CN115340387A - Boron nitride superhard material containing high-entropy ceramic phase and preparation method and application thereof - Google Patents
Boron nitride superhard material containing high-entropy ceramic phase and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of superhard composite materials, and particularly relates to a boron nitride superhard material containing a high-entropy ceramic phase, and a preparation method and application thereof. The boron nitride superhard material containing the high-entropy ceramic phase provided by the invention has high hardness, high strength and high toughness. According to the invention, a small amount of high-entropy ceramic phase powder is introduced into the boron nitride superhard material, and the wettability between the binding phase and the boron nitride can be effectively improved by utilizing the multi-principal-element high-entropy effect of the high-entropy ceramic phase, and the dissolution and precipitation process is adjusted, so that the microstructure of the boron nitride superhard material is optimized, and the strength, hardness and toughness of the boron nitride superhard material are improved at the same time. According to the invention, only 1-10 wt% of high-entropy ceramic phase powder is added, so that the comprehensive mechanical property of the boron nitride superhard material containing the high-entropy ceramic phase can be obviously improved, the production cost is reduced, and the service life of the boron nitride superhard material containing the high-entropy ceramic phase is prolonged.
Description
Technical Field
The invention belongs to the technical field of superhard composite materials, and particularly relates to a boron nitride superhard material containing a high-entropy ceramic phase, and a preparation method and application thereof.
Background
The main stream of the future cutting processing is a mode combining dry cutting, hard processing and high-speed cutting, and the mode is a green cutting mode with high efficiency, low energy consumption, resource saving and pollution reduction. Polycrystalline cubic boron nitride is most likely to occupy a seat in future cutting modes due to the characteristics of high hardness, excellent thermal stability, chemical stability, low friction coefficient and the like.
Cubic boron nitride is composed of covalent bonds of high strength, and thus sintering cubic boron nitride of high purity is rather difficult and not suitable for industrial production. Researchers have also obtained good cutting performance by adding a binder to cubic boron nitride to prepare polycrystalline cubic boron nitride. Commonly used binders are ceramic binders and metal binders: the ceramic binder has the problems of weak bending strength and fracture toughness and the like; when the metal binder works at a higher temperature, the metal is softened, so that the wear resistance of the cutting material is greatly reduced, and the red hardness of the cutting material is reduced.
Therefore, how to simultaneously improve the hardness, strength and toughness of the boron nitride superhard material is still a technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide a boron nitride superhard material containing a high-entropy ceramic phase, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a boron nitride superhard material containing a high-entropy ceramic phase, which is prepared from the following raw materials in percentage by mass:
40-91% of boron nitride powder, 8-50% of binder phase powder and 1-10% of high-entropy ceramic phase powder;
the high entropy ceramic phase powder comprises (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 、(CrZrTiNbV)N、(Ti 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 )C、Nb 2 O 3 And MoO 3 One or more of them.
Preferably, the binder phase powder comprises one or more of Ti, al, hf, zr, co and Ni.
Preferably, the particle size of the boron nitride powder is 1 to 22 μm, the particle size of the binder phase powder is 1 to 10 μm, and the particle size of the high-entropy ceramic phase powder is 1 to 20 μm.
Preferably, the (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 The preparation method comprises the following steps:
to mix HfO 2 、ZrO 2 、TiO 2 、Ta 2 O 5 、CrO 2 Mixing with amorphous boron powder, ball milling, drying, molding, and performing first heat treatment to obtain (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 High entropy ceramic phase powder.
Preferably, the (Ti) is 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 ) The preparation method of C comprises the following steps:
ZrO 2 is mixed with 2 、Ta 2 O 5 、Nb 2 O 5 、TiO 2 、WO 3 Mixing with carbon source, ball milling, drying, and sintering to obtain (Ti) 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 ) C high entropy ceramic phase powder.
