CN112194492B - Silicon nitride ceramic material, preparation method and application thereof, and bulletproof flashboard - Google Patents
Silicon nitride ceramic material, preparation method and application thereof, and bulletproof flashboard Download PDFInfo
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Abstract
The invention relates to a silicon nitride ceramic material, a preparation method and application thereof, and a bulletproof flashboard. The silicon nitride ceramic material comprises the following raw materials in percentage by mass: 80-90 wt% of silicon nitride powder, 1-6 wt% of carbon simple substance, 1-10 wt% of boron trioxide powder, 1-10 wt% of nitride whisker and carbide whisker, 1-10 wt% of rare earth oxide and 1-6 wt% of binder. The specific components and the proportion are adopted, wherein the bending strength and the fracture toughness of the silicon carbide ceramic material can be enhanced through the combined action of the nitride crystal whisker, the carbide crystal whisker and the rare earth oxide on the silicon nitride powder, and the elasticity resistance of the silicon carbide ceramic material can be improved through the matching of the nitride crystal whisker and the carbide crystal whisker. Meanwhile, the elemental carbon and the diboron trioxide powder can form a discontinuous boron carbide whisker component in the silicon nitride matrix under the catalysis of the rare earth oxide, so that the surface density of the material is reduced, and the hardness and the elastic modulus of the material are improved.
Description
Technical Field
The invention relates to the technical field of silicon nitride material preparation, in particular to a silicon nitride ceramic material, a preparation method and application thereof, and a bulletproof flashboard.
Background
The ceramic material has excellent comprehensive properties including high specific stiffness, high specific strength and good chemical inertness, and meanwhile, the ceramic material also has the advantages of low density, high hardness and high compressive strength. The excellent properties of the ceramic material make the ceramic material have great potential for application in armor protection systems.
The ceramic material prepared by the traditional technology is easy to break and weak in multiple-strike resistance, so that the application of the ceramic material in the field of high-performance protective materials is greatly limited. Moreover, the performance of the materials of the existing armor piercing projectile is gradually upgraded, for example, the projectile of the existing armor piercing projectile is made of high-density alloy steel, tungsten carbide or tungsten, depleted uranium alloy steel and the like, the initial speed of the projectile is 0.9 km/s-1.8 km/s, the armor piercing thickness reaches more than 1m, the armor piercing capability is strong, the flight speed loss is small, and the armor piercing material has great threat force, so that the armor piercing material faces great challenges.
At present, B is the main component4C. SiC and Al2O3However, the three types of ceramic bulletproof inserting plates have the performance defects of low fracture toughness, low bending strength and the like, so that the bulletproof performance, particularly the multi-strike resistance, is weak, and therefore, a silicon nitride ceramic material with high fracture toughness, high bending strength and high bulletproof performance is urgently needed to be developed.
Disclosure of Invention
Based on the silicon nitride ceramic material, the silicon nitride ceramic material with high fracture toughness, high bending strength and high anti-elasticity performance, the preparation method and the application thereof, and the bulletproof flashboard are provided.
The technical scheme of the invention is as follows.
The invention provides a silicon nitride ceramic material which comprises the following raw materials in percentage by mass: 80-90 wt% of silicon nitride powder, 1-6 wt% of carbon simple substance, 1-10 wt% of boron trioxide powder, 1-10 wt% of nitride whisker and carbide whisker, 1-10 wt% of rare earth oxide and 1-6 wt% of binder.
In some embodiments, the nitride whiskers have an aspect ratio of (5-20) 1; the length-diameter ratio of the carbide whisker is (50-100): 1.
In some embodiments, the mass ratio of the nitride whiskers to the carbide whiskers is 1 (1-3).
In some of these embodiments, the rare earth oxide is selected from the group consisting of yttrium oxide, lanthanum oxide, praseodymium oxide, and scandium oxide.
The invention also provides a preparation method of the silicon nitride ceramic material, which comprises the following steps:
providing the following raw materials: 80-90 wt% of silicon nitride powder, 1-6 wt% of carbon simple substance, 1-10 wt% of boron trioxide powder, 1-10 wt% of nitride whisker and carbide whisker, 1-10 wt% of rare earth oxide and 1-6 wt% of binder;
mixing the raw materials in a solvent for pulping, and then drying and granulating to obtain granulated powder;
preparing the granulated powder into a green body;
and sintering and molding the green body to obtain the silicon nitride ceramic material.
