CN113004052A - Multi-walled carbon nanotube toughened boron carbide-based ceramic material and preparation method and application thereof - Google Patents
Multi-walled carbon nanotube toughened boron carbide-based ceramic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of boron carbide-based ceramic materials, and particularly relates to a multiwalled carbon nanotube toughened boron carbide-based ceramic material and a preparation method and application thereof. The method comprises the step of preparing tower entering slurry of a spray granulation tower; the preparation process of the tower entering slurry comprises the following steps: preparing a multi-wall carbon nano tube prefabricated body; preparing a boron carbide premix; preparing a multi-wall carbon nanotube premix; and (5) preparing tower slurry. According to the method, the specific surfactant is selected to pre-disperse the multi-walled carbon nanotubes, and meanwhile, the multi-walled carbon nanotubes are doped in batches, the doping proportion of the multi-walled carbon nanotubes is controlled, and the matched mixing mode is selected according to the characteristics of material systems at all stages, so that the problem of dispersion of the multi-walled carbon nanotubes in the ceramic slurry is solved, the high strength and the high hardness of the ceramic material are maintained, the toughness and the bending strength of the ceramic material are obviously improved, the preparation time of the slurry entering a tower is shortened, and the production efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of boron carbide-based ceramic materials, and particularly relates to a multiwalled carbon nanotube toughened boron carbide-based ceramic material and a preparation method and application thereof.
Background
The boron carbide-based ceramic material has the advantages of high strength, low density, corrosion resistance and the like by virtue of the unique rhombohedral structure, so that the boron carbide-based ceramic material is widely applied to the field of individual protective products. However, the toughness of boron carbide-based ceramic materials is relatively poor, and has been an index of interest and effort for researchers.
The existing method for improving the toughness of the boron carbide-based ceramic material is mainly to add a low-melting-point metal/metal oxide and other sintering two-phase means, such as CN112079642A, and the method is to add toughening phase alumina, yttrium oxide and cerium oxide into boron carbide powder; and a toughening phase generated by in-situ synthesis and other modes, such as CN111018530A, wherein boron carbide, titanium-coated carbon nanotubes and silicon-coated carbon nanotubes are used as raw materials, and the toughening phase titanium boride and silicon carbide are generated by in-situ reaction. Although the toughening method improves the toughness of the boron carbide material to a certain degree, the improvement effect is insufficient, and the fracture toughness is not more than 7MPa1/2。
The multi-wall carbon nano tube has the characteristic of high toughness, and provides a new research direction for the toughening research and development of the boron carbide-based ceramic material by combining the multi-wall carbon nano tube with the high strength and high hardness of the boron carbide-based ceramic material, but the dispersibility of the multi-wall carbon nano tube is always the most main factor for restricting the application of the multi-wall carbon nano tube.
CN102557641A discloses a technical solution for reinforcing and toughening silicon carbide ceramics in a silicon carbide material dispersed by carbon nanotubes, which teaches that under the action of a dispersant ethanol, the carbon nanotubes are in a relatively stable suspension state in a single or small bundle form, which is beneficial to being uniformly distributed in a silicon carbide suspension; then, the carbon nano tube suspension and the silicon carbide suspension are uniformly mixed through a ball milling process, an ultrasonic stirring process and the like; and the adding amount of the carbon nano tube is limited to be controlled at 0.5-3%.
However, spray granulation technology is mainly adopted in the current ceramic industrial production, and slurry entering a tower usually contains a binder and a dispersant. The disperse carrier ethanol adopted by the method is not dissolved with the binder and the dispersant in the existing slurry entering the tower, and the layering phenomenon can occur in the slurry manufacturing process; meanwhile, due to the high temperature in the tower, the ethanol carrier has explosion risk; therefore, although the method solves the problem of dispersion of the carbon nanotubes in the boron carbide suspension, the carbon nanotubes cannot be used as tower-entering slurry in the spray granulation process.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a boron carbide-based ceramic material. The method solves the problem of dispersion of the multi-walled carbon nanotubes in the ceramic slurry, and also solves the problem that the slurry containing the multi-walled carbon nanotubes cannot be used in the spray granulation technology. Research shows that the boron carbide-based ceramic material obtained by the method has the performances of high toughness, bending strength, high hardness and the like.
