CN113292343A - Method for preparing boron carbide-based multiphase ceramic through in-situ reaction pressureless sintering - Google Patents
Method for preparing boron carbide-based multiphase ceramic through in-situ reaction pressureless sintering Download PDFInfo
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Abstract
The invention provides a method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering, which comprises the steps of taking boron carbide, a transition metal simple substance Me, phenolic resin and a dispersing agent as raw materials, and performing ball milling, mixing, heating, rotating and drying to obtain precursor powder; and then, granulating the precursor powder, and carrying out dry pressing forming to obtain a ceramic green body, heating to 2100-2300 ℃ at the speed of 5-20 ℃/min in the atmosphere of argon protective gas, keeping the temperature for 0.5-2 h, and cooling to room temperature by circulating water to obtain the in-situ growth second-phase toughened boron carbide-based multiphase ceramic. In addition, the product prepared by the preparation method is also disclosed. The invention has simple process and low cost, and adopts pressureless sintering for in-situ synthesis of MeB2The toughening phase is dispersed and uniformly distributed, and has good combination with the interface of the boron carbide matrix and a microstructureUniform, high density, excellent comprehensive mechanical property and suitability for industrial mass production.
Description
Technical Field
The invention belongs to the field of preparation of structural ceramic materials, and particularly relates to a boron carbide-based ceramic material synthesized by using a transition metal simple substance and boron carbide powder as raw materials and adopting an in-situ reaction pressureless sintering method.
Background
The boron carbide is called black diamond, is a superhard material with the hardness of secondary diamond and cubic boron nitride, has the high-temperature hardness of more than 30GPa, and is better than the high-temperature hardness of diamond and cubic boron nitride. Boron carbide has many properties suitable for technical applications, such as high melting point (2447 ℃), high Young's modulus (450 ℃) 470GPa, low density (2.52g/cm3), chemical neutrality, excellent electrical and thermal properties, etc. And the boron carbide material has low price, rich raw material sources and easy treatment of waste materials. Boron carbide has many excellent characteristics and can keep a good state under extreme conditions, so that the boron carbide is widely used in high precision fields such as military affairs, nuclear reaction, aerospace and the like. For example, the characteristics of high hardness and low density make the material have unique advantages when being used for manufacturing bulletproof vests, light armors, space engines and other materials; the characteristics of ultrahigh hardness and excellent wear resistance make the material become the first choice for manufacturing wear-resistant materials such as a sand blasting nozzle, a nozzle of a cutter, a cutting tool, industrial abrasive and the like.
However, since the content of covalent bonds in boron carbide is very high and only at 2000 ℃ or higher does boron carbide grain boundary and volume diffusion occur to accelerate densification, the fracture toughness of single-phase boron carbide is low (2.2MPa · m)1/2) And sintering densification is extremely difficult. This has limited its industrial application to some extent. In order to solve the problems of densification and strengthening and toughening of boron carbide, researchers often utilize additives to promote sintering of boron carbide and enhance the comprehensive mechanical properties of the material through second phase toughening. Common toughening modes include fiber toughening, layered material toughening and particle toughening. Compared with the former two, the toughening of the particles is easier to ensure that the second phase particles are uniformly dispersed in the matrix and are more tightly combined with the matrix.
The existing research shows that the addition of transition metal and compounds thereof in boron carbide is beneficial to realizing the densification and the strengthening and toughening of the boron carbide, wherein the compounds comprise carbide, boride, oxide and the like. However, the carbide reacts to leave graphite in the matrix, resulting in a decrease in hardness; boride does not have in-situ reaction and has poor bonding degree with a matrix; the gas generated by the reaction of the oxide can not be discharged in time at the crystal boundary, so that the density of the material is reduced. Therefore, it is a key technical problem to find an additive which reacts in situ and does not generate harmful substances. In addition, the boron carbide-based complex phase ceramic sintering process with high density and good comprehensive mechanical properties is usually hot-pressing sintering or electric spark plasma sintering, and the sintering modes have high cost and complex requirements on a mold, cannot be applied to large-scale production, and cannot realize batch production in industrial application.
