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WO2025081863A1 - Method for preparing high-activity submicron boron carbide ceramic powder - Google Patents

Method for preparing high-activity submicron boron carbide ceramic powder Download PDF

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Publication number
WO2025081863A1
WO2025081863A1 PCT/CN2024/099234 CN2024099234W WO2025081863A1 WO 2025081863 A1 WO2025081863 A1 WO 2025081863A1 CN 2024099234 W CN2024099234 W CN 2024099234W WO 2025081863 A1 WO2025081863 A1 WO 2025081863A1
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boric acid
boron carbide
carbide ceramic
ceramic powder
amount
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Chinese (zh)
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尹邦进
陈冲
尹志勇
文建荣
柏飞
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Zhejiang Jicheng Advanced Ceramics Co Ltd
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Zhejiang Jicheng Advanced Ceramics Co Ltd
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Definitions

  • the invention belongs to the technical field of boron carbide materials, and in particular relates to a method for preparing high-activity submicron boron carbide ceramic powder.
  • Boron carbide is an important special ceramic material with excellent properties such as high hardness, low density, excellent thermal neutron absorption performance, high melting point, stable chemical properties and high temperature resistance. Therefore, it is widely used as high-end military bulletproof armor materials, nuclear industry shielding and control materials, advanced grinding materials, engineering ceramics and advanced refractory materials. Among them, high-end military bulletproof armor and nuclear shielding materials require boron carbide ceramics to have higher density and mechanical properties.
  • Boron carbide has a high covalent bond content of more than 93%, and has a large resistance to grain boundary movement, making sintering densification very difficult.
  • the ceramic obtained by pressureless sintering has low density and low strength and toughness. Studies have shown that reducing the particle size of boron carbide raw materials can greatly improve the density and strength of ceramics, and the use of submicron boron carbide powder is the key to preparing high-performance boron carbide ceramics.
  • Patent announcement number CN101570438B discloses a method for preparing ultrafine boron carbide powder. This production method has high energy consumption and low production efficiency, and the average particle size of the obtained original powder is relatively large, between 20-40 ⁇ m. It is also necessary to add a crushing process before sintering, which greatly increases the production cost.
  • Patent application number CN106006644A uses graphene as a carbon source, boron powder, boron oxide or boric acid as a boron source, and synthesizes nano boron carbide powder by carbon thermal reduction reaction at 900-2500 ° C under an inert protective atmosphere.
  • Patent application number CN105314636A discloses a method for preparing high-purity ultrafine boron carbide powder by plasma, which requires methane as a reaction gas and argon as a carrier. The equipment is expensive, the operation is complicated, the cost is high, and the output is low.
  • Patent application number CN105541332A discloses a method for preparing micron-sized boron carbide bulletproof ceramic powder, using 45-106 ⁇ m boron carbide powder as the The raw materials are crushed twice, pickled and impurity removed, washed multiple times, filtered, hydraulically classified, and dried by microwaves to obtain micro-nano boron carbide powder. The process is lengthy and complicated.
  • the object of the present invention is to provide a method for preparing high-activity submicron boron carbide ceramic powder which can prepare submicron material with uniform, small and controllable particle size.
  • a method for preparing high-activity submicron boron carbide ceramic powder comprising:
  • the present invention prepares boric acid gel powder containing a borate ester structure by mixing polyvinyl alcohol and boric acid, and then mixes the boric acid gel powder with organic acid salt and metal element, and fully mixes the boric acid gel powder with organic acid salt and metal element under the action of the borate ester structure, polyvinyl alcohol structure and organic acid salt in the boric acid gel powder, and forms a blank under pressure in the preparation process, and finally prepares the boron carbide ceramic powder through two-stage heat treatment.
  • the particle size of the boron carbide ceramic powder prepared by the above method of the present invention is relatively uniform, and all are processed at the submicron level. Therefore, the method of the present invention can excellently control the particle size of the prepared boron carbide ceramic powder.
  • the preparation temperature of the boric acid gel powder is 70-90°C.
  • the medium for mixing polyvinyl alcohol and boric acid is distilled water; or, the metal element is magnesium; or, the organic acid salt is sodium gluconate.
  • the amount of the metal element used is 200-400 wt % of the boric acid gel powder.
  • the preparation process includes mixing, grinding, forming, heat treatment and acid treatment.
  • the mixing is processed by mechanical roller, and the mixing time is 12-48h; or, the pressure of the billet is 150-250MPa; or, the heat treatment includes roasting at 500-900°C for 1-4h and treating at 1400-1800°C for 1-4h; or, the acid treatment is immersion in concentrated hydrochloric acid.
  • the shape of the green body obtained by green body making is cylindrical.
  • the preparation of boric acid gel powder also includes the preparation of polyvinyl alcohol solution and boric acid solution.
  • polyvinyl alcohol is added to distilled water, stirred for 2-10 minutes, and then allowed to stand for 20-60 minutes. After being evenly dispersed, the temperature is raised to 70-90° C. and stirred to dissolve to obtain the polyvinyl alcohol solution.
  • the content of polyvinyl alcohol in the polyvinyl alcohol solution is 20-40 wt %.
  • boric acid is added to distilled water and stirred and dissolved at 40-70° C. to obtain the boric acid solution.
  • the content of boric acid in the boric acid solution is 4-8 wt %.
  • a polyvinyl alcohol solution is mixed with a boric acid solution, stirred at 70-90° C. to generate a white gel precipitate, which is then dried and ground to obtain the boric acid gel powder.
  • the amount of polyvinyl alcohol in the polyvinyl alcohol solution is used as the measurement basis, and the amount of boric acid in the boric acid solution is used as the measurement basis.
  • the amount of polyvinyl alcohol used is 80-160wt% of the boric acid.
  • sodium alginate can be added in the preparation of the boric acid gel powder, the amount of polyvinyl alcohol in the polyvinyl alcohol solution is used as the measurement basis, and the amount of sodium alginate used is 30-60wt% of the polyvinyl alcohol.
  • sodium alginate can also be added, and when sodium alginate is mixed with polyvinyl alcohol and boric acid to prepare the gel powder, a composite gel structure containing borate is formed, which is combined with metal elements and organic acid salts in subsequent processes to ensure that the particle size of the boron carbide ceramic powder is controllable and is at the submicron level.
  • boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanically drum mixed for 12-48 hours, the mixture is ground, sieved, and then made into a cylindrical body at 150-250MPa, and then placed in a sealed reaction device, sealed, evacuated and then argon is introduced, roasted at 500-900°C for 1-4h, and then reacted at 1400-1800°C for 1-4h. After the reaction is completed, it is cooled, crushed, placed in concentrated hydrochloric acid, stirred at 70-90°C for 12-48h, filtered, washed, and dried to obtain boron carbide. Ceramic powder.
  • the amount of metallic magnesium used is 200-400wt% of the boric acid gel powder.
  • the organic acid salt is sodium gluconate, and the amount of the organic acid salt used is 10-30wt% of the boric acid gel powder.
  • concentrated hydrochloric acid is used in an appropriate amount to cover the solid powder, in order to remove the magnesium element.
  • the invention discloses high-activity submicron boron carbide ceramic powder prepared by the method.
  • the invention discloses the use of the high-activity submicron boron carbide ceramic powder in preparing bulletproof materials, shielding materials or ceramic materials.
  • the high-activity submicron boron carbide ceramic powder prepared in the present invention can be densified and sintered, and has good density, thereby making the ceramic have better mechanical properties.
  • the present invention adopts dissolving polyvinyl alcohol and boric acid in distilled water respectively, and then mixing to form boric acid gel powder, and finally mixing the boric acid gel powder with metal magnesium and organic acid salt and processing through subsequent processes to form boron carbide ceramic powder.
  • the particle size of the boron carbide ceramic powder prepared by the method of the present invention reaches submicron level.
  • the particle size of the boron carbide ceramic powder in the method of the present invention is related to two key steps, one is the preparation of boric acid gel powder, and the other is the mixed use of boric acid gel powder with metal magnesium and organic acid salt, so it has the following beneficial effects: submicron material can be successfully obtained, and the obtained submicron boron carbide ceramic powder has uniform particle size, small particle size and controllable particle size. Therefore, the present invention is a preparation method of high-activity submicron boron carbide ceramic powder that can prepare submicron material, uniform particle size, small particle size and controllable particle size.
  • FIG1 is an infrared spectrum of the boric acid gel powder prepared in Example 1;
  • FIG. 2 is a statistical diagram of the average particle size of boron carbide ceramic powders prepared in Examples 1-8 and Comparative Examples 1-5.
  • Example 1 A method for preparing high-activity submicron boron carbide ceramic powder
  • Preparation of polyvinyl alcohol solution add polyvinyl alcohol to distilled water, stir for 5 minutes, then stand for 30 minutes, heat to 80°C after uniform dispersion, stir and dissolve to obtain polyvinyl alcohol solution.
  • the content of polyvinyl alcohol in the polyvinyl alcohol solution is 30wt%.
  • the polyvinyl alcohol solution is 1000g, in which the content of polyvinyl alcohol is 300g.
  • boric acid solution Add boric acid into distilled water, stir and dissolve at 60°C to obtain boric acid solution.
  • the content of boric acid in the boric acid solution is 6wt%.
  • the boric acid solution is 1000g, in which the content of boric acid is 60g.
  • boric acid gel powder polyvinyl alcohol solution and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder.
  • the polyvinyl alcohol solution is measured by the amount of polyvinyl alcohol in the solution
  • the boric acid solution is measured by the amount of boric acid in the solution.
  • the amount of polyvinyl alcohol used is 110wt% of the boric acid.
  • the amount of polyvinyl alcohol solution used is 220g, that is, the amount of polyvinyl alcohol used is 66g, and the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g.
  • boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanical drum mixing for 24 hours, the mixture is ground by a vertical planetary ball mill for 30 minutes, passed through a 100 mesh sieve, and then made into a cylindrical body at 200MPa, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700°C for 2 hours, and then reacted at 1600°C for 2 hours.
  • the reaction After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30 minutes, and the crushed powder is placed in concentrated hydrochloric acid, stirred at 80°C for 24 hours, filtered, washed with deionized water, and dried at 100°C for 24 hours to obtain boron carbide ceramic powder.
  • the amount of metal magnesium used is 300wt% of the boric acid gel powder, and the amount of sodium gluconate used is 20wt% of the boric acid gel powder.
  • Concentrated hydrochloric acid is submerged in solid powder and used in an appropriate amount to remove magnesium.
  • the usage amount of boric acid gel powder is 100g
  • the usage amount of metal magnesium is 300g
  • the usage amount of sodium gluconate is 20g.
  • Example 2 A method for preparing high-activity submicron boron carbide ceramic powder
  • Example 1 Compared with Example 1, the difference between this example and Example 1 lies in the preparation of boric acid gel powder.
  • boric acid gel powder polyvinyl alcohol solution and boric acid solution were mixed, stirred at 80°C to generate a white gel precipitate, dried at 100°C for 24h, and ground in a vertical planetary ball mill for 30min to obtain boric acid gel powder.
  • the polyvinyl alcohol solution is measured by the amount of polyvinyl alcohol in the solution
  • the boric acid solution is measured by the amount of boric acid in the solution.
  • the amount of polyvinyl alcohol used is 140wt% of the boric acid.
  • the amount of polyvinyl alcohol solution used is 280g, that is, the amount of polyvinyl alcohol used is 84g, and the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g.
  • Example 3 A method for preparing high-activity submicron boron carbide ceramic powder
  • Example 1 Compared with Example 1, the preparation steps and component usage amounts of the boric acid gel powder in this example are the same, but the difference lies in the preparation of the boron carbide ceramic powder.
  • boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanical drum mixing for 24 hours, the mixture is ground by a vertical planetary ball mill for 30 minutes, passed through a 100 mesh sieve, and then made into a cylindrical body at 200MPa, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700°C for 2 hours, and then reacted at 1600°C for 2 hours. After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30 minutes, placed in concentrated hydrochloric acid, stirred at 80°C for 24 hours, filtered, washed with deionized water, and dried at 100°C for 24 hours to obtain boron carbide ceramic powder.