The preparation method of the multiwalled carbon nanotube toughened boron carbide-based ceramic material comprises the steps of preparing tower entering slurry of a spray granulation tower; the preparation of the tower entering slurry comprises the following steps:
preparing a multi-wall carbon nano tube preform: preparing a multi-walled carbon nanotube preform by using a surfactant with a K value of more than 10 and assisting ultrasonic dispersion and mechanical stirring;
preparing a boron carbide premix: adding a small amount of multi-walled carbon nanotube preforms into a boron carbide base material containing a sintering two-phase, and performing ball milling to prepare a boron carbide premix;
preparing a multi-wall carbon nanotube premix: uniformly mixing the rest multi-walled carbon nanotube prefabricated bodies by three rollers to prepare a multi-walled carbon nanotube premix;
preparing tower slurry: sequentially adding additives into the boron carbide premix, and mechanically stirring; and adding the multiwalled carbon nanotube premix, performing ultrasonic dispersion and three-roller mixing to obtain tower entering slurry.
According to the invention, through research, the dispersion degree of the multi-walled carbon nano-tube in the slurry entering the tower can be obviously improved by screening a proper surfactant and matching the surfactant with a specific doping mode, and the obtained slurry entering the tower has good compatibility of all components, can be directly input into a spray granulation tower, and solves the technical problems.
Specifically, the surfactant with the K value of more than 10 is selected to pre-disperse the multi-walled carbon nanotube, so that the dispersion degree of the multi-walled carbon nanotube in a system is improved, and the compatibility of the multi-walled carbon nanotube with a sintering two-phase and an additive is good, so that the occurrence of a layering phenomenon in the slurry manufacturing process is avoided, and the production safety is higher. Meanwhile, the dispersion degree of the multi-walled carbon nanotubes in the tower slurry is further improved by a batch doping mode of the multi-walled carbon nanotubes, controlling the doping proportion of the multi-walled carbon nanotubes and selecting a matched mixing mode according to the characteristics of a material system at each stage, the toughness and the bending strength of the ceramic material are obviously improved while the high strength and the high hardness of the ceramic material are maintained, the preparation time of the tower slurry is shortened, and the production efficiency is improved.
The multi-walled carbon nanotube of the present invention has the following characteristics: the diameter is 10-20 nm, the length is less than 0.5 mu m, the purity is more than 97%, the gray level wt is less than 3%, and the specific surface area is 40-70 m2(ii) a bulk density of 0.03 to 0.16g/m3。
As is well known, the amount of the surfactant is very large, and the surfactant is further researched in the invention in order to better improve the dispersion degree of the multi-wall carbon nano tubes. The surfactant is preferably one or more of Sodium Dodecyl Benzene Sulfonate (SDBS), bile salt sodium deoxycholate (NaDC), Cetyl Trimethyl Ammonium Bromide (CTAB) or polyvinylpyrrolidone (PVP). Compared with other surfactants with K value more than 10, the surfactants are easier to improve the dispersion degree of the multi-wall carbon nano-tube, have better compatibility with a sintering two-phase and an additive, and have higher quality of obtained particles, thereby ensuring the high strength and high hardness of the boron carbide ceramic material and further improving the toughness and the bending strength of the ceramic material. More preferably, the addition amount of the surfactant is 0.6 to 1.2% of the total mass of the multi-walled carbon nanotube.
The multi-walled carbon nanotube preform is prepared by the following method: adding surfactant and multi-wall carbon nano-tube into water as carrier, and obtaining the carbon nano-tube preform through ultrasonic dispersion and mechanical stirring. The research shows that the cavitation and energization of the ultrasonic wave based on the mechanical stirring can obviously improve the dispersion degree of the multi-wall carbon nano-tube in water.
Preferably, the conditions of the ultrasonic dispersion are: the wavelength is 60% -80%, the time is 6-12 h, the ultrasonic interval is 2-3 s, and the amplitude transformer of the disperser is 20 mm. Under the condition, the dispersion degree of the multi-wall carbon nano tubes in the carbon nano tube preform is more uniform. Further, after ultrasonic dispersion, the mixed system is magnetically stirred for 10-30 min, so that the dispersion effect is more stable.