Preferably, the preparation method of the (CrZrTiNbV) N comprises the following steps:
and mixing and ball-milling CrN, zrN, nbN, tiN and VN powder in a protective atmosphere, and sequentially carrying out second heat treatment and annealing treatment on the obtained pre-alloyed ceramic mixture to obtain (CrZrTiNbV) N high-entropy ceramic phase powder.
The invention also provides a preparation method of the boron nitride superhard material containing the high-entropy ceramic phase, which comprises the following steps:
(1) Mixing boron nitride powder, bonding phase powder and high-entropy ceramic phase powder, and then sequentially performing ball milling, sieving and drying to obtain mixed powder;
(2) And (3) sintering the mixed powder after molding to obtain the boron nitride superhard material containing the high-entropy ceramic phase.
Preferably, the sintering temperature is 1400-1600 ℃, the heating rate is 20-50 ℃/min, and the heat preservation time is 5-30 min.
Preferably, the ball milling is wet ball milling, the time of the wet ball milling is 2-6 h, and the medium of the wet ball milling is one or more of ethanol, propanol and methanol.
The invention also provides an application of the boron nitride superhard material containing the high-entropy ceramic phase or the boron nitride superhard material containing the high-entropy ceramic phase obtained by the preparation method in the scheme as a cutting material.
The invention provides a boron nitride superhard material containing a high-entropy ceramic phase, which has high hardness, high strength and high toughness, wherein the bending strength can reach 1280MPa, the Vickers hardness can reach 42.8MPa, and the fracture toughness can reach 8.72MPa 1/2 . According to the invention, a small amount of high-entropy ceramic phase powder is introduced into the boron nitride superhard material, and the multi-principal-element high-entropy effect of the high-entropy ceramic phase is utilized, so that the wettability between the binding phase and the boron nitride can be effectively improved, and the dissolution and precipitation process is adjusted, so that the microstructure of the superhard material is optimized, various substances in the material can be tightly combined, and the strength, hardness and toughness of the boron nitride superhard material are improved at the same time. According to the invention, only high-entropy ceramic phase powder accounting for 1-10 wt% of the whole mass of the boron nitride superhard material containing the high-entropy ceramic phase is added, so that the comprehensive mechanical property of the boron nitride superhard material can be obviously improved, the production cost is reduced, and the service life of the boron nitride superhard material is prolonged.
The invention also provides a preparation method of the boron nitride superhard material containing the high-entropy ceramic phase. The preparation method provided by the invention is based on the production process of the traditional boron nitride superhard material, only needs to add a high-entropy ceramic phase when improving the prior art, does not need to add new process steps, can reduce the equipment improvement investment, is simple to operate, and has the potential of industrial production.
The invention also provides an application of the boron nitride superhard material containing the high-entropy ceramic phase in the scheme or the boron nitride superhard material containing the high-entropy ceramic phase obtained by the preparation method in the scheme as a cutting material. The boron nitride superhard material containing the high-entropy ceramic phase is manufactured into a cutting tool, and has the advantages of strong cutting capability, long service life, excellent comprehensive performance and the like.
Detailed Description
The invention provides a boron nitride superhard material containing a high-entropy ceramic phase, which is prepared from the following raw materials in percentage by mass:
40-91% of boron nitride powder, 8-50% of binder phase powder and 1-10% of high-entropy ceramic phase powder;
the high-entropy ceramic phase powder comprises (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 、(CrZrTiNbV)N、(Ti 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 )C、Nb 2 O 3 And MoO 3 One or more of them.
The raw material of the boron nitride superhard material containing the high-entropy ceramic phase comprises, by mass, 40% -91% of boron nitride powder, preferably 50% -80%, and more preferably 60% -70%; the particle diameter of the boron nitride powder is preferably 1 to 22 μm, more preferably 5 to 15 μm, and still more preferably 8 to 12 μm.