  • the amount of metal magnesium used is 300wt% of the boric acid gel powder, the organic acid salt is sodium gluconate, and the amount of organic acid salt used is 25wt% of the boric acid gel powder. Concentrated hydrochloric acid is submerged in the solid powder and used in an appropriate amount to remove the magnesium element.
  • the usage amount of boric acid gel powder is 100g, the usage amount of metal magnesium is 300g, and the usage amount of sodium gluconate is 25g.
  • Example 4 A method for preparing high-activity submicron boron carbide ceramic powder
  • Example 1 Compared with Example 1, the difference between this example and Example 1 lies in the preparation of boric acid gel powder.
  • boric acid gel powder Preparation of boric acid gel powder: polyvinyl alcohol solution, sodium alginate and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder.
  • the polyvinyl alcohol solution is measured based on the amount of polyvinyl alcohol in the solution
  • the boric acid solution is measured based on the amount of boric acid in the solution.
  • the amount of polyvinyl alcohol used is 110wt% of boric acid
  • the amount of sodium alginate used is 40wt% of polyvinyl alcohol.
  • the amount of polyvinyl alcohol solution used is 220g, that is, the amount of polyvinyl alcohol used is 66g, the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g, and the amount of sodium alginate used is 26.4g.
  • Example 4 The subsequent preparation steps of the boron carbide ceramic powder and the amounts of each component used in Example 4 are the same as those in Example 1.
  • Example 5 A method for preparing high-activity submicron boron carbide ceramic powder
  • Example 2 Compared with Example 2, the present embodiment differs in that the preparation of the boric acid gel powder, the subsequent preparation steps of the boron carbide ceramic powder, and the amount of each component used are the same as those in Example 2.
  • boric acid gel powder Preparation of boric acid gel powder: polyvinyl alcohol solution, sodium alginate and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder.
  • the polyvinyl alcohol solution is measured based on the amount of polyvinyl alcohol in the solution
  • the boric acid solution is measured based on the amount of boric acid in the solution.
  • the amount of polyvinyl alcohol used is 140wt% of boric acid
  • the amount of sodium alginate used is 40wt% of polyvinyl alcohol.
  • the amount of polyvinyl alcohol solution used is 280g, that is, the amount of polyvinyl alcohol used is 84g, the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g, and the amount of sodium alginate used is 33.6g.
  • Example 6 A method for preparing high-activity submicron boron carbide ceramic powder
  • Example 3 Compared with Example 3, the difference between this embodiment lies in the preparation of the boric acid gel powder, the subsequent preparation steps of the boron carbide ceramic powder, and the amount of each component used are the same as those in Example 3.
  • boric acid gel powder Preparation of boric acid gel powder: polyvinyl alcohol solution, sodium alginate and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder.
  • the polyvinyl alcohol solution is measured based on the amount of polyvinyl alcohol in the solution
  • the boric acid solution is measured based on the amount of boric acid in the solution.
  • the amount of polyvinyl alcohol used is 110wt% of boric acid
  • the amount of sodium alginate used is 40wt% of polyvinyl alcohol.
  • the amount of polyvinyl alcohol solution used is 220g, that is, the amount of polyvinyl alcohol used is 66g, the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g, and the amount of sodium alginate used is 26.4g.
  • Example 7 A method for preparing high-activity submicron boron carbide ceramic powder
  • Example 4 Compared with Example 4, the preparation steps of the boric acid gel powder and the usage amounts of each component in this example are the same, but the difference lies in the preparation of the boron carbide ceramic powder.
  • boron carbide ceramic powder Boric acid gel powder was mixed with magnesium metal and organic acid salt, and the mixture was mixed in a mechanical drum for 24 hours. The mixture was ground in a vertical planetary ball mill for 30 minutes, passed through a 100-mesh sieve, and then 200MPa, a cylindrical body is made, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700°C for 2h, and then reacted at 1600°C for 2h.
  • the reaction After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30min, and the crushed powder is placed in concentrated hydrochloric acid, stirred at 80°C for 24h, filtered, washed with deionized water, and dried at 100°C for 24h to obtain boron carbide ceramic powder.
  • the amount of metallic magnesium used is 300wt% of the boric acid gel powder, and the amount of sodium gluconate used is 25wt% of the boric acid gel powder.
  • Concentrated hydrochloric acid is used to cover the solid powder and is used in an appropriate amount to remove the magnesium element.
  • the amount of boric acid gel powder used is 100g, the amount of metallic magnesium used is 300g, and the amount of sodium gluconate used is 25g.
  • Example 8 A method for preparing high-activity submicron boron carbide ceramic powder
  • Example 5 Compared with Example 5, the preparation steps of the boric acid gel powder and the usage amounts of each component in this example are the same, but the difference lies in the preparation of the boron carbide ceramic powder.
  • boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanical drum mixing for 24 hours, the mixture is ground by a vertical planetary ball mill for 30 minutes, passed through a 100 mesh sieve, and then made into a cylindrical body at 200MPa, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700°C for 2 hours, and then reacted at 1600°C for 2 hours.
  • the reaction After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30 minutes, and the crushed powder is placed in concentrated hydrochloric acid, stirred at 80°C for 24 hours, filtered, washed with deionized water, and dried at 100°C for 24 hours to obtain boron carbide ceramic powder.
  • the amount of metal magnesium used is 300wt% of the boric acid gel powder, and the amount of sodium gluconate used is 25wt% of the boric acid gel powder.
  • Concentrated hydrochloric acid is submerged in solid powder and used in an appropriate amount to remove magnesium.
  • the usage amount of boric acid gel powder is 100g
  • the usage amount of metal magnesium is 300g
  • the usage amount of sodium gluconate is 25g.
  • Comparative Example 1 A method for preparing boron carbide ceramic powder
  • boric acid gel powder polyvinyl alcohol solution and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder.
  • the polyvinyl alcohol solution is measured by the amount of polyvinyl alcohol in the solution
  • the boric acid solution is measured by the amount of boric acid in the solution.
  • the amount of polyvinyl alcohol used is 50wt% of the boric acid.
  • the amount of polyvinyl alcohol solution used is 100g, that is, the amount of polyvinyl alcohol used is 30g, and the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g.
  • Comparative Example 2 A method for preparing boron carbide ceramic powder
  • boric acid gel powder polyvinyl alcohol solution and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder.
  • the polyvinyl alcohol solution is measured by the amount of polyvinyl alcohol in the solution
  • the boric acid solution is measured by the amount of boric acid in the solution.
  • the amount of polyvinyl alcohol used is 200wt% of boric acid.
  • the amount of polyvinyl alcohol solution used is 400g, that is, the amount of polyvinyl alcohol used is 120g, and the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g.
  • Comparative Example 3 A method for preparing boron carbide ceramic powder
  • Example 1 The difference between this comparative example and Example 1 lies in the preparation of the boron carbide ceramic powder.
  • boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanical drum mixing for 24 hours, the mixture is ground by a vertical planetary ball mill for 30 minutes, passed through a 100 mesh sieve, and then made into a cylindrical body at 200MPa, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700°C for 2 hours, and then reacted at 1600°C for 2 hours.
  • the reaction After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30 minutes, and the crushed powder is placed in concentrated hydrochloric acid, stirred at 80°C for 24 hours, filtered, washed with deionized water, and dried at 100°C for 24 hours to obtain boron carbide ceramic powder.
  • the amount of metal magnesium used is 300wt% of the boric acid gel powder
  • the organic acid salt is sodium gluconate
  • the amount of organic acid salt used is 5wt% of the boric acid gel powder.
  • Concentrated hydrochloric acid is not enough to cover the solid powder, and it is used in an appropriate amount.
  • Comparative Example 4 A method for preparing boron carbide ceramic powder
  • Example 1 The difference between this comparative example and Example 1 lies in the preparation of the boron carbide ceramic powder.
  • boric acid gel powder is mixed with metal magnesium and organic acid salt, and the mixture is mixed by mechanical drum for 24 hours.
  • the mixture is ground by vertical planetary ball mill for 30 minutes, passed through a 100-mesh sieve, and then made into a cylindrical body at 200 MPa, and then placed in a sealed reaction device, sealed, evacuated and then introduced with argon, baked at 700°C for 2 hours, and then reacted at 1600°C for 2 hours. After the reaction is completed, it is cooled and crushed by vertical planetary ball mill for 30 minutes.
  • the crushed powder is placed in concentrated hydrochloric acid, stirred at 80°C for 24 hours, filtered, washed with deionized water, and dried at 100°C for 24 hours to obtain boron carbide ceramic powder.
  • the amount of metal magnesium used is 300wt% of the boric acid gel powder, the organic acid salt is sodium gluconate, and the amount of organic acid salt used is 35wt% of boric acid gel powder.
  • Concentrated hydrochloric acid is used in an appropriate amount until the solid powder is submerged.
  • the amount of boric acid gel powder used is 100g, the amount of magnesium metal used is 300g, and the organic acid salt is sodium gluconate, and the amount of organic acid salt used is 35g.
  • Comparative Example 5 A method for preparing boron carbide ceramic powder
  • Example 4 The difference between this comparative example and Example 4 lies in the preparation of the boric acid gel powder, in which only the amount of polyvinyl alcohol is completely replaced by sodium alginate, and other reagents and their amounts remain unchanged.
  • the boric acid gel powder prepared in Example 1 was characterized by infrared spectroscopy. The results are shown in FIG1 .
  • the infrared absorption peak of hydroxyl group is at 3251 cm -1
  • the infrared absorption peak of carbon-oxygen double bond is at 1732 cm -1
  • the infrared absorption peak of boron-oxygen-carbon is at 1278 cm -1
  • the infrared absorption peak of carbon-oxygen-carbon is at 1091 cm -1 .
  • the present invention uses a laser particle size analyzer to analyze the particle size of the boron carbide ceramic powder prepared in each embodiment 1-8 and comparative example 1-5.
  • the scattering angle of the laser particle size analyzer is 90 degrees, and the particle size range is 10 nanometers to 3000 microns.
  • the particle size analysis results are shown in Figure 2, wherein: S1 is embodiment 1, S2 is embodiment 2, S3 is embodiment 3, S4 is embodiment 4, S5 is embodiment 5, S6 is embodiment 6, S7 is embodiment 7, S8 is embodiment 8, D1 is comparative example 1, D2 is comparative example 2, D3 is comparative example 3, D4 is comparative example 4, and D5 is comparative example 5.
  • the particle size of the obtained boron carbide ceramic powder is relatively uniform, and the distribution amount of oversized or undersized particle powder is small, that is, the distribution amount under the average particle size of the particle size treatment is high.
  • the invention prepares boron carbide ceramic powder by dissolving polyvinyl alcohol and boric acid in distilled water respectively, mixing the mixture to prepare boric acid gel powder, and finally mixing the boric acid gel powder with metal magnesium and organic acid salt and treating the mixture through subsequent steps.
  • the particle size of the boron carbide ceramic powder prepared by the method of the invention reaches submicron level.
  • the particle size of boron carbide ceramic powder in the method of the present invention is related to two key steps: the preparation of boric acid gel powder and the mixing of boric acid gel powder with metal magnesium and organic acid salt.
  • the amount of polyvinyl alcohol and boric acid used is very important. Under the condition that the boric acid gel powder prepared therefrom is mixed with metal magnesium and organic acid salt, a submicron boron carbide ceramic powder is successfully obtained. If the usage of polyvinyl alcohol and boric acid is outside the specific usage disclosed in the present invention, the average particle size of the obtained boron carbide ceramic powder is above 1 micron, that is, the usage of polyvinyl alcohol relative to boric acid is too low or too high, which is not good.
  • the usage of organic acid salt in the next step is also very important.
  • the average particle size of the obtained boron carbide ceramic powder is above 1 micron, and the particle size is uneven.
  • the specific usage of polyvinyl alcohol and boric acid in the boric acid gel powder boron carbide ceramic powders with different average particle sizes can be obtained, but the particle sizes are all at the submicron level.
  • the organic acid salt can also obtain boron carbide ceramic powders with different average particle sizes under the specific usage of the present invention, and the particle size is still at the submicron level.
  • the present invention has been further developed and found that sodium alginate is used in the step of preparing boric acid gel powder.
  • the use of sodium alginate can reduce the average particle size of boron carbide ceramic powder. If the polyvinyl alcohol in the preparation of boric acid gel powder is completely replaced by sodium alginate, the average particle size of the boron carbide ceramic powder is above 1 micron; that is, using sodium alginate alone cannot obtain submicron boron carbide ceramic powder.

