CN111116203A - Preparation method of high-density nano boron carbide ceramic material - Google Patents
Preparation method of high-density nano boron carbide ceramic material Download PDFInfo
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Abstract
A preparation method of a high-density nano boron carbide ceramic material is characterized by comprising the following steps: (1) uniformly mixing an initial material of nano boron carbide or nano carbon material and amorphous boron powder in proportion to form a mixture, wherein the proportion of the initial material is BxThe B/C atomic ratio in C is 4-x<10; (2) ball-milling the mixture for 4-24h, further uniformly mixing, and refining large particles to obtain mixed powder; (3) prepressing the mixed powder into an initial blank in forming equipment; (4) and (3) sintering the primary blank in a sintering device by a high-pressure sintering method or a discharge plasma method for short time at low temperature to obtain the high-density nano boron carbide ceramic material. The preparation method of the high-density nano boron carbide ceramic material is simple and feasible, the conditions are easy to control, the adjustable range of the product components is large, and the high-density nano boron carbide ceramic material is suitable for large-scale production and preparationThe nano boron carbide ceramic material has the advantages of super hardness, high modulus, high fracture toughness and obviously higher mechanical property than common boron carbide ceramic.
Description
Technical Field
The invention relates to a preparation method of a nano ceramic material, in particular to a preparation method of a high-density nano boron carbide ceramic.
Background
With the need of industrial development and the continuous breakthrough and innovation of material science, various novel materials with high strength, high hardness, corrosion resistance and high temperature resistance are produced. Boron carbide ceramic as the third hard material (Vickers hardness) in nature>30GPa, mohs hardness 9.3), second only to diamond and cubic boron nitride, and has a low density (2.52 g/cm)3) High modulus, high melting point (2450)oC) High neutron absorption cross section, excellent oxidation resistance, wear resistance, high-temperature thermoelectricity and the like, and can be used as light ceramic armor materials, nuclear protection materials, wear-resistant part materials for nozzles and grinding, high-temperature thermoelectricity materials and the like. However, brittleness is a fatal weakness of ceramic materials, boron carbide materials are no exception, and fracture toughness is 2-3 MPa.m1/2. The brittle and hard characteristics cause the material to have poor processing performance, and microcracks are easily generated, so that the consistency and reliability of the material performance are greatly influenced, and the popularization and application of the material are severely restricted. Therefore, how to improve brittleness while maintaining high hardness and high strength becomes a key point for whether the material can be widely applied in practice.
To suppress brittle fracture and achieve an overall improvement in the mechanical properties of ceramics, "nanocrystallization" is one of the best choices. The nano ceramic is a ceramic material with a microstructure in which the grain size, the crystal boundary width, the second phase distribution, the pore size and the defect size are all on a nano scale (1-100 nm), and is widely concerned by people because the nano ceramic overcomes the fatal defect of high brittleness of the traditional ceramic and has special performances in the aspects of superplasticity, ferroelectric property, mechanical property and the like.
Studies have shown that the hardness and wear resistance, strength and toughness of ceramic materials are improved to varying degrees as the grain size is reduced to the nanometer scale. 2012, K, Madhav Red et al used nano boron carbide powder as the starting material to prepare nano boron carbide ceramic powderThe fracture toughness is about doubled compared with that of micron boron carbide (K.M. Reddy, J.Guo, Y.Shinoda, T.Fujita 1, A.Hirata 1, J.P. Singh, J.W. McCauley, M.W.Chen, Enhanced mechanical properties of nanocrystalline boron carbide and interface phases, nat. Commun., 3:1052, 2012). However, the density of the obtained bulk nano ceramic is only 92.8% due to the adoption of boron carbide nano powder containing redundant carbon elements and the limitation of the preparation method. Although the fracture toughness of the material is obviously improved, the hardness and the modulus are obviously reduced and are respectively only 21-28GPa and 200-290 GPa, which are lower than the performances of the traditional micron-crystal boron carbide ceramic. Therefore, how to improve the density and reduce the content of redundant carbon in the block material is the key for improving the nano boron carbide material. However, the density of nano boron carbide ceramics has been reported to be generally low, for example, 92.8% (k.m. Reddy, 2012), 94.6% (c. Ojalvo, f. Guiberteau, a.l. Ortiz, textile treated super-hard B4C compositions at lower temperature by transfer treated space ceramic sheet sintering with MoSi2additives, J. Eur. Ceram. Soc. 39, 2862, 2019），96.2%（L. Roumiguiera, A.Jankowiak, N. Pradeilles, G. Antou, A. Maître, Mechanical properties ofsubmicronic and nanometric boron carbides obtained by Spark Plasma Sintering:Influence of B/C ratio and oxygen content, Ceram. Int. 45, 9912, 2019）。
The atomic ratio of x is not more than 4 and is not found yet<10BxC related patent application.