Disclosure of Invention
The invention aims to solve the problems of difficult densification, poor fracture toughness, complex sintering mode, high preparation cost and the like of boron carbide ceramics, provides the high-performance boron carbide-based complex-phase ceramics with uniformly dispersed second phase and uniform size, realizes sintering densification, well combines the second-phase transition metal boride generated in situ with a matrix to play a toughening and reinforcing role, and improves the mechanical property of the boron carbide-based complex-phase ceramics from the aspects of chemical bond energy and bonding energy. The invention adopts a sintering mode with simple and convenient operation, low production cost and high efficiency, and has great industrial application value.
The purpose of the invention is realized as follows:
a method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering comprises the following steps:
(1) ball milling: according to the molar ratio of B4Carrying out wet ball milling and mixing on boron carbide, a transition metal simple substance, phenolic resin and a dispersing agent by taking absolute ethyl alcohol as a medium, wherein the ratio of C to Me is 20: 1-4, and further obtaining precursor slurry;
(2) and (3) drying: heating and rotary drying the precursor slurry by using a rotary evaporation dryer, and sieving to obtain precursor powder;
(3) and (3) granulation: granulating and sieving the precursor powder through a dry granulation tower;
(4) molding: placing the screened powder into a die, prepressing and forming by using a press machine, and demoulding to obtain a ceramic green body;
(5) and (3) sintering: and (3) placing the ceramic green body in a graphite tray, placing the tray in a pressureless sintering furnace, heating to 2100-2300 ℃ at the speed of 5-20 ℃/min under the atmosphere of argon gas as protective gas in the furnace, keeping the temperature for 0.5-2 h, and cooling to room temperature by circulating water to obtain the transition metal element in-situ toughened boron carbide-based multiphase ceramic prepared by in-situ growth.
The dosage of the sintering aid phenolic resin in the step (1) is 1-5 wt% of boron carbide; the amount of the added dispersant sodium tripolyphosphate is 10-20 wt% of the transition metal simple substance. The rotating speed of ball milling is 200-400 r/min, the ball-material ratio is 20:1, the ball milling time is 12-24 h, the adopted ball material is tungsten carbide, and the ball milling tank material is hard alloy.
And (3) continuously heating and rotationally drying the precursor slurry in the step (2) at the water bath temperature of 60-90 ℃ for 2-8 h.
The granulation conditions in the step (3) are as follows: the inlet temperature is 150-300 ℃, the outlet temperature is 80-150 ℃, and the feeding rate is 2-8 kg/h; sieving the dried particles, and selecting the particles with the particle size of less than or equal to 50 mu m for the next operation;
the pressure condition in the step (4) is 50-200 MPa;
the product phase is composed of B4C matrix and MeB2(Me is a transition metal element such as Ti, Zr, Nb, Ta or W) second phase crystal grains having an average size of about 2 to 5 μm, and MeB2The second phase toughening crystal grains are uniformly and dispersedly distributed in the boron carbide matrix.
Compared with the prior art, the invention has the beneficial effects that:
(1) the transition metal simple substance selected by the invention reacts with the boron carbide matrix in situ during sintering to generate a second phase boride MeB2(Me is transition metal element such as Ti, Zr, Nb, Ta or W), not only can be tightly combined with the matrix, but also can avoid the generation of harmful substances which reduce the performance, and ensure the generated B4C-MeB2The complex phase ceramic has the characteristics of high tissue uniformity and good mechanical property.
(2) According to the invention, ethanol is added as a medium to perform wet ball milling on the powder, so that the uniform distribution of all substances in the precursor is ensured, and the occurrence of agglomeration and caking in the traditional dry milling method is effectively overcome. Meanwhile, compared with the drying box for directly drying the precursor slurry, the rotary evaporator can effectively overcome segregation.
(3) The sintering process selected by the invention is pressureless sintering, and has the main advantages of low cost, simple operation, capability of preparing products with complex shapes, high production efficiency and suitability for large-scale production. The boron carbide-based complex phase ceramic prepared by using the transition metal simple substance under the pressureless condition has high density and good mechanical property, and the prepared product can be practically applied in the industrial field.
