CN112125680A - Boron carbide micro powder purification method, boron carbide ceramic and preparation method of boron carbide ceramic - Google Patents
Boron carbide micro powder purification method, boron carbide ceramic and preparation method of boron carbide ceramic Download PDFInfo
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Abstract
The invention discloses a boron carbide micro powder purification method, boron carbide ceramic and a preparation method of the boron carbide ceramic. The purification method of boron carbide micropowder is characterized by that it uses commercially available W3.5 series boron carbide micropowder as raw material, and makes the above-mentioned materials undergo the processes of homogenizing grinding, vacuum heat treatment purification and secondary grinding, and makes the boron carbide slurry undergo the process of spray granulation to obtain the invented boron carbide micropowder. The boron carbide ceramic consists of boron carbide micro powder, liquid carbon black, submicron aluminum nitride micro powder, titanate coupling agent, water-soluble phenolic resin, water-soluble acrylic glue, polyethylene glycol, glycerol, deionized water, whisker type multi-wall carbon nano tube and Ti-Si-C ternary MAX phase micro powder. The preparation method of the boron carbide ceramic comprises the steps of weighing the components, carrying out high-speed ball milling pulping, spraying granulation, green pressing and pressureless sintering. Solves the problem of low purity of the boron carbide micro powder in the prior art, and simultaneously realizes the pressureless sintering preparation of the boron carbide ceramic.
Description
Technical Field
The invention relates to the field of ceramics, in particular to the technical field of preparation of boron carbide ceramics.
Background
The boron carbide ceramic material has many excellent properties, such as high melting point, high hardness, high modulus, low density and the like, has good wear resistance, strong oxidation resistance and good neutron absorption capacity, and is widely applied to the fields of abrasive materials, wear-resistant parts, atomic reactors, light bulletproof armors, sand blasting nozzles, special chemical corrosion-resistant materials and the like.
Boron carbide has a high covalent bond content of up to 94%, which makes it extremely difficult to sinter densify. At present, boron carbide ceramics are mainly prepared by a hot pressing process, the size and the shape of the prepared ceramics are greatly limited due to the limitation of the hot pressing process, and only some ceramics with simple shapes can be prepared at present. Meanwhile, the hot pressing process has the defects of complex operation, low single-furnace yield and the like, so that the hot pressing boron carbide ceramic is high in price, and the popularization and application of the boron carbide ceramic are limited. Therefore, the pressureless sintering boron carbide ceramic preparation process has great significance for promoting the wide application of boron carbide ceramic.
Although the pressureless sintering process can well solve the problems that the hot pressing process only can prepare small-size products, simple shapes, high price and the like, the pressureless sintering process puts more rigorous requirements on technological links such as boron carbide ceramic raw materials, sintering equipment and the like.
The method for producing boron carbide in the prior art is an electric arc furnace carbothermic reduction method, the main raw materials of the method are boric acid, coke, artificial conductive graphite and the like, and because the temperature in the electric arc furnace is not uniform, the temperature close to the electrode exceeds the decomposition temperature of the boron carbide, the boron carbide is subjected to peritectic decomposition, and free carbon and high boron compounds are separated out; the furnace wall is not completely reacted due to low temperature, so that a large amount of boron oxide, free carbon, free boron and the like are remained; after the boron carbide is smelted, the boron carbide is discharged from the furnace in a red hot state (shown in figure 1), and is placed in air for cooling, so that the surface of a smelted large block is oxidized, and a large amount of boron trioxide is generated; this results in boron carbide prepared by the arc furnace carbothermic process containing a large amount of free carbon, free boron and boron trioxide; in addition, because the proportion of the boron anhydride and the carbon is different and the smelting process is different during smelting of various production enterprises, the stoichiometric ratio of the prepared boron carbide is greatly different; therefore, the boron carbide micro powder sold in the market at present is mixed powder of boron carbide, boron trioxide, free boron, free carbon and impurities, the purity of the boron carbide micro powder is generally low, and the quality stability of the micro powder is also poor.
The two main key technical problems of the prior pressureless sintering process comprise that the components of the raw materials of the commercially available boron carbide micro powder are complex, the purity of the micro powder is low, and the technical standard required by the pressureless sintering process is difficult to achieve; secondly, the temperature field and the atmosphere field in the ultrahigh-temperature vacuum sintering furnace for sintering are not uniform, so that the finished product rate of the sintered ceramic product is low.
