CN115286396B - Hafnium boride ceramic powder with micro-nano topological structure and preparation method thereof - Google Patents
Hafnium boride ceramic powder with micro-nano topological structure and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of nano material preparation, and particularly relates to a method for preparing hafnium boride powder with a micro-nano topological structure by using a sol-gel method and the prepared hafnium boride ceramic powder. The invention adopts a sol-gel-carbothermic reduction method to prepare hafnium boride powder with a micro-nano topological structure, boric acid, sorbitol and hafnium n-propanol are used as raw materials to form gel in an acetic acid system, the gel is fully dried and ground into powder after gelation, organic impurities in the powder are discharged by calcination, and the powder is calcined in a high-temperature tube furnace, so that the hafnium boride powder with the micro-nano topological structure can be prepared. The preparation method only needs common equipment in a laboratory, does not need special equipment, has simple preparation process, easily controlled reaction process and short production period, and the prepared hafnium boride powder has higher purity and good micro-morphology and can enhance the mechanical property of a sintered body in the subsequent forming process.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a method for preparing hafnium boride powder with a micro-nano topological structure by using a sol-gel method and the prepared hafnium boride ceramic powder.
Background
Ultra-high temperature ceramics (UHTC) refer to a class of ceramic materials having an ultra-high melting point (greater than 3000 ℃), high hardness, high stability, and good high-temperature strength. Due to the excellent performance, the ultrahigh-temperature ceramic has good potential application value in extreme service environments, such as the nose cone and the wing leading edge part of equipment of hypersonic aircrafts, reentry spacecrafts and the like. Common ultrahigh-temperature ceramics include boride ceramics, carbide ceramics and nitride ceramics, and common boride ceramics include hafnium boride and zirconium boride.
Hafnium diboride (HfB) 2 ) With hexagonal AlB 2 The layered structure contains B atoms in a two-dimensional graphite ring and alternately forms hexagonal tightly-filled Hf layers, and strong Hf-B ionic bonds and B-B covalent bonds lead to excellent characteristics of extremely high melting point at 3250 ℃, high oxidation resistance, high hardness and the like, so that the layered structure is one of the best candidate materials for hypersonic aircrafts, rocket propulsion systems, cutting tools, wear-resistant coatings, molten metal crucibles, plasma arc electrodes, nuclear reactor neutron absorbers and the like.
For the thermal protection material for the aerospace aircraft, the thermal protection material not only needs to have high temperature resistance, oxidation resistance and the like, but also needs to have high toughness and good impact resistance. The conventional boride ceramic powder is granular or flaky, and toughening is often needed in the application process of subsequent forming so as to improve the mechanical property of the boride ceramic powder and overcome the defect of insufficient mechanical property of the boride ceramic powder.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing hafnium boride powder with a micro-nano topological structure by a sol-gel method, which has the advantages of simple preparation process, easily controlled reaction process and short production period, and the prepared hafnium boride powder has high purity, uniform and good micro morphology and can enhance the mechanical property of a sintered body in the subsequent forming process.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of hafnium boride ceramic powder with a micro-nano topological structure comprises the following steps:
step A, weighing boric acid and sorbitol with the weight ratio of 1 (1-3), adding the boric acid and sorbitol into acetic acid, stirring at constant temperature to completely dissolve the boric acid and sorbitol in the acetic acid to obtain a clear solution, and cooling to room temperature;
step B, uniformly and slowly dripping n-propyl hafnium into the clear solution, wherein the ratio of the added n-propyl hafnium to the boric acid substance in the step A is 1 (4-5), and continuously stirring to prepare yellow-brown hafnium boride precursor sol;
step C, sealing the hafnium boride precursor sol, and placing the sol at a constant temperature to ensure that the sol is fully gelatinized to prepare a hafnium boride precursor gel;
and D, fully drying the hafnium boride precursor gel, grinding the dried hafnium boride precursor gel into powder, and then calcining the powder at a high temperature to finally prepare the hafnium boride ceramic powder with the micro-nano topological structure.