The generation of the second-phase boride in the invention has a remarkable effect on toughening of boron carbide and maintains the original characteristics of high hardness and high bending strength of boron carbide. The prepared boron carbide-based complex phase ceramic has a mixed fracture mode of transgranular fracture and intergranular fracture, and the second phase particles effectively block crack propagation, are distributed in a matrix in a fine and dispersed manner, play a role in pinning, and enable cracks to have deflection, bridging, bifurcation and other phenomena. The invention overcomes the defect of poor toughness of the traditional ceramic material, and the prepared boron carbide-based multiphase ceramic has excellent mechanical property, the Vickers hardness of 27-32 GPa, the bending strength of 480-650 MPa and the fracture toughness of 7-9 MPa.m1/2。
Drawings
FIG. 1 is an XRD pattern of a boron carbide-based complex phase ceramic prepared according to an embodiment of the present invention;
FIG. 2 is an SEM plan view of a boron carbide-based composite ceramic prepared according to an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1:
a method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering by using transition metal simple substances comprises the following steps:
(1) ball milling: weighing boron carbide powder (the particle size is less than or equal to 2 microns and the purity is 99.5%) and titanium powder (the particle size is less than or equal to 5 microns and the purity is 99.5%) in a molar ratio of 20:1, phenolic resin with the mass of 5 wt% of the boron carbide powder and sodium tripolyphosphate with the mass of 10 wt% of the titanium powder, taking absolute ethyl alcohol (the purity is 99.7%) with the total mass of the substances as a medium, adding the medium into a high-energy ball milling tank, and carrying out ball milling and mixing at the rotating speed of 400r/min for 18 hours to obtain precursor slurry;
(2) and (3) drying: pouring the precursor slurry into a rotary evaporation dryer, continuously heating and rotationally drying for 6 hours at the water bath temperature of 60 ℃, and sieving by a 120-mesh sieve to obtain precursor powder;
(3) and (3) granulation: granulating and sieving the precursor powder through a dry granulation tower; the granulation conditions were: the inlet temperature was 230 ℃, the outlet temperature was 118 ℃ and the feed rate was 5 kg/h; sieving the dried particles, and selecting the particles with the particle size of 10-40 mu m for the next operation;
(4) molding: placing the screened powder into a die, performing pre-pressing molding under the pressure of 150MPa by using a press machine, and demolding to obtain a ceramic green body;
(5) and (3) sintering: and placing the ceramic green body in a graphite tray, placing the tray in a pressureless sintering furnace, heating to 2150 ℃ at the speed of 20 ℃/min, keeping the temperature for 1h, wherein the atmosphere of protective gas in the furnace is argon, and the introduced argon is argon flow of 1.5 Pa. Cooling the mixture to room temperature by circulating water to obtain the transition metal in-situ toughened boron carbide-based multiphase ceramic prepared by in-situ growth.