Disclosure of Invention
The invention aims to provide a boron carbide micro powder purification method for effectively improving the purity of boron carbide micro powder aiming at the defects in the prior art.
In order to realize the purpose, the technical scheme of the purification method of the boron carbide micro powder is as follows:
a method for purifying boron carbide micro powder comprises the following steps:
1) homogenizing and grinding, namely preparing a slurry with the solid content of 50% from a commercially available W3.5 series boron carbide micro powder raw material, grinding the boron carbide micro powder raw material to 2 +/-0.2 mu m by adopting a high-speed stirring mill, stopping grinding, adding 0.05-0.15% by weight of a high-molecular precipitator into the ground slurry, introducing the slurry into a standing barrel for standing, removing supernatant to obtain boron carbide mud blocks, taking out the boron carbide mud blocks, further dehydrating the boron carbide mud blocks by using a mud extruder, extruding the boron carbide mud blocks into rectangular mud strips, and drying for later use;
2) performing vacuum heat treatment purification, namely performing reaction purification on boron carbide by adopting a vacuum high-temperature sintering mode, placing the dried boron carbide mud block into a vacuum sintering furnace, keeping the heat treatment temperature at 1600-1700 ℃, keeping the temperature for 3-4h, keeping the vacuum degree in the furnace below 30Pa, stopping the furnace, cooling to 80 ℃, and discharging the furnace;
3) and (3) secondary grinding, namely taking out the boron carbide mud blocks after the heat treatment, crushing the boron carbide mud blocks into fragments with the diameter of less than 5mm by using a jaw crusher, adding the crushed fragments into a ball mill for coarse grinding and fine grinding, finishing grinding when the micro powder D50 is 2.0 +/-0.2 mu m, and drying the boron carbide slurry in a spray granulation mode to prepare powder.
In the step 1), a single-cycle high-speed stirring mill is adopted to grind the boron carbide micro powder raw material, and the grinding parameters are as follows: the high-speed stirring and grinding capacity is 500L, the rotating speed is 650r/min, the grinding medium is boron carbide microspheres with the diameter of 3mm, the loading capacity of the boron carbide microspheres is 120kg, the loading capacity of single-grinding micro powder is 200kg, and the deionized water is 200 kg.
And (2) introducing the slurry in the step 1) into a standing barrel, adding 0.05-0.15% by weight of polyacrylamide, and standing for 48 hours.
And 2) the vacuum sintering furnace is a graphite crucible furnace.
The main parameters of the ball mill for coarse grinding in the step 3) are as follows: the ball-material ratio is 2.5:1, the grinding ball is a boron carbide ball with the diameter of 16mm, the water-material ratio is 1:1, and the grinding time is 24 hours; the fine grinding adopts a single-cycle high-speed stirring mill, and the grinding parameters are as follows: the high-speed stirring and grinding capacity is 500L, the rotating speed is 650r/min, the grinding medium is boron carbide microspheres with the diameter of 3mm, the loading capacity of the boron carbide microspheres is 120kg, the loading capacity of single-grinding micro powder is 200kg, and the deionized water is 200 kg.
Another object of the present invention is to provide a formulation for boron carbide ceramic that facilitates pressureless sintering of the boron carbide ceramic.
In order to realize the purpose, the boron carbide ceramic adopts the following technical scheme:
the boron carbide ceramic comprises the following components in parts by weight: 100 parts of boron carbide micro powder, 5-8 parts of liquid carbon black, 0.5-1 part of submicron aluminum nitride micro powder, 2-6 parts of titanate coupling agent, 10-15 parts of water-soluble phenolic resin, 5-8 parts of water-soluble acrylic adhesive, 2-4 parts of polyethylene glycol, 1-2 parts of glycerol, 80-100 parts of deionized water, 0-2 parts of whisker-type multi-walled carbon nanotube and 0-3 parts of Ti-Si-C ternary MAX phase micro powder, wherein the solid content of the liquid carbon black is 40 wt%, the content of Ti MAX element in the titanate coupling agent is 10 wt%, the carbon residue rate of the water-soluble phenolic resin is 35%, and the content of Ti-Si-C ternary phase micro powder D50 is 1.5 micrometers. The whisker type carbon nano tube and the Ti-Si-C ternary MAX phase are toughening auxiliary agents.
The Ti-Si-C ternary MAX phase micro powder is Ti3SiC2Mixed powder of MAX phase and TiC, wherein Ti3SiC2The mass fraction of the MAX phase is 88-92%, and the rest is TiC phase.