As can be seen, the mechanical properties of the nano boron carbide materials reported at present are greatly different from expectations. The main factors limiting the performance of the nano boron carbide ceramic are as follows: 1. the purity of the nano boron carbide powder raw material in the market is low, most of the nano boron carbide powder has redundant carbon, namely the B/C atomic ratio is less than 4, and the mechanical property of the nano boron carbide powder is weakened by free carbon; 2. the density of the nano boron carbide obtained by the existing preparation method is relatively low (< 97%), and the mechanical property is greatly influenced.
Disclosure of Invention
The key technical problem to be solved by the invention is to provide high-density nano carbonThe preparation method of the boron nitride ceramic material obtains the superhard nano ceramic material. The invention provides a method for combining reactive sintering and rapid sintering, which can realize the preparation of high-density nano boron carbide materials, and the density of the nano ceramics is more than 99 percent and the mechanical property is excellent. Firstly, adding boron powder into nano raw material, reacting and sintering to form BxC（4≤x<10) The method not only can effectively improve the density of the material, but also can eliminate the influence of free carbon on the mechanical property of the nano boron carbide ceramic material through the reaction of boron and carbon. Meanwhile, the growth of crystal grains can be effectively controlled by adopting a short-time low-temperature rapid sintering technology, such as a spark plasma sintering technology or a static high-pressure sintering technology, so that the density is improved, and the preparation of the block body nano ceramic is ensured. So far, there is no report on this.
The invention adopts the specific technical scheme that:
a preparation method of a high-density nano boron carbide ceramic material is characterized by comprising the following steps:
(1) uniformly mixing the nano boron carbide or nano carbon material as the initial material with amorphous boron powder in proportion to form a mixture, wherein the proportion of the initial material is BxThe B/C atomic ratio in C is 4-x<10, designing to obtain excellent mechanical properties;
(2) ball-milling the mixture for 4-24h to further uniformly mix the mixture, and meanwhile, refining partial large particles to obtain mixed powder, wherein the ball-milling can be dry ball-milling or wet ball-milling;
(3) prepressing the mixed powder into a primary blank in a forming device, wherein the forming device can be various common devices;
(4) sintering the primary blank in a sintering device by using a short-time low-temperature sintering method to obtain the high-density nano boron carbide ceramic material, wherein the sintering device can be common high-pressure sintering equipment, discharge plasma sintering equipment and the like;
the short-time low-temperature sintering method is a high-pressure sintering method, and the sintering conditions are as follows: the sintering temperature is 1300 + 1600 ℃, the sintering pressure is 3-6 GPa, and the sintering time is 2-10 minutes;
alternatively, the short-time low-temperature sintering method may be a spark plasma method, and the sintering conditions are as follows: the sintering temperature is 1400 + 1700 ℃, the sintering pressure is 30-100 MPa, and the sintering time is 2-10 minutes.
The short-time low-temperature sintering method can also adopt other common sintering methods.
The further scheme is as follows: in the initial material, the nanometer boron carbide material is boron carbide nanometer particles, and the particle size is less than 100 nm.
The further scheme is as follows: in the initial material, the nanometer boron carbide material is boron carbide nanometer wire or nanometer fiber with the diameter less than 200 nm.
The further scheme is as follows: in the starting material, the nanocarbon material is nanoparticles, the particle size being less than 100 nm.
The further scheme is as follows: the amorphous boron particle size is less than 1 μm.
Experiments show that when boron carbide nanoparticles with the particle size of less than 100nm or boron carbide nanowires or nanofibers with the diameter of less than 200nm are used, the nano carbon material with the particle size of less than 100nm and amorphous boron particles with the particle size of less than 1 mu m can obtain the high-density nano boron carbide ceramic material with excellent quality.
The further scheme is as follows: and adding a low-boiling-point liquid with stable performance into the mixture to form a mixed liquid, performing ultrasonic treatment on the mixed liquid for 10-30min, performing wet ball milling for 4-24h, and drying the mixed liquid subjected to ball milling at 80-100 ℃ to obtain uniformly mixed powder. The ultrasound can also be changed into stirring and the like.
The further scheme is as follows: the low boiling point liquid with stable performance is alcohol or isopropanol and the like.
Similar results are achieved with dry ball milling, but the environmental requirements may be higher.
In the invention, amorphous boron is adopted to adjust the B/C ratio in the boron carbide to be within the range of 4-10, the B/C ratio coverage range is large, and in order to ensure that no redundant carbon exists in the nano boron carbide ceramic material, the boron carbide ceramic material with excellent mechanical property is obtained. The low temperature short time (2-10 minutes) sintering method is used to ensure that the particle size remains in the nanometer range during sintering.