(6) The average size of the second phase particles was 3.5 μm; the final product is tested for mechanical property, the hardness is 30.2GPa, the bending strength is 485MPa, and the fracture toughness is 7.8 MPa.m1/2。
Example 2:
a method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering by using transition metal simple substances comprises the following steps:
(1) ball milling: weighing boron carbide powder (the particle size is less than or equal to 2 microns and the purity is 99.5%) and titanium powder (the particle size is less than or equal to 5 microns and the purity is 99.5%) in a molar ratio, phenolic resin with the mass of 5 wt% of the boron carbide powder and sodium tripolyphosphate with the mass of 10 wt% of the titanium powder, taking absolute ethyl alcohol (the purity is 99.7%) with the total mass of the substances as a medium, adding the medium into a high-energy ball milling tank, and carrying out ball milling and mixing at the rotating speed of 400r/min for 18h to obtain precursor slurry;
(2) and (3) drying: pouring the precursor slurry into a rotary evaporation dryer, continuously heating and rotationally drying for 6 hours at the water bath temperature of 60 ℃, and sieving by a 120-mesh sieve to obtain precursor powder;
(3) and (3) granulation: granulating and sieving the precursor powder through a dry granulation tower; the granulation conditions were: the inlet temperature was 230 ℃, the outlet temperature was 118 ℃ and the feed rate was 5 kg/h; sieving the dried particles, and selecting the particles with the particle size of 10-40 mu m for the next operation;
(4) molding: placing the screened powder into a die, performing pre-pressing molding under the pressure of 150MPa by using a press machine, and demolding to obtain a ceramic green body;
(5) and (3) sintering: and placing the ceramic green body in a graphite tray, placing the tray in a pressureless sintering furnace, heating to 2100 ℃ at the speed of 20 ℃/min, keeping the temperature for 1h, wherein the atmosphere of protective gas in the furnace is argon, and the introduced argon is argon flow of 1.5 Pa. Cooling the mixture to room temperature by circulating water to obtain the transition metal in-situ toughened boron carbide-based multiphase ceramic prepared by in-situ growth.
(6) The average size of the second phase particles was 4.4 μm; the final product is tested for mechanical property, the hardness is 27.4GPa, the bending strength is 541MPa, and the fracture toughness is 8.9 MPa.m1/2。
Example 3:
a method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering by using transition metal simple substances comprises the following steps:
(1) ball milling: weighing boron carbide powder (the particle size is less than or equal to 2 microns and the purity is 99.5%) and zirconium powder (the particle size is less than or equal to 5 microns and the purity is 99.5%) in a molar ratio of 10:1, phenolic resin with the mass of 5 wt% of the boron carbide powder, sodium tripolyphosphate with the mass of 10 wt% of the zirconium powder, and adding absolute ethyl alcohol (the purity is 99.7%) with the total mass of the substances as a medium into a high-energy ball milling tank to perform ball milling and mixing at the rotating speed of 400r/min for 20 hours to obtain precursor slurry;
(2) and (3) drying: pouring the precursor slurry into a rotary evaporation dryer, continuously heating and rotationally drying for 6 hours at the water bath temperature of 60 ℃, and sieving by a 120-mesh sieve to obtain precursor powder;
(3) and (3) granulation: granulating and sieving the precursor powder through a dry granulation tower; the granulation conditions were: the inlet temperature was 230 ℃, the outlet temperature was 120 ℃ and the feed rate was 5 kg/h; sieving the dried particles, and selecting the particles with the particle size of 10-40 mu m for the next operation;
(4) molding: placing the screened powder into a die, performing pre-pressing molding under the pressure of 150MPa by using a press machine, and demolding to obtain a ceramic green body;
(5) and (3) sintering: and placing the ceramic green body in a graphite tray, placing the tray in a pressureless sintering furnace, heating to 2150 ℃ at the speed of 20 ℃/min, keeping the temperature for 1h, wherein the atmosphere of protective gas in the furnace is argon, and the introduced argon is argon flow of 1.3 Pa. Cooling the mixture to room temperature by circulating water to obtain the transition metal in-situ toughened boron carbide-based multiphase ceramic prepared by in-situ growth.