The third purpose of the invention is to provide a preparation method of pressureless sintering boron carbide ceramic.
In order to realize the purpose, the preparation method of the boron carbide ceramic adopts the following technical scheme:
the preparation method of the boron carbide ceramic comprises the following steps:
s1 ball milling and pulping: weighing the components, and then adding the components into a ball mill once, wherein the grinding medium is a boron carbide ball with the diameter of 12mm, the ball-material ratio is 3:1, the rotating speed of the ball mill is 30r/min, and the ball milling time is 48 h;
s2 spray granulation: after the ball milling is finished, slurry is guided into a low-speed stirring barrel, and is sprayed by a centrifugal spray granulation tower, wherein the main parameters of the spray granulation tower are as follows: the air inlet temperature is 200-220 ℃, the air outlet temperature is 100-120 ℃, the rotating speed of a spray head is 300r/min, the slurry inlet amount is 50L/h, and the granulated powder is a solid sphere;
s3 green pressing: molding by adopting a dry pressing-isostatic pressing mode, dry pressing the granulated powder into a green body with the required size and shape by adopting a hydraulic press, then carrying out vacuum sealing on the green body, carrying out secondary pressing on the vacuum sealed green body by using isostatic pressing so as to improve the density of the green body, wherein the green body density of the obtained boron carbide green body is 1.75 +/-0.2 g/cm3；
S4, sintering under no pressure: and (2) carrying out vacuum degumming treatment on the pressed green bodies, keeping the degumming temperature of 1650 ℃ for 2h, completely decomposing and exerting organic matters in the green bodies, sequentially placing the degummed green bodies in a graphite kiln furniture, pushing the kiln furniture into a kiln, wherein the used high-temperature vacuum sintering furnace is a microwave-assisted sintering vacuum sintering furnace, microwave generating devices are additionally arranged on furnace doors at two sides of the microwave-assisted sintering vacuum sintering furnace, and microwaves are radiated into the kiln from the furnace doors at the two sides, so that the temperature field in the kiln is more uniform, the sintering temperature range is 2180-2230 ℃, and the time is 1 h.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, a grinding homogenization, high-temperature vacuum purification and grinding refinement process route is adopted to treat boron carbide, a vacuum high-temperature sintering mode is adopted to carry out reaction purification on a boron carbide micro powder raw material, the boron carbide micro powder raw material mainly comprises boron carbide, free boron, free carbon and diboron trioxide, and the free carbon in the micro powder is further reacted with the free boron and the diboron trioxide through a high-temperature vacuum heat treatment mode, so that the impurity content in the micro powder is reduced, and the purity of the boron carbide micro powder is improved; the heat treatment temperature of the boron carbide mud blocks after heat treatment is far lower than the sintering temperature of the boron carbide micro powder, and the boron carbide mud blocks after heat treatment are extremely loose accumulation bodies in structure and are convenient to break;
2. non-oxide eutectic liquid phase is utilized to promote pressureless sintering densification of boron carbide ceramic, and B-Ti-Al-C eutectic liquid phase is used as a liquid phase provider to be matched with traditional Al2O3-Y2O3Compared with the oxide eutectic liquid phase, the non-oxide liquid phase (shown in figure 2) has the advantages of good wettability with ceramic particles, difficult decomposition and volatilization and the like, and can remarkably improve the sintering compactness of the ceramic; the liquid carbon black and the water-soluble phenolic resin are sources of carbon elements in the ceramic sintering aid, and the liquid carbon black and the water-soluble phenolic resin have good dispersibility and are not easy to agglomerate; the submicron aluminum nitride micro powder is a source of Al element, and aluminum nitride is hydrolyzed in the preparation process of the slurry to form nano alumina colloidal particles which can be uniformly dispersed in the ceramic slurry; the titanate coupling agent has one alkoxy and three alcohol-containing molecular chains, and the alkoxy can be combined with the hydroxyl on the surface of the powder in the slurry so as to be uniformly coated on the surface of the ceramic micro powder particles, so that on one hand, the dispersibility of the powder in the slurry can be improved through the coating effect on the surface of the powder, and the problem of powder agglomeration is solved, and on the other hand, the titanate coupling agent can be used as a source of Ti element in a sintering aid system in a high-temperature sintering process. Because the sintering aid system has low content of each element and is uniformly dispersed in the ceramic, the sintering aid system is generally only formed on the surface of ceramic particles at high temperatureForming a trace amount of eutectic liquid phase, forming the eutectic liquid phase at grain boundaries, converting solid phase diffusion of the grain boundaries into liquid phase diffusion, accelerating the material transmission efficiency and enabling the ceramics to rapidly realize sintering densification; the toughening auxiliary agent mainly comprises 0-2 parts by weight of whisker type carbon nano tube and 0-3 parts by weight of Ti-Si-C ternary MAX phase, wherein the whisker type carbon nano tube is a highly linear carbon nano tube (shown in figure 3), is obviously different from common winding type and curling type carbonized nano tubes, and has good dispersity, complete crystallization and better mechanical property;