Although the multi-walled carbon nanotubes can significantly improve the toughness of the ceramic material after being added with a certain mass, the excessive addition can reduce the strength and hardness of the ceramic material. Therefore, the addition amount of the multi-wall carbon nano tube preform is controlled to be 0.1-0.5 percent of the total mass of the boron carbide base material, and preferably 0.3-0.5 percent, so that the toughness and the bending strength of the ceramic material can be improved while the high-strength and high-hardness performance of the ceramic material is ensured.
The boron carbide premix is obtained by the following method: mixing the boron carbide base material with the sintering two phases and then ball-milling; adding multi-walled carbon nanotube preforms in batches during the ball milling process; the ball milling conditions are as follows: grinding balls are 6mm, 8mm and 10mm zirconium dioxide balls which are added according to a ratio of 1:2: 1; the ball-material ratio is controlled to be 2.5: 1-3.5: 1; the rotating speed of the rolling rod is 10-15 r/min.
Research shows that the ball milling under the condition can ensure that the materials are fully mixed, improve the dispersion degree of the multi-walled carbon nano tube, and simultaneously avoid the influence on the toughness effect caused by the damage of the carbon nano tube form due to over grinding.
Preferably, the first batch of multi-walled carbon nanotube preforms are added after ball milling for 30-60 min for 3-5 times, so that the dispersion of the carbon nanotubes is considered, the mixing time is shortened, and the production efficiency is improved.
As a specific embodiment of the invention, the two sintered phases are alumina and silicon carbide、Y2O3The sintered biphase and the boron carbide base material have the same grain diameter, and the grain diameter range is between 0.5 and 1.0 mu m; the mass ratio of the boron carbide base material to the sintering two phase is (8-9): 1.
researches show that the toughness of the boron carbide ceramic material can be further improved by adding a proper sintering two phase, and the original high-strength and high-hardness properties of the boron carbide ceramic material can not be influenced.
The multi-walled carbon nanotube premix is obtained by uniformly mixing the multi-walled carbon nanotube premix by a three-roller uniformly mixing device. Wherein the model can be an EXAKT 120EH-450 three-roll grinder; the parameters of the three-roller mixing are as follows: the roller rotating speed (n 1: n 2: n3) is 8-9: 2-3: 1, the roller spacing is 5-10 mu m, and grinding is carried out for 6-10 times after automatic calibration, wherein each time lasts for 5-10 hours.
According to the invention, aiming at the system characteristics of the multi-walled carbon nanotube preform, a three-roller blending device is selected for treatment, so that the dispersion degree of the multi-walled carbon nanotube in the system can be further improved, the multi-walled carbon nanotube can be uniformly dispersed in the boron carbide premix, the subsequent blending time is shortened, and the overall production efficiency is improved.
The tower entering slurry is obtained by the following method: adding an additive into the boron carbide premix, and mechanically stirring; then adding the multiwalled carbon nanotube premix, performing ultrasonic dispersion, and then placing the mixture in a three-roller mixing device for mixing.
Aiming at the characteristics of slurry and additives entering the tower, the invention selects a mixing mode of firstly mechanically stirring, then ultrasonically dispersing and finally uniformly mixing by three rollers, so as to improve the uniform mixing degree of the system, shorten the mixing time and improve the production efficiency.
Wherein the mechanical stirring conditions are as follows: the speed is 60-70r/min, and the stirring time is 9-10 h. And fully combining the additive and the surface functional groups of the boron carbide premix by mechanical stirring to ensure that the solid content of the slurry entering the tower is over 65 percent.
The operation parameters of ultrasonic dispersion are the same as those of ultrasonic dispersion in the multi-walled carbon nanotube preform.
The three-roller blending device adopts an EXAKT 120EH-450 three-roller grinding machine, and the parameters are as follows: the roller rotating speed (n 1: n 2: n3) is 8-9: 2-3: 1, the roller spacing is 1-5 mu m, and grinding is carried out for 10-24 h after automatic calibration.