(6) The average size of the second phase particles was 2.8 μm; the final product is tested for mechanical property, the hardness is 28.7GPa, the bending strength is 584MPa, and the fracture toughness is 7.3 MPa.m1/2。
Example 4:
a method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering by using transition metal simple substances comprises the following steps:
(1) ball milling: weighing boron carbide powder (the particle size is less than or equal to 2 microns and the purity is 99.5%) and niobium powder (the particle size is less than or equal to 5 microns and the purity is 99.5%) in a molar ratio of 20:1, phenolic resin with the mass of 5 wt% of the boron carbide powder and sodium tripolyphosphate with the mass of 20 wt% of the niobium powder, taking absolute ethyl alcohol (the purity is 99.7%) with the same total mass as the above substances as a medium, adding the medium into a high-energy ball milling tank, and carrying out ball milling and mixing at the rotating speed of 400r/min for 24 hours to obtain precursor slurry;
(2) and (3) drying: pouring the precursor slurry into a rotary evaporation dryer, continuously heating and rotationally drying for 6 hours at the water bath temperature of 60 ℃, and sieving by a 120-mesh sieve to obtain precursor powder;
(3) and (3) granulation: granulating and sieving the precursor powder through a dry granulation tower; the granulation conditions were: the inlet temperature was 250 ℃, the outlet temperature was 120 ℃ and the feed rate was 5 kg/h; sieving the dried particles, and selecting the particles with the particle size of 10-40 mu m for the next operation;
(4) molding: placing the screened powder into a die, prepressing and molding the powder under the pressure of 200MPa by using a press machine, and demolding to obtain a ceramic green body;
(5) and (3) sintering: and (3) placing the ceramic green body in a graphite tray, placing the tray in a pressureless sintering furnace, heating to 2250 ℃ at the speed of 20 ℃/min, keeping the temperature for 2h, wherein the atmosphere of protective gas in the furnace is argon, and the introduced argon is argon flow of 1.5 Pa. Cooling the mixture to room temperature by circulating water to obtain the transition metal in-situ toughened boron carbide-based multiphase ceramic prepared by in-situ growth.
(6) The average size of the second phase particles was 2.2 μm; the final product is tested for mechanical property, the hardness is 30.7GPa, the bending strength is 623MPa, and the fracture toughness is 9.4 MPa.m1/2。
Example 5:
a method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering by using transition metal simple substances comprises the following steps:
(1) ball milling: weighing boron carbide powder (the particle size is less than or equal to 2 microns and the purity is 99.5%) and tantalum powder (the particle size is less than or equal to 5 microns and the purity is 99.5%) in a molar ratio of 20:3, phenolic resin with the mass of 5 wt% of the boron carbide powder, sodium tripolyphosphate with the mass of 20 wt% of the tantalum powder, and adding absolute ethyl alcohol (the purity is 99.7%) with the total mass of the substances as a medium into a high-energy ball milling tank to perform ball milling and mixing at the rotating speed of 400r/min for 24 hours to obtain precursor slurry;
(2) and (3) drying: pouring the precursor slurry into a rotary evaporation dryer, continuously heating and rotationally drying for 6 hours at the water bath temperature of 60 ℃, and sieving by a 120-mesh sieve to obtain precursor powder;
(3) and (3) granulation: granulating and sieving the precursor powder through a dry granulation tower; the granulation conditions were: the inlet temperature was 250 ℃, the outlet temperature was 120 ℃ and the feed rate was 5 kg/h; sieving the dried particles, and selecting the particles with the particle size of 10-40 mu m for the next operation;
(4) molding: placing the screened powder into a die, prepressing and molding the powder under the pressure of 200MPa by using a press machine, and demolding to obtain a ceramic green body;
(5) and (3) sintering: and (3) placing the ceramic green body in a graphite tray, placing the tray in a pressureless sintering furnace, heating to 2250 ℃ at the speed of 20 ℃/min, keeping the temperature for 2h, wherein the atmosphere of protective gas in the furnace is argon, and the introduced argon is argon flow of 1.8 Pa. Cooling the mixture to room temperature by circulating water to obtain the transition metal in-situ toughened boron carbide-based multiphase ceramic prepared by in-situ growth.