The invention has the advantages and effects that: the density of the nano ceramic is more than 99 percent, and the mechanical property is excellent. Firstly, adding boron powder into nano raw material, reacting and sintering to form BxC（4≤x<10) The method not only can effectively improve the density of the material, but also can eliminate the influence of free carbon on the mechanical property of the nano boron carbide ceramic material through the reaction of boron and carbon. Meanwhile, the growth of crystal grains can be effectively controlled by adopting a short-time low-temperature rapid sintering technology, such as a spark plasma sintering technology or a static high-pressure sintering technology, so that the density is improved, and the preparation of the block body nano ceramic is ensured. So far, there is no report on this.
The preparation method of the high-density nano boron carbide ceramic material is simple and easy to implement, the experimental conditions are easy to control, the adjustable range of the product components is large, and the high-density nano boron carbide ceramic material is suitable for large-scale production; the nano boron carbide ceramic material prepared by the invention has the advantages of super hardness, high modulus, high fracture toughness and obviously higher mechanical property than common boron carbide ceramic, and can be used in industrial production.
Drawings
FIG. 1 is an SEM image of a high-density nano boron carbide ceramic material obtained by the method.
FIG. 2 is an HRTEM image of the high-density nano boron carbide ceramic material obtained by the invention.
FIG. 3 is a comparison graph of hardness, Young's modulus and fracture toughness of the high-density nano boron carbide ceramic material and the low-density nano boron carbide and micro-crystal boron carbide ceramic material obtained by the method.
Detailed Description
The preparation of the high-density nano boron carbide ceramic of the invention is further illustrated by the following specific examples.
Example 1
(1) Putting 1.0 g of nano boron carbide powder and 0.1 g of amorphous boron into 40 g of alcohol, and ultrasonically mixing the solution for 20 min; then ball milling is carried out for 6 h, so that the mixture is uniformly mixed, and meanwhile, part of large particles are refined; and finally, stirring and drying the mixed liquor after ball milling at the temperature of 90 ℃ to obtain uniformly mixed powder.
(2) The mixed powder was pressed in a tablet press into a cylindrical preform with a diameter of 12 mm.
(3) And (3) placing the primary blank into a cubic press, and sintering for 5 min at 1350 ℃ and 4.5 GPa to obtain the high-density nano boron carbide ceramic material.
Example 2
(1) Putting 2.0 g of boron carbide nanowires and 1.0 g of amorphous boron into 50 g of alcohol, and ultrasonically mixing the solution for 30 min; then ball milling is carried out for 12 h, so that the mixture is uniformly mixed, and meanwhile, part of large particles are refined; and finally, stirring and drying the mixed solution after ball milling at the temperature of 100 ℃ to obtain uniformly mixed powder.
(2) The mixed powder was placed in a discharge plasma furnace with a mold diameter of 20 mm.
(3) And adjusting the sintering parameters of the point-released plasma to 1500 ℃, 60 MPa and 10 min, and sintering to obtain the high-density nano boron carbide ceramic material.
Example 3
(1) Putting 0.5 g of nano carbon powder and 2.5 g of amorphous boron into 50 g of alcohol, and ultrasonically mixing the solution for 30 min; then ball milling is carried out for 6 h, so that the mixture is uniformly mixed, and meanwhile, part of large particles are refined; and finally, stirring and drying the mixed solution after ball milling at the temperature of 80 ℃ to obtain uniformly mixed powder.
(2) The mixed powder was pressed in a tablet press into cylindrical preforms with a diameter of 15 mm.
(3) And (3) placing the primary blank into a cubic press, and sintering for 3 min at 1400 ℃ and 5 GPa to obtain the high-density nano boron carbide ceramic material.
Example 4
(1) Putting 1.0 g of boron carbide nano-fiber and 1.0 g of amorphous boron into 50 g of alcohol, and ultrasonically mixing the solution for 30 min; then ball milling is carried out for 15 h, so that the mixture is uniformly mixed, and meanwhile, part of large particles are refined; and finally, stirring and drying the mixed solution after ball milling at the temperature of 100 ℃ to obtain uniformly mixed powder.
(2) The mixed powder was placed in a discharge plasma furnace with a mold diameter of 30 mm.
(3) And adjusting the sintering parameters of the point-released plasma to 1600 ℃, 80 MPa and 5 min, and sintering to obtain the high-density nano boron carbide ceramic material.
Example 5
(1) Putting 0.5 g of nano carbon powder and 2.0 g of amorphous boron into 40 g of alcohol, and ultrasonically mixing the solution for 30 min; then ball milling is carried out for 10 hours, so that the mixture is uniformly mixed, and meanwhile, part of large particles are refined; and finally, stirring and drying the mixed solution after ball milling at the temperature of 100 ℃ to obtain uniformly mixed powder.
(2) The mixed powder was pressed in a tablet press into cylindrical preforms having a diameter of 18 mm.
