CN113480314A - Boron carbide ceramic pressureless sintering preparation process - Google Patents
Boron carbide ceramic pressureless sintering preparation process Download PDFInfo
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- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 63
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 238000001272 pressureless sintering Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000004697 Polyetherimide Substances 0.000 claims 1
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/563—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on boron carbide
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Abstract
The invention belongs to the technical field of ceramic composite materials, and provides a boron carbide ceramic pressureless sintering preparation process, which comprises the following steps: s1, preparing boron carbide submicron powder: grinding a boron carbide raw material into boron carbide submicron powder with the grain diameter of 0.5-1.0um in a sand mill; s2, preparing slurry: sequentially adding a water solvent, boron carbide submicron powder and a dispersing agent into a high-speed dispersion machine for dispersing for 1-2 h; pumping the slurry into a stirring ball mill, sequentially adding a sintering aid, an adhesive, a plasticizer, a dispersant and a defoaming agent into the stirring ball mill, and mutually circulating the stirring ball mill and a low-speed disperser for 3-8 hours to obtain the slurry; s3, preparing granulated powder: spray drying the slurry to obtain granulation powder; s4, press forming: pressing the granulation powder into a green body with the relative density being equal to or greater than 60% by adjusting the pressure and isostatic pressure of a hydraulic press; the relative density is the green density/product density; and S5, pressureless sintering, wherein the pressureless sintering is carried out in a sintering furnace and comprises a vacuum degumming stage, a vacuum high-temperature stage, a high-temperature sintering stage and a cooling stage to obtain the boron carbide ceramic.
Description
Technical Field
The invention generally relates to the technical field of composite ceramic preparation, and particularly provides a non-pressure sintering preparation process of boron carbide ceramic.
Background
Ceramic composite structures are excellent ballistic protection solutions today, and among many ceramic materials, boron carbide ceramics have a lower density (2.52 g/cm)3) The hardness of the diamond is second only, and the excellent corrosion resistance meets the requirements of high strength, high wear resistance, high hardness and low density (three high and one low for short) of the bulletproof material, can effectively crush the shot, disperse kinetic energy, increase the protection capability of the equipment, and meet the requirements of light weight of the equipment and light weight of individual soldiers.
In the prior art, boron carbide ceramic products have inherent defects due to the formula, the preparation process and the like, and the uniformity and the stability of the products are poor.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a pressureless sintering preparation process of boron carbide ceramic, which adopts submicron boron carbide powder to improve the strength, toughness and stability of a product through the optimization of a formula and a process.
The invention provides a boron carbide ceramic pressureless sintering preparation process, which comprises the following steps:
s1, preparing boron carbide submicron powder: grinding a boron carbide raw material into boron carbide submicron powder with the grain diameter of 0.5-1.0um in a sand mill;
s2, preparing slurry: sequentially adding a water solvent, boron carbide submicron powder and a dispersing agent into a high-speed dispersion machine for dispersing for 1-2 h; pumping the slurry into a stirring ball mill, sequentially adding a sintering aid, an adhesive, a plasticizer, a dispersant and a defoaming agent into the stirring ball mill, and mutually circulating the stirring ball mill and a low-speed disperser for 3-8 hours to obtain the slurry;
s3, preparing granulated powder: spray drying the slurry obtained in the step S2 to obtain granulated powder;
s4, press forming: pressing the granulation powder into a green body with the relative density being equal to or greater than 60% by adjusting the pressure and isostatic pressure of a hydraulic press; the relative density is the green density/product density;
s5, pressureless sintering, wherein the pressureless sintering is carried out in a sintering furnace and comprises the following three stages:
s51, a vacuum degumming stage, wherein the temperature range is 200-1000 ℃;
s52, vacuum high temperature stage, temperature interval 1100-;
s53, high-temperature sintering, wherein the temperature range is 2000-2250 ℃;
and S54, cooling, namely cooling in an argon protection atmosphere after heat preservation is finished to obtain the boron carbide ceramic.
Further, in step S1: placing boron carbide microsphere grinding medium within the range of 0.5-1.0mm in a sand mill, and grinding the boron carbide raw powder for 10-15h at the linear speed of 13-18m/s to obtain 0.5-1.0um boron carbide submicron powder.