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Abstract

Disclosed is a method for preparing a high-activity submicron boron carbide ceramic powder, belonging to the technical field of boron carbide materials, and specifically relating to: separately dissolving a polyvinyl alcohol and boric acid in distilled water, then mixing to form a boric acid gel powder, and finally mixing the boric acid gel powder with metallic magnesium and an organic acid salt, and treating in a subsequent process, to prepare boron carbide ceramic powder. The particle size of the boron carbide ceramic powder prepared by the method of the present invention reaches the submicron level. In the method of the present invention, the particle size of the boron carbide ceramic powder is related to two key steps: one is the preparation of the boric acid gel powder, and the other is the mixing of the boric acid gel powder with the metallic magnesium and organic acid salt. The submicron boron carbide ceramic powder material prepared by the method of the present invention has uniform particle size, small particle size and controllable particle size.

Description

一种高活性亚微米级碳化硼陶瓷粉体的制备方法A method for preparing high-activity submicron boron carbide ceramic powder 技术领域Technical Field

本发明属于碳化硼材料技术领域，具体涉及一种高活性亚微米级碳化硼陶瓷粉体的制备方法。The invention belongs to the technical field of boron carbide materials, and in particular relates to a method for preparing high-activity submicron boron carbide ceramic powder.

背景技术Background Art

碳化硼是一种重要的特种陶瓷材料，具有高硬度、低密度、优良的热中子吸收性能、高熔点、化学性质稳定和耐高温等优良特性，因此被广泛用作高端军工防弹装甲材料、核工业屏蔽和控制材料、高级研磨材料、工程陶瓷以及高级耐火材料等，其中高端军工防弹装甲和核屏蔽材料等领域均要求碳化硼陶瓷具有较高的致密度和力学性能。Boron carbide is an important special ceramic material with excellent properties such as high hardness, low density, excellent thermal neutron absorption performance, high melting point, stable chemical properties and high temperature resistance. Therefore, it is widely used as high-end military bulletproof armor materials, nuclear industry shielding and control materials, advanced grinding materials, engineering ceramics and advanced refractory materials. Among them, high-end military bulletproof armor and nuclear shielding materials require boron carbide ceramics to have higher density and mechanical properties.

碳化硼共价键含量较高，高达93％以上，晶界移动阻力大，烧结致密化非常困难，以普通微米级碳化硼粉体为原料，采用无压烧结所得陶瓷致密度低且强度和韧性都偏低。研究表明，降低碳化硼原料粒度可大幅度提高陶瓷的致密度和强度，其中采用亚微米碳化硼粉体是制备高性能碳化硼陶瓷的关键。Boron carbide has a high covalent bond content of more than 93%, and has a large resistance to grain boundary movement, making sintering densification very difficult. Using ordinary micron-sized boron carbide powder as raw material, the ceramic obtained by pressureless sintering has low density and low strength and toughness. Studies have shown that reducing the particle size of boron carbide raw materials can greatly improve the density and strength of ceramics, and the use of submicron boron carbide powder is the key to preparing high-performance boron carbide ceramics.

专利公告号CN101570438B公布了一种超细碳化硼粉的制备方法，这种生产方法能耗大，生产效率低，而且所得原始粉末平均粒径较大，在20-40μm之间，烧结前还需要增加破碎处理工艺，大大增加了生产成本。专利公开号为CN106006644A的专利申请，以石墨烯为碳源，硼粉、氧化硼或硼酸为硼源，在惰性保护气氛下，在900-2500℃下经碳热还原反应合成纳米碳化硼粉体，该方法以石墨烯为原料，价格昂贵难得，且需在惰性保护气氛下进行，难以实施工业化生产。专利公开号为CN105314636A的专利申请公开了一种等离子体制备高纯超细碳化硼粉体的方法，需以甲烷为反应气体，氩气为载体，设备昂贵，操作复杂，成本较高，产量较低。专利公开号CN105541332A的专利申请公开了一种微米级碳化硼防弹陶瓷粉体的制备方法，以45-106μm的碳化硼粉体为 原料，经两次破碎、酸洗除杂、多次水洗、压滤、水力分级、微波干燥等工序得到微纳米级的碳化硼粉体，工艺冗长复杂。Patent announcement number CN101570438B discloses a method for preparing ultrafine boron carbide powder. This production method has high energy consumption and low production efficiency, and the average particle size of the obtained original powder is relatively large, between 20-40 μm. It is also necessary to add a crushing process before sintering, which greatly increases the production cost. Patent application number CN106006644A uses graphene as a carbon source, boron powder, boron oxide or boric acid as a boron source, and synthesizes nano boron carbide powder by carbon thermal reduction reaction at 900-2500 ° C under an inert protective atmosphere. This method uses graphene as a raw material, which is expensive and rare, and needs to be carried out under an inert protective atmosphere, making it difficult to implement industrial production. Patent application number CN105314636A discloses a method for preparing high-purity ultrafine boron carbide powder by plasma, which requires methane as a reaction gas and argon as a carrier. The equipment is expensive, the operation is complicated, the cost is high, and the output is low. Patent application number CN105541332A discloses a method for preparing micron-sized boron carbide bulletproof ceramic powder, using 45-106μm boron carbide powder as the The raw materials are crushed twice, pickled and impurity removed, washed multiple times, filtered, hydraulically classified, and dried by microwaves to obtain micro-nano boron carbide powder. The process is lengthy and complicated.

因此，针对目前亚微米碳化硼陶瓷粉体不断增加的需求量和现有大规模生产和制备存在的诸多弊端。Therefore, in view of the increasing demand for submicron boron carbide ceramic powder and the many drawbacks of existing large-scale production and preparation.

发明内容Summary of the invention

本发明的目的在于提供一种可以制备得到亚微米级材料、粒径均匀、粒径小以及粒径可控的高活性亚微米级碳化硼陶瓷粉体的制备方法。The object of the present invention is to provide a method for preparing high-activity submicron boron carbide ceramic powder which can prepare submicron material with uniform, small and controllable particle size.