In some embodiments, the step of making the granulated powder into a green body specifically comprises the steps of:
dry pressing the granulated powder by bidirectional compression molding to obtain a powder with a density of 1.5g/cm3～1.8g/cm3The green compact of (a);
wherein the pressure of the two-way compression molding is 120MPa to 180 MPa.
In some embodiments, the step of sintering and shaping the green body specifically includes the following steps:
degreasing the green body at 400-600 ℃, filling protective gas at 800-900 ℃ and pressurizing to 1-2 MPa; then sintering the mixture for 2 to 8 hours at a temperature of between 1600 and 1900 ℃ under the pressure of between 5 and 7 MPa;
wherein, the temperature control step of the sintering is as follows:
heating from 400-600 ℃ to 800-900 ℃ at 3-5 ℃/min per minute, and pressurizing to 1-2 MPa;
heating from 800-900 ℃ to 1600-1900 ℃ at 2-3 ℃/min per minute, wherein the pressure is increased to 2-3 MPa when the temperature is increased to 1100-1200 ℃, and the pressure is increased to 3-5 MPa when the temperature is increased to 1400-1500 ℃; heating to 1600-1900 deg.c and pressurizing to 5-7 MPa.
The invention also provides the application of any silicon nitride ceramic material or the silicon nitride ceramic material prepared by any preparation method in the preparation of protective products.
The invention further provides a bulletproof flashboard, and the bulletproof flashboard is made of any silicon nitride ceramic material or any silicon nitride ceramic material prepared by the preparation method.
The invention also provides armor protection equipment which comprises the bulletproof flashboard.
Advantageous effects
The silicon nitride ceramic material adopts the specific components and proportion. The bending strength and the fracture toughness of the silicon carbide ceramic material can be enhanced through the combined action of the nitride crystal whiskers, the carbide crystal whiskers and the rare earth oxide on the silicon nitride powder, and the elasticity resistance of the silicon carbide ceramic material can be improved through the matching of the nitride crystal whiskers and the carbide crystal whiskers. Meanwhile, the elemental carbon and the diboron trioxide powder can form a discontinuous boron carbide whisker component in the silicon nitride matrix under the catalysis of the rare earth oxide, so that the surface density of the material is reduced, and the hardness and the elastic modulus of the material are improved. When the silicon nitride ceramic material is applied to a protective product, the elasticity resistance and the bending resistance of the protective product can be improved, so that the protective performance of the protective product is improved.
Further, in the silicon nitride ceramic material, the aspect ratio of the nitride whiskers is (5-20): 1, and the aspect ratio of the carbide whiskers is (50-100): 1. The nitride whisker with shorter long diameter is perfectly matched with the carbide whisker with longer long diameter, so that the bonding capability of the carbide whisker and the silicon nitride substrate is further enhanced, and the mechanical elasticity resistance of the silicon nitride ceramic material is further improved.
The preparation method of the silicon nitride composite ceramic material comprises the steps of mixing the raw materials in a solvent for pulping, drying and granulating to obtain granulated powder, preparing the granulated powder into raw powder, and sintering and molding the raw powder to obtain the silicon nitride ceramic material with low surface density, high fracture toughness and bending strength and high elasticity resistance.
The invention further provides a bulletproof flashboard, the material of the bulletproof flashboard is any one of the silicon nitride ceramic materials or the silicon nitride ceramic material prepared by the preparation method, and the bulletproof flashboard has high fracture toughness, high bending strength and high elasticity resistance.
Drawings
FIG. 1 is a photograph of a green compact prepared in example 1 of the present invention.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a silicon nitride ceramic material, which comprises the following raw materials in percentage by mass: 80-90 wt% of silicon nitride powder, 1-6 wt% of carbon simple substance, 1-10 wt% of boron trioxide powder, 1-10 wt% of nitride whisker and carbide whisker, 1-10 wt% of rare earth oxide and 1-6 wt% of binder.
The silicon nitride ceramic material adopts the specific components and proportion. The bending strength and the fracture toughness of the silicon carbide ceramic material can be enhanced through the combined action of the nitride whiskers, the carbide whiskers and the rare earth oxide on the silicon nitride powder, and the elasticity resistance of the silicon carbide ceramic material can be improved through the matching of the nitride whiskers and the carbide whiskers; meanwhile, the elemental carbon and the diboron trioxide powder can form discontinuous boron carbide whisker components in the silicon nitride matrix under the catalysis of rare earth oxide, so that the surface density of the material is reduced, and the hardness and the elastic modulus of the material are improved. When the silicon nitride ceramic material is applied to a protective product, the elasticity resistance and the bending resistance of the protective product can be improved, so that the protective performance of the protective product is improved.