3. the boron carbide ceramic has high sintering temperature and narrow sintering temperature range, the uniformity of a temperature field in a kiln is improved by additionally arranging a microwave generating device in a low-temperature region of the kiln (the structural schematic diagram of the kiln is shown in figure 5), a microwave auxiliary heating mode is adopted to improve the uniformity of the temperature field in the kiln, furnace doors on two sides of the kiln are the low-temperature region of the kiln, the boron carbide ceramic at the position is difficult to sinter and densify, a microwave generator is arranged outside a heat insulating layer of the furnace doors on two sides of the kiln, the material of an outer heat insulating layer is polycrystalline alumina fiber cotton, an inner layer is a gradient heat insulating material formed by compounding a carbon felt and a graphite plate, the polycrystalline alumina fiber cotton is a wave transmitting material, the composite gradient heat insulating material formed by the carbon felt and the graphite plate is a semi-wave transmitting material, the composite gradient heat insulating material can absorb, the high-temperature vacuum sintering furnace shell is composed of a steel shell, and can reflect microwaves without worrying about the safety problem that microwaves leak to hurt human bodies.
Drawings
FIG. 1 is a boron carbide frit just as it was smelted out of a furnace;
FIG. 2 is a boron carbide B-Ti-Al-C eutectic liquid phase molten ball;
FIG. 3 is a whisker type multi-walled carbon nanotube;
FIG. 4 is a photograph of boron carbide granulated powder;
FIG. 5 is a schematic view of a microwave-assisted vacuum sintering furnace configuration;
FIG. 6 is a photograph of the optical microstructure of the boron carbide ceramic of example 1;
FIG. 7 is a photograph of the optical microstructure of the boron carbide ceramic of example 2;
FIG. 8 is a photograph of the optical microstructure of boron carbide ceramic of example 3;
FIG. 9 is a photograph of the optical microstructure of the boron carbide ceramic of example 5.
Detailed Description
The present invention is further illustrated by the following description in conjunction with the accompanying drawings, which are to be construed as merely illustrative and not limitative of the remainder of the disclosure, and on reading the disclosure, various equivalent modifications thereof will become apparent to those skilled in the art and fall within the limits of the appended claims.
A method for purifying boron carbide micro powder comprises the following steps:
1) homogenizing and grinding, based on a commercially available W3.5 (about 3 mu m D50) series boron carbide micro powder raw material, preparing the boron carbide micro powder raw material into slurry with the solid content of 50%, grinding the boron carbide micro powder raw material, and grinding the boron carbide micro powder raw material by adopting a single-cycle high-speed stirring mill, wherein the grinding parameters are as follows: stirring at a high speed for grinding with the capacity of 500L and the rotation speed of 650r/min, grinding media are boron carbide microspheres with the diameter of 3mm, the load capacity of the boron carbide microspheres is 120kg, the load capacity of single-grinding micropowder is 200kg, deionized water is 200kg, grinding is stopped when the micropowder is ground to 2 +/-0.2 mu m, 0.05-0.15% of high-molecular precipitator is added into the ground slurry, the slurry is led into a standing barrel to stand, 0.05-0.15% of polyacrylamide is added according to the weight ratio, standing is carried out for 48h, supernatant is removed to obtain boron carbide mud blocks, the boron carbide mud blocks are taken out and are further dehydrated through a mud extruder, rectangular mud strips are extruded, and the boron carbide mud blocks are dried for later use;
2) performing vacuum heat treatment purification, namely performing reaction purification on boron carbide by adopting a vacuum high-temperature sintering mode, wherein the vacuum sintering furnace is a graphite crucible furnace, placing dried boron carbide mud blocks into the vacuum sintering furnace, keeping the heat treatment temperature at 1600-1700 ℃, keeping the temperature for 3-4h, keeping the vacuum degree in the furnace below 30Pa, stopping the furnace, cooling to 80 ℃, and discharging the furnace;
3) secondary grinding, the boron carbide mud block after heat treatment is taken out, a jaw crusher is adopted to crush the boron carbide mud block into fragments with the diameter smaller than 5mm, the crushed fragments are added into a ball mill to be subjected to coarse grinding and fine grinding, and the main parameters of the ball mill for coarse grinding are as follows: the ball-material ratio is 2.5:1, the grinding ball is a boron carbide ball with the diameter of 16mm, the water-material ratio is 1:1, and the grinding time is 24 hours; the fine grinding adopts a single-cycle high-speed stirring mill, and the grinding parameters are as follows: the high-speed stirring and grinding capacity is 500L, the rotating speed is 650r/min, the grinding medium is boron carbide microspheres with the diameter of 3mm, the loading capacity of the boron carbide microspheres is 120kg, the loading capacity of single-grinding micro powder is 200kg, and the deionized water is 200 kg; and when the micro powder D50 is 2.0 +/-0.2 mu m, finishing grinding, and drying the boron carbide slurry in a spray granulation (as shown in figure 4) mode to prepare powder.