本发明为实现上述目的所采取的技术方案为：The technical solution adopted by the present invention to achieve the above-mentioned purpose is:

一种高活性亚微米级碳化硼陶瓷粉体的制备方法，包括：A method for preparing high-activity submicron boron carbide ceramic powder, comprising:

S1，将聚乙烯醇和硼酸混合，经反应制成硼酸凝胶粉体；聚乙烯醇的使用量为硼酸的80-160wt％；S1, mixing polyvinyl alcohol and boric acid to form boric acid gel powder through reaction; the amount of polyvinyl alcohol used is 80-160wt% of the boric acid;

S2，将硼酸凝胶粉体、有机酸盐和金属元素混合，经制备工序制成高活性亚微米级碳化硼陶瓷粉体；有机酸盐的使用量为硼酸凝胶粉体的10-30wt％。本发明通过将聚乙烯醇和硼酸混合制成含有硼酸酯结构的硼酸凝胶粉体，然后再将其与有机酸盐、金属元素混合，在硼酸凝胶粉体中硼酸酯结构、聚乙烯醇结构及有机酸盐的作用下，使硼酸凝胶粉体与有机酸盐、金属元素充分混合，并在制备工序中通过在压力下成型制坯，最后经两段热处理制备得到碳化硼陶瓷粉体，本发明上述方法制备得到的碳化硼陶瓷粉体的粒径较为均匀，且均处理于亚微米级，因此，本发明方法可以优异的控制制备的碳化硼陶瓷粉体的粒径。S2, mixing boric acid gel powder, organic acid salt and metal element, and preparing high-activity submicron boron carbide ceramic powder through a preparation process; the amount of organic acid salt used is 10-30wt% of the boric acid gel powder. The present invention prepares boric acid gel powder containing a borate ester structure by mixing polyvinyl alcohol and boric acid, and then mixes the boric acid gel powder with organic acid salt and metal element, and fully mixes the boric acid gel powder with organic acid salt and metal element under the action of the borate ester structure, polyvinyl alcohol structure and organic acid salt in the boric acid gel powder, and forms a blank under pressure in the preparation process, and finally prepares the boron carbide ceramic powder through two-stage heat treatment. The particle size of the boron carbide ceramic powder prepared by the above method of the present invention is relatively uniform, and all are processed at the submicron level. Therefore, the method of the present invention can excellently control the particle size of the prepared boron carbide ceramic powder.

优选地，硼酸凝胶粉体的制备温度为70-90℃。Preferably, the preparation temperature of the boric acid gel powder is 70-90°C.

优选地，聚乙烯醇和硼酸混合的介质为蒸馏水；或，金属元素为镁元素；或，有机酸盐为葡萄糖酸钠。Preferably, the medium for mixing polyvinyl alcohol and boric acid is distilled water; or, the metal element is magnesium; or, the organic acid salt is sodium gluconate.

优选地，金属元素的使用量为硼酸凝胶粉体的200-400wt％。Preferably, the amount of the metal element used is 200-400 wt % of the boric acid gel powder.

优选地，制备工序包括混料、研磨、制坯、热处理和酸处理。Preferably, the preparation process includes mixing, grinding, forming, heat treatment and acid treatment.

更优选地，混料采用机械滚筒处理，混料时间为12-48h；或，制坯的压力为150-250MPa；或，热处理包括500-900℃下焙烧1-4h，以及在1400-1800℃下处理1-4h；或，酸处理为浸于浓盐酸中处理。 More preferably, the mixing is processed by mechanical roller, and the mixing time is 12-48h; or, the pressure of the billet is 150-250MPa; or, the heat treatment includes roasting at 500-900℃ for 1-4h and treating at 1400-1800℃ for 1-4h; or, the acid treatment is immersion in concentrated hydrochloric acid.

更优选地，制坯得到的坯体的形状为圆柱状。More preferably, the shape of the green body obtained by green body making is cylindrical.

优选地，硼酸凝胶粉体的制备中还包括聚乙烯醇溶液的配制和硼酸溶液的配制。Preferably, the preparation of boric acid gel powder also includes the preparation of polyvinyl alcohol solution and boric acid solution.

更优选地，聚乙烯醇溶液的配制中，将聚乙烯醇加入蒸馏水中，搅拌2-10min，然后静置处理20-60min，分散均匀后再升温至70-90℃，搅拌溶解，得到聚乙烯醇溶液。More preferably, in the preparation of the polyvinyl alcohol solution, polyvinyl alcohol is added to distilled water, stirred for 2-10 minutes, and then allowed to stand for 20-60 minutes. After being evenly dispersed, the temperature is raised to 70-90° C. and stirred to dissolve to obtain the polyvinyl alcohol solution.

更优选地，聚乙烯醇溶液的配制中，聚乙烯醇溶液中聚乙烯醇的含量为20-40wt％。More preferably, in the preparation of the polyvinyl alcohol solution, the content of polyvinyl alcohol in the polyvinyl alcohol solution is 20-40 wt %.

更优选地，硼酸溶液的配制中，将硼酸加入蒸馏水中，在40-70℃下搅拌溶解，得到硼酸溶液。More preferably, in the preparation of the boric acid solution, boric acid is added to distilled water and stirred and dissolved at 40-70° C. to obtain the boric acid solution.

更优选地，硼酸溶液的配制中，硼酸溶液中硼酸的含量为4-8wt％。More preferably, in the preparation of the boric acid solution, the content of boric acid in the boric acid solution is 4-8 wt %.

优选地，硼酸凝胶粉体的制备中，将聚乙烯醇溶液与硼酸溶液混合，在70-90℃下搅拌，生成白色凝胶沉淀，干燥，研磨，得到硼酸凝胶粉体。Preferably, in the preparation of the boric acid gel powder, a polyvinyl alcohol solution is mixed with a boric acid solution, stirred at 70-90° C. to generate a white gel precipitate, which is then dried and ground to obtain the boric acid gel powder.

更优选地，硼酸凝胶粉体的制备中，聚乙烯醇溶液以其溶液中聚乙烯醇的量为计量基准，硼酸溶液以其溶液中硼酸的量为计量基准，聚乙烯醇溶液与硼酸溶液混合中，聚乙烯醇的使用量为硼酸的80-160wt％。More preferably, in the preparation of boric acid gel powder, the amount of polyvinyl alcohol in the polyvinyl alcohol solution is used as the measurement basis, and the amount of boric acid in the boric acid solution is used as the measurement basis. In the mixing of the polyvinyl alcohol solution and the boric acid solution, the amount of polyvinyl alcohol used is 80-160wt% of the boric acid.

优选地，硼酸凝胶粉体的制备中还可以加入海藻酸钠，聚乙烯醇溶液以其溶液中聚乙烯醇的量为计量基准，海藻酸钠的使用量为聚乙烯醇的30-60wt％。本发明在制备硼酸凝胶粉体时，还可以加入海藻酸钠，海藻酸钠与聚乙烯醇、硼酸混合进行制备凝胶粉体时，形成含有硼酸酯的复合凝胶结构，与后续工序中金属元素、有机酸盐相互结合，保证碳化硼陶瓷粉体的粒径可控，处于亚微米级。Preferably, sodium alginate can be added in the preparation of the boric acid gel powder, the amount of polyvinyl alcohol in the polyvinyl alcohol solution is used as the measurement basis, and the amount of sodium alginate used is 30-60wt% of the polyvinyl alcohol. In the preparation of the boric acid gel powder of the present invention, sodium alginate can also be added, and when sodium alginate is mixed with polyvinyl alcohol and boric acid to prepare the gel powder, a composite gel structure containing borate is formed, which is combined with metal elements and organic acid salts in subsequent processes to ensure that the particle size of the boron carbide ceramic powder is controllable and is at the submicron level.

优选地，碳化硼陶瓷粉体的制备中，将硼酸凝胶粉体与金属镁、有机酸盐混合，机械滚筒混料12-48h，混合物研磨，过筛，然后在150-250MPa下制成圆柱状坯体，然后置于密封反应装置中，密封，抽真空后通入氩气，在500-900℃下焙烧1-4h，然后在1400-1800℃下反应1-4h，反应完成后，冷却，破碎，置于浓盐酸中，在70-90℃下搅拌处理12-48h，抽滤，洗涤，干燥，得到碳化硼 陶瓷粉体。Preferably, in the preparation of boron carbide ceramic powder, boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanically drum mixed for 12-48 hours, the mixture is ground, sieved, and then made into a cylindrical body at 150-250MPa, and then placed in a sealed reaction device, sealed, evacuated and then argon is introduced, roasted at 500-900°C for 1-4h, and then reacted at 1400-1800°C for 1-4h. After the reaction is completed, it is cooled, crushed, placed in concentrated hydrochloric acid, stirred at 70-90°C for 12-48h, filtered, washed, and dried to obtain boron carbide. Ceramic powder.

更优选地，碳化硼陶瓷粉体的制备中，金属镁的使用量为硼酸凝胶粉体的200-400wt％。More preferably, in the preparation of boron carbide ceramic powder, the amount of metallic magnesium used is 200-400wt% of the boric acid gel powder.

更优选地，碳化硼陶瓷粉体的制备中，有机酸盐为葡萄糖酸钠，有机酸盐的使用量为硼酸凝胶粉体的10-30wt％。More preferably, in the preparation of boron carbide ceramic powder, the organic acid salt is sodium gluconate, and the amount of the organic acid salt used is 10-30wt% of the boric acid gel powder.

更优选地，碳化硼陶瓷粉体的制备中，浓盐酸没过固体粉末，适量使用，目的是除去镁元素。More preferably, in the preparation of boron carbide ceramic powder, concentrated hydrochloric acid is used in an appropriate amount to cover the solid powder, in order to remove the magnesium element.

本发明公开了上述方法制备得到的高活性亚微米级碳化硼陶瓷粉体。The invention discloses high-activity submicron boron carbide ceramic powder prepared by the method.

本发明公开了上述高活性亚微米级碳化硼陶瓷粉体在制备防弹材料、屏蔽材料或陶瓷材料中的用途。The invention discloses the use of the high-activity submicron boron carbide ceramic powder in preparing bulletproof materials, shielding materials or ceramic materials.

本发明中制备的高活性亚微米级碳化硼陶瓷粉体可以致密化烧结，致密度好，进而使陶瓷力学性能较好。The high-activity submicron boron carbide ceramic powder prepared in the present invention can be densified and sintered, and has good density, thereby making the ceramic have better mechanical properties.

