CN112457018A - Method for preparing high-entropy boron ceramic surface material by vacuum sintering - Google Patents
Method for preparing high-entropy boron ceramic surface material by vacuum sintering Download PDFInfo
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Abstract
The invention discloses a method for preparing a high-entropy boron ceramic surface material by vacuum sintering, which comprises the following components in percentage by weight: 55-78 wt% of boron carbide powder, 5-9 wt% of carbon black powder, 15-17 wt% of sintering aid and 8-11 wt% of ceramic additive, and the method comprises the following steps: and carrying out spray granulation on the boron carbide powder, the carbon black powder, the sintering aid and the ceramic additive to obtain boron carbide granulated powder. The beneficial effects are that: another key to pressureless sintered boron carbide ceramic sinter densification is the mechanism of sinter densification of the ceramic. The pressureless sintering of boron carbide ceramics generally uses carbon black as a sintering aid to promote the densification of the boron carbide ceramics by sintering. The hot-pressing sintering or the spark plasma sintering is adopted, so that the densification of the boron carbide material is ensured, the toughness and the strength of the boron carbide material are improved, and a technical basis is laid for reducing the cost of the boron carbide, promoting the industrial production and expanding the application range.
Description
Technical Field
The invention relates to the technical field of fire extinguishing devices, in particular to a method for preparing a high-entropy boron ceramic surface material by utilizing vacuum sintering.
Background
Boron carbide ceramic plays an important role in structural ceramics, has excellent characteristics, and is characterized by high hardness and low density, and the hardness of the boron carbide ceramic at normal temperature is second to that of diamond and cubic boron nitride. In addition, the material has high modulus, good corrosion resistance, excellent neutron absorption property and the like, so that the material is widely used as a high-end bulletproof material, a neutron absorption material, a high-temperature structural material, a wear-resistant material and the like, and has wide application in the fields of nuclear energy, national defense and the like. Especially in the field of protection, boron carbide ceramics are the most promising next-generation protective ceramic materials. Compared with alumina ceramics and silicon carbide ceramics, the hardness is higher and the density is lower. Therefore, the protective device has better protective performance, and can realize the light weight of the equipment, thereby improving the anti-striking capability and the maneuverability of the equipment. At present, boron carbide bulletproof ceramics are hot spots of research in various countries.
The prior pressureless sintering boron carbide ceramic technology mainly has the following problems: the pressureless sintering of the boron carbide ceramic is difficult to sinter and densify, and a proper sintering aid is required to promote the sintering and densification of the boron carbide ceramic; the pressureless sintering boron carbide ceramic has high sintering temperature, is sensitive to the sintering temperature, and is easy to generate abnormal growth of crystal grains, thereby deteriorating the performance of the ceramic.
Disclosure of Invention
The invention aims to provide a method for preparing a high-entropy boron ceramic surface material by using vacuum sintering, which avoids the problems that the traditional method for sintering boron carbide ceramic adopts carbon black as a sintering aid to promote the sintering densification of the boron carbide ceramic, and adopts a pure solid-phase sintering mechanism by only adopting the carbon black as the sintering aid, so that the sintering temperature is high, the requirement on kiln equipment is high, the sintering process is difficult to control, and the like. And hot-pressing sintering or spark plasma sintering is adopted, so that the densification of the boron carbide material is ensured, and the toughness and the strength of the boron carbide material are improved.
The technical scheme of the invention is realized as follows:
a method for preparing a high-entropy boron ceramic surface material by utilizing vacuum sintering comprises the following components in percentage by weight: 55-78 wt% of boron carbide powder, 5-9 wt% of carbon black powder, 15-17 wt% of sintering aid and 8-11 wt% of ceramic additive, and the method comprises the following steps:
(1) carrying out spray granulation on boron carbide powder, carbon black powder, a sintering aid and a ceramic additive to obtain boron carbide granulated powder;
(2) heating and stirring the boron carbide granulation powder obtained in the step (1), a surfactant and a high polymer binder, mixing, crushing, ball-milling and drying;
(3) sintering by a hot-pressing sintering or discharge plasma sintering method under the protection of vacuum or inert gas, cooling and grinding to obtain the high-entropy boron ceramic surface material.
Further, the sintering aid is one or more of modified nano carbon black, modified silicon carbide sub-micro powder, gas-phase white carbon black, titanium diboride micro powder and titanium dioxide.
Further, the ceramic additive is one or more of polyethylene glycol, amino alcohol, polyvinyl alcohol resin, maltodextrin, maltose syrup and low-viscosity water-soluble phenolic resin.