(3) And (3) placing the primary blank into a cubic press, and sintering for 3 min at 1450 ℃ and 5 GPa to obtain the high-density nano boron carbide ceramic material.
Example 6
(1) 2.0 g of nano boron carbide powder and 1.4 g of amorphous boron are put into 60 g of alcohol, and the mixture is subjected to ultrasonic treatment for 20 min; then ball milling is carried out for 8 hours, so that the mixture is uniformly mixed, and meanwhile, part of large particles are refined; and finally, stirring and drying the mixed liquor after ball milling at the temperature of 90 ℃ to obtain uniformly mixed powder.
(2) The mixed powder was placed in a discharge plasma furnace with a mold diameter of 40 mm.
(3) And adjusting the sintering parameters of the point-released plasma to 1500 ℃, 100 MPa and 8 min, and sintering to obtain the high-density nano boron carbide ceramic material.
The dimensions of the starting materials used in the above examples were: boron carbide nanoparticles with a particle size of less than 100nm, boron carbide nanowires or nanofibers with a diameter of less than 200nm, nanocarbon materials with a particle size of less than 100nm, amorphous boron particles with a particle size of less than 1 μm.
The appearance of the high-density nano boron carbide ceramic material is characterized as follows:
FIG. 1 is an SEM image of a high-density nano boron carbide ceramic material, and the image shows that the nano boron carbide ceramic material has high density and the grain size is in a nano range.
FIG. 2 is an HRTEM image of the high-density nano boron carbide ceramic material, and it can be seen from the image that the nano ceramic is compact, has no hollow, has a large number of stacking faults and twin crystals (c), and has clean grain boundaries (d).
The following are the hardness, fracture toughness and other performance tests of the nano boron carbide ceramic material:
FIG. 3 is a graph comparing the mechanical properties of boron carbide ceramic materials. The first group of data corresponds to the performance of micron boron carbide ceramic, the second group of data corresponds to the performance of low-density nano boron carbide ceramic prepared by directly sintering nano powder, and the third group corresponds to the high-density nano ceramic material obtained by the method. Therefore, the hardness and the fracture toughness of the high-density nano ceramic material are improved compared with those of the other two materials, and the modulus is equivalent to that of the high-density micro boron carbide (the modulus is determined by the intrinsic characteristics and the density of the material).
Claims (7)
1. A preparation method of a high-density nano boron carbide ceramic material is characterized by comprising the following steps:
(1) uniformly mixing the nano boron carbide or nano carbon material as the initial material with amorphous boron powder in proportion to form a mixture, wherein the proportion of the initial material is BxThe B/C atomic ratio in C is 4-x<10, designing;
(2) ball-milling the mixture for 4-24h to further uniformly mix the mixture, and meanwhile, refining partial large particles to obtain mixed powder;
(3) prepressing the mixed powder into an initial blank in forming equipment;
(4) sintering the primary blank in a sintering device by using a short-time low-temperature sintering method to obtain a high-density nano boron carbide ceramic material;
the short-time low-temperature sintering method is a high-pressure sintering method, and the sintering conditions are as follows: the sintering temperature is 1300 + 1600 ℃, the sintering pressure is 3-6 GPa, and the sintering time is 2-10 minutes;
alternatively, the short-time low-temperature sintering method may be a spark plasma method, and the sintering conditions are as follows: the sintering temperature is 1400 + 1700 ℃, the sintering pressure is 30-100 MPa, and the sintering time is 2-10 minutes.
2. The preparation method of the high-density nano boron carbide ceramic material according to claim 1, characterized by comprising the following steps: in the initial material, the nanometer boron carbide material is boron carbide nanometer particles, and the particle size is less than 100 nm.
3. The preparation method of the high-density nano boron carbide ceramic material according to claim 1, characterized by comprising the following steps: in the initial material, the nanometer boron carbide material is boron carbide nanometer wire or nanometer fiber with the diameter less than 200 nm.
4. The preparation method of the high-density nano boron carbide ceramic material according to claim 1, characterized by comprising the following steps: in the starting material, the nanocarbon material is nanoparticles, the particle size being less than 100 nm.
5. The preparation method of the high-density nano boron carbide ceramic material according to claim 1, characterized by comprising the following steps: the amorphous boron particle size is less than 1 μm.
6. The preparation method of the high-density nano boron carbide ceramic material according to claim 1, characterized by comprising the following steps: and adding a low-boiling-point liquid with stable performance into the mixture to form a mixed liquid, performing ultrasonic treatment on the mixed liquid for 10-30min, performing wet ball milling for 4-24h, and drying the mixed liquid subjected to ball milling at 80-100 ℃ to obtain uniformly mixed powder.
7. The method for preparing the high-density nano boron carbide ceramic material according to claim 6, wherein the method comprises the following steps: the low boiling point liquid with stable performance is alcohol or isopropanol.
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