CN115093233A - Preparation method of high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production - Google Patents
Preparation method of high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production Download PDFInfo
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Abstract
A preparation method of high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production relates to a preparation method of high-entropy ceramic powder. The invention aims to solve the problems that the existing preparation method of the high-entropy ceramic powder of the transition refractory metal carbon (nitrogen) compound generally has one or more defects of high raw material cost, complex process, poor dispersibility of a synthesized product, large granularity, low purity, low yield and the like. The method comprises the following steps: firstly, weighing materials; secondly, preparing slurry; thirdly, ball milling and mixing; fourthly, spray drying; fifthly, carbothermal reduction nitridation. The high-purity superfine transition metal carbonitride high-entropy ceramic powder prepared by the invention is suitable for industrial mass production, the particle size distribution is uniform, the grain size is small (200-400nm), and the carbon: a nitrogen ratio of about (7-3) to (3-7), and an oxygen content of 0.26 wt.% to 0.36 wt.%.
Description
Technical Field
The invention relates to a preparation method of high-entropy ceramic powder.
Background
The transition refractory metal carbide and nitride have excellent performances such as ultrahigh hardness, melting point, corrosion resistance and the like, are widely applied to extreme environments such as cutting processing, aerospace, nuclear energy and the like, but the single-component ceramic material cannot meet the use requirement along with the continuous improvement of the requirement on stable service under the extreme conditions. The design and research thought of the high-entropy alloy provides a new thought for expanding a multi-element high-entropy solid solution material system of the transition group refractory metal carbide and nitride, and the transition group refractory metal carbide (nitride) high-entropy ceramic draws great attention of researchers since 2016 research results of oxide high-entropy ceramic are published.
At present, the preparation method of the transition group refractory metal carbon (nitrogen) compound high-entropy ceramic powder mainly comprises the following steps: (1) transition metal carbide (nitride) is used as a raw material, and the high-temperature solid-phase synthesis method is adopted for preparation; (2) transition metal simple substance is used as raw material, and the direct carbonization (nitridation) method is adopted for preparation; (3) the transition metal chloride is used as a raw material and is prepared by adopting a liquid-phase precursor synthesis method. The preparation method usually has one or more of the disadvantages of high raw material cost, complex process, poor dispersibility of the synthesized product, large granularity, low purity, lower yield (rate) and the like, thereby limiting the industrial scale production of the product.
Disclosure of Invention
The invention aims to solve the problems that the existing preparation method of the high-entropy ceramic powder of the transition metal carbon (nitrogen) compound is generally one or more of high raw material cost, complex process, poor dispersibility of a synthesized product, large granularity, low purity, low yield and the like, and provides the preparation method of the high-purity ultrafine transition metal carbon nitride high-entropy ceramic powder suitable for industrial mass production.
A preparation method of high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production is specifically completed according to the following steps:
firstly, weighing materials:
according to the chemical formula (A) 0.2 B 0.2 C 0.2 D 0.2 E 0.2 )(C x N 1-x ) Weighing the transition metal oxide according to the molar ratio, and then weighing the carbon black to obtain a raw material;
the chemical formula (A) in the step one 0.2 B 0.2 C 0.2 D 0.2 E 0.2 )(C x N 1-x ) Wherein A, B, C, D and E are respectively one element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W;
the chemical formula (A) described in the step one 0.2 B 0.2 C 0.2 D 0.2 E 0.2 )(C x N 1-x ) Wherein the value range of x is more than 0 and less than 1;
secondly, preparing slurry:
preparing the raw materials into slurry by using absolute ethyl alcohol;
thirdly, ball milling and mixing:
ball-milling and mixing the slurry by adopting a roller ball-milling or stirring ball-milling mode to obtain ball-milled slurry;
fourthly, spray drying:
carrying out spray drying on the ball-milled slurry under the protection of nitrogen atmosphere to obtain mixed powder;
fifthly, carbothermic reduction nitridation:
placing the mixed powder in an atmosphere furnace, vacuumizing to below 50Pa, starting heating, heating to 1400-1800 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature at 1400-1800 ℃ for 1-3 h, heating to 1500-1900 ℃, introducing nitrogen into the atmosphere furnace, controlling the nitrogen flow rate at 0.5-5.5L/min, keeping the temperature under flowing nitrogen for 1-3 h, and cooling to room temperature along with the furnace to obtain the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro production.