Example 1
100 parts of boron carbide micro powder, 5 parts of liquid carbon black (solid content is 40 wt%), 0.5 part of submicron aluminum nitride micro powder, 2 parts of titanate coupling agent (Ti element content is 10 wt%), 10 parts of water-soluble phenolic resin (carbon residue rate is 35%), 8 parts of water-soluble acrylic glue, 2 parts of polyethylene glycol, 1 part of glycerol and 80 parts of deionized water.
The method for manufacturing the boron carbide ceramic comprises the following steps:
ball milling and pulping: weighing the components, and then adding the components into a ball mill once, wherein the grinding medium is a boron carbide ball with the diameter of 12mm, the ball-material ratio is 3:1, the rotating speed of the ball mill is 30r/min, and the ball milling time is 48 h;
spray granulation: after the ball-milling is finished, slurry is guided into a low-speed stirring barrel, a centrifugal spray granulation tower is used for granulation, the moisture of granulation powder is adjusted by controlling the temperature of an air outlet, the rotating speed of a spray head and the slurry inlet amount are controlled to regulate and control the particle size distribution of the granulation powder, and the main parameters of the spray granulation tower are as follows: the air inlet temperature is 200-220 ℃, the air outlet temperature is 100-120 ℃, the rotating speed of the spray head is 300r/min, and the pulp inlet amount is 50L/h;
green pressing: molding by dry pressing-isostatic pressing, namely firstly adopting a four-column hydraulic pressDry pressing the granulated powder into green bodies with required size and shape, then vacuum sealing the green bodies, and carrying out secondary pressurization on the vacuum sealed green bodies by isostatic pressing, thereby improving the density of the green bodies and controlling the density of the boron carbide green bodies to be 1.75 +/-0.2 g/cm3；
And (3) pressureless sintering: the pressed green body is firstly subjected to vacuum degumming treatment, the degumming temperature is 1650 ℃ and the heat preservation is carried out for 2 hours, so that the organic matters in the green body are completely decomposed and exerted, the degummed green body is sequentially placed in a graphite kiln furniture, the kiln furniture is pushed into a kiln after being filled, the used high-temperature vacuum sintering furnace is a microwave-assisted sintering vacuum sintering furnace (shown in an attached figure 5) after special modification, microwave generating devices are additionally arranged on the positions of furnace doors on two sides, microwaves are radiated from the furnace doors on the two sides to the inside of the kiln, the temperature of a temperature zone at the position of the furnace door is increased through the microwave effect, so that the temperature field in the furnace is more uniform, the sintering temperature range is 2180-2230 ℃, and.
In the embodiment, the optimal sintering temperature of the boron carbide ceramic is 2210 ℃ for 1h, and the sintering density of the ceramic is in the range of 2.44-2.46g/cm3The basic performance indexes of the ceramics are as follows: the ceramic sintering density range is 97-97.6%, the structure is compact, the optical microstructure picture is shown in figure 6, and the Vickers hardness HV of the ceramic is0.52800-3000MPa, bending strength 330-360MPa, and ceramic fracture roughness and abnormal grain growth.
