CN115611636A - Surface modified cubic boron nitride powder and preparation method and application thereof - Google Patents
Surface modified cubic boron nitride powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of composite material preparation, and discloses surface modified cubic boron nitride powder and a preparation method and application thereof. The method is to mix cubic boron nitride powder and nano TiO 2 Mixing the powder with the powder C, and treating in a vibrating screen with a screen disc to obtain the plastically deformed nano TiO 2 Mixing the powder and the C powder to coat the cubic boron nitride powder, and keeping the temperature at 1250-1350 ℃ in a nitrogen atmosphere to obtain the surface modified cubic boron nitride powder. The ceramic composite material prepared by the surface modified cubic boron nitride powder can improve the bonding strength between a ceramic matrix and cubic boron nitride, simultaneously inhibit the surface phase change of cubic boron nitride particles, and improve the mechanical property and the wear resistance of the composite material. The surface modified cubic boron nitride powder can be applied to the preparation of wear-resistant and corrosion-resistant parts such as bearings, high-speed cutting tools, aerospace and marine equipment and the like.
Description
Technical Field
The invention belongs to the technical field of ceramic composite materials, and particularly relates to surface-modified cubic boron nitride powder as well as a preparation method and application thereof.
Technical Field
Cubic boron nitride is the second hard material next to diamond. Polycrystalline cubic boron nitride has been widely used for machining tools of hard ferrous materials (hardened alloy steels, tool steels, cast iron, etc.) or as a reinforcing phase to increase the hardness and wear resistance of other ceramic materials (e.g., al2O3, siAlON) due to its ultra-high hardness, good thermal conductivity and good chemical resistance.
However, cubic boron nitride has poor binding force with the matrix, and even when a sintering aid (such as TiN, alN, and TiC) is incorporated into cubic boron nitride particles for solid phase sintering, the ability to effectively function as or bond the material is limited, and cubic boron nitride grains only have mechanical interaction with the matrix. Cubic boron nitride grains are easily pulled out of the interaction layer and wear resistant articles or cutting tools made from these materials often fail prematurely. On the other hand, the cubic boron nitride is only stable at high temperature, if a low-pressure mode (< 100 MPa) is adopted to prepare the multiphase material taking the cubic boron nitride as a reinforcing phase, the phase transition temperature is different between 1300 ℃ and 1650 ℃, which causes the material to be accompanied with phase transition in the sintering and densification process, the initial phase transition occurs from the boundary of the cubic boron nitride and a matrix, and the integral phase transition occurs after a certain temperature is reached, which causes the hardness and the wear resistance of the material to be greatly reduced after the final sintering is completed, so that the reinforcing effect cannot be achieved. Therefore, the influence of the bonding strength and the phase change of cubic boron nitride on the material is not negligible in the preparation of the composite material. The surface modification of the cubic boron nitride powder is a method for well solving the problem, and the mechanical property and the cutting property of the ceramic cutting tool material prepared by the method can be greatly improved. At present, chemical methods such as a chemical deposition method, a salt bath plating method, a sol-gel method and the like are generally adopted for surface modification to prepare cubic boron nitride powder with a layer of different substances on the surface, and heat treatment is carried out in the atmosphere of nitrogen and hydrogen or ammonia, however, the method is complicated in process, high in cost and not beneficial to application to actual production.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of surface modified cubic boron nitride powder. The method generates nano powder by mechanical mixing and carbothermic reduction methodTiO adhered to the surface of cubic boron nitride particles by plastic deformation in the nitrogen atmosphere 2 Converted to TiN. The process is simple, the cost is low, the bonding strength of the obtained surface modified cubic boron nitride powder and a ceramic matrix is improved, and the mechanical property and the wear resistance of the prepared ceramic composite material are improved.
The invention also aims to provide the surface modified cubic boron nitride powder prepared by the method.
The invention also aims to provide application of the surface modified cubic boron nitride powder.