本发明采用了将聚乙烯醇和硼酸分别于蒸馏水中溶解，然后再经混合制成硼酸凝胶粉体，最后再由硼酸凝胶粉体与金属镁、有机酸盐混合并经后续工序处理，制成碳化硼陶瓷粉体，本发明方法制备的碳化硼陶瓷粉体粒径达到亚微米级，本发明方法中碳化硼陶瓷粉体粒径跟两个关键步骤相关，一是硼酸凝胶粉体的制备，二是硼酸凝胶粉体与金属镁、有机酸盐的混合使用，因而具有如下有益效果：可以成功得到亚微米级材料、得到的亚微米级碳化硼陶瓷粉体的粒径均匀、粒径小且粒径可控。因此，本发明是一种可以制备得到亚微米级材料、粒径均匀、粒径小以及粒径可控的高活性亚微米级碳化硼陶瓷粉体的制备方法。The present invention adopts dissolving polyvinyl alcohol and boric acid in distilled water respectively, and then mixing to form boric acid gel powder, and finally mixing the boric acid gel powder with metal magnesium and organic acid salt and processing through subsequent processes to form boron carbide ceramic powder. The particle size of the boron carbide ceramic powder prepared by the method of the present invention reaches submicron level. The particle size of the boron carbide ceramic powder in the method of the present invention is related to two key steps, one is the preparation of boric acid gel powder, and the other is the mixed use of boric acid gel powder with metal magnesium and organic acid salt, so it has the following beneficial effects: submicron material can be successfully obtained, and the obtained submicron boron carbide ceramic powder has uniform particle size, small particle size and controllable particle size. Therefore, the present invention is a preparation method of high-activity submicron boron carbide ceramic powder that can prepare submicron material, uniform particle size, small particle size and controllable particle size.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为实施例1中制备得到的硼酸凝胶粉体的红外光谱图；FIG1 is an infrared spectrum of the boric acid gel powder prepared in Example 1;

图2为实施例1-8以及对比例1-5制备得到的碳化硼陶瓷粉体的平均粒径统计图。FIG. 2 is a statistical diagram of the average particle size of boron carbide ceramic powders prepared in Examples 1-8 and Comparative Examples 1-5.

具体实施方式DETAILED DESCRIPTION

以下结合具体实施方式和附图对本发明的技术方案作进一步详细描述： The technical solution of the present invention is further described in detail below in conjunction with specific implementations and drawings:

实施例1：一种高活性亚微米级碳化硼陶瓷粉体的制备方法Example 1: A method for preparing high-activity submicron boron carbide ceramic powder

聚乙烯醇溶液的配制：将聚乙烯醇加入蒸馏水中，搅拌5min，然后静置处理30min，分散均匀后再升温至80℃，搅拌溶解，得到聚乙烯醇溶液。聚乙烯醇溶液中聚乙烯醇的含量为30wt％。聚乙烯醇溶液为1000g，其中，聚乙烯醇的含量为300g。Preparation of polyvinyl alcohol solution: add polyvinyl alcohol to distilled water, stir for 5 minutes, then stand for 30 minutes, heat to 80°C after uniform dispersion, stir and dissolve to obtain polyvinyl alcohol solution. The content of polyvinyl alcohol in the polyvinyl alcohol solution is 30wt%. The polyvinyl alcohol solution is 1000g, in which the content of polyvinyl alcohol is 300g.

硼酸溶液的配制：将硼酸加入蒸馏水中，在60℃下搅拌溶解，得到硼酸溶液。硼酸溶液中硼酸的含量为6wt％。硼酸溶液为1000g，其中，硼酸的含量为60g。Preparation of boric acid solution: Add boric acid into distilled water, stir and dissolve at 60°C to obtain boric acid solution. The content of boric acid in the boric acid solution is 6wt%. The boric acid solution is 1000g, in which the content of boric acid is 60g.

硼酸凝胶粉体的制备：将聚乙烯醇溶液与硼酸溶液混合，在80℃下搅拌，生成白色凝胶沉淀，在100℃干燥24h，立式行星式球磨机研磨30min，得到硼酸凝胶粉体。聚乙烯醇溶液以其溶液中聚乙烯醇的量为计量基准，硼酸溶液以其溶液中硼酸的量为计量基准，聚乙烯醇溶液与硼酸溶液混合中，聚乙烯醇的使用量为硼酸的110wt％。聚乙烯醇溶液的使用量为220g，即聚乙烯醇的用量为66g，硼酸溶液的使用量为1000g，即硼酸的用量为60g。Preparation of boric acid gel powder: polyvinyl alcohol solution and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder. The polyvinyl alcohol solution is measured by the amount of polyvinyl alcohol in the solution, and the boric acid solution is measured by the amount of boric acid in the solution. In the mixing of polyvinyl alcohol solution and boric acid solution, the amount of polyvinyl alcohol used is 110wt% of the boric acid. The amount of polyvinyl alcohol solution used is 220g, that is, the amount of polyvinyl alcohol used is 66g, and the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g.

碳化硼陶瓷粉体的制备：将硼酸凝胶粉体与金属镁、有机酸盐混合，机械滚筒混料24h，混合物经立式行星式球磨机研磨30min，过100目筛，然后在200MPa下制成圆柱状坯体，然后置于密封反应装置中，密封，抽真空后通入氩气，在700℃下焙烧2h，然后在1600℃下反应2h，反应完成后，冷却，立式行星式球磨机破碎30min，破碎后的粉体置于浓盐酸中，在80℃下搅拌处理24h，抽滤，去离子水洗涤，在100℃干燥24h，得到碳化硼陶瓷粉体。金属镁的使用量为硼酸凝胶粉体的300wt％，葡萄糖酸钠的使用量为硼酸凝胶粉体的20wt％。浓盐酸没过固体粉末，适量使用，目的是除去镁元素。硼酸凝胶粉体的使用量为100g，金属镁的使用量为300g，葡萄糖酸钠的使用量为20g。Preparation of boron carbide ceramic powder: boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanical drum mixing for 24 hours, the mixture is ground by a vertical planetary ball mill for 30 minutes, passed through a 100 mesh sieve, and then made into a cylindrical body at 200MPa, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700℃ for 2 hours, and then reacted at 1600℃ for 2 hours. After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30 minutes, and the crushed powder is placed in concentrated hydrochloric acid, stirred at 80℃ for 24 hours, filtered, washed with deionized water, and dried at 100℃ for 24 hours to obtain boron carbide ceramic powder. The amount of metal magnesium used is 300wt% of the boric acid gel powder, and the amount of sodium gluconate used is 20wt% of the boric acid gel powder. Concentrated hydrochloric acid is submerged in solid powder and used in an appropriate amount to remove magnesium. The usage amount of boric acid gel powder is 100g, the usage amount of metal magnesium is 300g, and the usage amount of sodium gluconate is 20g.

实施例2：一种高活性亚微米级碳化硼陶瓷粉体的制备方法Example 2: A method for preparing high-activity submicron boron carbide ceramic powder

本实施例与实施例1相比，不同之处在于硼酸凝胶粉体的制备。Compared with Example 1, the difference between this example and Example 1 lies in the preparation of boric acid gel powder.

硼酸凝胶粉体的制备：将聚乙烯醇溶液与硼酸溶液混合，在80℃下搅拌，生成白色凝胶沉淀，在100℃干燥24h，立式行星式球磨机研磨30min，得到硼 酸凝胶粉体。聚乙烯醇溶液以其溶液中聚乙烯醇的量为计量基准，硼酸溶液以其溶液中硼酸的量为计量基准，聚乙烯醇溶液与硼酸溶液混合中，聚乙烯醇的使用量为硼酸的140wt％。聚乙烯醇溶液的使用量为280g，即聚乙烯醇的用量为84g，硼酸溶液的使用量为1000g，即硼酸的用量为60g。Preparation of boric acid gel powder: polyvinyl alcohol solution and boric acid solution were mixed, stirred at 80°C to generate a white gel precipitate, dried at 100°C for 24h, and ground in a vertical planetary ball mill for 30min to obtain boric acid gel powder. Acid gel powder. The polyvinyl alcohol solution is measured by the amount of polyvinyl alcohol in the solution, and the boric acid solution is measured by the amount of boric acid in the solution. When the polyvinyl alcohol solution and the boric acid solution are mixed, the amount of polyvinyl alcohol used is 140wt% of the boric acid. The amount of polyvinyl alcohol solution used is 280g, that is, the amount of polyvinyl alcohol used is 84g, and the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g.

本实施例中的后续碳化硼陶瓷粉体的制备步骤、各组分使用量与实施例1中均相同。The subsequent preparation steps of the boron carbide ceramic powder and the amount of each component used in this embodiment are the same as those in Example 1.

实施例3：一种高活性亚微米级碳化硼陶瓷粉体的制备方法Example 3: A method for preparing high-activity submicron boron carbide ceramic powder

本实施例与实施例1相比，硼酸凝胶粉体的制备步骤和组分使用量相同，不同之处在于碳化硼陶瓷粉体的制备。Compared with Example 1, the preparation steps and component usage amounts of the boric acid gel powder in this example are the same, but the difference lies in the preparation of the boron carbide ceramic powder.

碳化硼陶瓷粉体的制备：将硼酸凝胶粉体与金属镁、有机酸盐混合，机械滚筒混料24h，混合物经立式行星式球磨机研磨30min，过100目筛，然后在200MPa下制成圆柱状坯体，然后置于密封反应装置中，密封，抽真空后通入氩气，在700℃下焙烧2h，然后在1600℃下反应2h，反应完成后，冷却，立式行星式球磨机破碎30min，置于浓盐酸中，在80℃下搅拌处理24h，抽滤，去离子水洗涤，在100℃干燥24h，得到碳化硼陶瓷粉体。金属镁的使用量为硼酸凝胶粉体的300wt％，有机酸盐为葡萄糖酸钠，有机酸盐的使用量为硼酸凝胶粉体的25wt％。浓盐酸没过固体粉末，适量使用，目的是除去镁元素。硼酸凝胶粉体的使用量为100g，金属镁的使用量为300g，葡萄糖酸钠的使用量为25g。Preparation of boron carbide ceramic powder: boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanical drum mixing for 24 hours, the mixture is ground by a vertical planetary ball mill for 30 minutes, passed through a 100 mesh sieve, and then made into a cylindrical body at 200MPa, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700°C for 2 hours, and then reacted at 1600°C for 2 hours. After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30 minutes, placed in concentrated hydrochloric acid, stirred at 80°C for 24 hours, filtered, washed with deionized water, and dried at 100°C for 24 hours to obtain boron carbide ceramic powder. The amount of metal magnesium used is 300wt% of the boric acid gel powder, the organic acid salt is sodium gluconate, and the amount of organic acid salt used is 25wt% of the boric acid gel powder. Concentrated hydrochloric acid is submerged in the solid powder and used in an appropriate amount to remove the magnesium element. The usage amount of boric acid gel powder is 100g, the usage amount of metal magnesium is 300g, and the usage amount of sodium gluconate is 25g.