Example 2:
100 parts of boron carbide micro powder, 8 parts of liquid carbon black (solid content is 40 wt%), 1 part of submicron aluminum nitride micro powder, 6 parts of titanate coupling agent (Ti element content is 10 wt%), 15 parts of water-soluble phenolic resin (carbon residue rate is 35%), 5 parts of water-soluble acrylic glue, 4 parts of polyethylene glycol, 2 parts of glycerol and 100 parts of deionized water.
The main difference between this example and example 1 is that liquid carbon black is used to replace resin carbon, and the addition amount of titanate and aluminum nitride micro powder is increased, that is, the content of sintering aid in the formula system is increased, the ceramic preparation process is the same as that in specific example 1, because the sintering aid is increased, the ceramic sintering temperature is obviously reduced, the optimal sintering temperature is 2190 ℃, the temperature is kept for 1h, and the optimal sintering temperature is reduced by 20 ℃ compared with that in specific example 1.
The basic properties of the ceramic prepared in this example are as follows:
the sintered density of the ceramic is within the range of 2.45-2.47g/cm3The ceramic sintering compactness range is 96.8-97.5%, the increase of the sintering aid is not beneficial to the sintering compactness of the ceramic from the viewpoint of the sintering compactness, the Vickers hardness HV0.5 of the ceramic is 2600-2900MPa, the bending strength is 360-400MPa, and the ceramic fracture is fine and smooth and has metallic luster. The optical microstructure of the ceramic is shown in figure 7. In the embodiment, because the carbon addition amount in the sintering aid is relatively high, a large amount of agglomerated carbon exists in the ceramic due to excessive carbon. The existence of the carbon can block sintering, so that the sintering density is reduced, and meanwhile, the abnormal growth of ceramic grains can be inhibited, so that the bending strength of the ceramic is improved. In addition, the presence of excess agglomerated carbon also reduces the vickers hardness of the ceramic.
Example 3:
the preparation method comprises the following steps of 100 parts by weight of boron carbide micro powder, 6 parts by weight of liquid carbon black (with a solid content of 40 wt%), 0.75 part by weight of submicron aluminum nitride micro powder, 3 parts by weight of titanate coupling agent (with a Ti element content of 10 wt%), 12 parts by weight of water-soluble phenolic resin (with a carbon residue rate of 35%), 6 parts by weight of water-soluble acrylic glue, 3 parts by weight of polyethylene glycol, 2 parts by weight of glycerol and 100 parts by weight of deionized water.
The ceramic preparation process flow of the embodiment is the same as that of the embodiment 1, the optimal sintering temperature of the ceramic is 2215 ℃, and the temperature is kept for 1 h.
The basic properties of the ceramic prepared in this example are as follows:
the sintered density of the ceramic is within the range of 2.46-2.48g/cm3The ceramic sintering density range is 97.6-98.5%, and the sintering density can be close to the level of hot-pressing boron carbide in terms of the sintering density. The Vickers hardness HV0.5 of the ceramic is more than or equal to 3000MPa, the bending strength is 370-400MPa, and the fracture toughness is 2.0-2.5 MPa.m1/2. The ceramic fracture is fine and smooth and has metallic luster. The optical microstructure of the ceramic is shown in figure 8.
Example 4:
in order to further improve the toughness of the pressureless sintered boron carbide ceramic and better exert the anti-elasticity performance of the pressureless sintered boron carbide ceramic. In this embodiment, the fracture toughness of the ceramic is improved by adding the toughening aid.
100 parts of boron carbide micro powder, 1 part of liquid carbon black (solid content is 40 wt%), 0.75 part of submicron aluminum nitride micro powder, 3 parts of titanate coupling agent (Ti element content is 10 wt%), 12 parts of water-soluble phenolic resin (carbon residue rate is 35%), 6 parts of water-soluble acrylic adhesive, 3 parts of polyethylene glycol, 2 parts of glycerol, 100 parts of deionized water, 2 parts of whisker type multi-walled carbon nano tube and 3 parts of Ti-Si-C ternary MAX phase micro powder (D50 is 1.5 micrometers). In the formula system, the whisker type multi-walled carbon nano-tube (shown in figure 3) and the liquid carbon black are equivalently replaced according to consistent carbon content.