The preparation method of the hafnium boride ceramic powder with the micro-nano topological structure is further improved:
preferably, the temperature of constant-temperature stirring in the step A is 60-90 ℃, and the stirring mode is magnetic stirring.
Preferably, the hafnium n-propanol is slowly and uniformly added in step B at a rate of 1-5 mL/min.
Preferably, the specific process of placing under constant temperature condition in the step C to fully gelatinize the gel comprises the following steps: standing at 10-60 deg.C for 0.5-2h.
Preferably, the temperature for fully drying the hafnium boride precursor gel in the step D is 60-120 ℃, and the time is 8-12h.
Preferably, the grinding in step D is performed by ball milling at 50-400rpm for 0.5-1h.
Preferably, in step D, the specific process of the high-temperature calcination is as follows: taking high-purity argon with Ar being more than or equal to 99.999wt% as protective gas, heating the high-temperature tube furnace from room temperature to 1000 ℃ at the speed of 1-5 ℃/min, then heating the high-temperature tube furnace to 1500-1800 ℃ at the speed of 0.5-2 ℃/min, preserving the heat for 60-180min, then cooling the high-temperature tube furnace to 1000 ℃ at the speed of 0.5-2 ℃/min, then cooling the high-temperature tube furnace to 300 ℃ at the speed of 1-5 ℃/min, and finally naturally cooling the high-temperature tube furnace to room temperature.
The invention also aims to provide the hafnium boride ceramic powder with the micro-nano topological structure, which is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention adopts a sol-gel-carbothermic reduction method to prepare hafnium boride powder with a micro-nano topological structure, boric acid, sorbitol and hafnium n-propanol are used as raw materials to form gel in an acetic acid system, the gel is fully dried and ground into powder after gelation, organic impurities in the powder are discharged by calcination, and the powder is calcined in a high-temperature tube furnace, so that the hafnium boride powder with the micro-nano topological structure can be prepared. The preparation method only needs common equipment in a laboratory, does not need special equipment, and has the advantages of simple and easily controlled process and short production period. Can be produced in large scale, and is very suitable for the macro and large-scale production and preparation of related ceramic materials.
2) The hafnium boride ceramic powder prepared by the sol-gel method has higher purity, can be directly used, does not show any impurity peak in an XRD (X-ray diffraction) spectrum, and does not need to be subjected to impurity removal treatment. The hafnium boride has a uniform and good micro-morphology, each micro-nano topological structure hafnium boride has about eight branches, the length of each branch of the rod-shaped hafnium boride reaches tens of micrometers, the average diameter is about 300-600nm, and the distribution range of included angles among the short rods is 10-60 degrees.
3) The boride ceramic powder in the prior art is granular or flaky, and toughening is often needed to improve the mechanical property of the boride ceramic powder in application. The hafnium boride powder disclosed by the invention can further optimize and improve the mechanical properties of the hafnium boride powder on the basis of keeping the original thermal protection performance, such as compression performance, shearing performance, bending performance, torsion performance, buckling performance, impact performance and the like. Therefore, the hafnium boride ultrahigh-temperature ceramic and the composite material thereof obtained by sintering the hafnium boride powder with the micro-nano topological structure certainly have outstanding mechanical properties such as impact resistance, bending resistance and the like on the basis of keeping the original good thermal protection performance; suitable for aerospace vehicles used in complex environments.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIGS. 1 (a) to (g) are XRD patterns of the hafnium boride powders prepared in examples 1 to 7 of the present invention, respectively, for substance detection.
FIGS. 2 (a) - (f) are scanning electron micrographs obtained by performing morphology detection on the hafnium boride powder prepared in examples 1-6 of the invention at a magnification of 3k, respectively.
FIGS. 3 (a) - (g) are HRTEM images of the hafnium boride powder prepared in examples 1-7 of the present invention, respectively, characterized by a transmission electron microscope.