Preferably, the raw materials of the silicon nitride ceramic material comprise the following components in percentage by mass: 83 wt% of silicon nitride powder, 3 wt% of carbon simple substance, 3 wt% of boron trioxide powder, 5 wt% of nitride whisker and carbide whisker, 4 wt% of rare earth oxide and 2 wt% of binder.
In some preferred embodiments, the aspect ratio of the nitride whisker is (5-20): 1; the aspect ratio of the carbide whisker is (50-100): 1.
In general, carbide whiskers are long and have weak bonding ability with silicon nitride materials, so that ideal reinforcing effect is difficult to achieve. Therefore, the nitride whisker with shorter length-diameter ratio and the carbide whisker with longer length-diameter ratio are perfectly compounded, so that the bonding capability of the carbide whisker and the silicon nitride substrate is further enhanced, and the mechanical elasticity resistance of the silicon nitride ceramic material is further improved.
In some of these embodiments, the nitride whiskers are selected from at least one of aluminum nitride whiskers and silicon nitride whiskers; and/or the carbide whiskers are selected from silicon carbide whiskers.
In some of these embodiments, the rare earth oxide has a particle size D50 of 0.5 microns to 3.0 microns.
It is understood that the rare earth metal in the above rare earth metal oxide includes the rare earth elements found so far, including 17 elements of scandium, yttrium, lanthanoid, etc. in IIIB group of the periodic Table.
In some of these embodiments, the rare earth oxide is selected from the group consisting of yttrium oxide, lanthanum oxide, praseodymium oxide, and scandium oxide. Further, the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
The mixed rare earth oxide of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide can further catalyze the reaction of simple substance carbon and boron trioxide in the sintering process of the silicon nitride ceramic material, so that a non-continuous boron carbide whisker component is formed in a silicon carbide matrix, and the elasticity resistance of the material is further remarkably improved.
In some embodiments, the elemental carbon is selected from at least one of graphite powder, charcoal powder, coke powder and activated carbon powder.
In some embodiments, the elemental carbon is selected from 200-600 mesh graphite powder.
In some embodiments, the silicon nitride powder is alpha-phase silicon nitride with a mass content of more than 91% and a particle size D50 of 0.6-0.8 microns.
The binder may be any type of binder commonly used in the art, and in some embodiments, the binder is selected from at least one of polyvinyl alcohol, polyvinyl butyral, and cellulose.
An embodiment of the present invention provides a method for preparing a silicon nitride ceramic material, including the following steps S10 to S40.
Step S10, providing the following raw materials: 80-90 wt% of silicon nitride powder, 1-6 wt% of carbon simple substance, 1-10 wt% of boron trioxide powder, 1-10 wt% of nitride whisker and carbide whisker, 1-10 wt% of rare earth oxide and 1-6 wt% of binder.
And S20, mixing the raw materials obtained in the step S10 in a solvent for pulping, and then drying and granulating to obtain granulated powder.
Step S30, the granulated powder obtained in step S20 is made into a green body.
And S40, sintering and molding the green body obtained in the step S30 to obtain the silicon nitride ceramic material.
The preparation method of the silicon nitride composite ceramic material comprises the steps of mixing the raw materials in a solvent for pulping, drying and granulating to obtain granulated powder, preparing the granulated powder into raw materials, and sintering and molding the raw materials to obtain the silicon nitride ceramic material with low surface density, high fracture toughness and bending strength and high elasticity resistance. In one embodiment, in step S20, the solvent used is selected from water or an organic solvent, and further, the solvent is selected from at least one of water, acetone and absolute ethyl alcohol.
In one embodiment, the slurry preparation step of step S20 adopts a ball milling process or a roller milling process, specifically, ball milling is performed by using a sand mill, silicon nitride balls are used as a ball milling medium, and the ball milling time is 0.5 to 3 hours. Wherein the diameter of the ball milling medium is 0.6-0.8 mm, the rotating speed of the sand mill is 2000-2800 r/min, and the lining of the sand mill is made of silicon nitride or polyurethane.
By adopting the ball milling process, the granularity of the mixed raw materials can be reduced, the uniformity of the granularity is improved, and the comprehensive performance of the material is improved.