The principle of the invention is as follows:
the invention aims to provide a preparation method of high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro-production, and the powder is suitable for being used as a basic raw material of cutting tool materials, ultrahigh-temperature thermal protection materials, coating materials in fusion environment and the like; the preparation method provided by the invention is characterized in that a mixed raw material of transition metal oxide and carbon black is prepared by adopting a spray drying method under the protection of a nitrogen atmosphere, superfine high-purity transition metal carbonitride high-entropy ceramic powder is prepared by a two-step carbothermic nitridation method, namely, on the basis of the one-step carbothermic nitridation method, carbothermic reduction and nitridation reaction are carried out by two steps, wherein the furnace in the first stage is in high vacuum to reduce the temperature of the carbothermic reduction reaction, prevent the aggregation and growth of particles, and carry out nitridation treatment at a relatively higher temperature in the second stage; the method has the advantages of low cost of raw materials, simple process, small grain size of the obtained ceramic powder, high purity, extremely low oxygen content and controllable nitrogen content, and is suitable for large-scale industrial production.
The invention has the following beneficial effects:
firstly, preparing high-purity superfine transition metal carbonitride high-entropy ceramic powder by adopting a two-step carbothermic reduction nitridation method, and regulating and controlling the proportion of C and N by regulating nitridation temperature and nitridation time;
secondly, the mixed powder of the transition metal oxide and the carbon black is obtained by adopting a spray drying method under the protection of nitrogen atmosphere, so that the impurity content is favorably reduced, the mixing uniformity of the transition metal oxide and the carbon black in the raw material powder is improved, the contact area of the transition metal oxide and the carbon black is increased, the diffusion distance of atoms in the subsequent carbothermic reduction nitridation process is reduced, the reaction temperature is reduced, the heat preservation time is shortened, and the aggregation and growth of particles are reduced;
the method adopts a two-step method to prepare the transition metal carbonitride high-entropy ceramic powder, and the prepared transition metal carbonitride high-entropy ceramic powder has small particle size, uniform distribution, high purity, extremely low oxygen content and controllable nitrogen content, and is suitable for serving as a basic raw material of cutter materials, ultrahigh temperature thermal protection materials, coating materials in fusion environments and the like;
fourthly, the high-purity superfine transition metal carbonitride high-entropy ceramic powder prepared by the method is suitable for industrial mass production, the particle size distribution is uniform, the grain size is small (200-400nm), and the carbon: a nitrogen ratio of about (7-3) to (3-7), and an oxygen content of 0.26 wt.% to 0.36 wt.%.
Drawings
FIG. 1 is an SEM photograph of a transition metal carbonitride high-entropy ceramic powder prepared in example 1;
FIG. 2 is an XRD spectrum of the transition metal carbonitride high-entropy ceramic powder prepared in example 1;
FIG. 3 is an SEM photograph of the transition metal carbonitride high-entropy ceramic powder prepared in example 2;
FIG. 4 is an XRD spectrum of the transition metal carbonitride high entropy ceramic powder prepared in example 2;
FIG. 5 is an SEM photograph of the transition metal carbonitride high-entropy ceramic powder prepared in example 3;
FIG. 6 is an XRD spectrum of the transition metal carbonitride high entropy ceramic powder prepared in example 3.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment of the invention relates to a preparation method of high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production, which is specifically completed according to the following steps:
firstly, weighing materials:
according to the chemical formula (A) 0.2 B 0.2 C 0.2 D 0.2 E 0.2 )(C x N 1-x ) Weighing the transition metal oxide according to the molar ratio, and then weighing the carbon black to obtain a raw material;
the chemical formula (A) in the step one 0.2 B 0.2 C 0.2 D 0.2 E 0.2 )(C x N 1-x ) A, B, C, D and E are respectively one element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W;
the chemical formula (A) described in the step one 0.2 B 0.2 C 0.2 D 0.2 E 0.2 )(C x N 1-x ) Wherein the value range of x is more than 0 and less than 1;
secondly, preparing slurry:
preparing the raw materials into slurry by using absolute ethyl alcohol;
thirdly, ball milling and mixing:
ball-milling and mixing the slurry by adopting a roller ball-milling or stirring ball-milling mode to obtain ball-milled slurry;
fourthly, spray drying:
carrying out spray drying on the ball-milled slurry under the protection of nitrogen atmosphere to obtain mixed powder;
fifthly, carbothermic reduction nitridation:
placing the mixed powder in an atmosphere furnace, vacuumizing to below 50Pa, starting heating, heating to 1400-1800 ℃ at a heating rate of 5-10 ℃/min, preserving heat at 1400-1800 ℃ for 1-3 h, then heating to 1500-1900 ℃, introducing nitrogen into the atmosphere furnace, controlling the nitrogen flow rate to be 0.5-5.5L/min, preserving heat under flowing nitrogen for 1-3 h, and cooling to room temperature along with the furnace to obtain the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro production.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the transition metal oxide in the step one is TiO 2 、ZrO 2 、HfO 2 、V 2 O 5 、Nb 2 O 5 、Ta 2 O 5 、Cr 2 O 3 、MoO 3 And WO 3 . Other steps are the same as in the first embodiment.