实施例4：一种高活性亚微米级碳化硼陶瓷粉体的制备方法Example 4: A method for preparing high-activity submicron boron carbide ceramic powder

本实施例与实施例1相比，不同之处在于硼酸凝胶粉体的制备。Compared with Example 1, the difference between this example and Example 1 lies in the preparation of boric acid gel powder.

硼酸凝胶粉体的制备：将聚乙烯醇溶液、海藻酸钠与硼酸溶液混合，在80℃下搅拌，生成白色凝胶沉淀，在100℃干燥24h，立式行星式球磨机研磨30min，得到硼酸凝胶粉体。聚乙烯醇溶液以其溶液中聚乙烯醇的量为计量基准，硼酸溶液以其溶液中硼酸的量为计量基准，聚乙烯醇溶液与硼酸溶液混合中，聚乙烯醇的使用量为硼酸的110wt％，海藻酸钠的使用量为聚乙烯醇的40wt％。聚乙烯醇溶液的使用量为220g，即聚乙烯醇的用量为66g，硼酸溶液的使用量为1000g，即硼酸的用量为60g，海藻酸钠的使用量为26.4g。 Preparation of boric acid gel powder: polyvinyl alcohol solution, sodium alginate and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder. The polyvinyl alcohol solution is measured based on the amount of polyvinyl alcohol in the solution, and the boric acid solution is measured based on the amount of boric acid in the solution. In the mixing of polyvinyl alcohol solution and boric acid solution, the amount of polyvinyl alcohol used is 110wt% of boric acid, and the amount of sodium alginate used is 40wt% of polyvinyl alcohol. The amount of polyvinyl alcohol solution used is 220g, that is, the amount of polyvinyl alcohol used is 66g, the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g, and the amount of sodium alginate used is 26.4g.

本实施例4中的后续碳化硼陶瓷粉体的制备步骤、各组分使用量与实施例1中均相同。The subsequent preparation steps of the boron carbide ceramic powder and the amounts of each component used in Example 4 are the same as those in Example 1.

实施例5：一种高活性亚微米级碳化硼陶瓷粉体的制备方法Example 5: A method for preparing high-activity submicron boron carbide ceramic powder

本实施例与实施例2相比，不同之处在于硼酸凝胶粉体的制备，后续碳化硼陶瓷粉体的制备步骤、各组分使用量与实施例2中均相同。Compared with Example 2, the present embodiment differs in that the preparation of the boric acid gel powder, the subsequent preparation steps of the boron carbide ceramic powder, and the amount of each component used are the same as those in Example 2.

硼酸凝胶粉体的制备：将聚乙烯醇溶液、海藻酸钠与硼酸溶液混合，在80℃下搅拌，生成白色凝胶沉淀，在100℃干燥24h，立式行星式球磨机研磨30min，得到硼酸凝胶粉体。聚乙烯醇溶液以其溶液中聚乙烯醇的量为计量基准，硼酸溶液以其溶液中硼酸的量为计量基准，聚乙烯醇溶液与硼酸溶液混合中，聚乙烯醇的使用量为硼酸的140wt％，海藻酸钠的使用量为聚乙烯醇的40wt％。聚乙烯醇溶液的使用量为280g，即聚乙烯醇的用量为84g，硼酸溶液的使用量为1000g，即硼酸的用量为60g，海藻酸钠的使用量为33.6g。Preparation of boric acid gel powder: polyvinyl alcohol solution, sodium alginate and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder. The polyvinyl alcohol solution is measured based on the amount of polyvinyl alcohol in the solution, and the boric acid solution is measured based on the amount of boric acid in the solution. In the mixing of polyvinyl alcohol solution and boric acid solution, the amount of polyvinyl alcohol used is 140wt% of boric acid, and the amount of sodium alginate used is 40wt% of polyvinyl alcohol. The amount of polyvinyl alcohol solution used is 280g, that is, the amount of polyvinyl alcohol used is 84g, the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g, and the amount of sodium alginate used is 33.6g.

实施例6：一种高活性亚微米级碳化硼陶瓷粉体的制备方法Example 6: A method for preparing high-activity submicron boron carbide ceramic powder

本实施例与实施例3相比，不同之处在于硼酸凝胶粉体的制备，后续碳化硼陶瓷粉体的制备步骤、各组分使用量与实施例3中均相同。Compared with Example 3, the difference between this embodiment lies in the preparation of the boric acid gel powder, the subsequent preparation steps of the boron carbide ceramic powder, and the amount of each component used are the same as those in Example 3.

硼酸凝胶粉体的制备：将聚乙烯醇溶液、海藻酸钠与硼酸溶液混合，在80℃下搅拌，生成白色凝胶沉淀，在100℃干燥24h，立式行星式球磨机研磨30min，得到硼酸凝胶粉体。聚乙烯醇溶液以其溶液中聚乙烯醇的量为计量基准，硼酸溶液以其溶液中硼酸的量为计量基准，聚乙烯醇溶液与硼酸溶液混合中，聚乙烯醇的使用量为硼酸的110wt％，海藻酸钠的使用量为聚乙烯醇的40wt％。聚乙烯醇溶液的使用量为220g，即聚乙烯醇的用量为66g，硼酸溶液的使用量为1000g，即硼酸的用量为60g，海藻酸钠的使用量为26.4g。Preparation of boric acid gel powder: polyvinyl alcohol solution, sodium alginate and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder. The polyvinyl alcohol solution is measured based on the amount of polyvinyl alcohol in the solution, and the boric acid solution is measured based on the amount of boric acid in the solution. In the mixing of polyvinyl alcohol solution and boric acid solution, the amount of polyvinyl alcohol used is 110wt% of boric acid, and the amount of sodium alginate used is 40wt% of polyvinyl alcohol. The amount of polyvinyl alcohol solution used is 220g, that is, the amount of polyvinyl alcohol used is 66g, the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g, and the amount of sodium alginate used is 26.4g.

实施例7：一种高活性亚微米级碳化硼陶瓷粉体的制备方法Example 7: A method for preparing high-activity submicron boron carbide ceramic powder

本实施例与实施例4相比，硼酸凝胶粉体的制备步骤、各组分使用量相同，不同之处在于碳化硼陶瓷粉体的制备。Compared with Example 4, the preparation steps of the boric acid gel powder and the usage amounts of each component in this example are the same, but the difference lies in the preparation of the boron carbide ceramic powder.

碳化硼陶瓷粉体的制备：将硼酸凝胶粉体与金属镁、有机酸盐混合，机械滚筒混料24h，混合物经立式行星式球磨机研磨30min，过100目筛，然后在 200MPa下制成圆柱状坯体，然后置于密封反应装置中，密封，抽真空后通入氩气，在700℃下焙烧2h，然后在1600℃下反应2h，反应完成后，冷却，立式行星式球磨机破碎30min，破碎后的粉体置于浓盐酸中，在80℃下搅拌处理24h，抽滤，去离子水洗涤，在100℃干燥24h，得到碳化硼陶瓷粉体。金属镁的使用量为硼酸凝胶粉体的300wt％，葡萄糖酸钠的使用量为硼酸凝胶粉体的25wt％。浓盐酸没过固体粉末，适量使用，目的是除去镁元素。硼酸凝胶粉体的使用量为100g，金属镁的使用量为300g，葡萄糖酸钠的使用量为25g。Preparation of boron carbide ceramic powder: Boric acid gel powder was mixed with magnesium metal and organic acid salt, and the mixture was mixed in a mechanical drum for 24 hours. The mixture was ground in a vertical planetary ball mill for 30 minutes, passed through a 100-mesh sieve, and then 200MPa, a cylindrical body is made, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700℃ for 2h, and then reacted at 1600℃ for 2h. After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30min, and the crushed powder is placed in concentrated hydrochloric acid, stirred at 80℃ for 24h, filtered, washed with deionized water, and dried at 100℃ for 24h to obtain boron carbide ceramic powder. The amount of metallic magnesium used is 300wt% of the boric acid gel powder, and the amount of sodium gluconate used is 25wt% of the boric acid gel powder. Concentrated hydrochloric acid is used to cover the solid powder and is used in an appropriate amount to remove the magnesium element. The amount of boric acid gel powder used is 100g, the amount of metallic magnesium used is 300g, and the amount of sodium gluconate used is 25g.

实施例8：一种高活性亚微米级碳化硼陶瓷粉体的制备方法Example 8: A method for preparing high-activity submicron boron carbide ceramic powder

本实施例与实施例5相比，硼酸凝胶粉体的制备步骤、各组分使用量相同，不同之处在于碳化硼陶瓷粉体的制备。Compared with Example 5, the preparation steps of the boric acid gel powder and the usage amounts of each component in this example are the same, but the difference lies in the preparation of the boron carbide ceramic powder.

碳化硼陶瓷粉体的制备：将硼酸凝胶粉体与金属镁、有机酸盐混合，机械滚筒混料24h，混合物经立式行星式球磨机研磨30min，过100目筛，然后在200MPa下制成圆柱状坯体，然后置于密封反应装置中，密封，抽真空后通入氩气，在700℃下焙烧2h，然后在1600℃下反应2h，反应完成后，冷却，立式行星式球磨机破碎30min，破碎后的粉体置于浓盐酸中，在80℃下搅拌处理24h，抽滤，去离子水洗涤，在100℃干燥24h，得到碳化硼陶瓷粉体。金属镁的使用量为硼酸凝胶粉体的300wt％，葡萄糖酸钠的使用量为硼酸凝胶粉体的25wt％。浓盐酸没过固体粉末，适量使用，目的是除去镁元素。硼酸凝胶粉体的使用量为100g，金属镁的使用量为300g，葡萄糖酸钠的使用量为25g。Preparation of boron carbide ceramic powder: boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanical drum mixing for 24 hours, the mixture is ground by a vertical planetary ball mill for 30 minutes, passed through a 100 mesh sieve, and then made into a cylindrical body at 200MPa, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700℃ for 2 hours, and then reacted at 1600℃ for 2 hours. After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30 minutes, and the crushed powder is placed in concentrated hydrochloric acid, stirred at 80℃ for 24 hours, filtered, washed with deionized water, and dried at 100℃ for 24 hours to obtain boron carbide ceramic powder. The amount of metal magnesium used is 300wt% of the boric acid gel powder, and the amount of sodium gluconate used is 25wt% of the boric acid gel powder. Concentrated hydrochloric acid is submerged in solid powder and used in an appropriate amount to remove magnesium. The usage amount of boric acid gel powder is 100g, the usage amount of metal magnesium is 300g, and the usage amount of sodium gluconate is 25g.