The purpose of the invention is realized by the following technical scheme:
a preparation method of surface modified cubic boron nitride powder comprises the following specific steps:
s1, mixing cubic boron nitride powder and nano TiO 2 Adding the powder and the C powder into a coating machine for stirring, and placing the powder and the C powder into a vibration screening machine for vibration to obtain the nano TiO subjected to plastic deformation 2 Powder and C powder are mixed and coated with cubic boron nitride powder;
s2, placing the coated cubic boron nitride powder in a boron nitride crucible, placing the boron nitride crucible in a tubular furnace or a vacuum sintering furnace, heating to 1250-1350 ℃ at a speed of 5-15 ℃/min under a nitrogen atmosphere, preserving heat for 1-3 h for heat treatment, cooling to 600-800 ℃ at a speed of 5-15 ℃/min, and then cooling with the furnace to prepare surface modified cubic boron nitride powder; the surface modified cubic boron nitride powder is of a core-shell structure in which TiN particles are adhered to the cubic boron nitride powder, the particle size of the TiN particles is 20-300nm, and the layer thickness of the shell TiN is 20-90 nm.
Preferably, the nano TiO in step S1 2 The powder is anatase type TiO 2 Powder; the C powder is graphite powder, carbon powder or carbon black; the cubic boron nitride and the nano TiO 2 The purity of the powder C and the powder C is more than 97 percent; the grain diameter of the cubic boron nitride is 1-10 mu m, and the nano TiO 2 The particle diameters of the powder and the powder C are both 20-50 nm.
Preferably, the cubic boron nitride and the nano TiO in the step S1 2 The mass ratio of the powder to the C powder is (90-98): (2-10): 0.47-3.33).
Preferably, the rotation speed of the stirring in the step S1 is 2500-3000 r/min, and the stirring time is 10-20 min.
Preferably, the coated cubic boron nitride powder in step S1 is plastically deformed nano TiO 2 The powder and the C powder are adhered to the surface of the cubic boron nitride powder to form a coating layer, and the thickness of the coating layer is 20-70 nm.
Preferably, the amplitude of the vibration in step S1 is 1000 to 1400r/min, and the time of the vibration is 20 to 60min.
Preferably, the cladding machine in the step S1 consists of a servo motor, a cavity and an elliptical rotor, a small gap is reserved between the rotor and the cavity, and the length of the gap is 0.4-2.0 mm; the stirring process comprises the following steps: the rotating speed of the motor is 2500-3000 r/min, and the stirring time is 10-20 min.
Preferably, the vibration screening machine in step S2 is a standard inspection screening machine available in the market, and the number of the screen discs attached to the standard inspection screening machine is 1600-2000 meshes.
Preferably, the powder taken out in step S2 is processed by a vibration screening machine to remove nano TiO that is not attached to the surface of cubic boron nitride 2 And (4) after the powder and the C powder are obtained, the powder is left on the sieve tray.
Preferably, the high-temperature furnace in step S3 is a tube furnace or a vacuum sintering furnace, wherein the heat treatment process is as follows: the heat treatment atmosphere adopts nitrogen, the purity is more than or equal to 99 percent, and the flow rate is 100-300 m/s.
The surface modified cubic boron nitride powder is prepared by the method.
A reinforced ceramic composite material is prepared by mixing surface modified cubic boron nitride powder and ceramic powder,
preferably, the ceramic powder is Al 2 O 3 、Si 3 N 4 AlN or SiAlON.
The reinforced ceramic composite material is applied to bearings, high-speed cutting tools or aerospace wear-resistant and corrosion-resistant parts.
The principle of the invention is shown in fig. 1. Under the high-speed mechanical stirring, the top of the rotor and the cavity have a narrow gap, so that cubic boron nitride and nano TiO in the gap are easily caused in the rotation 2 The powder and the C powder are mutually rubbed, the powder and the rotor are rubbed to generate a shearing force, and the high instantaneous temperature is generated near the rotor tip due to the high rotating speed of the rotor, so that the nano TiO powder 2 The powder and the C powder generate plastic deformation under the shearing force and are uniformly adhered on the cubic boron nitride powder, the adhesion force is very strong at normal temperature, and then the nano TiO powder flows under the atmosphere of flowing nitrogen at about 1300 DEG C 2 Powders C and C in N 2 The carbon thermal reduction is generated, and TiO is adhered on the surface of the cubic boron nitride powder 2 The phase change of the cubic boron nitride is changed to TiN, C flows away along with nitrogen in a CO gas form, tiN formed on the surface of the cubic boron nitride powder has good affinity with a ceramic material matrix, and substances promoting the phase change of the cubic boron nitride are isolated from contacting with cubic boron nitride particles to a certain extent, and meanwhile, the TiN can inhibit the phase change of the cubic boron nitride at high temperature, so that the bonding strength and the high-temperature stability of the cubic boron nitride and the ceramic matrix are effectively improved.