The process flow of the ceramic preparation in the embodiment is the same as that in the embodiment 1, the optimal sintering temperature of the ceramic is 2230 ℃, and the temperature is kept for 1 h. The addition of the carbon nano tube obviously improves the sintering temperature of the ceramic, mainly because the specific surface area of the whisker type carbon nano tube is far higher than that of carbon black with the same mass, and the sintering inhibition effect of the whisker type carbon nano tube on boron carbide ceramic is obvious. The sintered density of the ceramic is within the range of 2.48-2.51g/cm3The ceramic sintering density range is 96.1-97.3%. The introduction of the carbon nano tube and the ternary MAX phase obviously reduces the sintering compactness of the ceramic. The Vickers hardness HV0.5 of the ceramic is 2400-2800MPa, the bending strength is 330-380MPa, and the fracture toughness is 3.3-4.2 MPa.m1/2。
Although the introduction of the carbon nano tube and the ternary MAX phase improves the fracture toughness of the ceramic, the hardness and the bending strength of the ceramic are reduced.
Example 5:
in order to improve the comprehensive mechanical property of the ceramic, the adding amount of the carbon nano tube and the MAX phase is adjusted, and the optimal adding amount is as follows:
100 parts of boron carbide micro powder, 4 parts of liquid carbon black (solid content is 40 wt%), 0.75 part of submicron aluminum nitride micro powder, 3 parts of titanate coupling agent (Ti element content is 10 wt%), 12 parts of water-soluble phenolic resin (carbon residue rate is 35%), 6 parts of water-soluble acrylic adhesive, 3 parts of polyethylene glycol, 2 parts of glycerol, 100 parts of deionized water, 0.8 part of whisker type multi-walled carbon nanotube and 1.5 parts of Ti-Si-C ternary MAX phase micro powder (D50 is 1.5 micrometers).
The process flow of the ceramic preparation in the embodiment is the same as that in the embodiment 1, the optimal sintering temperature of the ceramic is 2215 ℃, and the temperature is kept for 1 h. The optimum sintering temperature is consistent with that of example 3, and the sintering density of the ceramic is in the range of 2.47-2.50g/cm3The ceramic sintering density range is 97-98%. The Vickers hardness HV0.5 of the ceramic is 2800-3050MPa, the bending strength is 380-410MPa, and the fracture toughness is 3.8-4.3 MPa.m1/2. By introducing a proper amount of carbon nano tubes and ternary MAX phases, the comprehensive mechanical property of the ceramic is optimized. The microstructure of the ceramic is shown in figure 9. It can be seen from the figure that there are many layered structure substances in the ceramic, which are consistent with the ternary MAX phase structure, and it can be seen from the low magnification microstructure photo that the structure of the carbon nanotube is destroyed under the high temperature, and the carbon nanotube is converted into layered graphite. It can be seen that the layered graphite has a significant pull-out effect, which results in a significant improvement in the toughness of the ceramic.
Claims (8)
1. The method for purifying the boron carbide micro powder is characterized by comprising the following steps:
1) homogenizing and grinding, namely preparing a slurry with the solid content of 50% from a commercially available W3.5 series boron carbide micro powder raw material, grinding the boron carbide micro powder raw material to 2 +/-0.2 mu m by adopting a high-speed stirring mill, stopping grinding, adding 0.05-0.15% by weight of a high-molecular precipitator into the ground slurry, introducing the slurry into a standing barrel for standing, removing supernatant to obtain boron carbide mud blocks, taking out the boron carbide mud blocks, further dehydrating the boron carbide mud blocks by using a mud extruder, extruding the boron carbide mud blocks into rectangular mud strips, and drying for later use;
2) performing vacuum heat treatment purification, namely performing reaction purification on boron carbide by adopting a vacuum high-temperature sintering mode, placing the dried boron carbide mud block into a vacuum sintering furnace, keeping the heat treatment temperature at 1600-1700 ℃, keeping the temperature for 3-4h, keeping the vacuum degree in the furnace below 30Pa, stopping the furnace, cooling to 80 ℃, and discharging the furnace;
3) and (3) secondary grinding, namely taking out the boron carbide mud blocks after the heat treatment, crushing the boron carbide mud blocks into fragments with the diameter of less than 5mm by using a jaw crusher, adding the crushed fragments into a ball mill for coarse grinding and fine grinding, finishing grinding when the micro powder D50 is 2.0 +/-0.2 mu m, and drying the boron carbide slurry in a spray granulation mode to prepare powder.
2. The method for purifying the boron carbide micropowder according to claim 1, wherein the boron carbide micropowder raw material is ground by a single-cycle high-speed stirring mill in the step 1), and the grinding parameters are as follows: the high-speed stirring and grinding capacity is 500L, the rotating speed is 650r/min, the grinding medium is boron carbide microspheres with the diameter of 3mm, the loading capacity of the boron carbide microspheres is 120kg, the loading capacity of single-grinding micro powder is 200kg, and the deionized water is 200 kg.