对比例1：一种碳化硼陶瓷粉体的制备方法Comparative Example 1: A method for preparing boron carbide ceramic powder

本对比例与实施例1相比，不同之处在于硼酸凝胶粉体的制备。The difference between this comparative example and Example 1 lies in the preparation of boric acid gel powder.

硼酸凝胶粉体的制备：将聚乙烯醇溶液与硼酸溶液混合，在80℃下搅拌，生成白色凝胶沉淀，在100℃干燥24h，立式行星式球磨机研磨30min，得到硼酸凝胶粉体。聚乙烯醇溶液以其溶液中聚乙烯醇的量为计量基准，硼酸溶液以其溶液中硼酸的量为计量基准，聚乙烯醇溶液与硼酸溶液混合中，聚乙烯醇的使用量为硼酸的50wt％。聚乙烯醇溶液的使用量为100g，即聚乙烯醇的用量为30g，硼酸溶液的使用量为1000g，即硼酸的用量为60g。 Preparation of boric acid gel powder: polyvinyl alcohol solution and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder. The polyvinyl alcohol solution is measured by the amount of polyvinyl alcohol in the solution, and the boric acid solution is measured by the amount of boric acid in the solution. In the mixing of polyvinyl alcohol solution and boric acid solution, the amount of polyvinyl alcohol used is 50wt% of the boric acid. The amount of polyvinyl alcohol solution used is 100g, that is, the amount of polyvinyl alcohol used is 30g, and the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g.

对比例2：一种碳化硼陶瓷粉体的制备方法Comparative Example 2: A method for preparing boron carbide ceramic powder

本对比例与实施例1相比，不同之处在于硼酸凝胶粉体的制备。The difference between this comparative example and Example 1 lies in the preparation of boric acid gel powder.

硼酸凝胶粉体的制备：将聚乙烯醇溶液与硼酸溶液混合，在80℃下搅拌，生成白色凝胶沉淀，在100℃干燥24h，立式行星式球磨机研磨30min，得到硼酸凝胶粉体。聚乙烯醇溶液以其溶液中聚乙烯醇的量为计量基准，硼酸溶液以其溶液中硼酸的量为计量基准，聚乙烯醇溶液与硼酸溶液混合中，聚乙烯醇的使用量为硼酸的200wt％。聚乙烯醇溶液的使用量为400g，即聚乙烯醇的用量为120g，硼酸溶液的使用量为1000g，即硼酸的用量为60g。Preparation of boric acid gel powder: polyvinyl alcohol solution and boric acid solution are mixed, stirred at 80°C to generate white gel precipitation, dried at 100°C for 24 hours, and ground in a vertical planetary ball mill for 30 minutes to obtain boric acid gel powder. The polyvinyl alcohol solution is measured by the amount of polyvinyl alcohol in the solution, and the boric acid solution is measured by the amount of boric acid in the solution. In the mixing of polyvinyl alcohol solution and boric acid solution, the amount of polyvinyl alcohol used is 200wt% of boric acid. The amount of polyvinyl alcohol solution used is 400g, that is, the amount of polyvinyl alcohol used is 120g, and the amount of boric acid solution used is 1000g, that is, the amount of boric acid used is 60g.

对比例3：一种碳化硼陶瓷粉体的制备方法Comparative Example 3: A method for preparing boron carbide ceramic powder

本对比例与实施例1相比，不同之处在于碳化硼陶瓷粉体的制备。The difference between this comparative example and Example 1 lies in the preparation of the boron carbide ceramic powder.

碳化硼陶瓷粉体的制备：将硼酸凝胶粉体与金属镁、有机酸盐混合，机械滚筒混料24h，混合物经立式行星式球磨机研磨30min，过100目筛，然后在200MPa下制成圆柱状坯体，然后置于密封反应装置中，密封，抽真空后通入氩气，在700℃下焙烧2h，然后在1600℃下反应2h，反应完成后，冷却，立式行星式球磨机破碎30min，破碎后的粉体置于浓盐酸中，在80℃下搅拌处理24h，抽滤，去离子水洗涤，在100℃干燥24h，得到碳化硼陶瓷粉体。金属镁的使用量为硼酸凝胶粉体的300wt％，有机酸盐为葡萄糖酸钠，有机酸盐的使用量为硼酸凝胶粉体的5wt％。浓盐酸没过固体粉末，适量使用。Preparation of boron carbide ceramic powder: boric acid gel powder is mixed with metal magnesium and organic acid salt, mechanical drum mixing for 24 hours, the mixture is ground by a vertical planetary ball mill for 30 minutes, passed through a 100 mesh sieve, and then made into a cylindrical body at 200MPa, and then placed in a sealed reaction device, sealed, argon is introduced after vacuuming, roasted at 700°C for 2 hours, and then reacted at 1600°C for 2 hours. After the reaction is completed, it is cooled, crushed by a vertical planetary ball mill for 30 minutes, and the crushed powder is placed in concentrated hydrochloric acid, stirred at 80°C for 24 hours, filtered, washed with deionized water, and dried at 100°C for 24 hours to obtain boron carbide ceramic powder. The amount of metal magnesium used is 300wt% of the boric acid gel powder, the organic acid salt is sodium gluconate, and the amount of organic acid salt used is 5wt% of the boric acid gel powder. Concentrated hydrochloric acid is not enough to cover the solid powder, and it is used in an appropriate amount.

对比例4：一种碳化硼陶瓷粉体的制备方法Comparative Example 4: A method for preparing boron carbide ceramic powder

本对比例与实施例1相比，不同之处在于碳化硼陶瓷粉体的制备。The difference between this comparative example and Example 1 lies in the preparation of the boron carbide ceramic powder.

碳化硼陶瓷粉体的制备：将硼酸凝胶粉体与金属镁、有机酸盐混合，机械滚筒混料24h，混合物经立式行星式球磨机研磨30min，过100目筛，然后在200MPa下制成圆柱状坯体，然后置于密封反应装置中，密封，抽真空后通入氩气，在700℃下焙烧2h，然后在1600℃下反应2h，反应完成后，冷却，立式行星式球磨机破碎30min，破碎后的粉体置于浓盐酸中，在80℃下搅拌处理24h，抽滤，去离子水洗涤，在100℃干燥24h，得到碳化硼陶瓷粉体。金属镁的使用量为硼酸凝胶粉体的300wt％，有机酸盐为葡萄糖酸钠，有机酸盐的使用量为 硼酸凝胶粉体的35wt％。浓盐酸没过固体粉末，适量使用。硼酸凝胶粉体的使用量为100g，金属镁的使用量为300g，有机酸盐为葡萄糖酸钠，有机酸盐的使用量为35g。Preparation of boron carbide ceramic powder: boric acid gel powder is mixed with metal magnesium and organic acid salt, and the mixture is mixed by mechanical drum for 24 hours. The mixture is ground by vertical planetary ball mill for 30 minutes, passed through a 100-mesh sieve, and then made into a cylindrical body at 200 MPa, and then placed in a sealed reaction device, sealed, evacuated and then introduced with argon, baked at 700°C for 2 hours, and then reacted at 1600°C for 2 hours. After the reaction is completed, it is cooled and crushed by vertical planetary ball mill for 30 minutes. The crushed powder is placed in concentrated hydrochloric acid, stirred at 80°C for 24 hours, filtered, washed with deionized water, and dried at 100°C for 24 hours to obtain boron carbide ceramic powder. The amount of metal magnesium used is 300wt% of the boric acid gel powder, the organic acid salt is sodium gluconate, and the amount of organic acid salt used is 35wt% of boric acid gel powder. Concentrated hydrochloric acid is used in an appropriate amount until the solid powder is submerged. The amount of boric acid gel powder used is 100g, the amount of magnesium metal used is 300g, and the organic acid salt is sodium gluconate, and the amount of organic acid salt used is 35g.

对比例5：一种碳化硼陶瓷粉体的制备方法Comparative Example 5: A method for preparing boron carbide ceramic powder

本对比例与实施例4相比，不同之处在于硼酸凝胶粉体的制备，仅将聚乙烯醇的用量全部替换为海藻酸钠，其他试剂及使用量不变。The difference between this comparative example and Example 4 lies in the preparation of the boric acid gel powder, in which only the amount of polyvinyl alcohol is completely replaced by sodium alginate, and other reagents and their amounts remain unchanged.

试验例：Test example:

本发明对实施例1制备得到的硼酸凝胶粉体进行了红外表征，其结果如附图1所示，在3251cm-1处为羟基的红外吸收峰，在1732cm-1处为碳氧双键的红外吸收峰，在1278cm-1处为硼氧碳的红外吸收峰，在1091cm-1处为碳氧碳的红外吸收峰。The boric acid gel powder prepared in Example 1 was characterized by infrared spectroscopy. The results are shown in FIG1 . The infrared absorption peak of hydroxyl group is at 3251 cm -1 , the infrared absorption peak of carbon-oxygen double bond is at 1732 cm -1 , the infrared absorption peak of boron-oxygen-carbon is at 1278 cm -1 , and the infrared absorption peak of carbon-oxygen-carbon is at 1091 cm -1 .