Further, in step S2, the method includes: the sintering aid is selected from 3-5 of silicon carbide powder with the grain size range of 0.3-0.8um, yttrium oxide with the grain size range of 0.3-0.8um, aluminum oxide with the grain size range of 0.2-0.8um, titanium carbide with the grain size range of 0.5-1.0um, titanium boride with the grain size range of 0.5-1um, carbon nano-tubes and silicon carbide whiskers; the adhesive is selected from 2-3 of phenolic resin, hydroxypropyl methyl cellulose, polyvinyl alcohol and lignin; the dispersing agent is selected from 1-2 of KH550, KH560, PEG2000, PEG4000 and PEI; the plasticizer is selected from 1-2 of dioctyl phthalate, BBP and DEP.
Further, in step S2, the method includes: the boron carbide submicron powder, the sintering aid, the adhesive, the dispersant and the plasticizer are as follows in parts by weight: 100: (5-20): (5-10): (0.1-1): (0.01-0.2).
Further, in step S2, the method includes: after materials are sequentially added into a high-speed dispersion machine, water is used as a solvent, and the solid content of the water is within the range of 50% -60%; the high speed dispersion machine speed is: 200-400 r/min.
Further, in step S3, the method includes: after spray drying, the water content of the granules is controlled between 0.5 and 1.5 percent by mass.
Further, in step S4, the method includes: the method for adjusting the pressure and isostatic pressure of the hydraulic press comprises the following steps: three-section hydraulic pressing by a hydraulic machine and then isostatic pressing; the parameters of three-stage hydraulic pressing of the hydraulic press are as follows: the first-stage pressing pressure is 0.3-1.5MPa, and the pressing time is as follows: 20-40 s; the two-stage pressing pressure is 2.0-10.0MPa, and the pressing time is as follows: 20-30 s; the three-stage pressing pressure is 50-60MPa, and the pressing time is as follows: 15-30 s; the parameters of the isostatic pressing are as follows: pressure range of 120-180MPa, pressure maintaining time: 20-40 s.
Further, in step S5, the method includes: the vacuum degumming stage of S51 is to raise the temperature from room temperature to 1000 ℃ at a heating rate of 3-5 ℃/min in a vacuum environment; the vacuum high-temperature stage of S52 is to increase the temperature from degumming temperature to 1850 ℃ at the temperature increase rate of 2-4 ℃/min in a vacuum environment; the high-temperature sintering stage of S53 is that the temperature is manually increased to 2250 ℃ from the vacuum high-temperature of the step S52 at the heating rate of 2-3 ℃/min, and the temperature is kept for 1-1.5 h; the cooling stage of S54 is that after the heat preservation of the step S53 is finished, the furnace is cooled in the argon protection atmosphere, and when the temperature is reduced to 500 ℃, the inner container door in the sintering furnace is opened for quick cooling; the vacuum of the steps S51 and S52 means that the pressure is kept within the range of 10-60Pa, argon is filled in the high-temperature sintering process of the step S53, the pressure of the argon reaches the range of 50-90KPa, and the argon atmosphere sintering is carried out until the heat preservation is finished.
Further, the pressureless sintering furnace in the step S5 is a self-grinding high-temperature sintering furnace with the application number of CN202020299896.9, the name of the invention is: a boron carbide ceramic pressureless sintering device is a high-temperature, vacuum and pressureless sintering furnace, the temperature difference of a temperature field is less than or equal to 5 ℃, the problems of high temperature and narrow interval are solved, the high vacuum is less than or equal to 102Pa, and the problem of oxidation is solved.
Further, in step S5, the method includes: the gas emission after the reaction adopts a self-developed RTO device, CN202021336013.3, the invention name is an atmospheric diffusion type VOC tail gas combustion device, the combustion of the gas emission can be catalyzed, the pollution-free emission is realized, and the environment pollution is avoided.
The boron carbide sintering has the following technical problems:
1) the sintering temperature is high;
2) the sintering temperature range is narrow, the temperature is too high, and the green body is collapsed and melted; the temperature is too low, the density is not dense, and the performance does not reach the standard;
3) the size and the shape of the boron carbide sintering process are difficult to control;
4) the boron carbide is very easy to oxidize in the sintering process;
5) the emission of sintering waste gas pollutes the environment.