The third concrete implementation mode: the difference between this embodiment and the first or second embodiment is: TiO 2 2 、ZrO 2 、HfO 2 、V 2 O 5 、Nb 2 O 5 、Ta 2 O 5 、Cr 2 O 3 、MoO 3 And WO 3 The purity of the product is 99-99.99%, and the particle size is 0.1-2.0 μm. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode is as follows: the difference between this embodiment and one of the first to third embodiments is as follows: the purity of the carbon black in the step one is 99-99.99%, and the particle size is 0.1-10.0 μm. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode is as follows: the difference between this embodiment and one of the first to fourth embodiments is: the solid content of the slurry in the step two is 40-70%. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the grinding balls used in the ball milling mixing in the third step are hard alloy balls, the ball material ratio is 10:1, and the ball milling time is 12-48 h. The other steps are the same as those in the first to fifth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: the preparation method of the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production is completed according to the following steps:
firstly, weighing materials:
according to the formula:
2TiO 2 +V 2 O 5 +Nb 2 O 5 +Ta 2 O 5 +2MoO 3 +32C+3/2N 2 ＝10(Ti 0.2 V 0.2 Nb 0.2 Ta 0.2 Mo 0.2 )(C 0.7 N 0.3 ) +25CO, by reacting TiO 2 、V 2 O 5 、Nb 2 O 5 、Ta 2 O 5 、MoO 3 Weighing the carbon black and the carbon black according to the molar ratio of 2:1:1:2: 32 to obtain a raw material;
secondly, preparing slurry:
preparing raw materials into slurry with solid content of 50% by using absolute ethyl alcohol;
thirdly, ball milling and mixing:
ball-milling and mixing the slurry by adopting a roller ball-milling or stirring ball-milling mode to obtain ball-milled slurry;
the grinding balls used in the ball milling mixing in the third step are hard alloy balls, the ball material ratio is 10:1, the ball milling time is 24 hours, and the ball milling speed is 50 r/min;
fourthly, spray drying:
carrying out spray drying on the ball-milled slurry under the protection of nitrogen atmosphere to obtain mixed powder;
fifthly, carbothermic reduction nitridation:
and placing the mixed powder in an atmosphere furnace, vacuumizing the atmosphere furnace to below 50Pa, starting to heat, heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h at 1500 ℃, heating to 1600 ℃, introducing nitrogen into the atmosphere furnace, controlling the nitrogen flow rate to be 0.5L/min, preserving heat for 2h under flowing nitrogen, and cooling to room temperature along with the furnace to obtain the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro-production.
The high-purity ultrafine transition metal carbonitride high-entropy ceramic powder prepared in example 1 and suitable for industrial mass production has uniform particle size distribution, fine grain size (200-400nm), C: N ratio of about 7:3 and oxygen content of 0.36 wt.%.
FIG. 1 is an SEM photograph of a transition metal carbonitride high-entropy ceramic powder prepared in example 1;
as can be seen from FIG. 1, the grain size of the transition metal carbonitride high-entropy ceramic powder prepared in example 1 is about 200-400 nm.