In some of these embodiments, the drying and pelletizing step of step S20 employs a spray drying and pelletizing process. Specifically, the temperature of an air outlet of spray drying granulation is set to be 90-100 ℃, the temperature of an air inlet is set to be 350-400 ℃, and the granularity D50 of the granulated powder is 60-80 microns.
In some of these embodiments, the viscosity of the slurry in step S20 is 20mPa S to 50mPa S.
It is understood that, in step S20, the amount of the solvent is determined according to the viscosity of the slurry.
In step S20, the nitride whiskers and the carbide whiskers may be added to the solvent separately or separately, or the nitride whiskers and the carbide whiskers may be added to the solvent after being combined.
In some embodiments, the step of making the granulated powder into a green compact in step S30 specifically includes the steps of:
dry pressing the granulated powder by two-way compression molding to obtain a powder with a density of 1.5g/cm3～1.8g/cm3The green compact of (a);
wherein the pressure of the bidirectional compression molding is 120MPa to 180 MPa.
In one specific example, the shape of the green article produced in step S20 is an arc shape, as shown in fig. 1.
The granulated powder is made into a green body with an arc shape, so that a ceramic material with the arc shape is obtained, and the arc-shaped ceramic material is beneficial to improving the anti-elasticity performance of the ceramic material.
In some of the embodiments, the material of the mold used in the step of forming the granulated powder into the green compact in the step S30 is tungsten alloy, and the mass of tungsten in the hard alloy accounts for 1 wt% to 10 wt%.
It should be noted that the thickness of the green body can be adjusted within the range of 5.0mm to 15.0mm according to the requirements of the surface density and the elastic resistance when the ceramic material is actually applied.
In some embodiments, the step of sintering and shaping the green body in step S30 specifically includes the following steps:
degreasing the green body obtained in the step S20 at 400-600 ℃, filling protective gas at 800-900 ℃, pressurizing to 1-2 MPa, and sintering at 1600-1900 ℃ for 2-8 h under 5-7 MPa.
Further, the temperature control procedure in the step of sintering and shaping the green body in step S30 is as follows:
heating from 400-600 ℃ to 800-900 ℃ at 3-5 ℃/min per minute, and pressurizing to 1-2 MPa;
heating from 800-900 ℃ to 1600-1900 ℃ at 2-3 ℃/min per minute, wherein the pressure is increased to 2-3 MPa when the temperature is 1100-1200 ℃, and the pressure is increased to 3-5 MPa when the temperature is 1400-1500 ℃; heating to 1600-1900 deg.c and pressurizing to 5-7 MPa. Wherein, the temperature is increased by 3 ℃/min to 5 ℃/min per minute, the vacuum pumping is carried out in the process of the temperature being increased from 400 ℃ to 600 ℃ to 800 ℃ to 900 ℃, and the subsequent pressurization is carried out by filling protective gas such as nitrogen and the like.
In some of the embodiments, the sintering jig used in the step of sintering and shaping the green body in step S30 has a concave structure.
The sintering jig with the concave surface structure can be matched with the green body with the arc surface shape. Further, the material of the sintering jig has a density of 1.7g/cm3～1.8g/cm3The high-purity high-strength graphite. The sintering jig with a specific structure and materials ensures the dense sintering of the ceramic materials, and on one hand, the controllability of the sintering shape is ensured; on the other hand, the heating uniformity of the green body in the sintering process is improved, so that the silicon nitride ceramic material can be accurately controlledThe size is shrunk, and the problems that the size of the product is difficult to control and the production is unstable are solved.
It will be appreciated that other shapes may be used for the green body, and accordingly, the structure of the sintering jig matches the shape of the green body. Meanwhile, the prepared silicon nitride ceramic material can be cut and polished according to actual requirements.
An embodiment of the invention also provides an application of any one of the silicon nitride ceramic materials or the silicon nitride ceramic material prepared by any one of the preparation methods in preparation of protective products.
When the silicon nitride ceramic material is applied to preparing a protective product, the elasticity resistance and bending resistance of the protective product can be improved, so that the protective performance of the protective product is improved.
Such protective articles include, but are not limited to, armor protective gear, automotive armor, protective doors, and the like.
Further, an embodiment of the present invention further provides a bulletproof insert plate, wherein the material of the bulletproof insert plate is any one of the silicon nitride ceramic materials or the silicon nitride ceramic material prepared by any one of the preparation methods.