Aiming at the technical problems, the invention adopts a self-grinding high-temperature sintering furnace (high-temperature, vacuum and pressureless sintering), the temperature difference of a temperature field is less than or equal to 5 ℃ (the high-temperature problem is solved, the interval is narrow), and the high vacuum is less than or equal to 102Pa (to address oxidation); and a sintering process control scheme is designed. A large amount of gas is generated in the sintering process, the atmosphere in the furnace is disordered, and the product is easy to move, deform and change in size, so that the gas release speed is controlled by slowly raising the temperature or keeping the temperature in the gas generation stage; meanwhile, the gas emission after the reaction pollutes the environment: by self-grinding the RTO device, the combustion of the catalytic exhaust gas is realized, and pollution-free emission is realized.
The invention also provides the application of the boron carbide ceramic obtained by the boron carbide ceramic pressureless sintering preparation process in bulletproof products.
Compared with the prior art, the invention has the advantages that:
1) according to the formula, the density and the strength of the product can be improved by using submicron boron carbide powder, a sintering agent, an adhesive, a dispersing agent and the content combination of the submicron boron carbide powder, the sintering agent, the adhesive and the dispersing agent.
2) In the method, three-section forming of a hydraulic machine and isostatic pressing are combined, so that the density of the product can reach more than 2.5 and the uniformity is better; meanwhile, the process ensures that boron carbide ceramic has fine crystal grains and more crystal boundaries, and when the boron carbide ceramic is used for bulletproof products, the ceramic bullet-facing surface has good crushing state, more kinetic energy of bullets is consumed, and the protective performance is good (after the ceramic is impacted, two forms of crystal-through fracture and crystal-following fracture exist, and the crystal-through fracture absorbs more energy;
3) the method of the invention adopts the step sintering, so that the product is degummed completely, the compactness is good, and the consistency of the density and the hardness of the product is optimal.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a photograph showing the fracture surface of a curved ceramic plate made of boron carbide ceramic according to an embodiment of the present invention after a live impact.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following detailed description of the invention is provided in conjunction with the accompanying drawings and the detailed description of the invention.
Example 1
A boron carbide ceramic pressureless sintering preparation process comprises the following raw material formula: boron carbide: 100 parts by mass of (0.5um) and 10 parts by mass of silicon carbide (0.3 um); 1 part by mass of yttrium oxide (0.2 um); 3 parts by mass of titanium boride (0.5 um); 8 parts of phenolic resin, 550-0.15 part of KH and 0.05 part of DOP. Pressing relative density: 60 percent.
The preparation method comprises the following steps:
pumping the boron carbide submicron powder ground by the sand mill into a high-speed dispersion machine, taking water as a solvent, and adding a dispersing agent for high-speed dispersion (the speed is 200-; pumping into a stirring ball mill (the rotating speed is 300-;
preparing granulation powder, namely performing spray drying, wherein the slurry in the previous step is subjected to spray drying, and the water content of granules is controlled to be 0.5-1.5%;
molding: designing a mold according to the shrinkage coefficient of a product, and preparing a green body with the relative density of not less than 60% by adjusting the pressure and isostatic pressure of a hydraulic press, wherein the relative density is the green body density/the product density;
and (3) sintering: the sintering process flow can be divided into three stages:
(1) the method comprises the following steps of (1) degumming, (2) high-temperature sintering, (3) cooling, and controlling the process parameters of the specific sintering process as shown in the following table 1.
TABLE 1 sintering Process and parameter control
The product performance is as follows: the density is more than or equal to 2.51g/m3HV0.5 is more than or equal to 29GPa, and the breaking strength is more than or equal to 433 MPa;
the sintering aid has fine particles and higher surface energy, is favorable for reducing the sintering temperature to promote sintering, and can simultaneously improve the density and toughen the product. The action mechanism of the sintering aid is as follows: the silicon carbide, the yttrium oxide and the titanium carbide can effectively pin the grain boundary, inhibit the growth of boron carbide grains, play a role in fine grain strengthening, simultaneously hinder the expansion of cracks, improve the fracture toughness of the complex phase ceramic and reduce the porosity.