FIG. 2 is an XRD spectrum of the transition metal carbonitride high-entropy ceramic powder prepared in example 1;
as can be seen from fig. 2, the transition metal carbonitride high-entropy ceramic powder prepared in example 1 has a single-phase face-centered cubic structure.
Example 2: the preparation method of the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production is completed according to the following steps:
firstly, weighing materials:
according to the formula:
2TiO 2 +V 2 O 5 +Nb 2 O 5 +2MoO 3 +2WO 3 +33C+3/2N 2 ＝10(Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )(C 0.7 N 0.3 ) +26CO, to TiO 2 、V 2 O 5 、Nb 2 O 5 、MoO 3 、WO 3 Weighing the carbon black and the carbon black according to the molar ratio of 2:1:1:2:2:33 to obtain a raw material;
II, preparing slurry:
preparing raw materials into slurry with solid content of 50% by using absolute ethyl alcohol;
thirdly, ball milling and mixing:
ball-milling and mixing the slurry by adopting a roller ball-milling or stirring ball-milling mode to obtain ball-milled slurry;
the grinding balls used in the ball milling mixing in the third step are hard alloy balls, the ball material ratio is 10:1, the ball milling time is 24 hours, and the ball milling speed is 50 r/min;
fourthly, spray drying:
carrying out spray drying on the ball-milled slurry under the protection of nitrogen atmosphere to obtain mixed powder;
fifthly, carbothermic reduction nitridation:
and placing the mixed powder in an atmosphere furnace, vacuumizing the atmosphere furnace to below 50Pa, starting heating, heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving the heat at 1500 ℃ for 1h, heating to 1600 ℃, introducing nitrogen into the atmosphere furnace, controlling the nitrogen flow rate to be 0.5L/min, preserving the heat for 2h under flowing nitrogen, and cooling to room temperature along with the furnace to obtain the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro production.
The high-purity ultra-fine transition metal carbonitride high-entropy ceramic powder prepared in example 2 and suitable for industrial mass production has uniform particle size distribution, fine grain size (200-400nm), C: N ratio of about 7:3 and oxygen content of 0.32 wt.%.
FIG. 3 is an SEM photograph of the transition metal carbonitride high-entropy ceramic powder prepared in example 2;
as can be seen from FIG. 3, the grain size of the transition metal carbonitride high-entropy ceramic powder prepared in example 2 is about 200-400 nm.
FIG. 4 is an XRD spectrum of the transition metal carbonitride high entropy ceramic powder prepared in example 2;
as can be seen from fig. 4, the transition metal carbonitride high-entropy ceramic powder prepared in example 2 has a single-phase face-centered cubic structure.
Example 3: the preparation method of the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production is completed according to the following steps:
firstly, weighing materials:
according to the formula:
2TiO 2 +V 2 O 5 +Nb 2 O 5 +Ta 2 O 5 +2MoO 3 +28C+7/2N 2 ＝10(Ti 0.2 V 0.2 Nb 0.2 Ta 0.2 Mo 0.2 )(C 0.3 N 0.7 ) +25CO, by reacting TiO 2 、V 2 O 5 、Nb 2 O 5 、Ta 2 O 5 、MoO 3 Weighing the carbon black and the carbon black according to the molar ratio of 2:1:1:1:2:28 to obtain a raw material;
secondly, preparing slurry:
preparing raw materials into slurry with solid content of 50% by using absolute ethyl alcohol;
thirdly, ball milling and mixing:
ball-milling and mixing the slurry by adopting a roller ball-milling or stirring ball-milling mode to obtain ball-milled slurry;
the grinding balls used in the ball milling mixing in the third step are hard alloy balls, the ball material ratio is 10:1, the ball milling time is 24 hours, and the ball milling speed is 50 r/min;
fourthly, spray drying:
carrying out spray drying on the ball-milled slurry under the protection of nitrogen atmosphere to obtain mixed powder;
fifthly, carbothermic reduction nitridation:
and placing the mixed powder in an atmosphere furnace, vacuumizing the atmosphere furnace to below 50Pa, starting heating, heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving the heat at 1500 ℃ for 1h, heating to 1600 ℃, introducing nitrogen into the atmosphere furnace, controlling the nitrogen flow rate to be 1.5L/min, preserving the heat for 3h under flowing nitrogen, and cooling to room temperature along with the furnace to obtain the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro production.