The bulletproof flashboard has high fracture toughness, high bending strength and high bulletproof performance.
The invention further provides armor protection equipment which comprises the bulletproof flashboard.
Such armor protection equipment includes, but is not limited to, armor doors, bulletproof helmets, bulletproof shields, and the like.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The silicon nitride ceramic material and the preparation method and application thereof according to the present invention are exemplified herein, but the present invention is not limited to the following examples.
Example 1
According to the mass percentage, the following components are provided: 80 wt% of silicon nitride powder, 8 wt% of silicon carbide whisker and silicon carbonitride whisker, 3 wt% of graphite powder (325 meshes), 3 wt% of boron trioxide powder (the granularity D50 is 50 nanometers), 4 wt% of rare earth oxide and 2% of binder; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 50:1, the length-diameter ratio of the silicon nitride whisker is 10:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 1: 1; the rare earth oxide is selected from yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide, the particle size D50 is 1.0 micron, and the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
2) Mixing the components provided in the step 1) with absolute ethyl alcohol, and performing ball milling to obtain slurry. The method comprises the following steps of taking silicon nitride balls with the diameter of 3.6 millimeters as a ball milling medium, stirring the grinding balls for 2 hours, taking out slurry, and then ball milling for 1 hour by using a sand mill, wherein the ball milling medium in the sand mill is silicon nitride balls with the diameter of 0.8mm, the rotating speed is 2600 r/min, and the lining of the sand mill is made of a silicon nitride material. And finally, performing spray drying granulation on the slurry, wherein the temperature of an air inlet is set to be 280 ℃, the temperature of an air outlet is set to be 105 ℃, the inner diameter of a spray tower is 2.5 meters, the rotating speed of a spray disc is 9000 r/min, and the granularity D50 of the obtained granulated powder is 80 microns.
3) Putting the granulated powder obtained in the step 2) into a hard alloy dry pressing die with 5 wt% of tungsten for dry pressing to obtain a green body, wherein the forming pressure is 150MPa as shown in the attached drawing 1. The density of the finally prepared green body reaches 1.7g/cm3The thickness of the blank is 6.3mm, and the shape of the blank is in an arc shape.
4) And (3) placing the green body obtained in the step 3) into a sintering jig, wherein the sintering jig has a concave surface structure and is matched with the green body in the shape of an arc surface. Degreasing at 600 deg.C or below for 8h in vacuum environment, charging nitrogen gas to 1MPa when the temperature is raised to 800 deg.C at 3 deg.C per minute, pressurizing to 2MPa when the temperature is raised to 1200 deg.C at 3 deg.C per minute, pressurizing to 3MPa when the temperature is raised to 1500 deg.C, pressurizing to 6MPa when the temperature is raised to 1800 deg.C, and sintering under heat preservation for 3 h. And after sintering, reducing the temperature to 800 ℃ by 2 ℃ per minute, and then reducing the temperature to room temperature along with the furnace, and taking out to obtain the silicon carbide ceramic material used as a bulletproof flashboard. The sintering jig is made of high-purity high-strength graphite with the density of 1.8.
Example 2
1) According to the mass percentage, the following components are provided: 90 wt% of silicon nitride powder, 3 wt% of silicon carbide whisker and silicon carbonitride whisker, 1 wt% of graphite powder (325 meshes), 2 wt% of boron trioxide powder (the granularity D50 is 50 nanometers), 2 wt% of rare earth oxide and 2% of binder; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 100:1, the length-diameter ratio of the silicon nitride whisker is 10:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 1: 2; the rare earth oxide is selected from yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide, the particle size D50 is 1.0 micron, and the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
The other steps and the process conditions were the same as in example 1.
Example 3
1) According to the mass percentage, the following components are provided: 85 wt% of silicon nitride powder, 5 wt% of silicon carbide whisker and silicon carbonitride whisker, 6 wt% of graphite powder (325 meshes), 2 wt% of boron trioxide powder (the granularity D50 is 50 nanometers), 1 wt% of rare earth oxide and 1% of binder; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 70:1, the length-diameter ratio of the silicon nitride whisker is 20:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 1: 3; the rare earth oxide is selected from yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide, the particle size D50 is 1.0 micron, and the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
The other steps and the process conditions were the same as in example 1.