The raw material of the boron nitride superhard material containing the high-entropy ceramic phase comprises, by mass, 8-50% of bonding phase powder, preferably 10-40% of bonding phase powder, and more preferably 20-30% of bonding phase powder; the particle size of the binder phase powder is preferably 1 to 10 μm, more preferably 3 to 8 μm, and still more preferably 5 to 7 μm; the binder phase powder preferably comprises one or more of Ti, al, hf, zr, co and Ni.
The raw material of the boron nitride superhard material containing the high-entropy ceramic phase comprises 1-10% of high-entropy ceramic phase powder, preferably 3-8% and more preferably 5-7% by mass percent; the entropy value of the high-entropy ceramic phase powder is preferably 0.1 to 0.5, more preferably 0.2 to 0.4, and further preferably 0.2; the particle size of the high-entropy ceramic phase powder is preferably 1 to 20 μm, more preferably 3 to 15 μm, and further preferably 5 to 10 μm; the high entropy potteryThe ceramic phase powder comprises (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 、(CrZrTiNbV)N、(Ti 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 )C、Nb 2 O 3 And MoO 3 Preferably (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 (CrZrTiNbV) N and (Ti) 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 ) C, one or more of C. The invention can further optimize the microstructure of the boron nitride superhard material and improve the comprehensive performance of the polycrystalline cubic boron nitride by limiting the components of the bonding phase powder and the high-entropy ceramic phase powder.
In the present invention, the (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 The preparation method of (a) preferably comprises the steps of: to mix HfO 2 、ZrO 2 、TiO 2 、Ta 2 O 5 、CrO 2 Mixing amorphous boron powder, ball milling (marking as first ball milling), drying (marking as first drying), molding the obtained mixed powder, and carrying out first heat treatment to obtain the (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 High entropy ceramic phase powder. In the present invention, the HfO 2 、ZrO 2 、TiO 2 、Ta 2 O 5 And CrO 2 Independently, a purity of (b) is preferably 99.0 to 99.9wt%, more preferably 99.5 to 99.9wt%, and a particle diameter is independently preferably 0.1 to 10 μm, more preferably 1 to 5 μm; the purity of the amorphous boron powder is preferably 95-99 wt%, more preferably 97-99 wt%, and the particle size is preferably 0.1-10 μm, more preferably 1-5 μm; the HfO 2 And the amorphous boron powder is preferably 1; the ZrO 2 And the amorphous boron powder is preferably 1; the TiO is 2 And amorphous boron powder in a molar ratio of preferably 1; said Ta 2 O 5 And amorphous boron powder, preferably in a molar ratio of 1; the CrO 2 And amorphous boronThe molar ratio of the powders is preferably 1; the first ball milling medium preferably comprises one or both of ethanol and n-heptane; the HfO 2 、ZrO 2 、TiO 2 、Ta 2 O 5 、CrO 2 And the ratio of the total mass of the amorphous boron powder to the mass of the first ball-milling medium is preferably 100; the ball-to-material ratio of the first ball milling is preferably 3-10, more preferably 5-8; the first ball milling time is preferably 20-50 h, and more preferably 30h; the first ball milling equipment is preferably a ball milling tank; the first ball milling grinding ball preferably comprises titanium balls or hard alloy balls; the particle size of the mixed powder obtained by the first ball milling is preferably 5-30 μm, and more preferably 10-30 μm; the temperature of the first drying is preferably 80 to 200 ℃, more preferably 100 to 160 ℃, and the time is preferably 3 to 8 hours, more preferably 4 to 7 hours.
In the present invention, the molding is preferably press molding; the invention has no special requirements on the pressure and time of compression molding, and mixed powder is filled into a die and is manually compressed into powder blanks; the degree of vacuum of the first heat treatment is preferably 10 -1 ～10 -3 Pa, more preferably 10 -2 Pa; the procedure of the first heat treatment is preferably: heating to 1000-1200 ℃ at the heating rate of 5-20 ℃/min, preserving heat for 0.5-2 h, then heating to 1500-1700 ℃ at the heating rate of 5-15 ℃/min, and preserving heat for 0.5-2 h; the procedure of the first heat treatment is more preferably: heating to 1050-1150 ℃ at the heating rate of 10-15 ℃/min, preserving heat for 1-1.5 h, then heating to 1550-1650 ℃ at the heating rate of 8-12 ℃/min, and preserving heat for 1-1.5 h; the first heat treatment process is further preferably performed by: heating to 1200 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, heating to 1600 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h to obtain (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 The high-entropy ceramic phase powder is high-entropy solid solution powder.