The obtained product is used for the multi-curved-surface boron carbide ceramic plate, the fracture effect formed by the bullet-facing surface of the multi-curved-surface boron carbide ceramic plate after the ball firing experiment is shown in figure 1, and it can be seen that the ceramic bullet-facing surface is good in fracture state, local fracture occurs, and the fracture of non-firing parts is not caused.
Example 2
A boron carbide ceramic pressureless sintering preparation process comprises the following raw material formula: boron carbide: 100 parts by mass of (0.8um), 5 parts by mass of carbon nanotubes and 3 parts by mass of yttrium oxide (0.3 um); 5 parts by mass of titanium carbide (0.5 um); 10 parts by mass of polyvinyl alcohol, 4000-0.5 part by mass of PEG, 0.05 part by mass of DEP, and the relative density of the pressed material is as follows: 60 percent.
The preparation process is the same as in example 1.
The product performance is as follows: the density is more than or equal to 2.52g/m3HV0.5 is more than or equal to 30.5GPa, and breaking strength is more than or equal to 450MPa
The sintering aid has fine particles and higher surface energy, is favorable for reducing the sintering temperature to promote sintering, and can simultaneously improve the density and toughen the product. The toughening mechanism of the carbon nano tube is as follows: increased pull-out effect, bridging toughening, crack deflection toughening and residual stress toughening.
Example 3
A boron carbide ceramic pressureless sintering preparation process comprises the following raw material formula: boron carbide: 100 parts by mass of (0.6um), 5 parts by mass of silicon carbide whisker and 5 parts by mass of silicon carbide (0.5 um); 2 parts by mass of yttrium oxide (0.3 um); 10 parts by mass of hydroxypropyl methyl cellulose, 2000-0.5 part by mass of PEG and 0.1 part by mass of DOP, and the relative density of the pressed material is as follows: 60 percent.
The preparation process is the same as in example 1.
The product performance is as follows: the density is more than or equal to 2.53g/m3HV0.5 is more than or equal to 31GPa, and the breaking strength is more than or equal to 455MPa
The sintering aid has fine particles and higher surface energy, is favorable for reducing the sintering temperature to promote sintering, and can simultaneously improve the density and toughen the product. Adding whiskers to increase strength: for a particular direction and distribution of fibers, the crack is difficult to deflect and can only continue to propagate in the original propagation direction. The fibres immediately adjacent the tip of the crack are not broken but instead a small bridge is set up on both sides of the crack, joining the two sides together. This creates a compressive stress on the crack surface to counteract the effect of the applied stress, thereby making it difficult for the crack to propagate further and serving as a toughening effect.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The pressureless sintering preparation process of the boron carbide ceramic is characterized by comprising the following steps of:
s1, preparing boron carbide submicron powder: grinding a boron carbide raw material into boron carbide submicron powder with the grain diameter of 0.5-1.0um in a sand mill;
s2, preparing slurry: sequentially adding a water solvent, boron carbide submicron powder and a dispersing agent into a high-speed dispersion machine for dispersing for 1-2 h; pumping the slurry into a stirring ball mill, sequentially adding a sintering aid, an adhesive, a plasticizer, a dispersant and a defoaming agent into the stirring ball mill, and mutually circulating the stirring ball mill and a low-speed disperser for 3-8 hours to obtain the slurry;
s3, preparing granulated powder: spray drying the slurry obtained in the step S2 to obtain granulated powder;
s4, press forming: pressing the granulation powder into a green body with the relative density being equal to or greater than 60% by adjusting the pressure and isostatic pressure of a hydraulic press; the relative density is the green density/product density;
s5, pressureless sintering, wherein the pressureless sintering is carried out in a sintering furnace and comprises the following three stages:
s51, a vacuum degumming stage, wherein the temperature range is 200-1000 ℃;
s52, vacuum high temperature stage, temperature interval 1100-;
s53, high-temperature sintering, wherein the temperature range is 2000-2250 ℃;
and S54, cooling, namely cooling in an argon protection atmosphere after heat preservation is finished to obtain the boron carbide ceramic.