Compared with the prior art, the method has the following beneficial effects:
1. the invention leads the nano powder to generate plastic deformation and adhere to the surface of the cubic boron nitride particles through a mechanical mixing mode, and compared with the coated cubic boron nitride powder prepared by the traditional chemical method, the preparation method is simpler and has lower cost.
2. The invention adopts a carbothermic method to adhere TiO on the surface of cubic boron nitride only in nitrogen atmosphere 2 The conversion of the metal into TiN is safer and lower in cost than direct reduction in ammonia or hydrogen atmosphere.
3. The surface modified cubic boron nitride powder prepared by the invention has good ceramic matrix associativity and high-temperature stability.
Drawings
FIG. 1 is a schematic diagram of the preparation of surface-modified cubic boron nitride powder by a mechanical mixing method and a carbothermic method according to the present invention;
FIG. 2 is SEM photographs of the screened coated cubic boron nitride powder (a) and the surface-modified cubic boron nitride powder (b) obtained after heat treatment prepared in example 1;
fig. 3 is SEM photographs of the surface-ground composite sintered ceramic materials prepared from cubic boron nitride powder (a) and surface-modified cubic boron nitride powder (b) of example 1.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The materials, methods and apparatus used in the present invention are, unless otherwise indicated, conventional in the art.
Example 1
1. Cubic boron nitride powder (purity 99.9%, particle size 5 μm): nano TiO 2 2 Powder (purity 99.9%, particle size 20 nm): mixing carbon powder (with the purity of 99.9% and the particle size of 20 nm) according to a mass ratio of 90.
2. And (3) placing the mixed powder on a standard vibration screening machine attached with a 1800-mesh type screening disc for screening, wherein the amplitude is 1200r/min, and the holding time is 30min, so as to obtain the coated cubic boron nitride powder.
3. Placing the coated cubic boron nitride powder in a boron nitride crucible, and placing the boron nitride crucible in a tube furnace at the flow speed of 300m/s and N 2 Heating to 1300 ℃ at the speed of 10 ℃/min in the atmosphere, preserving the heat for 1h, then cooling to 800 ℃ at the speed of 10 ℃/min along with the furnace, and obtaining the surface modified cubic boron nitride powder.
FIG. 2 is an SEM photograph of a surface-modified cubic boron nitride powder (b) obtained after heat treatment of the screened coated cubic boron nitride powder (a) prepared in example 1; as can be seen from FIG. 2, the powder C and the nano TiO 2 The cubic boron nitride powder coated by the powder is subjected to heat treatment to obtain the surface modified cubic boron nitride powder with continuous TiN particles of different sizes on the surface, wherein the TiN particles are 20-300nm.
Example 2
The difference from example 1 is that:step 1 cubic boron nitride and TiO 2 And carbon powder at a mass ratio of 95.
Example 3
The difference from example 1 is that: step 1, cubic boron nitride (purity 99.9%, particle size 10 μm), and nano TiO 2 Powder (purity 99.9%, particle size 50 nm) and carbon powder (purity 99.9%, particle size 50 nm); the rotating speed of the rotor is 2700r/min, the holding time is 9min, and the powder is mechanically mixed.
Example 4
The difference from example 1 is that: in step 1, cubic boron nitride (purity 99.9%, particle size 10 μm) and nano TiO are added 2 Powder (purity 99.9%, particle size 50 nm) and carbon black (purity 99.9%, particle size 20 nm).
Example 5
The difference from the embodiment 1 is that the amplitude in the step 2 is 1000r/min, the holding time is 20min, and the cubic boron nitride powder to be coated is obtained.