In the present invention, the (Ti) is 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 ) Preparation method of C preferable bagThe method comprises the following steps: is reacted with ZrO 2 、Ta 2 O 5 、Nb 2 O 5 、TiO 2 、WO 3 Mixing with a carbon source, ball milling (recording as second ball milling), drying (recording as second drying), and sintering the obtained mixed powder (recording as first sintering) to obtain the (Ti) 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 ) C high entropy ceramic phase powder. In the present invention, the carbon source preferably includes one or both of carbon black and sucrose; the ZrO 2 、Ta 2 O 5 、Nb 2 O 5 、TiO 2 And WO 3 Independently preferably 1.5 to 2.5 μm, more preferably 1.7 to 2.2 μm, and independently preferably not less than 99.9% pure, more preferably 99.9% to 99.99% pure; the purity of the carbon black is preferably not less than 99%, and more preferably 99-99.9%; the ZrO 2 And Ta 2 O 5 Preferably 1 to 2, more preferably 1; said Ta 2 O 5 And Nb 2 O 5 Preferably 1 to 2, more preferably 1; the Nb 2 O 5 And TiO 2 Preferably 1; the TiO is 2 And WO 3 Preferably 1 to 2, more preferably 1; said WO 3 And the molar ratio of the carbon source is preferably 1 to 4, more preferably 1.
In the invention, the second ball milling device is preferably a mixing tank; the material of the mixing tank preferably comprises zirconium oxide, stainless steel or titanium; the ball milling medium of the second ball milling is preferably distilled water; the second ball milling grinding ball preferably comprises zirconia balls, titanium balls or hard alloy balls; the rotation speed of the second ball mill is preferably 200-500 r/min, more preferably 300-400 r/min, and the time is preferably 8-24 h, more preferably 12-20 h; the second drying is preferably carried out in a drying oven; the second drying temperature is preferably 80-200 ℃, more preferably 150-200 ℃, and the time is preferably 4-10 h, more preferably 6-8 h; the first sintering is preferably vacuum sintering, the temperature of the first sintering is preferably 1600-1800 ℃, more preferably 1650-1750 ℃, the heating rate is preferably 60-100 ℃/min,more preferably 70 to 90 ℃/min, and the degree of vacuum is preferably not higher than 5X 10 -3 Pa, more preferably 5X 10 -3 Pa～5×10 -5 Pa, the pressure is preferably 1-3 MPa, more preferably 1.5-2.5 MPa, and the holding time is preferably 5-15 min, more preferably 8-12 min; the first sintering is preferably carried out by adding the mixed powder into a graphite mould and then placing the graphite mould into a spark plasma sintering furnace; after the first sintering is finished, preferably cooling a first sintering product along with the furnace; the final temperature of the furnace cooling is preferably room temperature. The invention prepares (Ti) through wet mixing and high-temperature carbothermic reduction reaction 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 )C。
In the present invention, the preparation method of the (CrZrTiNbV) N preferably comprises the following steps: and mixing and ball-milling CrN, zrN, nbN, tiN and VN powder in a protective atmosphere (marked as third ball milling), and sequentially carrying out second heat treatment and annealing treatment on the obtained pre-alloyed ceramic mixture to obtain the (CrZrTiNbV) N high-entropy ceramic phase powder. In the present invention, the shielding gas is preferably argon; the molar ratio of CrN to ZrN is preferably 18 to 22, more preferably 16 to 22; the molar ratio of ZrN to NbN is preferably 12 to 28, more preferably 15 to 20; the molar ratio of NbN to TiN is preferably 18 to 22, more preferably 18 to 21, and still more preferably 1; the molar ratio of TiN to VN is preferably 18 to 22, more preferably 18 to 20, and still more preferably 1.