Further, the first step comprises: and carrying out spray granulation on the obtained boron carbide granulation powder by using a centrifugal spray granulation tower, wherein the inlet temperature of the centrifugal spray granulation tower is controlled to be 180-230 ℃, the outlet temperature is controlled to be 80-90 ℃, and the particle size of the granulation powder is controlled to be 50-150 meshes.
Further, the hot-pressing sintering is carried out under the protection of vacuum or reducing atmosphere, the heating rate is 20 ℃/min, after the hot-pressing sintering is carried out to 1600 ℃, pressure is applied, the sintering pressure is 30-50 MPa, the temperature is raised to 1800-1900 ℃, the heat preservation time is 5min, then the temperature is reduced to the room temperature at the rate of 100-150 ℃/min, and the product is taken out of the furnace.
Further, the spark plasma sintering is vacuum sintering, the sintering pressure is 30-50 MPa, the heating rate is 50-100 ℃/min, the heat preservation time is 10-20 min, and the sintering temperature is 1800-1900 ℃. And after the heat preservation is finished, cooling to 300-800 ℃ at the speed of 80-120 ℃/min, and cooling to room temperature along with the furnace to obtain a finished product.
The invention has the beneficial effects that: the invention adopts the boron carbide powder with large grain size, reduces the cost of pressureless sintering of the boron carbide powder, has low temperature sensitivity of the boron carbide powder with large grain size, has high grain size concentration, is not easy to generate abnormal growth of grains in the sintering process, and is beneficial to the homogenization of the internal structure of the ceramic. Another key to the sintering densification of hot pressed sintered boron carbide ceramics is the sintering densification mechanism of the ceramic. The problems that the common hot-pressing sintering of boron carbide ceramic adopts carbon black as a sintering aid to promote the sintering densification of the boron carbide ceramic, and the carbon black is adopted as the sintering aid and is a pure solid-phase sintering mechanism, so that the sintering temperature is high, the requirement on kiln equipment is high, the sintering process is not easy to control, and the like are solved. The hot-pressing sintering or the spark plasma sintering is adopted, so that the densification of the boron carbide material is ensured, the toughness and the strength of the boron carbide material are improved, and a technical basis is laid for reducing the cost of the boron carbide, promoting the industrial production and expanding the application range.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
According to an embodiment of the present invention, a method for preparing a high-entropy boron ceramic surface material using vacuum sintering is provided.
The method for preparing the high-entropy boron ceramic surface material by using vacuum sintering according to the embodiment of the invention comprises the following components in percentage by weight: 55-78 wt% of boron carbide powder, 5-9 wt% of carbon black powder, 15-17 wt% of sintering aid and 8-11 wt% of ceramic additive, and the method comprises the following steps:
(1) carrying out spray granulation on boron carbide powder, carbon black powder, a sintering aid and a ceramic additive to obtain boron carbide granulated powder;
(2) heating and stirring the boron carbide granulation powder obtained in the step (1), a surfactant and a high polymer binder, mixing, crushing, ball-milling and drying;
(3) sintering by a hot-pressing sintering or discharge plasma sintering method under the protection of vacuum or inert gas, cooling and grinding to obtain the high-entropy boron ceramic surface material.
Further, the sintering aid is one or more of modified nano carbon black, modified silicon carbide sub-micro powder, gas-phase white carbon black, titanium diboride micro powder and titanium dioxide.
Further, the ceramic additive is one or more of polyethylene glycol, amino alcohol, polyvinyl alcohol resin, maltodextrin, maltose syrup and low-viscosity water-soluble phenolic resin.
Further, the first step comprises: and carrying out spray granulation on the obtained boron carbide granulation powder by using a centrifugal spray granulation tower, wherein the inlet temperature of the centrifugal spray granulation tower is controlled to be 180-230 ℃, the outlet temperature is controlled to be 80-90 ℃, and the particle size of the granulation powder is controlled to be 50-150 meshes.
Further, the hot-pressing sintering is carried out under the protection of vacuum or reducing atmosphere, the heating rate is 20 ℃/min, after the hot-pressing sintering is carried out to 1600 ℃, pressure is applied, the sintering pressure is 30-50 MPa, the temperature is raised to 1800-1900 ℃, the heat preservation time is 5min, then the temperature is reduced to the room temperature at the rate of 100-150 ℃/min, and the product is taken out of the furnace.
Further, the spark plasma sintering is vacuum sintering, the sintering pressure is 30-50 MPa, the heating rate is 50-100 ℃/min, the heat preservation time is 10-20 min, and the sintering temperature is 1800-1900 ℃. And after the heat preservation is finished, cooling to 300-800 ℃ at the speed of 80-120 ℃/min, and cooling to room temperature along with the furnace to obtain a finished product.