Example 6
The difference from example 1 is that: step 3, placing the cubic boron nitride powder into a tube furnace at the flow speed N of 200m/s 2 Heating to 1350 ℃ at the speed of 5 ℃/min in the atmosphere, preserving heat for 2h, then symmetrically cooling, cooling to 600 ℃ along with the furnace, and obtaining the surface modified cubic boron nitride powder.
Example 7
The difference from example 1 is that: step 3, placing the coated cubic boron nitride powder into a pressureless furnace at the flow speed of 100m/s and the flow speed of N 2 Heating to 1300 ℃ at the speed of 10 ℃/min in the atmosphere, preserving the heat for 3h, then symmetrically cooling, cooling to 700 ℃ along with the furnace, and obtaining the surface modified cubic boron nitride powder.
Application example 1
The surface-modified cubic boron nitride powder obtained in examples 1 to 7, unmodified cubic boron nitride powder (i.e., raw material cubic boron nitride powder) and a ceramic material base material were subjected to ball-milling and mixing in a roll, and then, the mixture was put into a graphite mold having a diameter of 20mm, and the graphite mold was placed in a spark plasma high-temperature furnace to perform a sintering experimentThe ceramic material matrix is beta-SiAlON (made of Si) 3 N 4 、AlN、Al 2 O 3 Surface-modified cubic boron nitride powder or untreated cubic boron nitride powder, and sintering aid Y 2 O 3 Formed in the sintering process), the preparation parameters of the ceramic composite material based on the surface modified cubic boron nitride powder and the untreated cubic boron nitride powder are shown in table 1, the mechanical property of a sample is represented, then the sample is ground and processed into a common tool with the model number of SNGN120412T02020 on the market, cast iron QT500-7 is processed on a numerical control machine, the cutting property is represented, and the representation result is shown in table 2.
TABLE 1 application of surface modified cubic boron nitride powder in preparing ceramic composite material
TABLE 2 characterization of the application of surface modified cubic boron nitride powder to ceramic composites
The preparation parameters of the ceramic composite material to which the surface-modified cubic boron nitride powder is applied are shown in table 1, and the characterization results of the ceramic composite material to which the surface-modified cubic boron nitride powder is applied are shown in table 2. As can be seen from tables 1 and 2, the hardness and the fracture toughness of the beta-SiAlON ceramic composite material sample prepared by the modified cubic boron nitride powder of the embodiment of the invention are improved to some extent, wherein the hardness is obviously improved, and the hardness of all the samples of the embodiment is more than 17GPa and is 15.54GPa higher than that of the sample of the comparative example 1; the cutting performance of the sample is improved, and the total cutting length of all the samples of the embodiment before the set abrasion standard is longer than that of the sample prepared in the comparative example 1; the composite material prepared from the surface modified cubic boron nitride powder in example 1 has the optimal performance, the hardness is increased from 15.54GPa to 17.81GPa, and the fracture toughness is increased from 4.5MPa m 1/2 Rise to 5.54MPa m 1/2 Tool life extension from 150s to 210s, indicating implementationThe surface-modified cubic boron nitride powder obtained by the modification method of example 1 had the best performance.
FIG. 3 shows the surface microscopic structure of the surface modified cubic boron nitride powder applied to ceramic composite material. Wherein, (a) is a surface micrograph of the beta-SiAlON ceramic composite prepared from the cubic boron nitride powder, and (b) is a surface micrograph of the beta-SiAlON ceramic composite prepared from the surface-modified cubic boron nitride powder obtained in example 1. As can be seen from fig. 3, the particles falling off from the surface cubic boron nitride particles after grinding are reduced, which further verifies that the obtained surface modified cubic boron nitride powder of the present invention can improve the bonding property of cubic boron nitride with the ceramic material matrix.
Application example 2
The surface modified cubic boron nitride powder and the unmodified cubic boron nitride powder prepared in the example 2 are respectively mixed with a ceramic material substrate raw material Si 3 N 4 And Y 2 O 3 And performing roller ball milling and mixing, performing rotary evaporation and drying, then putting the mixture into a graphite die with the diameter of 20mm, and putting the graphite die into a discharge plasma high-temperature furnace for sintering to obtain the reinforced ceramic composite material.
