g of molybdenum trioxide, 12.9g of hafnium dioxide, 13.5g of tantalum pentoxide, 14.2g of tungsten trioxide and 18g of carbon powder, and putting the materials into a ball-milling tank for high-energy ball milling for 1 hour under the conditions that the rotating speed is 1200rpm and the ball-to-material ratio is 5: 1. Putting the ball-milled materials into an oven for drying for 4 hours at the temperature of 80 ℃, and then putting the materials into a heat treatmentHeating to 1800 deg.C under flowing nitrogen (nitrogen flow: 2L/min) in furnace, heat treating for 0.5 hr, cooling with furnace, taking out, crushing, and sieving to obtain component (Ti)1/9V1/9Cr1/9Zr1/9Nb1/9Mo1/9Hf1/9Ta1/9W1/9)(C0.3N0.7) The transition metal carbonitride high entropy ceramic powder of (1) as a hard phase.
(2) Mixing and forming
Weighing 85g of the transition metal carbonitride high-entropy ceramic powder prepared in the step (1), 2.46g of Ti powder, 2.62g of V powder, 3.03g of Co powder, 2.31g of Sc powder and 4.57g of Y powder, putting into a ball milling tank, wherein the ball milling ratio is 12:1, the ball milling medium is acetone, ball milling and mixing for 24h, taking out the mixture, putting into an oven, further drying for 4h at 80 ℃, then uniformly doping paraffin with the weight fraction of 3%, sieving and granulating, putting into a mold, and pressing into a preset shape by a press.
(3) Sintering
And (3) transferring the pressed compact prepared in the step (2) into a hot-pressing sintering furnace, degumming and sintering, wherein the sintering temperature is 1500 ℃, and the sintered compact is cooled along with the furnace after being sintered and insulated for 2h to prepare the (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W) (C, N) -TiVCoScY transition metal carbonitride-based high-entropy metal ceramic material.
Example 3
(1) Preparation of hard phases
Weighing 10g of titanium dioxide, 11.3g of vanadium pentoxide, 9.5g of chromium trioxide, 17.9g of molybdenum trioxide, 28.9g of tungsten trioxide and 22.4g of carbon black, putting into a ball milling tank, and performing high-energy ball milling for 8 hours under the conditions that the rotating speed is 500rpm and the ball-to-material ratio is 8: 1. Drying the ball-milled material in an oven at 70 deg.C for 6h, placing in a heat treatment furnace, heating to 1600 deg.C under flowing nitrogen (nitrogen flow: 500mL/min), heat treating for 2h, cooling with the furnace, taking out, crushing, and sieving to obtain component (Ti)0.2V0.2Cr0.2Mo0.2W0.2)(C0.6N0.4) The transition metal carbonitride high entropy ceramic powder of (1) as a hard phase.
(2) Mixing and forming
Weighing 65g of the transition metal carbonitride high-entropy ceramic powder prepared in the step (1), 3.92g of Co powder, 3.90g of Ni powder, 4.22g of Cu powder, 4.35g of Zn powder, 6.06g of Zr powder, 6.17g of Nb powder and 6.38g of Mo powder, putting into a ball-milling tank, wherein the ball-milling ratio is 8:1, the ball-milling medium is absolute ethyl alcohol, carrying out ball-milling mixing for 48h, taking out the mixture, putting into an oven, further drying for 6h at 65 ℃, then uniformly doping polyethylene glycol with the weight fraction of 1%, sieving, granulating, putting into a die, and pressing into a preset shape by using a press.
(3) Sintering
And (3) transferring the pressed compact prepared in the step (2) into a low-pressure sintering furnace, degumming and sintering at the sintering temperature of 1450 ℃, and cooling along with the furnace after sintering and heat preservation for 2.5h to prepare the (Ti, V, Cr, Mo, W) (C, N) -CoNiCuZnZrNbMo transition metal carbonitride-based high-entropy metal ceramic material.
Example 4
(1) Preparation of hard phases
Weighing 12.1g of zirconium dioxide, 13.1g of niobium pentoxide, 14.2g of molybdenum trioxide, 21.8g of tantalum pentoxide, 22.8g of tungsten trioxide and 16g of graphite, putting into a ball milling tank, and carrying out high-energy ball milling for 12h under the conditions that the rotating speed is 800rpm and the ball-to-material ratio is 6: 1. Drying the ball-milled material in an oven at 65 deg.C for 5h, placing in a heat treatment furnace, heating to 1650 deg.C under flowing nitrogen (nitrogen flow: 1.5mL/min), heat treating for 2h, cooling, taking out, crushing, and sieving to obtain (Zr) component0.2Nb0.2Mo0.2Ta0.2W0.2)(C0.1N0.9) The transition metal carbonitride high entropy ceramic powder of (1) as a hard phase.