3. The method for purifying boron carbide micropowder according to claim 1, wherein the slurry in the step 1) is introduced into a standing barrel, and 0.05 to 0.15 weight percent of polyacrylamide is added and allowed to stand for 48 hours.
4. The method for purifying the boron carbide micropowder according to claim 1, wherein the vacuum sintering furnace in the step 2) is a graphite crucible furnace.
5. The method for purifying the boron carbide micropowder according to claim 1, wherein the main parameters of the rough grinding of the ball mill in the step 3) are as follows: the ball-material ratio is 2.5:1, the grinding ball is a boron carbide ball with the diameter of 16mm, the water-material ratio is 1:1, and the grinding time is 24 hours; the fine grinding adopts a single-cycle high-speed stirring mill, and the grinding parameters are as follows: the high-speed stirring and grinding capacity is 500L, the rotating speed is 650r/min, the grinding medium is boron carbide microspheres with the diameter of 3mm, the loading capacity of the boron carbide microspheres is 120kg, the loading capacity of single-grinding micro powder is 200kg, and the deionized water is 200 kg.
6. The boron carbide ceramic of the purified boron carbide micropowder obtained by the method according to any one of claims 1 to 5, characterized by comprising the following components in parts by weight: 100 parts of boron carbide micro powder, 5-8 parts of liquid carbon black, 0.5-1 part of submicron aluminum nitride micro powder, 2-6 parts of titanate coupling agent, 10-15 parts of water-soluble phenolic resin, 5-8 parts of water-soluble acrylic adhesive, 2-4 parts of polyethylene glycol, 1-2 parts of glycerol, 80-100 parts of deionized water, 0-2 parts of whisker-type multi-walled carbon nanotube and 0-3 parts of Ti-Si-C ternary MAX phase micro powder, wherein the solid content of the liquid carbon black is 40 wt%, the content of Ti MAX element in the titanate coupling agent is 10 wt%, the carbon residue rate of the water-soluble phenolic resin is 35%, and the content of Ti-Si-C ternary phase micro powder D50 is 1.5 micrometers.
7. The boron carbide ceramic of claim 6, wherein the Ti-Si-C ternary MAX phase micropowder is a Ti3SiC2Mixed powder of MAX phase and TiC, wherein Ti3SiC2The mass fraction of the MAX phase is 88-92%, and the rest is TiC phase.
8. The method for preparing a boron carbide ceramic according to claim 6 or 7, comprising the steps of:
s1 ball milling and pulping: weighing the components, and then adding the components into a ball mill once, wherein the grinding medium is a boron carbide ball with the diameter of 12mm, the ball-material ratio is 3:1, the rotating speed of the ball mill is 30r/min, and the ball milling time is 48 h;
s2 spray granulation: after the ball milling is finished, slurry is guided into a low-speed stirring barrel, and is sprayed by a centrifugal spray granulation tower, wherein the main parameters of the spray granulation tower are as follows: the air inlet temperature is 200-220 ℃, the air outlet temperature is 100-120 ℃, the rotating speed of a spray head is 300r/min, the slurry inlet amount is 50L/h, and the granulated powder is a solid sphere; s3 green pressing: molding by adopting a dry pressing-isostatic pressing mode, dry pressing the granulated powder into a green body with the required size and shape by adopting a hydraulic press, then carrying out vacuum sealing on the green body, carrying out secondary pressing on the vacuum sealed green body by using isostatic pressing so as to improve the density of the green body, wherein the green body density of the obtained boron carbide green body is 1.75 +/-0.2 g/cm3；
S4, sintering under no pressure: and (2) carrying out vacuum degumming treatment on the pressed green bodies, keeping the degumming temperature of 1650 ℃ for 2h, completely decomposing and exerting organic matters in the green bodies, sequentially placing the degummed green bodies in a graphite kiln furniture, pushing the kiln furniture into a kiln, wherein the used high-temperature vacuum sintering furnace is a microwave-assisted sintering vacuum sintering furnace, microwave generating devices are additionally arranged on furnace doors at two sides of the microwave-assisted sintering vacuum sintering furnace, and microwaves are radiated into the kiln from the furnace doors at the two sides, so that the temperature field in the kiln is more uniform, the sintering temperature range is 2180-2230 ℃, and the time is 1 h.
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