Compared with the reinforced ceramic composite material prepared from the unmodified cubic boron nitride powder, the hardness of the reinforced ceramic composite material prepared from the surface-modified cubic boron nitride powder is increased from 15.54GPa to 17.23GPa, and the fracture toughness is increased from 4.5MPa m 1/2 Rise to 4.82MPa m 1/2 The tool cutting life was extended 180s from 150 s.
Application example 3
The surface-modified cubic boron nitride powder and the unmodified cubic boron nitride powder obtained in example 3 were mixed with AlN and Y, which are ceramic material base materials, respectively 2 O 3 And performing roller ball milling and mixing, performing rotary evaporation and drying, then putting the mixture into a graphite die with the diameter of 20mm, and putting the graphite die into a discharge plasma high-temperature furnace for sintering to obtain the reinforced ceramic composite material.
Compared with the reinforced ceramic composite material prepared from the unmodified cubic boron nitride powder, the hardness of the reinforced ceramic composite material prepared from the surface-modified cubic boron nitride powder is increased from 15.54GPa to 17.42GPa, and the fracture toughness is increased from 4.5MPa m 1/2 Rise to 5.13MPa m 1/2 Tool cutting life was extended 193s from 150 s.
Application example 4
The surface modified cubic boron nitride powder and the unmodified cubic boron nitride powder prepared in the example 4 are respectively mixed with a ceramic material matrix material Al 2 O 3 And Y 2 O 3 And performing roller ball milling and mixing, performing rotary evaporation and drying, then putting the mixture into a graphite die with the diameter of 20mm, and putting the graphite die into a discharge plasma high-temperature furnace for sintering to obtain the reinforced ceramic composite material.
Compared with the reinforced ceramic composite material prepared from the unmodified cubic boron nitride powder, the hardness of the reinforced ceramic composite material prepared from the surface-modified cubic boron nitride powder is increased from 15.54GPa to 17.64GPa, and the fracture toughness is increased from 4.5MPa m 1/2 Rise to 5.35MPa m 1/2 The tool cutting life was extended from 150s to 201s.
Application example 5
The surface modified cubic boron nitride powder and the unmodified cubic boron nitride powder prepared in the example 5 are respectively mixed with a ceramic material matrix material Al 2 O 3 And Y 2 O 3 And performing roller ball milling and mixing, performing rotary steaming and drying, then filling the materials into a graphite mould with the diameter of 20mm, and putting the graphite mould into a discharge plasma high-temperature furnace for sintering to obtain the reinforced ceramic composite material.
Compared with the reinforced ceramic composite material prepared from the unmodified cubic boron nitride powder, the hardness of the reinforced ceramic composite material prepared from the surface-modified cubic boron nitride powder is increased from 15.54GPa to 17.73GPa, and the fracture toughness is increased from 4.5MPa m 1/2 Rise to 5.02MPa m 1/2 The tool cutting life was extended 184s from 150 s.
Application example 6
The surface modified cubic boron nitride powder and the unmodified cubic boron nitride powder prepared in the example 6 are respectively mixed with a ceramic material matrix material Al 2 O 3 And Y 2 O 3 And performing roller ball milling and mixing, performing rotary evaporation and drying, then putting the mixture into a graphite die with the diameter of 20mm, and putting the graphite die into a discharge plasma high-temperature furnace for sintering to obtain the reinforced ceramic composite material.
Preparation of surface modified cubic boron nitride powderCompared with the reinforced ceramic composite material prepared from the unmodified cubic boron nitride powder, the hardness of the strong ceramic composite material is increased from 15.54GPa to 17.04GPa, and the fracture toughness is increased from 4.5MPa m 1/2 Up to 4.66MPa m 1/2 The tool life was extended from 150s to 176s.
Application example 7
The surface-modified cubic boron nitride powder and the unmodified cubic boron nitride powder obtained in example 7 were mixed with Al, a ceramic material substrate material, respectively 2 O 3 And Y 2 O 3 And performing roller ball milling and mixing, performing rotary evaporation and drying, then putting the mixture into a graphite die with the diameter of 20mm, and putting the graphite die into a discharge plasma high-temperature furnace for sintering to obtain the reinforced ceramic composite material.