Through the parameter control of the three mixing modes, the obtained slurry entering the tower can be better and more uniformly dispersed, the ceramic material in the tower can be fully modified, and the comprehensive performance of the ceramic product can be improved.
Wherein the admixture comprises a water reducing agent, a water retaining agent and a binder; the water reducing agent is selected from one or more of polycarboxylic acid water reducing agent, ammonium citrate or PEG, and the adding amount of the water reducing agent is 0.5-1.5% of the mass of the boron carbide premix.
The water-retaining agent is faint yellow hydroxypropyl methyl cellulose ether, and the adding amount of the water-retaining agent is 0.3-0.5% of the mass of the boron carbide premix.
The binder is polyacrylic acid aqueous solution resin or a combination of wax PVA and water-based PVA; the addition amount of the polyacrylic acid aqueous solution resin is 0.05-0.08% of the mass of the boron carbide premix; the addition amount of the combination of the wax PVA and the water system PVA is 0.03-0.07% of the mass of the boron carbide premix, and the mass ratio of the wax PVA to the water system PVA after the wax decomposition and the hydrolysis is (1-1.4): 0.5.
the preparation method of the invention also comprises the following steps: spray granulation, standing and aging, cold pressing, cold isostatic pressing and hot pressed sintering. The strength of the matrix is enhanced from the cold blank layer surface through the steps, and the toughness of the whole ceramic is enhanced from the sintered finished product layer surface.
The conditions of spray granulation and standing aging are as follows: the inlet temperature is 240-300 ℃, the feeding rate of the peristaltic pump is 30-90 g/min, the outlet temperature is 80-120 ℃, the speed of the atomizer is 3000-5000 r/min, and the negative pressure is kept in the tower; sealing and standing for more than 12h, and carrying out subsequent cold pressing; the water content of the granulation is controlled to be 3 to 5 percent.
The cold pressing adopts a four-beam 5000t bidirectional press, and the near-net forming is carried out through a profiling die. The cold pressing conditions are as follows: the pressure is 300-500 t, the pressing rate is 0.3-0.5 mm/min, and the pressure is maintained for 15-30 min; the cold-pressing release agent is boron nitride spray lubricant or high-purity graphite powder.
The cold isostatic pressing process comprises the following steps: sealing the formed part in a nylon vacuum bag, placing the nylon vacuum bag in an oil pressure isostatic pressing device, raising the pressure to 180-200 MPa by a pressure raising mechanism at 1-10 MPa/min, maintaining the pressure for 30-60 min, and slowly releasing the pressure by a pressure releasing mechanism at 5-20 MPa/min.
The high-strength cold blank is obtained through the cold pressing and the cold isostatic pressing. The test shows that the strength of the cold blank can be improved by more than 15%.
The hot-pressing sintering process comprises the following steps: and placing the graphite powder in a graphite mold, wherein the sintering temperature is 1700-2100 ℃, the heating rate is 5-10 ℃/min, and the sintering pressure is 20-50 MPa. The high-toughness high-strength boron carbide-based ceramic material is obtained by setting sintering processes at different reaction stages.
The second purpose of the invention is to provide the multi-wall carbon nano tube toughened boron carbide-based ceramic material prepared by the preparation method.
The average hardness of the multi-walled carbon nanotube toughened boron carbide-based ceramic material is 40.64GPa, and the fracture toughness can reach 8.3MPa.m1/2Above, the bending strength can reach more than 566 MPa.
The third purpose of the invention is to provide a bulletproof inserting plate which is prepared by using the multi-walled carbon nanotube toughened boron carbide-based ceramic material.
The invention has the following beneficial effects:
the surfactant with the K value of more than 10 is selected to carry out pre-dispersion treatment on the multi-wall carbon nano-tube, so that the dispersion degree of the multi-wall carbon nano-tube in a system is improved, and the compatibility of the multi-wall carbon nano-tube with a sintering two-phase and an additive is good, so that the occurrence of a layering phenomenon in the slurry manufacturing process is avoided, and the production safety is improved. Meanwhile, according to the characteristics of different material systems, the dispersion degree of the multi-walled carbon nanotubes in the slurry entering the tower is further improved by adopting a batch doping mode, controlling a proper doping proportion and carrying out multi-stage treatment such as ball milling, ultrasonic dispersion and three-roller mixing devices, the preparation time of the slurry entering the tower is obviously shortened while the subsequent particle quality is improved, and the production efficiency is improved.