The high-purity superfine transition metal carbonitride high-entropy ceramic powder prepared in example 3 and suitable for industrial mass production has uniform particle size distribution, fine grain size (200-400nm), C: N ratio of about 3:7 and oxygen content of 0.32 wt.%.
FIG. 5 is an SEM photograph of the transition metal carbonitride high-entropy ceramic powder prepared in example 3;
as can be seen from FIG. 5, the grain size of the transition metal carbonitride high-entropy ceramic powder prepared in example 3 is about 200-400 nm.
Fig. 6 is an XRD spectrum of the transition metal carbonitride high-entropy ceramic powder prepared in example 3.
As can be seen from fig. 6, the transition metal carbonitride high-entropy ceramic powder prepared in example 3 has a single-phase face-centered cubic structure.
Example 4: the preparation method of the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production is completed according to the following steps:
firstly, weighing materials:
according to the formula:
2TiO 2 +V 2 O 5 +Nb 2 O 5 +2MoO 3 +2WO 3 +31C+5/2N 2 ＝10(Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )(C 0.5 N 0.5 ) +26CO, converting TiO 2 、V 2 O 5 、Nb 2 O 5 、MoO 3 、WO 3 Weighing the carbon black and the carbon black according to the molar ratio of 2:1:1:2:2:31 to obtain a raw material;
secondly, preparing slurry:
preparing raw materials into slurry with solid content of 50% by using absolute ethyl alcohol;
thirdly, ball milling and mixing:
ball-milling and mixing the slurry by adopting a roller ball-milling or stirring ball-milling mode to obtain ball-milled slurry;
the grinding balls used in the ball milling mixing in the third step are hard alloy balls, the ball material ratio is 10:1, the ball milling time is 24 hours, and the ball milling speed is 50 r/min;
fourthly, spray drying:
carrying out spray drying on the ball-milled slurry under the protection of nitrogen atmosphere to obtain mixed powder;
fifthly, carbothermic reduction nitridation:
and placing the mixed powder in an atmosphere furnace, vacuumizing the atmosphere furnace to below 50Pa, starting heating, heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving the heat at 1500 ℃ for 1h, heating to 1600 ℃, introducing nitrogen into the atmosphere furnace, controlling the nitrogen flow rate to be 1L/min, preserving the heat under flowing nitrogen for 3h, and cooling to room temperature along with the furnace to obtain the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro-production.
The high-purity ultra-fine transition metal carbonitride high-entropy ceramic powder prepared in example 4 and suitable for industrial mass production has uniform particle size distribution, fine grain size (200-400nm), C: N ratio of about 5:5 and oxygen content of 0.29 wt.%.
Example 5: the present example is different from example 1 in that: in the first step, according to a formula: 2TiO 2 2 +2ZrO 2 +2HfO 2 +Nb 2 O 5 +Ta 2 O 5 +29C+3/2N 2 ＝10(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 )(C 0.7 N 0.3 )+22CO，TiO 2 、ZrO 2 、HfO 2 、Nb 2 O 5 、Ta 2 O 5 And carbon black are weighed according to the molar ratio of 2:2:2:1:1:29 to obtain the raw material. The other steps and parameters were the same as in example 1.
The high-purity ultra-fine transition metal carbonitride high-entropy ceramic powder prepared in example 5 and suitable for industrial mass production has uniform particle size distribution, fine grain size (200-400nm), C: N ratio of about 7:3 and oxygen content of 0.34 wt.%.
Example 6: the present embodiment is different from embodiment 1 in that: in the first step, according to a formula: 2TiO 2 2 +2ZrO 2 +2HfO 2 +V 2 O 5 +Ta 2 O 5 +29C+3/2N 2 ＝10(Ti 0.2 Zr 0.2 Hf 0.2 V 0.2 Ta 0.2 )(C 0.7 N 0.3 ) +22CO, to TiO 2 、ZrO 2 、HfO 2 、V 2 O 5 、Ta 2 O 5 And carbon black are weighed according to the molar ratio of 2:2:2:1:1:29 to obtain the raw material. The other steps and parameters were the same as in example 1.
The high-purity superfine transition metal carbonitride high-entropy ceramic powder prepared in example 6 and suitable for industrial mass production has uniform particle size distribution, fine grain size (200-400nm), C: N ratio of about 7:3 and oxygen content of 0.26 wt.%.