FIG. 4 shows TEM images and diffraction spots of the hafnium boride ceramic powder prepared in example 1 of the present invention, which are characterized by a transmission electron microscope.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
A preparation method of hafnium boride ceramic powder with a micro-nano topological structure comprises the following steps:
step a1, weighing 2.473g of boric acid and 2.429g of sorbitol, putting the boric acid and the sorbitol into the same beaker, mixing, then pouring 10mL of acetic acid (purifying), gradually heating the mixture to 60 ℃ by using a water bath magnetic stirrer, and stirring at constant temperature until the boric acid and the sorbitol are completely dissolved in the acetic acid, so that the solution is completely clarified, thereby obtaining a clarified solution.
And step b1, stopping heating, continuously stirring until the temperature is cooled to room temperature, and then slowly dropwise adding 6.914mL of n-propyl alcohol hafnium at a constant speed of 0.5-5mL/min (10 min in use) under the state of continuous stirring, thereby preparing the hafnium boride precursor sol.
And c1, sealing the hafnium boride precursor sol, standing for 1h, and fully gelatinizing the hafnium boride precursor sol to obtain the hafnium boride precursor gel.
And d1, putting the hafnium boride precursor gel into a constant-temperature drying oven, and drying for 12 hours at the temperature of 80 ℃ to completely dry the hafnium boride precursor gel, thereby obtaining the hafnium boride precursor xerogel.
Step e1, grinding the hafnium boride precursor xerogel into powder by using a planetary ball mill, then placing the powder into a graphite crucible, placing the graphite crucible into a high-temperature tube furnace, taking high-purity argon (Ar is more than or equal to 99.999%) as protective gas, heating from room temperature to 1000 ℃ at the speed of 5 ℃/min, then heating to 1500 ℃ at the speed of 2 ℃/min, preserving heat for 60min, then cooling to 1000 ℃ at the speed of 2 ℃/min, then cooling to 300 ℃ at the speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the hafnium boride powder.
Example 2
A preparation method of hafnium boride ceramic powder with a micro-nano topological structure comprises the following steps:
step a1, weighing 2.473g of boric acid and 3.644g of sorbitol, putting the boric acid and the sorbitol into the same beaker for mixing, then pouring 10mL of acetic acid (for purification), gradually heating the mixture to 60 ℃ by using a water bath magnetic stirrer, and stirring at constant temperature until the boric acid and the sorbitol are completely dissolved in the acetic acid, so that the solution is completely clarified, thereby obtaining a clarified solution.
And step b1, stopping heating, continuously stirring until the temperature is cooled to room temperature, and then slowly dripping 6.914mL of n-propyl alcohol hafnium at a constant speed of 0.5-5mL/min (within 10 min) under the continuous stirring state to prepare the hafnium boride precursor sol.
And c1, sealing the hafnium boride precursor sol, standing for 1h, and fully gelatinizing the hafnium boride precursor sol to obtain the hafnium boride precursor gel.
And d1, putting the hafnium boride precursor gel into a constant-temperature drying oven, and drying for 12 hours at the temperature of 80 ℃ to completely dry the hafnium boride precursor gel, thereby obtaining the hafnium boride precursor xerogel.
Step e1, grinding the hafnium boride precursor xerogel into powder by using a planetary ball mill, then placing the powder into a graphite crucible, placing the graphite crucible into a high-temperature tube furnace, taking high-purity argon (Ar is more than or equal to 99.999%) as protective gas, heating from room temperature to 1000 ℃ at the speed of 5 ℃/min, then heating to 1500 ℃ at the speed of 2 ℃/min, preserving heat for 60min, then cooling to 1000 ℃ at the speed of 2 ℃/min, then cooling to 300 ℃ at the speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the hafnium boride powder.