By adopting the doping method, the multi-walled carbon nano-tube can be more uniformly dispersed in the slurry entering the tower, and can be acted together with the sintering biphase and the additive, so that the fracture toughness and the bending strength of the boron carbide-based ceramic material are obviously improved on the basis of not influencing the excellent performances of strong height, high hardness and the like of the boron carbide-based ceramic material.
In addition, the preparation method has the advantages of strong feasibility of the whole process and simple operation, and can be popularized and applied in boron carbide-based series ceramics.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
A preparation method of a multiwalled carbon nanotube (MWCNTS) toughened boron carbide/rare earth oxide based toughened ceramic material specifically comprises the following steps:
(1) preparing a multi-wall carbon nano tube preform:
in the embodiment, PVP (polyvinylpyrrolidone K30) is selected as a surfactant, and the addition amount of the PVP is 1.0% of the mass of the multi-wall carbon nanotube;
the method comprises the following specific steps: pure water is used as a solvent, PVP is added into the multi-wall carbon nano-tube in a small amount for multiple times, mechanical stirring and ultrasonic oscillation are assisted, and the carbon nano-tube is dispersed by utilizing cavitation and energization of ultrasonic waves.
Wherein the ultrasonic dispersion is carried out for 12h, the amplitude transformer of the disperser is 20mm, the wavelength is 80 percent, and the ultrasonic interval is 2 s. Taking out, and then continuing to magnetically stir for 30min to obtain a multi-walled carbon nanotube preform, and reserving for later use.
(2) Preparing a boron carbide premix:
selecting a three-bar double-layer horizontal dry ball mill for ball milling, and mixing a boron carbide-based ceramic base material with the particle size of 0.5 mu m and rare earth oxide REO with the same particle size according to the mass ratio of 8: 1;
wherein the ball barrel is made of polyurethane organic materials, the grinding balls are 6mm, 8mm and 10mm zirconium dioxide balls which are put in according to the ratio of 1:2:1, the ball-material ratio is controlled to be 2.5:1, and the powder loading is 15r/min of the rotating speed of an 1/3 rolling rod of the barrel body;
simultaneously removing the ball barrel every 60min, and adding the multi-walled carbon nanotube preform; adding for 5 times, wherein the total adding amount is controlled to be 0.5 percent of the total mass of the boron carbide base material.
(3) Preparing a multi-wall carbon nanotube premix:
putting the rest multi-walled carbon nanotube prefabricated body into a three-roller mixing device for mixing uniformly to obtain multi-walled carbon nanotube premix; wherein the machine type is an EXAKT 120EH-450 three-roll grinder, the rotating speed of a roller (n 1: n 2: n3) is 9:2:1, a scraper is coated by a PFA coating, the distance between the rollers is 5 mu m, and grinding is carried out for 6 times after automatic calibration, and each time lasts for 10 hours.
(4) Preparing tower slurry:
the selection of the admixture is respectively as follows:
firstly, water reducing agent: and selecting a polycarboxylic acid water reducing agent, wherein the adding amount of the polycarboxylic acid water reducing agent is controlled to be 0.5 percent of the mass of the boron carbide premix.
Water-retaining agent: selecting light yellow hydroxypropyl methyl cellulose ether, wherein the adding amount of the light yellow hydroxypropyl methyl cellulose ether is 0.3 percent of the mass of the boron carbide premix.
③ adhesive: the binder is polyacrylic acid aqueous solution resin, and the adding amount of the polyacrylic acid aqueous solution resin is 0.05% of the mass of the boron carbide premix.