(6) The average size of the second phase particles was 2.7 μm; the final product is tested for mechanical property, the hardness is 32.3GPa, the bending strength is 605MPa, and the fracture toughness is 7.8 MPa.m1/2。
Example 6:
a method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering by using transition metal simple substances comprises the following steps:
(1) ball milling: weighing boron carbide powder (the particle size is less than or equal to 2 microns and the purity is 99.5%) and tungsten powder (the particle size is less than or equal to 5 microns and the purity is 99.5%) in a molar ratio of 8:1, phenolic resin with the mass of 4 wt% of the boron carbide powder, sodium tripolyphosphate with the mass of 15 wt% of the tungsten powder, and adding absolute ethyl alcohol (the purity is 99.7%) with the total mass of the substances as a medium into a high-energy ball milling tank to perform ball milling and mixing at the rotating speed of 400r/min for 18 hours to obtain precursor slurry;
(2) and (3) drying: pouring the precursor slurry into a rotary evaporation dryer, continuously heating and rotationally drying for 6 hours at the water bath temperature of 60 ℃, and sieving by a 120-mesh sieve to obtain precursor powder;
(3) and (3) granulation: granulating and sieving the precursor powder through a dry granulation tower; the granulation conditions were: the inlet temperature was 220 ℃, the outlet temperature was 110 ℃ and the feed rate was 5 kg/h; sieving the dried particles, and selecting the particles with the particle size of 10-40 mu m for the next operation;
(4) molding: placing the screened powder into a die, performing pre-pressing molding under the pressure of 150MPa by using a press machine, and demolding to obtain a ceramic green body;
(5) and (3) sintering: and placing the ceramic green body in a graphite tray, placing the tray in a pressureless sintering furnace, heating to 2150 ℃ at the speed of 20 ℃/min, keeping the temperature for 1.5h, wherein the atmosphere of protective gas in the furnace is argon, and the introduced argon is argon flow of 1.3 Pa. Cooling the mixture to room temperature by circulating water to obtain the transition metal in-situ toughened boron carbide-based multiphase ceramic prepared by in-situ growth.
(6) The average size of the second phase particles was 3.8 μm; the final product is tested for mechanical property, the hardness is 27.5GPa, the bending strength is 572MPa, and the fracture toughness is 8.7 MPa.m1/2。
Example 7:
a method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering by using transition metal simple substances comprises the following steps:
(1) ball milling: weighing boron carbide powder (the particle size is less than or equal to 2 microns and the purity is 99.5%) and tantalum powder (the particle size is less than or equal to 5 microns and the purity is 99.5%) in a molar ratio, phenolic resin with the mass of 5 wt% of the boron carbide powder, sodium tripolyphosphate with the mass of 10 wt% of the tantalum powder, and absolute ethyl alcohol (the purity is 99.7%) with the mass equal to the total mass of the substances as a medium, adding the materials into a high-energy ball milling tank, and carrying out ball milling and mixing for 22 hours at the rotating speed of 400r/min to obtain precursor slurry;
(2) and (3) drying: pouring the precursor slurry into a rotary evaporation dryer, continuously heating and rotationally drying for 6 hours at the water bath temperature of 60 ℃, and sieving by a 120-mesh sieve to obtain precursor powder;
(3) and (3) granulation: granulating and sieving the precursor powder through a dry granulation tower; the granulation conditions were: the inlet temperature was 245 ℃, the outlet temperature was 121 ℃ and the feed rate was 5 kg/h; sieving the dried particles, and selecting the particles with the particle size of 10-40 mu m for the next operation;
(4) molding: placing the screened powder into a die, performing pre-pressing molding under the pressure of 150MPa by using a press machine, and demolding to obtain a ceramic green body;
(5) and (3) sintering: and placing the ceramic green body in a graphite tray, placing the tray in a pressureless sintering furnace, heating to 2200 ℃ at a speed of 20 ℃/min, keeping the temperature for 1h, wherein the atmosphere of protective gas in the furnace is argon, and the introduced argon is argon flow of 1.3 Pa. Cooling the mixture to room temperature by circulating water to obtain the transition metal in-situ toughened boron carbide-based multiphase ceramic prepared by in-situ growth.