In the invention, the third ball milling device is preferably an agate tank; the third grinding ball for ball milling preferably comprises titanium balls or hard alloy balls; the ball milling medium of the third ball milling is preferably ethanol; the mass ratio of CrN, zrN, nbN, tiN and VN to the volume of ethanol is preferably 10-100g, more preferably 30-70g; the ball-to-material ratio of the third ball milling is preferably 3 to 10, more preferably 5 to 8; the third ball milling mode is preferably that each ball milling is carried out for 2h and the interval is 10min; the rotating speed of the third ball milling is preferably 200-500 r/min, more preferably 300-400 r/min, and the time of the third ball milling (the time of ball milling and intermittence)And) preferably from 30 to 50h, more preferably from 35 to 45h; the particle size of the mixed powder obtained by the third ball milling is preferably 5-40 μm, and more preferably 5-20 μm; the temperature of the second heat treatment is preferably 700-900 ℃, more preferably 750-850 ℃, and the heat preservation time is preferably 0.5-1 h, more preferably 0.7-0.9 h; the final temperature of the annealing treatment is preferably 600 to 800 ℃, and more preferably 650 to 750 ℃. The (CrZrTiNbV) N high-entropy ceramic block obtained by pre-alloying is of a single-phase face-centered cubic structure with uniform components, has superfine crystals with nanometer sizes, and has high hardness, high strength and high toughness, wherein the bending strength reaches 1050-1280 MPa, the Vickers hardness reaches 35.8-42.8 MPa, and the fracture toughness reaches 6.72-8.72MPa.m 1/2 And the comprehensive mechanical property is excellent.
The invention also provides a preparation method of the boron nitride superhard material containing the high-entropy ceramic phase, which comprises the following steps:
(1) Mixing boron nitride powder, binding phase powder and high-entropy ceramic phase powder, and then sequentially performing ball milling, sieving and drying to obtain mixed powder;
(2) And (3) sintering the mixed powder after molding to obtain the boron nitride superhard material containing the high-entropy ceramic phase.
According to the invention, boron nitride powder, binding phase powder and high-entropy ceramic phase powder are mixed and then subjected to ball milling (marked as fourth ball milling), sieving and drying (marked as third drying) in sequence to obtain mixed powder. In the invention, the fourth ball milling is preferably wet ball milling, the time of the wet ball milling is preferably 2-6 h, more preferably 3-5 h, and the wet ball milling medium preferably comprises one or more of ethanol, propanol and methanol; the aperture of the screen mesh for sieving is preferably 50-200 meshes, and more preferably 100-150 meshes; the particle size of the mixed powder obtained by sieving is preferably not more than 50 meshes; the temperature of the third drying is preferably 80-200 ℃, more preferably 100-150 ℃, and the holding time is preferably 4-8 h, more preferably 5-7 h.
After the mixed powder is obtained, the mixed powder is molded and then sintered (marked as second sintering) to obtain the boron nitride superhard material containing the high-entropy ceramic phase. In the present invention, the molding is preferably press molding; the pressure for compression molding is preferably 10 to 20MPa, more preferably 14 to 16MPa, and the pressure maintaining time is preferably 15 to 30s, more preferably 20 to 28s; the temperature of the second sintering is preferably 1400-1600 ℃, more preferably 1450-1550 ℃, the heating rate is preferably 20-50 ℃/min, more preferably 30-40 ℃/min, and the heat preservation time is preferably 5-30 min, more preferably 10-20 min; the procedure of the second sintering is preferably: and putting the pressed compact into an assembly block, heating to the sintering temperature at the heating rate, preserving heat, and cooling along with a furnace after reaching the heat preservation time.