Adding the admixture into the boron carbide premix in a small quantity and multiple times mode, and mechanically stirring; the operating conditions were: the speed is about 60r/min, and the stirring time is 10h, so that the water reducing agent is fully combined with functional groups on the surface of the powder. Controlling the solid content of slurry entering the tower to reach more than 65%;
and then adding the multi-walled carbon nanotube premix in an ultrasonic dispersion mode, uniformly mixing, and then placing the slurry in a three-roller uniformly mixing device for uniformly mixing.
Wherein, the ultrasonic dispersion parameters refer to the step (1); the three-roller mixing device has the following operating parameters: the roller speed (n 1: n 2: n3) is 8:3:1, the scraper is coated by PFA coating, the roller spacing is 1 μm, and grinding is carried out for 24h after automatic calibration.
(5) Spray granulation and standing aging:
the inlet temperature is 300 ℃, the feeding rate of the peristaltic pump is 90g/min, the outlet temperature is 120 ℃, the speed of the atomizer is 5000r/min, and the negative pressure is kept in the tower. Sealing and standing for 24h, and carrying out subsequent cold pressing. The water content of the granules is controlled at 5%.
(6) Cold pressing and cold isostatic pressing:
cold pressing: and (3) carrying out near-net forming by adopting a four-beam 5000t bidirectional press through a profiling mold. The pressure is 500t, the pressing rate is 0.5mm/min, and the pressure is maintained for 30 min. The cold-pressing release agent adopts high-purity graphite powder.
Cold isostatic pressing: sealing the formed part in a nylon vacuum bag, placing the formed part in an oil pressure isostatic pressing device, and performing a boosting mechanism: 10MPa/min, increasing to 200MPa, keeping the pressure for 360min, and slowly releasing the pressure by a mechanism of 5 MPa/min.
(7) Hot-pressing and sintering:
and (4) placing the formed part obtained in the step (6) in a graphite die, wherein the sintering temperature is 1900 ℃, the heating rate is 10 ℃/min, and the sintering pressure is 50 MPa.
Through detection, the final cold blank strength can be improved by 16.4%, and the density of the sintered ceramic material is measured to be 98.5-99.6 g/cm by adopting an Archimedes drainage method3. The hardness of the finally sintered ceramic material is 39.65GPa, and the fracture toughness can reach 9.4MPa.m measured by adopting a single-side open beam method1/2The bending strength can reach 601 MPa.
Example 2
A preparation method of multiwalled carbon nanotubes (MWCNTS) toughened boron carbide/SiC ceramic specifically comprises the following steps:
(1) preparing a multi-wall carbon nano tube preform:
the surfactant is prepared by compounding SDBS and CTAB according to the mass ratio of 2:1, and the addition amount is 1.0 percent of the mass of the multi-wall carbon nano tube;
the method comprises the following specific steps: the preparation method comprises the steps of taking pure water as a solvent, adding a small amount of surfactant into the multi-wall carbon nano tubes for multiple times, assisting with mechanical stirring and ultrasonic oscillation, and dispersing the carbon nano tubes by utilizing cavitation and energization of ultrasonic waves.
Wherein the ultrasonic dispersion is carried out for 12h, the amplitude transformer of the disperser is 20mm, the wavelength is 80 percent, and the ultrasonic interval is 3 s. Taking out, and then continuing to magnetically stir for 30min to obtain a multi-walled carbon nanotube preform, and reserving for later use.
(2) Preparing a boron carbide premix:
selecting a three-bar double-layer horizontal dry ball mill for ball milling, and mixing boron carbide-based ceramic base materials with the particle size of 0.5 mu m and SiC with the same particle size in a mass ratio of 9: 1;
wherein the ball barrel is made of polyurethane organic materials, the grinding balls are 6mm, 8mm and 10mm zirconium dioxide balls which are put in according to the ratio of 1:2:1, the ball-material ratio is controlled to be 3:1, and the powder loading amount is 15r/min of the rotating speed of an 1/3 rolling bar of the barrel body;
simultaneously removing the ball barrel every 60min, and adding the multi-walled carbon nanotube preform; adding for 5 times, wherein the total adding amount is controlled to be 0.5 percent of the total mass of the boron carbide base material.