Example 7: the present example is different from example 1 in that: in the first step, according to a formula: 2TiO 2 2 +2ZrO 2 +2HfO 2 +V 2 O 5 +Nb 2 O 5 +29C+3/2N 2 ＝10(Ti 0.2 Zr 0.2 Hf 0.2 V 0.2 Nb 0.2 )(C 0.7 N 0.3 ) +22CO, to TiO 2 、ZrO 2 、HfO 2 、V 2 O 5 、Nb 2 O 5 And carbon black are weighed according to the molar ratio of 2:2:2:1:1:29 to obtain the raw material. The other steps and parameters were the same as in example 1.
The high-purity ultra-fine transition metal carbonitride high-entropy ceramic powder prepared in example 7 and suitable for industrial mass production has uniform particle size distribution, fine grain size (200-400nm), C: N ratio of about 7:3, and oxygen content of 0.28 wt.%.
Claims (6)
1. A preparation method of high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production is characterized by comprising the following steps:
firstly, weighing materials:
according to the chemical formula (A) 0.2 B 0.2 C 0.2 D 0.2 E 0.2 )(C x N 1-x ) Weighing the transition metal oxide according to the molar ratio, and then weighing the carbon black to obtain a raw material;
the chemical formula (A) in the step one 0.2 B 0.2 C 0.2 D 0.2 E 0.2 )(C x N 1-x ) Wherein A, B, C, D and E are respectively one element of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W;
the chemical formula (A) described in the step one 0.2 B 0.2 C 0.2 D 0.2 E 0.2 )(C x N 1-x ) Wherein the value range of x is more than 0 and less than 1;
secondly, preparing slurry:
preparing the raw materials into slurry by using absolute ethyl alcohol;
thirdly, ball-milling and mixing:
ball-milling and mixing the slurry by adopting a roller ball-milling or stirring ball-milling mode to obtain ball-milled slurry;
fourthly, spray drying:
carrying out spray drying on the ball-milled slurry under the protection of nitrogen atmosphere to obtain mixed powder;
fifthly, carbothermic reduction nitridation:
placing the mixed powder in an atmosphere furnace, vacuumizing to below 50Pa, starting heating, heating to 1400-1800 ℃ at a heating rate of 5-10 ℃/min, preserving heat at 1400-1800 ℃ for 1-3 h, then heating to 1500-1900 ℃, introducing nitrogen into the atmosphere furnace, controlling the nitrogen flow rate to be 0.5-5.5L/min, preserving heat under flowing nitrogen for 1-3 h, and cooling to room temperature along with the furnace to obtain the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro production.
2. The method for preparing high-purity ultra-fine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro production according to claim 1, wherein the transition metal oxide in the first step is TiO 2 、ZrO 2 、HfO 2 、V 2 O 5 、Nb 2 O 5 、Ta 2 O 5 、Cr 2 O 3 、MoO 3 And WO 3 。
3. A method as claimed in claim 2The preparation method of the high-purity superfine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production is characterized in that the method is characterized in that TiO 2 、ZrO 2 、HfO 2 、V 2 O 5 、Nb 2 O 5 、Ta 2 O 5 、Cr 2 O 3 、MoO 3 And WO 3 The purity of the product is 99-99.99%, and the grain diameter is 0.1-2.0 μm.
4. The method for preparing high-purity ultrafine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro production according to claim 1, wherein the carbon black in the first step has a purity of 99-99.99% and a particle size of 0.1-10.0 μm.
5. The method for preparing high-purity ultra-fine transition metal carbonitride high-entropy ceramic powder suitable for industrial mass production according to claim 1, characterized in that the solid content of the slurry in the second step is 40-70%.
6. The method for preparing high-purity ultrafine transition metal carbonitride high-entropy ceramic powder suitable for industrial macro production according to claim 1, wherein the grinding balls used in the ball milling mixing in the third step are hard alloy balls, the ball-material ratio is 10:1, and the ball milling time is 12-48 h.
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| CN115838291A (en) * | 2022-10-26 | 2023-03-24 | 山东大学 | Method for rapidly synthesizing high-entropy carbonitride ceramic powder by adopting microwaves |
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