The invention also provides an application of the boron nitride superhard material containing the high-entropy ceramic phase in the scheme or the boron nitride superhard material containing the high-entropy ceramic phase obtained by the preparation method in the scheme as a cutting material.
In the present invention, the application preferably comprises the steps of: preparing a blank from a boron nitride superhard material containing a high-entropy ceramic phase, and then sequentially carrying out flat grinding, linear cutting, welding and cutter grinding treatment to obtain a cutting tool; the sharpening process preferably grinds the rake and flank surfaces of the tool. The method for processing the boron nitride superhard material containing the high-entropy ceramic phase into the cutting tool has no special requirement, and can be realized by adopting a processing means commonly used in the field.
In order to further illustrate the present invention, the following examples are given as illustrative embodiments of the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
(Hf 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 Preparation of high-entropy boride powder: weighing HfO in equimolar ratio 2 、ZrO 2 、TiO 2 、Ta 2 O 5 、CrO 2 Taking 100g of amorphous boron powder as raw materials, adding 50mL of ethanol solvent, mixing with titanium balls as ball milling media, mixing for 30h in a ball mill, drying to obtain mixed powder, performing heat treatment on the mixed powder blank prepared by die pressing the mixed powder under the vacuum condition, and heating to the temperature of 20 ℃/minKeeping the temperature at 1000 ℃ for 1h, then heating to 1600 ℃ at the heating rate of 15 ℃/min for 1h, and carrying out vacuum heat treatment to obtain (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 High entropy boride powder;
weighing (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 3g of high-entropy boride powder, 90g of boron nitride superhard powder and 7g of binding phase Al powder are put into a ball milling tank for mixing, the ball milling tank is put on a ball mill for ball milling for 3 hours, and the ball milling medium is ethanol; after the ball milling is finished, sieving powder obtained by the ball milling through a 200-mesh screen, drying at 120 ℃ for 4 hours, and pressing the powder under the pressure of 20MPa by using a hydraulic machine to obtain a superhard material blank; putting the obtained superhard material blank into a metal cup, assembling into blocks, and putting into a cubic press for sintering, wherein the sintering process comprises the following steps: heating to 1500 ℃ at the heating rate of 50 ℃/min, sintering for 10min, and then cooling to room temperature along with the furnace to obtain the boron nitride superhard material containing the high-entropy ceramic phase;
and (3) testing mechanical properties: the boron nitride superhard material containing the high-entropy ceramic phase prepared in the embodiment has the bending strength (three-point bending resistance) of 1100MPa, the Vickers hardness (microhardness) of 41.8MPa and the fracture toughness (indentation method) of 6.72MPa 1/2 。
Example 2
(Hf 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 The preparation of the high-entropy boride powder was the same as in example 1;
weighing (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 Putting 6g of high-entropy boride powder, 80g of boron nitride superhard powder, 5g of bonding phase Al powder and 9g of Ti powder into a ball milling tank for mixing, and putting the ball milling tank on a ball mill for ball milling for 3 hours, wherein the ball milling medium is ethanol; after the ball milling is finished, sieving powder obtained by the ball milling through a 200-mesh screen, drying at 150 ℃ for 4h, and pressing the powder under the pressure of 20MPa by using a hydraulic machine to obtain a superhard material blank (the powder is pressed into a powder blank, and the time is only 30 s); putting the obtained superhard blank into a metal cup, assembling into a block, and putting into a cubic apparatus pressSintering in a machine, wherein the sintering process comprises the following steps: heating to 1500 ℃ at the heating rate of 50 ℃/min, sintering for 10min, and then cooling to room temperature along with the furnace to obtain the boron nitride superhard material containing the high-entropy ceramic phase;
and (3) testing mechanical properties: the boron nitride superhard material containing the high-entropy ceramic phase prepared in the example has the bending strength (three-point bending resistance) of 1250MPa, the Vickers hardness (microhardness) of 35.8MPa and the fracture toughness (indentation method) of 8.72MPa 1 /2 。
Example 3
(Ti 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 ) C, preparation of high-entropy carbide powder:
weighing an equimolar ratio of ZrO 2 、Ta 2 O 5 、Nb 2 O 5 、TiO 2 、WO 3 And C, 100g, placing the mixture into a stainless steel mixing tank, adding 50mL of ethanol, mixing the mixture for 20 hours by using a hard alloy ball at the rotating speed of 200r/min, drying the uniformly mixed raw material for 4 hours in a drying oven at the constant temperature of 120 ℃, placing the dried raw material powder into a graphite die, and placing the graphite die into a spark plasma sintering furnace for sintering, wherein the sintering parameters are as follows: vacuum degree of 5X 10 -3 Pa, average heating rate of 60 ℃/min, sintering temperature of 1700 ℃, pressure of 1MPa, and heat preservation time of 6min; after sintering, cooling the mixture to room temperature along with the furnace to obtain high-entropy carbide ceramic powder;
weighing (Ti) 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 ) 8g of C high-entropy carbide powder, 70g of boron nitride superhard powder, 16g of binding phase Ti powder and 6g of Al powder, putting the materials into a ball milling tank, mixing, and putting the ball milling tank on a ball mill for ball milling for 3 hours, wherein the ball milling medium is ethanol; after the ball milling is finished, sieving powder obtained by the ball milling through a 200-mesh screen, drying for 4 hours at 150 ℃, and pressing the powder material under the pressure of 20MPa by using a hydraulic machine to obtain a superhard material blank; putting the obtained superhard material blank into a metal cup, assembling into blocks, and putting into a cubic press for sintering, wherein the sintering process comprises the following steps: heating to 1500 ℃ at the heating rate of 50 ℃/min, sintering for 10min, and then cooling to room temperature along with the furnace to obtain the boron nitride superhard material containing the high-entropy ceramic phase；
And (3) testing mechanical properties: the boron nitride superhard material containing the high-entropy ceramic phase prepared in the embodiment has the bending strength (three-point bending resistance) of 1280MPa, the Vickers hardness (microhardness) of 35.8MPa and the fracture toughness (indentation method) of 7.8MPa.m 1/2 。
Example 4
Preparation of (CrZrTiNbV) N high entropy nitride powder:
weighing 50g of CrN, VN, nbN, tiN and ZrN in equal molar ratio in an argon atmosphere, putting the powder into an agate tank, adding 30mL of alcohol into the agate tank, wherein the ball-material ratio is 10, the rotation speed is 260r/min, the ball milling is stopped for 10min every 2h, and the ball milling is carried out for 40h in total to obtain a pre-alloyed ceramic mixture; carrying out heat treatment on the obtained pre-alloyed ceramic mixture at 900 ℃ for 1h, and then carrying out annealing treatment on the powder at 700 ℃ to obtain (CrZrTiNbV) N high-entropy nitride powder;
weighing 4g of (CrZrTiNbV) N high-entropy nitride powder, 90g of boron nitride superhard powder and 6g of binding phase Al powder, filling the mixture into a ball milling tank, mixing, and putting the ball milling tank on a ball mill for ball milling for 3 hours, wherein the ball milling medium is ethanol; after the ball milling is finished, sieving the powder obtained by the ball milling through a 200-mesh screen, drying the powder for 5 hours at 120 ℃, and pressing the powder into an ultra-hard material blank by using a hydraulic machine under the pressure of 20 MPa; putting the obtained superhard material blank into a metal cup, assembling into blocks, and putting into a cubic press for sintering, wherein the sintering process comprises the following steps: heating to 1500 ℃ at the heating rate of 50 ℃/min, sintering for 10min, and then cooling to room temperature along with the furnace to obtain the boron nitride superhard material containing the high-entropy ceramic phase;
and (3) testing mechanical properties: the boron nitride superhard material containing the high-entropy ceramic phase prepared in the embodiment has a bending strength (three-point bending resistance) of 1050MPa, a Vickers hardness (microhardness) of 42.8MPa, and a fracture toughness (indentation method) of 6.9MPa.m 1/2 。
From the above examples, the boron nitride superhard material containing the high-entropy ceramic phase provided by the invention has high hardness, high strength and high toughness, the bending strength reaches 1050-1280 MPa, the Vickers hardness reaches 35.8-42.8 MPa, and the fracture toughness reaches 6.72-8.72MPa 1/2 The method obviously improves the comprehensive mechanical property of the boron nitride superhard material, meets the performance requirement of a cutting tool, reduces the production cost and prolongs the service life of the boron nitride superhard material.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A boron nitride superhard material containing a high-entropy ceramic phase is prepared from the following raw materials in percentage by mass:
40-91% of boron nitride powder, 8-50% of binder phase powder and 1-10% of high-entropy ceramic phase powder;
the high entropy ceramic phase powder comprises (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 、(CrZrTiNbV)N、(Ti 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 )C、Nb 2 O 3 And MoO 3 One or more of them.