(3) Preparing a multi-wall carbon nanotube premix:
putting the rest multi-walled carbon nanotube prefabricated body into a three-roller mixing device for mixing uniformly to obtain multi-walled carbon nanotube premix; wherein the machine type is an EXAKT 120EH-450 three-roll grinder, the rotating speed of a roller (n 1: n 2: n3) is 9:2:1, a scraper is coated by a PFA coating, the distance between the rollers is 5 mu m, and grinding is carried out for 6 times after automatic calibration, and each time lasts for 5 hours.
(4) Preparing tower slurry:
the selection of the admixture is respectively as follows:
firstly, water reducing agent: and selecting a polycarboxylic acid water reducing agent, wherein the adding amount of the polycarboxylic acid water reducing agent is controlled to be 1% of the mass of the boron carbide premix.
Water-retaining agent: selecting light yellow hydroxypropyl methyl cellulose ether, wherein the adding amount of the light yellow hydroxypropyl methyl cellulose ether is 0.5 percent of the mass of the boron carbide premix.
And thirdly, selecting polyacrylic acid aqueous solution resin as the binder, wherein the addition amount of the polyacrylic acid aqueous solution resin is 0.05 percent of the mass of the boron carbide premix.
Adding the admixture into the boron carbide premix in a small quantity and multiple times mode, and mechanically stirring; the operating conditions were: the speed is about 60r/min, and the stirring time is 10h, so that the water reducing agent is fully combined with functional groups on the surface of the powder. Controlling the solid content of slurry entering the tower to reach more than 60 percent;
and then adding the multi-walled carbon nanotube premix in an ultrasonic dispersion mode, uniformly mixing, and then placing the slurry in a three-roller uniformly mixing device for uniformly mixing.
Wherein, the ultrasonic dispersion parameters refer to the step (1); the three-roller mixing device has the following operating parameters: the roller speed (n 1: n 2: n3) is 8:3:1, the scraper is coated by PFA coating, the roller spacing is 1 μm, and grinding is carried out for 24h after automatic calibration.
(5) Spray granulation and standing aging:
the inlet temperature is 240 ℃, the feeding rate of the peristaltic pump is 90g/min, the outlet temperature is 100 ℃, the speed of the atomizer is 4500r/min, and the negative pressure is maintained in the tower. Sealing and standing for more than 12h, and carrying out subsequent cold pressing. The water content of the granules is controlled at 5%.
(6) Cold pressing and cold isostatic pressing:
and (3) carrying out near-net forming by adopting a four-beam 5000t bidirectional press through a profiling mold. The pressure is selected to be 500t, the pressing rate is 0.5mm/min, and the pressure is maintained for 15-30 min. The cold-pressing mold release agent adopts a boron nitride spray lubricant.
Cold isostatic pressing: sealing the formed part in a nylon vacuum bag, placing in an oil pressure isostatic pressing device, increasing the pressure to 200MPa with a pressure increasing mechanism of 5MPa/min, maintaining the pressure for 30min, and slowly releasing the pressure with a pressure releasing mechanism of 5 MPa/min.
(7) Hot-pressing and sintering:
and (4) placing the formed part obtained in the step (6) in a graphite die, wherein the sintering temperature is 1850 ℃, the heating rate is 5 ℃/min, and the sintering pressure is 40 MPa.
Through detection, the final cold blank strength can be improved by 18.1%, and the density of the sintered ceramic material is measured to be 99.0-99.5 g/cm by adopting an Archimedes drainage method3. The hardness of the finally sintered ceramic material is 41.66GPa, and the fracture toughness of the finally sintered ceramic material can reach 8.9MPa.m measured by adopting a single-side open beam method1/2The bending strength can reach 636 MPa.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a multiwalled carbon nanotube toughened boron carbide-based ceramic material comprises the preparation step of tower entering slurry of a spray granulation tower; the method is characterized in that the preparation process of the tower entering slurry comprises the following steps:
preparing a multi-wall carbon nano tube preform: preparing a multi-walled carbon nanotube preform by using a surfactant with a K value of more than 10 and assisting ultrasonic dispersion and mechanical stirring;
preparing a boron carbide premix: adding a small amount of multi-walled carbon nanotube preforms into a boron carbide base material containing a sintering two-phase, and performing ball milling to prepare a boron carbide premix;
preparing a multi-wall carbon nanotube premix: uniformly mixing the rest multi-walled carbon nanotube prefabricated bodies by three rollers to prepare a multi-walled carbon nanotube premix;
preparing tower slurry: sequentially adding additives into the boron carbide premix, and mechanically stirring; and adding the multiwalled carbon nanotube premix, performing ultrasonic dispersion and three-roller mixing to obtain tower entering slurry.