Example 3
A preparation method of hafnium boride ceramic powder with a micro-nano topological structure comprises the following steps:
step a1, weighing 3.092g of boric acid and 3.037g of sorbitol, putting into the same beaker, mixing, then pouring 10mL of acetic acid (analytically pure), gradually heating to 60 ℃ by using a water bath magnetic stirrer, stirring at constant temperature until the boric acid and the sorbitol are completely dissolved in the acetic acid, and completely clarifying the solution to obtain a clear solution.
And step b1, stopping heating, continuously stirring until the temperature is cooled to room temperature, and then slowly dropwise adding 6.914mL of n-propyl alcohol hafnium at a constant speed of 0.5-5mL/min (10 min in use) under the state of continuous stirring, thereby preparing the hafnium boride precursor sol.
And c1, sealing the hafnium boride precursor sol, standing for 1h, and fully gelatinizing the hafnium boride precursor sol to obtain the hafnium boride precursor gel.
And d1, putting the hafnium boride precursor gel into a constant-temperature drying oven, and drying for 12 hours at the temperature of 80 ℃ to completely dry the hafnium boride precursor gel, thereby obtaining the hafnium boride precursor xerogel.
Step e1, grinding the hafnium boride precursor xerogel into powder by using a planetary ball mill, then placing the powder into a graphite crucible, placing the graphite crucible into a high-temperature tube furnace, taking high-purity argon (Ar is more than or equal to 99.999%) as protective gas, heating from room temperature to 1000 ℃ at the speed of 5 ℃/min, then heating to 1500 ℃ at the speed of 2 ℃/min, preserving heat for 60min, then cooling to 1000 ℃ at the speed of 2 ℃/min, then cooling to 300 ℃ at the speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the hafnium boride powder.
Example 4
Step a1, weighing 3.092g of boric acid and 4.555g of sorbitol, putting into the same beaker, mixing, then pouring 10mL of acetic acid (purifying), gradually heating to 60 ℃ by using a water bath magnetic stirrer, stirring at constant temperature until the boric acid and the sorbitol are completely dissolved in the acetic acid, and completely clarifying the solution to obtain a clarified solution.
And step b1, stopping heating, continuously stirring until the temperature is cooled to room temperature, and then slowly dropwise adding 6.914mL of n-propyl alcohol hafnium at a constant speed of 0.5-5mL/min (10 min in use) under the state of continuous stirring, thereby preparing the hafnium boride precursor sol.
And c1, sealing the hafnium boride precursor sol, standing for 1h, and fully gelatinizing the hafnium boride precursor sol to obtain the hafnium boride precursor gel.
And d1, putting the hafnium boride precursor gel into a constant-temperature drying oven, and drying for 12 hours at the temperature of 80 ℃ to completely dry the hafnium boride precursor gel, thereby obtaining the hafnium boride precursor xerogel.
Step e1, grinding the hafnium boride precursor xerogel into powder by using a planetary ball mill, then placing the powder into a graphite crucible, placing the graphite crucible into a high-temperature tube furnace, taking high-purity argon (Ar is more than or equal to 99.999%) as protective gas, heating from room temperature to 1000 ℃ at the speed of 5 ℃/min, then heating to 1500 ℃ at the speed of 2 ℃/min, preserving heat for 60min, then cooling to 1000 ℃ at the speed of 2 ℃/min, then cooling to 300 ℃ at the speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the hafnium boride powder.
Example 5
A preparation method of hafnium boride ceramic powder with a micro-nano topological structure comprises the following steps:
step a1, weighing 2.473g of boric acid and 2.429g of sorbitol, putting the boric acid and the sorbitol into the same beaker, mixing, then pouring 10mL of acetic acid (purifying), gradually heating the mixture to 60 ℃ by using a water bath magnetic stirrer, and stirring at constant temperature until the boric acid and the sorbitol are completely dissolved in the acetic acid, so that the solution is completely clarified, thereby obtaining a clarified solution.
And step b1, stopping heating, continuously stirring until the temperature is cooled to room temperature, and then slowly dropwise adding 6.914mL of n-propyl alcohol hafnium at a constant speed of 0.5-5mL/min (10 min in use) under the state of continuous stirring, thereby preparing the hafnium boride precursor sol.