Example 4
1) According to the mass percentage, the following components are provided: 82 wt% of silicon nitride powder, 4 wt% of silicon carbide whisker and silicon carbonitride whisker, 4 wt% of graphite powder (325 meshes), 2 wt% of boron trioxide powder (the granularity D50 is 50 nanometers), 7 wt% of rare earth oxide and 1% of binder; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 50:1, the length-diameter ratio of the silicon nitride whisker is 10:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 1: 1; the rare earth oxide is selected from yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide, the particle size D50 is 1.0 micron, and the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
The other steps and the process conditions were the same as in example 1.
Example 5
1) According to the mass percentage, the following components are provided: 80 percent of silicon nitride powder, 1 percent of silicon carbide whisker and silicon carbonitride whisker by weight, 6 percent of graphite powder (325 meshes) by weight, 10 percent of boron trioxide powder (the granularity D50 is 50 nanometers), 1 percent of rare earth oxide by weight and 2 percent of binder by weight; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 50:1, the length-diameter ratio of the silicon nitride whisker is 30:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 1: 1; the rare earth oxide is selected from yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide, the particle size D50 is 1.0 micron, and the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
The other steps and the process conditions were the same as in example 1.
Example 6
1) According to the mass percentage, the following components are provided: 83 wt% of silicon nitride powder, 5 wt% of silicon carbide whisker and silicon carbonitride whisker, 3 wt% of graphite powder (325 meshes), 3 wt% of boron trioxide powder (the granularity D50 is 50 nanometers), 4 wt% of rare earth oxide and 2% of binder; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 50:1, the length-diameter ratio of the silicon nitride whisker is 30:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 1: 1; the rare earth oxide is selected from yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide, the particle size D50 is 1.0 micron, and the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
The other steps and the process conditions were the same as in example 1.
Example 7
1) According to the mass percentage, the following components are provided: 80 wt% of silicon nitride powder, 8 wt% of silicon carbide whisker and silicon carbonitride whisker, 3 wt% of graphite powder (325 meshes), 3 wt% of boron trioxide powder (the granularity D50 is 50 nanometers), 4 wt% of rare earth oxide and 2% of binder; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 50:1, the length-diameter ratio of the silicon nitride whisker is 10:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 2: 1; the rare earth oxide is selected from yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide, the particle size D50 is 1.0 micron, and the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
The other steps and the process conditions were the same as in example 1.
Example 8
1) According to the mass percentage, the following components are provided: 80 wt% of silicon nitride powder, 8 wt% of silicon carbide whisker and silicon carbonitride whisker, 3 wt% of graphite powder (325 meshes), 3 wt% of boron trioxide powder (the granularity D50 is 50 nanometers), 4 wt% of rare earth oxide and 2% of binder; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 50:1, the length-diameter ratio of the silicon nitride whisker is 10:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 1: 1; the rare earth oxide is selected from a mixture of yttrium oxide, lanthanum oxide and praseodymium oxide, the particle size D50 is 1.0 micron, and the mass ratio of the yttrium oxide to the lanthanum oxide to the praseodymium oxide is 2:1: 1.
The other steps and the process conditions were the same as in example 1.
Comparative example 1
According to the mass percentage, the following components are provided: 80 wt% of silicon nitride powder, 8 wt% of silicon carbide whisker and silicon carbonitride whisker, 3 wt% of graphite powder (325 meshes), 3 wt% of boron trioxide powder (the granularity D50 is 50 nanometers), 4 wt% of rare earth oxide and 2% of binder; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 50:1, the length-diameter ratio of the silicon nitride whisker is 40:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 1: 1; the rare earth oxide is selected from yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide, the particle size D50 is 1.0 micron, and the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
The remaining steps and process conditions were the same as in example 1
Comparative example 2
According to the mass percentage, the following components are provided: 80 wt% of silicon nitride powder, 8 wt% of silicon carbide whisker and silicon carbide nitride whisker, 6 wt% of boron carbide powder (the granularity D50 is 50 nanometers), 4 wt% of rare earth oxide and 2% of binder; wherein, the purity of the silicon nitride powder is 99.6 percent, the mass content of the alpha-phase silicon nitride is 92 percent, and the granularity D50 of the silicon nitride powder is 0.6 micron; the length-diameter ratio of the silicon carbide whisker is 50:1, the length-diameter ratio of the silicon nitride whisker is 10:1, and the mass ratio of the silicon nitride whisker to the silicon carbide whisker is 1: 1; the rare earth oxide is selected from yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide, the particle size D50 is 1.0 micron, and the mass ratio of yttrium oxide, lanthanum oxide, praseodymium oxide and scandium oxide is 2:1:1: 1.