本发明采用激光粒径仪对各实施例1-8和对比例1-5制备得到的碳化硼陶瓷粉体的粒径进行分析，激光粒径仪的散射角度为90度，粒径范围10纳米到3000微米，粒径分析结果如附图2所示，其中：S1为实施例1，S2为实施例2，S3为实施例3，S4为实施例4，S5为实施例5，S6为实施例6，S7为实施例7，S8为实施例8，D1为对比例1，D2为对比例2，D3为对比例3，D4为对比例4，D5为对比例5。在对本发明实施例1-8制备得到的碳化硼陶瓷粉体进行粒径分析时，所得碳化硼陶瓷粉体的粒径较为均匀，过大或过小的颗粒粉体的分布量较小，即粒径处理平均粒径下的分布量较高。The present invention uses a laser particle size analyzer to analyze the particle size of the boron carbide ceramic powder prepared in each embodiment 1-8 and comparative example 1-5. The scattering angle of the laser particle size analyzer is 90 degrees, and the particle size range is 10 nanometers to 3000 microns. The particle size analysis results are shown in Figure 2, wherein: S1 is embodiment 1, S2 is embodiment 2, S3 is embodiment 3, S4 is embodiment 4, S5 is embodiment 5, S6 is embodiment 6, S7 is embodiment 7, S8 is embodiment 8, D1 is comparative example 1, D2 is comparative example 2, D3 is comparative example 3, D4 is comparative example 4, and D5 is comparative example 5. When the boron carbide ceramic powder prepared in embodiments 1-8 of the present invention is analyzed for particle size, the particle size of the obtained boron carbide ceramic powder is relatively uniform, and the distribution amount of oversized or undersized particle powder is small, that is, the distribution amount under the average particle size of the particle size treatment is high.

本发明通过将聚乙烯醇和硼酸分明于蒸馏水中溶解，然后再经混合制成硼酸凝胶粉体，最后再由硼酸凝胶粉体与金属镁、有机酸盐混合并经后续工序处理，制成碳化硼陶瓷粉体，本发明方法制备的碳化硼陶瓷粉体粒径达到亚微米级。The invention prepares boron carbide ceramic powder by dissolving polyvinyl alcohol and boric acid in distilled water respectively, mixing the mixture to prepare boric acid gel powder, and finally mixing the boric acid gel powder with metal magnesium and organic acid salt and treating the mixture through subsequent steps. The particle size of the boron carbide ceramic powder prepared by the method of the invention reaches submicron level.

本发明方法中碳化硼陶瓷粉体粒径跟两个关键步骤相关，一是硼酸凝胶粉体的制备，二是硼酸凝胶粉体与金属镁、有机酸盐的混合使用。在硼酸凝胶粉体的制备中，聚乙烯醇与硼酸的使用量十分关键，在本发明公开的特定使用量 下，由其制成的硼酸凝胶粉体与金属镁、有机酸盐混合，成功得到亚微米级的碳化硼陶瓷粉体。而如果聚乙烯醇与硼酸的使用量在本发明公开的特定使用量之外，则得到的碳化硼陶瓷粉体的平均粒径在1微米以上，即聚乙烯醇相对于硼酸的使用量过低或过高均不佳。本发明中碳化硼陶瓷粉体的制备中，除了聚乙烯醇与硼酸的特定使用量外，下一步中有机酸盐的使用量也十分重要。有机酸盐的使用量在本发明公开的特定使用量之外的情况下，所得碳化硼陶瓷粉体的平均粒径在1微米以上，并且粒径大小不均匀。通过调整硼酸凝胶粉体中聚乙烯醇和硼酸的特定使用量，可以得到不同平均粒径的碳化硼陶瓷粉体，但粒径均在亚微米级。在聚乙烯醇与硼酸的特定使用量下，有机酸盐在本发明公开的特定使用量下，同样可以得到不同平均粒径的碳化硼陶瓷粉体，粒径仍处于亚微米级。The particle size of boron carbide ceramic powder in the method of the present invention is related to two key steps: the preparation of boric acid gel powder and the mixing of boric acid gel powder with metal magnesium and organic acid salt. In the preparation of boric acid gel powder, the amount of polyvinyl alcohol and boric acid used is very important. Under the condition that the boric acid gel powder prepared therefrom is mixed with metal magnesium and organic acid salt, a submicron boron carbide ceramic powder is successfully obtained. If the usage of polyvinyl alcohol and boric acid is outside the specific usage disclosed in the present invention, the average particle size of the obtained boron carbide ceramic powder is above 1 micron, that is, the usage of polyvinyl alcohol relative to boric acid is too low or too high, which is not good. In the preparation of boron carbide ceramic powder in the present invention, in addition to the specific usage of polyvinyl alcohol and boric acid, the usage of organic acid salt in the next step is also very important. When the usage of organic acid salt is outside the specific usage disclosed in the present invention, the average particle size of the obtained boron carbide ceramic powder is above 1 micron, and the particle size is uneven. By adjusting the specific usage of polyvinyl alcohol and boric acid in the boric acid gel powder, boron carbide ceramic powders with different average particle sizes can be obtained, but the particle sizes are all at the submicron level. Under the specific usage of polyvinyl alcohol and boric acid, the organic acid salt can also obtain boron carbide ceramic powders with different average particle sizes under the specific usage of the present invention, and the particle size is still at the submicron level.

本发明进一步研发发现，在制备硼酸凝胶粉体的步骤中使用海藻酸钠，海藻酸钠的使用可以降低碳化硼陶瓷粉体平均粒径，而如果将硼酸凝胶粉体的制备中的聚乙烯醇全部替换为海藻酸钠，则碳化硼陶瓷粉体的平均粒径在1微米以上；即单独使用海藻酸钠，无法得到亚微米级的碳化硼陶瓷粉体。The present invention has been further developed and found that sodium alginate is used in the step of preparing boric acid gel powder. The use of sodium alginate can reduce the average particle size of boron carbide ceramic powder. If the polyvinyl alcohol in the preparation of boric acid gel powder is completely replaced by sodium alginate, the average particle size of the boron carbide ceramic powder is above 1 micron; that is, using sodium alginate alone cannot obtain submicron boron carbide ceramic powder.

以上实施方式仅用于说明本发明，而并非对本发明的限制，本领域的普通技术人员，在不脱离本发明的精神和范围的情况下，还可以做出各种变化和变型。因此，所有等同的技术方案也属于本发明的范畴，本发明的保护范围应由权利要求限定。 The above embodiments are only used to illustrate the present invention, but not to limit the present invention. A person skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention shall be defined by the claims.

Claims (8)

一种高活性亚微米级碳化硼陶瓷粉体的制备方法，包括：A method for preparing high-activity submicron boron carbide ceramic powder, comprising: S1，将聚乙烯醇和硼酸混合，经反应制成硼酸凝胶粉体；聚乙烯醇的使用量为硼酸的80-160wt％；S1, mixing polyvinyl alcohol and boric acid to form boric acid gel powder through reaction; the amount of polyvinyl alcohol used is 80-160wt% of the boric acid; S2，将硼酸凝胶粉体、有机酸盐和金属元素混合，经制备工序制成高活性亚微米级碳化硼陶瓷粉体；有机酸盐的使用量为硼酸凝胶粉体的10-30wt％；所述金属元素为镁元素；所述有机酸盐为葡萄糖酸钠；所述金属元素的使用量为硼酸凝胶粉体的200-400wt％；硼酸凝胶粉体的制备中还加入海藻酸钠，海藻酸钠的使用量为聚乙烯醇的30-60wt％；S2, mixing boric acid gel powder, organic acid salt and metal element, and preparing high-activity submicron boron carbide ceramic powder through a preparation process; the amount of organic acid salt used is 10-30wt% of the boric acid gel powder; the metal element is magnesium; the organic acid salt is sodium gluconate; the amount of the metal element used is 200-400wt% of the boric acid gel powder; sodium alginate is also added in the preparation of the boric acid gel powder, and the amount of sodium alginate used is 30-60wt% of polyvinyl alcohol; 所述制备工序中包括热处理，所述热处理包括500-900℃下焙烧1-4h，以及在1400-1800℃下处理1-4h。The preparation process includes heat treatment, which includes calcination at 500-900°C for 1-4h and treatment at 1400-1800°C for 1-4h. 根据权利要求1所述的一种高活性亚微米级碳化硼陶瓷粉体的制备方法，其特征是：所述硼酸凝胶粉体的制备温度为70-90℃。The method for preparing a high-activity submicron boron carbide ceramic powder according to claim 1 is characterized in that the preparation temperature of the boric acid gel powder is 70-90°C. 根据权利要求1所述的一种高活性亚微米级碳化硼陶瓷粉体的制备方法，其特征是：所述聚乙烯醇和硼酸混合的介质为蒸馏水。The method for preparing a high-activity submicron boron carbide ceramic powder according to claim 1 is characterized in that the medium for mixing the polyvinyl alcohol and the boric acid is distilled water. 根据权利要求1所述的一种高活性亚微米级碳化硼陶瓷粉体的制备方法，其特征是：所述制备工序还包括混料、研磨、制坯和酸处理。The method for preparing a high-activity submicron boron carbide ceramic powder according to claim 1 is characterized in that the preparation process also includes mixing, grinding, blanking and acid treatment. 根据权利要求4所述的一种高活性亚微米级碳化硼陶瓷粉体的制备方法，其特征是：所述混料采用机械滚筒处理，混料时间为12-48h；或，所述制坯的压力为150-250MPa；或，所述酸处理为浸于浓盐酸中处理。The method for preparing a high-activity submicron boron carbide ceramic powder according to claim 4 is characterized in that: the mixing is processed by a mechanical roller, and the mixing time is 12-48 hours; or, the pressure of the blank making is 150-250MPa; or, the acid treatment is immersion in concentrated hydrochloric acid. 根据权利要求4所述的一种高活性亚微米级碳化硼陶瓷粉体的制备方法，其特征是：所述制坯得到的坯体的形状为圆柱状。The method for preparing a high-activity submicron boron carbide ceramic powder according to claim 4 is characterized in that the shape of the green body obtained by the green body making is cylindrical. 权利要求1-6任一所述方法制备得到的高活性亚微米级碳化硼陶瓷粉体。A high-activity submicron boron carbide ceramic powder prepared by the method described in any one of claims 1 to 6. 权利要求7所述的高活性亚微米级碳化硼陶瓷粉体在制备防弹材料、屏蔽材料或陶瓷材料中的用途。 Use of the highly active submicron boron carbide ceramic powder as described in claim 7 in the preparation of bulletproof materials, shielding materials or ceramic materials.
PCT/CN2024/099234 2023-10-20 2024-06-14 Method for preparing high-activity submicron boron carbide ceramic powder Pending WO2025081863A1 (en)

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