Compared with the reinforced ceramic composite material prepared from the unmodified cubic boron nitride powder, the hardness of the reinforced ceramic composite material prepared from the surface-modified cubic boron nitride powder is increased from 15.54GPa to 17.12GPa, and the fracture toughness is increased from 4.5MPa m 1/2 Rise to 5.41MPa m 1/2 The tool cutting life was extended from 150s to 179s.
The ceramic composite material prepared by the surface modified cubic boron nitride powder can improve the bonding strength between a ceramic matrix and cubic boron nitride, inhibit the surface phase change of cubic boron nitride particles and improve the mechanical property and the wear resistance of the composite material. The hardness of the reinforced ceramic composite material prepared by the surface modified cubic boron nitride powder is more than 17GPa, and the fracture toughness is 4.62MPa 1/2 Above, the maximum value can reach 5.56MPa m 1/2 (ii) a The cutting life of the cutter is prolonged to more than 176 s; the maximum value can be prolonged to 210s, and the preparation method can be applied to the preparation of wear-resistant and corrosion-resistant parts such as bearings, high-speed cutting tools, aerospace and marine equipment and the like.
The above embodiments are only for the purpose of facilitating understanding of the method and the core idea of the present invention, but the embodiments of the present invention are not limited by the above embodiments and application examples, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent substitutions and shall be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of surface modified cubic boron nitride powder is characterized by comprising the following specific steps:
s1, mixing cubic boron nitride powder and nano TiO 2 Adding the powder and the C powder into a coating machine for stirring, and placing the powder and the C powder into a vibration screening machine for vibration to obtain the nano TiO subjected to plastic deformation 2 Powder and C powder are mixed and coated with cubic boron nitride powder;
s2, placing the coated cubic boron nitride powder in a boron nitride crucible, placing the boron nitride crucible in a tubular furnace or a vacuum sintering furnace, heating to 1250-1350 ℃ at a speed of 5-15 ℃/min under a nitrogen atmosphere, preserving heat for 1-3 h for heat treatment, cooling to 600-800 ℃ at a speed of 5-15 ℃/min, and then cooling with the furnace to prepare surface modified cubic boron nitride powder; the surface modified cubic boron nitride powder is of a core-shell structure in which TiN particles are adhered to the cubic boron nitride powder, the particle size of the TiN particles is 20-300nm, and the layer thickness of the shell TiN is 20-90 nm.
2. The method according to claim 1, wherein the TiO nanoparticles are used in step S1 to prepare the surface-modified cubic boron nitride powder 2 The powder is anatase type TiO 2 Powder; the C powder is graphite powder, carbon powder or carbon black; the cubic boron nitride and the nano TiO 2 The purity of the powder C and the powder C is more than 97 percent; the grain diameter of the cubic boron nitride is 1-10 mu m, and the nano TiO 2 The grain diameters of the powder and the powder C are both 20-50 nm.
3. The method of claim 1, wherein the step S1 comprises subjecting the cubic boron nitride or nano TiO powder to a reaction 2 The mass ratio of the powder to the C powder is (90-98): (2-10): 0.47-3.33).
4. The method for preparing surface-modified cubic boron nitride powder according to claim 1, wherein the rotation speed of the stirring in step S1 is 2500 to 3000r/min, and the stirring time is 10 to 20min.
5. The method according to claim 1, wherein the coated cubic boron nitride powder in step S1 is plastically deformed nano TiO 2 The powder and the C powder are adhered to the surface of the cubic boron nitride powder to form a coating layer, and the thickness of the coating layer is 20-70 nm.
6. The method according to claim 1, wherein the vibration amplitude in step S1 is 1000 to 1400r/min, and the vibration time is 20 to 60min.
7. A surface-modified cubic boron nitride powder, characterized in that the surface-modified cubic boron nitride powder is prepared by the method of any one of claims 1 to 6.
8. A reinforced ceramic composite material, characterized in that the ceramic composite material is prepared by mixing the surface-modified cubic boron nitride powder of claim 7 with a ceramic powder.
9. The reinforced ceramic composite of claim 8, wherein the ceramic powder is Al 2 O 3 、Si 3 N 4 AlN or SiAlON.
10. Use of the reinforced ceramic composite material of claim 8 or 9 in bearings, high speed cutting tools or aerospace wear and corrosion resistant components.
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