The binders used in examples 1 to 8 and comparative examples 1 to 2 were all polyvinyl butyral.
Example 9
1. The obtained bulletproof inserting plates prepared in the embodiments 1-8 and the comparative examples 1-2 are tested for bending strength, fracture toughness and elastic resistance, and the test standards of the bending strength and the fracture toughness refer to GB/T23806-2009 and GBT/23806-2009 respectively; the test of the elastic resistance refers to the standard China civil armed police force logistics department standard WHB 917-2015.
2. The areal density of the bulletproof plugboard prepared in the examples 1-8 and the comparative examples 1-2 is tested, and the test refers to the standard WHB 917-2015 of the civil armed police force logistics department of China.
The results obtained are shown in table 1 below.
TABLE 1
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The silicon nitride ceramic material is characterized by comprising the following raw materials in percentage by mass: 80-90 wt% of silicon nitride powder, 1-6 wt% of carbon simple substance, 1-10 wt% of boron trioxide powder, 1-10 wt% of nitride whisker and carbide whisker, 1-10 wt% of rare earth oxide and 1-6 wt% of binder;
wherein the length-diameter ratio of the nitride crystal whisker is (5-20) 1; the length-diameter ratio of the carbide whisker is (50-100) 1;
the mass ratio of the nitride whiskers to the carbide whiskers is 1 (1-3).
2. The silicon nitride ceramic material of claim 1, wherein the elemental carbon is at least one selected from the group consisting of graphite powder, charcoal powder, coke powder, activated carbon powder, and carbon black.
3. The silicon nitride ceramic material of claim 1, wherein the mass ratio of the nitride whiskers to the carbide whiskers is 1: 3.
4. The silicon nitride ceramic material of claim 1, wherein the rare earth oxide is selected from the group consisting of yttrium oxide, lanthanum oxide, praseodymium oxide, and scandium oxide.
5. The preparation method of the silicon nitride ceramic material is characterized by comprising the following steps of:
providing the following raw materials: 80-90 wt% of silicon nitride powder, 1-6 wt% of carbon simple substance, 1-10 wt% of boron trioxide powder, 1-10 wt% of nitride whisker and carbide whisker, 1-10 wt% of rare earth oxide and 1-6 wt% of binder; wherein the length-diameter ratio of the nitride crystal whisker is (5-20) 1; the length-diameter ratio of the carbide whisker is (50-100) 1; the mass ratio of the nitride whiskers to the carbide whiskers is 1 (1-3);
mixing the raw materials in a solvent for pulping, and then drying and granulating to obtain granulated powder;
preparing the granulated powder into a green body;
and sintering and molding the green body to obtain the silicon nitride ceramic material.
6. The method of claim 5, wherein the step of forming the granulated powder into a green body comprises the steps of:
dry pressing the granulated powder by two-way compression molding to obtain a powder with a density of 1.5g/cm3～1.8g/cm3The green compact of (a);
wherein the pressure of the two-way compression molding is 120MPa to 180 MPa.
7. The method according to any one of claims 5 to 6, wherein the step of sintering and shaping the green body comprises the following steps:
degreasing the green body at 400-600 ℃, filling protective gas at 800-900 ℃ and pressurizing to 1-2 MPa; then sintering the mixture for 2 to 8 hours at a temperature of between 1600 and 1900 ℃ under the pressure of between 5 and 7 MPa;
wherein the temperature control procedure in the step of sintering and molding the green body is as follows:
heating from 400-600 ℃ to 800-900 ℃ at 3-5 ℃/min per minute, and pressurizing to 1-2 MPa;
heating from 800-900 ℃ to 1600-1900 ℃ at 2-3 ℃/min per minute, wherein the pressure is increased to 2-3 MPa when the temperature is increased to 1100-1200 ℃, and the pressure is increased to 3-5 MPa when the temperature is increased to 1400-1500 ℃; heating to 1600-1900 deg.c and pressurizing to 5-7 MPa.
8. Use of a silicon nitride ceramic material according to any one of claims 1 to 4 for the preparation of protective articles.
9. A bulletproof insert plate, wherein the material of the bulletproof insert plate is the silicon nitride ceramic material according to any one of claims 1 to 4.
10. An armor protection rig, characterized in that it comprises a bulletproof insert according to claim 9.
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