(2) Mixing and forming
Weighing 80g of the transition metal carbonitride high-entropy ceramic powder prepared in the step (1), 1.85g of Co powder, 1.84g of Ni powder, 3.17g of Ru powder, 4.35g of La powder, 4.39g of Ce powder and 4.41g of Pr powder, putting the mixture into a ball milling tank, wherein the ball milling ratio is 8:1, the ball milling medium is absolute ethyl alcohol, mixing the mixture by ball milling for 48 hours, taking out the mixture, putting the mixture into an oven, further drying the mixture for 6 hours at 65 ℃, uniformly doping polyethylene glycol with the weight fraction of 1%, sieving, granulating, putting the mixture into a die, and pressing the mixture into a preset shape by a press.
(3) Sintering
And (3) transferring the pressed compact prepared in the step (2) into a low-pressure sintering furnace, degumming and sintering at 1450 ℃, and cooling along with the furnace after sintering and heat preservation for 2 hours to prepare the (Zr, Nb, Mo, Ta, W) (C, N) -CoNiRuCePr transition metal carbonitride-based high-entropy metal ceramic material.
Example 5
(1) Preparation of hard phases
Weighing 7.2g of metatitanic acid, 8.5g of ammonium metavanadate, 23.6g of zirconium oxychloride, 27.4g of ammonium niobium oxalate, 12.9g of ammonium molybdate and 20.4g of carbon black, dissolving in deionized water, stirring until the mixture is uniformly mixed, concentrating and drying to obtain mixed precursor powder. Placing the mixed precursor powder into an oven for further drying at 60 deg.C for 8h, placing into a heat treatment furnace, heating to 1500 deg.C under flowing nitrogen (nitrogen flow: 500mL/min), heat treating for 4h, cooling with the furnace, taking out, crushing, and sieving to obtain component (Ti)0.2V0.2Zr0.2Nb0.2Mo0.2)(C0.9N0.1) The transition metal carbonitride high entropy ceramic powder of (1) as a hard phase.
(2) Mixing and forming
Weighing 85g of the transition metal carbonitride high-entropy ceramic powder prepared in the step (1), 2.08g of Cr powder, 2.23g of Fe powder, 2.35g of Co powder, 2.34g of Ni powder and 6g of Sm powder, putting into a ball milling tank, wherein the ball-material ratio is 8:1, the ball milling medium is absolute ethyl alcohol, ball milling and mixing for 72h, taking out the mixture, putting into an oven, further drying for 6h at 65 ℃, then uniformly doping polyethylene glycol with the weight fraction of 3%, sieving and granulating, putting into a mold, and pressing into a preset shape by a press.
(3) Sintering
And (3) transferring the pressed compact prepared in the step (2) into a low-pressure sintering furnace, degumming and sintering at the sintering temperature of 1400 ℃, and cooling along with the furnace after sintering and heat preservation for 3h to prepare the (Ti, V, Zr, Nb, Mo) (C, N) -CrFeCoNiSm transition metal carbonitride-based high-entropy metal ceramic material.
Example 6
(1) Preparation of hard phases
Weighing 6.4g of metatitanic acid, 7.6g of ammonium metavanadate, 21.2g of zirconium oxychloride, 24.6g of ammonium niobium oxalate, 11.6g of ammonium molybdate and 28.6g of glucose, dissolving in deionized water, stirring until the mixture is uniformly mixed, transferring the mixture to a reaction kettleHeating the reaction kettle to 40 deg.C, keeping the temperature for 10h, repeatedly filtering, washing for more than 3 times, placing the mixed precursor powder into an oven at 80 deg.C, further drying for 6h, then placing into a heat treatment furnace, heating to 1450 deg.C under flowing nitrogen (nitrogen flow: 1L/min), heat treating for 4h, cooling with the furnace, taking out, crushing, and sieving to obtain the component (Ti)0.2V0.2Zr0.2Nb0.2Mo0.2)(C0.1N0.9) The transition metal carbonitride high-entropy ceramic powder can obtain a hard phase.
(2) Mixing and forming
Weighing 90g of the transition metal carbonitride high-entropy ceramic powder prepared in the step (1), 2.33g of Ni powder, 2.07g of Zr powder, 2.11g of Nb powder, 2.18g of Mo powder and 1.3g of Ru powder, putting the mixture into a ball milling tank, wherein the ball-material ratio is 8:1, the ball milling medium is absolute ethyl alcohol, ball milling and mixing for 72h, taking out the mixture, putting the mixture into an oven, further drying for 4h at 65 ℃, then uniformly doping paraffin with the weight fraction of 1%, sieving and granulating, putting the granules into a mold, and pressing the granules into a preset shape by a press.
(3) Sintering
And (3) transferring the pressed compact prepared in the step (2) into a low-pressure sintering furnace, degumming and sintering at the sintering temperature of 1400 ℃, and cooling along with the furnace after sintering and heat preservation for 4 hours to prepare the (Ti, V, Zr, Nb, Mo) (C, N) -NiZrNbMoRu transition metal carbonitride-based high-entropy metal ceramic material.