The average size of the second phase particles was 3.4 μm; the final product is tested for mechanical property, the hardness is 27.7GPa, the bending strength is 615MPa, and the fracture toughness is 8.8 MPa.m1/2。
In summary, the following steps: the invention discloses a method for preparing boron carbide-based multiphase ceramic by using transition metal simple substances through in-situ reaction, which takes boron carbide, transition metal simple substances Me (Me is transition metal elements such as Ti, Zr, Nb, Ta, W and the like), phenolic resin and a dispersing agent as raw materials, and obtains precursor powder by ball milling, mixing, heating, rotating and drying; and then, granulating the precursor powder, and carrying out dry pressing forming to obtain a ceramic green body, heating to 2100-2300 ℃ at the speed of 5-20 ℃/min in the atmosphere of argon protective gas, keeping the temperature for 0.5-2 h, and cooling to room temperature by circulating water to obtain the in-situ growth second-phase toughened boron carbide-based multiphase ceramic. In addition, the product prepared by the preparation method is also disclosed. The invention has simple process and low cost, and adopts pressureless sintering for in-situ synthesis of MeB2The toughening phase is uniformly dispersed and well combined with a boron carbide matrix interface, has uniform microstructure and high density, has excellent comprehensive mechanical property, and is suitable for industrial mass production.
Claims (8)
1. A method for preparing boron carbide-based multiphase ceramic by in-situ reaction pressureless sintering is characterized by comprising the following steps:
(1) ball milling: according to the molar ratio of B4Carrying out wet ball milling and mixing on boron carbide powder, a transition metal simple substance, phenolic resin and a dispersing agent by taking absolute ethyl alcohol as a medium, wherein the ratio of C to Me is 20: 1-4, and further obtaining precursor slurry;
(2) and (3) drying: heating and rotary drying the precursor slurry by using a rotary evaporation dryer, and sieving to obtain precursor powder;
(3) and (3) granulation: granulating and sieving the precursor powder through a dry granulation tower;
(4) molding: placing the screened powder into a die, prepressing and forming by using a press machine, and demoulding to obtain a ceramic green body;
(5) and (3) sintering: and (3) placing the ceramic green body in a graphite tray, placing the tray in a pressureless sintering furnace, heating to 2100-2300 ℃ at the speed of 5-20 ℃/min under the atmosphere of argon gas as protective gas in the furnace, keeping the temperature for 0.5-2 h, and cooling to room temperature by circulating water to obtain the transition metal element in-situ toughened boron carbide-based multiphase ceramic prepared by in-situ growth.
2. The method for preparing boron carbide-based complex phase ceramic according to claim 1, wherein: adding phenolic resin as a sintering aid in the step (1), wherein the amount of the sintering aid is 1-5 wt% of boron carbide; the amount of the added dispersant sodium tripolyphosphate is 10-20 wt% of the transition metal simple substance.
3. The method for preparing boron carbide-based multiphase ceramic through in-situ reaction according to claim 1 or 2, wherein the rotation speed of ball milling in the step (1) is 200-400 r/min, the ball-material ratio is 20:1, the ball milling time is 12-24 h, the adopted ball material is tungsten carbide, and the ball milling tank material is hard alloy.
4. The method for preparing boron carbide-based complex phase ceramic according to claim 1, wherein: and (3) continuously heating and rotationally drying the precursor slurry in the step (2) at the water bath temperature of 60-90 ℃ for 2-8 h.
5. The method for preparing boron carbide-based complex phase ceramic according to claim 1, wherein: the granulation conditions in the step (3) are as follows: the inlet temperature is 150-300 ℃, the outlet temperature is 80-150 ℃, and the feeding rate is 2-8 kg/h; sieving the dried granules, and selecting the granules with the particle size of less than or equal to 50 mu m for the next operation.
6. The method for preparing boron carbide-based complex phase ceramic according to claim 1, wherein: and (4) the pressure condition in the step (4) is 50-200 MPa.
7. The product obtained by the method for preparing boron carbide-based multiphase ceramic by using the in-situ reaction according to any one of claims 1 to 5, wherein: the product phase is composed of B4C matrix and MeB2Me is a transition metal element of Ti, Zr, Nb, Ta or W, the second phase has a crystal grain composition of MeB2The second phase toughening crystal grains are uniformly and dispersedly distributed in the boron carbide matrix.
8. The product obtained by the method for preparing the boron carbide-based complex phase ceramic by the in-situ reaction according to claim 5, is characterized in that: second phase MeB2The average size of the crystal grains is about 2 to 5 μm.
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