2. A boron nitride superhard material containing a high entropy ceramic phase as claimed in claim 1, wherein the binder phase powder comprises one or more of Ti, al, hf, zr, co and Ni.
3. A boron nitride superhard material containing a high entropy ceramic phase according to claim 1 or 2, wherein the boron nitride powder has a particle size of 1 to 22 μm, the binder phase powder has a particle size of 1 to 10 μm and the high entropy ceramic phase powder has a particle size of 1 to 20 μm.
4. A boron nitride superhard material containing a high entropy ceramic phase as claimed in claim 1, wherein the (Hf) is 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 The preparation method comprises the following steps:
to mix HfO 2 、ZrO 2 、TiO 2 、Ta 2 O 5 、CrO 2 Mixing with amorphous boron powder, ball milling, drying, molding, and performing first heat treatment to obtain (Hf) 0.2 Zr 0.2 Ta 0.2 Cr 0.2 Ti 0.2 )B 2 High entropy ceramic phase powder.
5. A boron nitride superhard material containing a high entropy ceramic phase as claimed in claim 1, wherein the (Ti) is 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 ) The preparation method of C comprises the following steps:
ZrO 2 is mixed with 2 、Ta 2 O 5 、Nb 2 O 5 、TiO 2 、WO 3 Mixing with carbon source, ball milling, drying, and sintering to obtain (Ti) 0.2 Zr 0.2 Nb 0.2 W 0.2 Ta 0.2 ) C high entropy ceramic phase powder.
6. A boron nitride superhard material containing a high entropy ceramic phase according to claim 1, wherein the preparation method of the (CrZrTiNbV) N comprises the following steps:
and mixing and ball-milling CrN, zrN, nbN, tiN and VN powder under a protective atmosphere, and sequentially carrying out second heat treatment and annealing treatment on the obtained pre-alloyed ceramic mixture to obtain (CrZrTiNbV) N high-entropy ceramic phase powder.
7. A method for preparing a boron nitride superhard material containing a high entropy ceramic phase as claimed in any one of claims 1 to 6, comprising the steps of:
(1) Mixing boron nitride powder, bonding phase powder and high-entropy ceramic phase powder, and then sequentially performing ball milling, sieving and drying to obtain mixed powder;
(2) And (3) sintering the mixed powder after molding to obtain the boron nitride superhard material containing the high-entropy ceramic phase.
8. The preparation method according to claim 7, wherein the sintering temperature is 1400-1600 ℃, the heating rate is 20-50 ℃/min, and the holding time is 5-30 min.
9. The preparation method of claim 7, wherein the ball milling is wet ball milling, the time of the wet ball milling is 2-6 h, and the medium of the wet ball milling is one or more of ethanol, propanol and methanol.
10. Use of the boron nitride superhard material containing a high entropy ceramic phase as defined in any one of claims 1 to 6 or the boron nitride superhard material containing a high entropy ceramic phase obtained by the method of manufacture as defined in any one of claims 7 to 9 as a cutting material.
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