The mechanical properties of the transition metal carbonitride-based high-entropy cermet prepared in examples 1 to 6 were tested, and the results are shown in table 1:
TABLE 1 mechanical properties of transition metal carbonitride based high entropy cermets of examples 1-6
| Fracture toughness/MPa·m1/2 | High temperature hardness/GPa | strength/MPa | |
| Test standard | ISO 28079:2009 | GB/T 7997-2014 | GB 3851-83 |
| Example 1 | 10.2 | 29.9 | 2100 |
| Example 2 | 15.3 | 25.1 | 2630 |
| Example 3 | 19.8 | 22.0 | 3450 |
| Example 4 | 13.7 | 28.3 | 2390 |
| Example 5 | 12.9 | 27.6 | 3050 |
| Example 6 | 16.8 | 22.5 | 2700 |
The "high temperature hardness" in Table 1 was measured as the hardness at 500 ℃. As shown in Table 1, the transition metal carbonitride-based high-entropy metal ceramic provided by the invention has good mechanical properties and fracture toughness of 10.2-19.8 MPa-m1/2The high-temperature hardness is 22.0-29.9 GPa, and the strength is 2100-3450 MPa, which shows that the transition metal carbonitride-based high-entropy metal ceramic provided by the invention effectively improves the strength performance of the transition metal carbonitride-based high-entropy metal ceramic by combining a hard phase and bonding and controlling the components of the hard phase and the bonding phase.
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 transition metal carbonitride-based high-entropy cermet is characterized in that the transition metal carbonitride-based high-entropy cermet is obtained by sintering a mixture of a hard phase and a binder phase, wherein the hard phase is transition metal carbonitride-based high-entropy ceramic powder, and the binder phase is high-entropy alloy powder;
the hard phase comprises a metal principal element and a non-metal principal element, wherein the metal principal element consists of five or more elements of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta and W; the nonmetal principal elements consist of C and N;
the binding phase is composed of five or more elements of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Sc, Y, La, Ce, Pr, Er and Sm.
2. The transition metal carbonitride-based high entropy cermet according to claim 1, characterized in that the mass fraction of the binder phase in the mixture of the carbonitride phase and the binder phase is 5 to 35%.
3. The transition metal carbonitride-based high entropy cermet according to claim 1 or 2, characterized in that the preparation method of the hard phase includes the following three side-by-side methods:
(i) mixing an oxide corresponding to a metal principal element and a carbon source, and then sequentially carrying out high-energy ball milling and heat treatment, wherein the heat treatment is carried out in a nitrogen atmosphere to obtain transition metal carbonitride high-entropy ceramic powder;
or, (ii) mixing the salt corresponding to the metal principal component, the carbon source and water, and then sequentially concentrating and drying to obtain precursor powder; then carrying out heat treatment on the precursor powder, wherein the heat treatment is carried out in a nitrogen atmosphere to obtain transition metal carbonitride high-entropy ceramic powder;
or (iii) mixing the salt corresponding to the metal principal element, a carbon source and water, carrying out hydrothermal reaction, and then carrying out heat treatment on the hydrothermal reaction product, wherein the heat treatment is carried out in a nitrogen atmosphere, so as to obtain the transition metal carbonitride high-entropy ceramic powder.
4. The transition metal carbonitride based high entropy cermet according to claim 3, characterized in that the heat treatment temperature in the (i), (ii) and (iii) ranges independently from 1400 ℃ to 1800 ℃ and the heat treatment time ranges independently from 0.5 to 4 hours.
5. A transition metal carbonitride based high entropy cermet according to claim 3, characterized in that the hydrothermal reaction in (iii) is carried out at a temperature of 160 to 240 ℃ for 4 to 16 hours.
6. A method for producing a transition metal carbonitride based high entropy cermet according to any one of claims 1 to 5, comprising the steps of:
and sequentially carrying out ball-milling mixing, granulating, pressing, sintering and cooling treatment on the hard phase and the binding phase to obtain the transition metal carbonitride-based high-entropy metal ceramic.
7. The preparation method of claim 6, wherein the ball-milling mixing ball-material ratio is 4-12: 1, the ball-milling medium is absolute ethanol and/or acetone, and the ball-milling mixing time is 24-72 hours.
8. The preparation method according to claim 6, wherein the sintering temperature is 1350-1500 ℃ and the sintering time is 0.5-4 h.
9. The preparation method according to claim 6, wherein the pressing pressure is 150 to 250MPa, and the pressing time is 10 to 30 s.
10. Use of the transition metal carbonitride based high entropy cermet according to any one of claims 1 to 5 or the transition metal carbonitride based high entropy cermet prepared by the method according to any one of claims 6 to 9 in ceramic cutting tools.
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