2. The method for preparing a multi-walled carbon nanotube-toughened boron carbide-based ceramic material as claimed in claim 1, wherein the surfactant is one or more of sodium dodecylbenzenesulfonate, bile salt sodium deoxycholate, cetyltrimethylammonium bromide or polyvinylpyrrolidone.
3. The method for preparing a multiwall carbon nanotube-toughened boron carbide-based ceramic material of claim 2, wherein in the preparation process of the multiwall carbon nanotube preform, the ultrasonic dispersion conditions are as follows: the wavelength is 60% -80%, the time is 6-12 h, and the ultrasonic interval is 2-3 s.
4. The method for preparing a multi-walled carbon nanotube toughened boron carbide-based ceramic material according to any one of claims 1 to 3, wherein the addition amount of the multi-walled carbon nanotube preform is 0.1 to 0.5 percent of the total mass of the boron carbide base material.
5. The method for preparing a multiwalled carbon nanotube toughened boron carbide-based ceramic material according to any of claims 1-3, wherein in the preparation process of the multiwalled carbon nanotube pre-mixture, the ball milling conditions are as follows: the ball-material ratio is controlled to be 2.5: 1-3.5: 1; the rotating speed of the rolling rod is 10-15 r/min.
6. The method for preparing a multiwalled carbon nanotube toughened boron carbide-based ceramic material as claimed in claim 5, wherein in the preparation process of the slurry entering the tower, the mechanical stirring conditions are as follows: the speed is 60-70r/min, and the stirring time is 9-10 h;
the ultrasonic dispersion conditions are as follows: the wavelength is 60% -80%, the time is 6-12 h, and the ultrasonic interval is 2-3 s;
the three-roller mixing parameters are as follows: roller speed n 1: n 2: n3 is 8-9: 2-3: 1, the roller spacing is 1-5 μm, and grinding is performed for 10-24 h after automatic calibration.
7. The method for preparing multi-walled carbon nanotube-toughened boron carbide-based ceramic material according to any one of claims 1 to 3 or 6, wherein the two sintered phases are alumina, silicon carbide, Y2O3The sintered two-phase material has the same grain size with the boron carbide base material, and the grain size ranges from 0.5 to 1.0 mu m; the mass ratio of the boron carbide base material to the sintering two phase is (8-9): 1.
8. the method for preparing a multi-walled carbon nanotube toughened boron carbide-based ceramic material as claimed in claim 7, wherein the admixture comprises a water reducing agent, a water retaining agent and a binder;
the water reducing agent is selected from one or more of polycarboxylic acid water reducing agent, ammonium citrate or PEG, and the adding amount of the water reducing agent is 0.5-1.5% of the mass of the boron carbide premix;
the water-retaining agent is hydroxypropyl methyl cellulose ether, and the adding amount of the water-retaining agent is 0.3-0.5% of the mass of the boron carbide premix;
the binder is polyacrylic acid aqueous solution resin or a combination of wax PVA and water-based PVA; the addition amount of the polyacrylic acid aqueous solution resin is 0.05-0.08% of the mass of the boron carbide premix; the addition amount of the combination of the wax PVA and the water system PVA is 0.03-0.07% of the mass of the boron carbide premix, and the mass ratio of the wax PVA to the water system PVA after the wax decomposition and the hydrolysis is (1-1.4): 0.5.
9. multi-walled carbon nanotube toughened boron carbide based ceramic material obtainable by the preparation process as claimed in any one of claims 1 to 8.
10. A ballistic resistant insert panel made using the multi-walled carbon nanotube-toughened boron carbide-based ceramic material of claim 9.
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