Example 1
Putting 55 wt% of boron carbide powder, 3 wt% of modified nano carbon black, 2 wt% of titanium diboride, 3 wt% of modified silicon carbide submicron powder, 2 wt% of maltodextrin, 2 wt% of polyvinyl alcohol resin, 7 wt% of maltose syrup and 2 wt% of polyethylene glycol into a stirring mill, adding a certain amount of deionized water, stirring and ball-milling for 7 hours, processing the slurry by a 4-time sand mill, pumping the slurry into the stirring mill, stirring and ball-milling for 48 hours, controlling the solid content of the ceramic slurry to be 50 wt%, carrying out centrifugal spray granulation on the milled ceramic slurry, controlling the stacking density of the granulated powder to be 0.8g/cm3, controlling the inlet temperature of a centrifugal spray granulation tower to be 180 ℃, controlling the outlet temperature to be 90 ℃, controlling the grain size of the granulated powder to be between 50 and 150 meshes, carrying out dry pressing and forming on the obtained granulated powder under the pressure of 150MPa to obtain a green body, wherein the density of the green body is 1.68g/cm3, and (2) putting the obtained green body into a graphite sagger, placing graphite spheres around the green body to bury the green body in the graphite spheres, then putting the graphite sagger into a high-temperature vacuum sintering furnace, sintering by adopting a pressureless sintering process, preserving heat for 2 hours at the temperature of 1400 ℃ in the sintering process, preserving heat for 3 hours at the temperature of 2250 ℃, and finally completing sintering to obtain the boron carbide ceramic. The ceramic has the density of 2.55g/cm3, the relative compactness of 97%, the Vickers hardness of 2800MPa, the fracture toughness of 3.5MPam1/2 and the bending strength of 300 MPa.
Adopting discharge plasma sintering, wherein the hot-pressing sintering pressure is 40MPa, the sintering temperature is 1900 ℃, the heating rate is 100 ℃/min, the heat preservation time is 5min, cooling is carried out for 20min along with the system after the heat preservation is finished, and discharging is carried out.
Example 2
Putting 69 wt% of boron carbide powder, 4 wt% of modified nano carbon black, 3 wt% of titanium dioxide, 9 wt% of fumed silica, 2 wt% of polyvinyl alcohol resin, 10 wt% of maltose syrup, 2 wt% of maltodextrin and 1 wt% of amino alcohol into a stirring mill, adding a certain amount of deionized water, stirring and ball-milling for 7 hours, processing the slurry by a 4-time sand mill, pumping the slurry into the stirring mill, stirring and ball-milling for 48 hours, controlling the solid content of ceramic slurry to be 45 wt%, carrying out centrifugal spray granulation on the ground ceramic slurry, controlling the stacking density of granulated powder to be 0.7g/cm3, controlling the inlet temperature of a centrifugal spray granulation tower to be 210 ℃, controlling the outlet temperature to be 90 ℃, controlling the grain size of the granulated powder to be between 50 and 150 meshes, carrying out dry pressing molding on the obtained granulated powder under the pressure of 150MPa to obtain a green blank, controlling the density of the green blank to be 1.66g/cm3, putting the obtained green blank into a graphite sagger, and placing graphite balls around the green body to bury the green body in the graphite balls, then placing the graphite sagger into a high-temperature vacuum sintering furnace, sintering by adopting a pressureless sintering process, and carrying out heat preservation at the temperature of 1400 ℃ for 2 hours and at the temperature of 2230 ℃ for 2.5 hours in the sintering process to finally finish sintering to obtain the boron carbide ceramic. The ceramic has a density of 2.48g/cm3, a relative compactness of 97%, a Vickers hardness of 2900MPa, a fracture toughness of 5.5 MPa-m 1/2, and a bending strength of 480 MPa.
Adopting hot-pressing sintering, under the protection of vacuum or reducing atmosphere, heating up to 1600 deg.C at a rate of 20 deg.C/min, applying pressure at 40MPa, heating up to 1900 deg.C, holding for 5min, cooling to room temperature at a rate of 100 deg.C/min, and discharging.