2. The pressureless sintering process for preparing boron carbide ceramic according to claim 1,
in the step S1: placing boron carbide microsphere grinding medium within the range of 0.5-1.0mm in a sand mill, and grinding the boron carbide raw powder for 10-15h at the linear speed of 13-18m/s to obtain 0.5-1.0um boron carbide submicron powder.
3. The pressureless sintering process for preparing boron carbide ceramic according to claim 1,
in the step S2: the sintering aid is selected from 3-5 of silicon carbide powder with the grain size range of 0.3-0.8um, yttrium oxide with the grain size range of 0.3-0.8um, aluminum oxide with the grain size range of 0.2-0.8um, titanium carbide with the grain size range of 0.5-1.0um, titanium boride with the grain size range of 0.5-1um, carbon nano-tubes and silicon carbide whiskers;
the adhesive is selected from 2-3 of phenolic resin, hydroxypropyl methyl cellulose, polyvinyl alcohol and lignin;
the dispersing agent is selected from 1-3 of KH550, KH560, PEG2000, PEG4000, TMAH, ammonia water, sodium hydroxide and PEI;
the plasticizer is selected from 1-2 of dioctyl phthalate, BBP and DEP.
4. The pressureless sintering process for preparing boron carbide ceramic according to claim 1,
in the step S2: the boron carbide submicron powder, the sintering aid, the adhesive, the dispersant and the plasticizer are as follows in parts by weight: 100: (5-20): (5-10): (0.1-1): (0.01-0.2).
5. The pressureless sintering process for preparing boron carbide ceramic according to claim 1,
in the step S2:
water is used as a solvent in the high-speed dispersion machine, and the addition amount of the water is that the solid content of the water is in the range of 50-60%;
the high-speed dispersion machine speed is as follows: 200-400 r/min.
6. The pressureless sintering process for preparing boron carbide ceramic according to claim 1,
in the step S3: after spray drying, the water content of the granules is controlled between 0.5 and 1.5 percent by mass.
7. The pressureless sintering process for preparing boron carbide ceramic according to claim 1, wherein in step S4:
the method for adjusting the pressure and isostatic pressure of the hydraulic press comprises the following steps: three-section hydraulic pressing by a hydraulic machine and then isostatic pressing;
the parameters of three-stage hydraulic pressing of the hydraulic press are as follows: the first-stage pressing pressure is 0.3-1.5MPa, and the pressing time is as follows: 20-40 s; the two-stage pressing pressure is 2.0-10.0MPa, and the pressing time is as follows: 20-30 s; the three-stage pressing pressure is 50-60MPa, and the pressing time is as follows: 15-30 s;
the parameters of the isostatic pressing are as follows: pressure range of 120-180MPa, pressure maintaining time: 20-40 s.
8. The pressureless sintering process for preparing boron carbide ceramic according to claim 1, wherein in step S5:
the vacuum degumming stage of S51 is to raise the temperature from room temperature to 1000 ℃ at the heating rate of 2-5 ℃/min in a vacuum environment;
the vacuum high-temperature stage of S52 is to increase the temperature from degumming temperature to 1850 ℃ at the temperature increase rate of 3-5 ℃/min in a vacuum environment;
the high-temperature sintering stage of S53 is that the temperature is manually increased to 2250 ℃ from the vacuum high-temperature of the step S52 at the heating rate of 2-3 ℃/min, and the temperature is kept for 1-1.5 h;
the cooling stage of S54 is that after the heat preservation of the step S53 is finished, the furnace is cooled in the argon protection atmosphere, and when the temperature is reduced to 500 ℃, the inner container door in the sintering furnace is opened for quick cooling;
the vacuum of the steps S51 and S52 means that the pressure is kept within the range of 10-60Pa, argon is filled in the high-temperature sintering process of the step S53, the pressure of the argon reaches the range of 50-90KPa, and the argon atmosphere sintering is carried out until the heat preservation is finished.
9. The pressureless sintering process for preparing boron carbide ceramic according to claim 1,
the pressureless sintering furnace in the step S5 is a high-temperature, vacuum and pressureless sintering furnace, the temperature difference of the temperature field is less than or equal to 5 ℃, and the high vacuum is less than or equal to 102Pa。
10. Use of a boron carbide ceramic prepared by a pressureless sintering process according to any of claims 1-9 in a ballistic resistant product.
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