Example 3
Putting 78 wt% of boron carbide powder, 4 wt% of modified nano carbon black, 2 wt% of titanium dioxide, 8 wt% of modified silicon carbide sub-micropowder, 2 wt% of maltodextrin, 0.5 wt% of polyvinyl alcohol resin, 6.5 wt% of low-viscosity water-soluble phenolic resin, 0.75 wt% of amino alcohol and 2 wt% of polyethylene glycol into a stirring mill, adding a certain amount of deionized water, stirring and ball-milling for 7 hours, processing the slurry by a 4-time sand mill, pumping the slurry into the stirring mill, stirring and ball-milling for 48 hours, controlling the solid content of ceramic slurry to be 70 wt%, carrying out centrifugal spray granulation on the milled ceramic slurry, controlling the stacking density of granulated powder to be 0.75g/cm3, controlling the inlet temperature of a centrifugal spray granulation tower to be 210 ℃, the outlet temperature to be 90 ℃, controlling the grain size of the granulated powder to be 50-150 meshes, and carrying out dry pressing and forming on the obtained granulated powder under the pressure of 200MPa to obtain a green body, the green body density is 1.69g/cm3, the obtained green body is placed in a graphite sagger, graphite balls are placed around the green body, the green body is buried in the graphite balls, then the graphite sagger is placed in a high-temperature vacuum sintering furnace, sintering is carried out by adopting a pressureless sintering process, heat preservation is carried out for 1.5 hours at the temperature of 1350 ℃ in the sintering process, heat preservation is carried out for 3 hours at the temperature of 2195 ℃, and finally, the boron carbide ceramic is obtained after sintering. The ceramic has a density of 2.52g/cm3, relative compactness of 98%, Vickers hardness of 3000MPa, fracture toughness of 4 MPa-m 1/2 and bending strength of 350 MPa.
Adopting discharge plasma sintering, wherein the sintering pressure is 40MPa, the sintering temperature is 1900 ℃, the heating rate is 100 ℃/min, the heat preservation time is 15min, cooling is carried out for 20min along with the system after the heat preservation is finished, and discharging is carried out.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A method for preparing a high-entropy boron ceramic surface material by utilizing vacuum sintering is characterized by comprising the following components in percentage by weight: 55-78 wt% of boron carbide powder, 5-9 wt% of carbon black powder, 15-17 wt% of sintering aid and 8-11 wt% of ceramic additive, and the method comprises the following steps:
(1) carrying out spray granulation on boron carbide powder, carbon black powder, a sintering aid and a ceramic additive to obtain boron carbide granulated powder;
(2) heating and stirring the boron carbide granulation powder obtained in the step (1), a surfactant and a high polymer binder, mixing, crushing, ball-milling and drying;
(3) sintering by a hot-pressing sintering or discharge plasma sintering method under the protection of vacuum or inert gas, cooling and grinding to obtain the high-entropy boron ceramic surface material.
2. The method for preparing the high-entropy boron ceramic surface material by using vacuum sintering as claimed in claim 1, wherein the sintering aid is one or more of modified nano carbon black, modified silicon carbide sub-micropowder, fumed silica, titanium diboride micropowder and titanium dioxide.
3. The method for preparing the high-entropy boron ceramic surface material by using vacuum sintering as claimed in claim 1, wherein the ceramic additive is one or more of polyethylene glycol, amino alcohol, polyvinyl alcohol resin, maltodextrin, maltose syrup and low-viscosity water-soluble phenolic resin.
4. The method for preparing the high-entropy boron ceramic surface material by using vacuum sintering as claimed in claim 1, wherein the step one comprises: and carrying out spray granulation on the obtained boron carbide granulation powder by using a centrifugal spray granulation tower, wherein the inlet temperature of the centrifugal spray granulation tower is controlled to be 180-230 ℃, the outlet temperature is controlled to be 80-90 ℃, and the particle size of the granulation powder is controlled to be 50-150 meshes.
5. The method for preparing a high-entropy boron ceramic surface material by using vacuum sintering as claimed in claim 1, wherein the hot-pressing sintering is carried out under vacuum or reducing atmosphere protection, the temperature rising rate is 20 ℃/min, after the hot-pressing sintering is carried out to 1600 ℃, pressure is applied, the sintering pressure is 30-50 MPa, the temperature is raised to 1800-1900 ℃, the temperature is kept for 15min, then the temperature is reduced to room temperature at the rate of 100-150 ℃/min, and the product is taken out of the furnace.
6. The method for preparing a high-entropy boron ceramic surface material by using vacuum sintering as claimed in claim 1, wherein the spark plasma sintering is vacuum sintering, the sintering pressure is 30-50 MPa, the temperature rise rate is 50-100 ℃/min, the heat preservation time is 10-20 min, and the sintering temperature is 1800-1900 ℃. And after the heat preservation is finished, cooling to 300-800 ℃ at the speed of 80-120 ℃/min, and cooling to room temperature along with the furnace to obtain a finished product.
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