And c1, sealing the hafnium boride precursor sol, standing for 1h, and fully gelatinizing the hafnium boride precursor sol to obtain the hafnium boride precursor gel.
And d1, putting the hafnium boride precursor gel into a constant-temperature drying oven, and drying for 12 hours at the temperature of 80 ℃ to completely dry the hafnium boride precursor gel, thereby obtaining the hafnium boride precursor xerogel.
Step e1, grinding the hafnium boride precursor xerogel into powder by using a planetary ball mill, then placing the powder into a graphite crucible, placing the graphite crucible into a high-temperature tube furnace, taking high-purity argon (Ar is more than or equal to 99.999%) as protective gas, heating from room temperature to 1000 ℃ at the speed of 5 ℃/min, then heating to 1500 ℃ at the speed of 2 ℃/min, preserving heat for 120min, then cooling to 1000 ℃ at the speed of 2 ℃/min, then cooling to 300 ℃ at the speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the hafnium boride powder.
Example 6
A preparation method of hafnium boride ceramic powder with a micro-nano topological structure comprises the following steps:
step a1, weighing 3.092g of boric acid and 3.037g of sorbitol, putting into the same beaker, mixing, then pouring 10mL of acetic acid (analytically pure), gradually heating to 60 ℃ by using a water bath magnetic stirrer, stirring at constant temperature until the boric acid and the sorbitol are completely dissolved in the acetic acid, and completely clarifying the solution to obtain a clear solution.
And step b1, stopping heating, continuously stirring until the temperature is cooled to room temperature, and then slowly dropwise adding 6.914mL of n-propyl alcohol hafnium at a constant speed of 0.5-5mL/min (10 min in use) under the state of continuous stirring, thereby preparing the hafnium boride precursor sol.
And c1, sealing the hafnium boride precursor sol, standing for 1h, and fully gelatinizing the hafnium boride precursor sol to obtain the hafnium boride precursor gel.
And d1, putting the hafnium boride precursor gel into a constant-temperature drying oven, and drying for 12 hours at the temperature of 80 ℃ to completely dry the hafnium boride precursor gel, thereby obtaining the hafnium boride precursor xerogel.
Step e1, grinding the hafnium boride precursor xerogel into powder by using a planetary ball mill, then placing the powder into a graphite crucible, placing the graphite crucible into a high-temperature tube furnace, taking high-purity argon (Ar is more than or equal to 99.999%) as protective gas, heating from room temperature to 1000 ℃ at the speed of 5 ℃/min, then heating to 1500 ℃ at the speed of 2 ℃/min, preserving heat for 120min, then cooling to 1000 ℃ at the speed of 2 ℃/min, then cooling to 300 ℃ at the speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the hafnium boride powder.
Example 7
Step a1, weighing 3.092g of boric acid and 4.555g of sorbitol, putting the boric acid and the sorbitol into the same beaker for mixing, then pouring 10mL of acetic acid (purity) into the beaker, gradually heating the mixture to 60 ℃ by using a water bath magnetic stirrer, and stirring at constant temperature until the boric acid and the sorbitol are completely dissolved in the acetic acid, so that the solution is completely clarified, thereby obtaining a clarified solution.
And step b1, stopping heating, continuously stirring until the temperature is cooled to room temperature, and then slowly dropwise adding 6.914mL of n-propyl alcohol hafnium at a constant speed of 0.5-5mL/min (10 min in use) under the state of continuous stirring, thereby preparing the hafnium boride precursor sol.
And c1, sealing the hafnium boride precursor sol, standing for 1h, and fully gelatinizing the hafnium boride precursor sol to obtain the hafnium boride precursor gel.
And d1, putting the hafnium boride precursor gel into a constant-temperature drying oven, and drying for 12 hours at the temperature of 80 ℃ to completely dry the hafnium boride precursor gel, thereby obtaining the hafnium boride precursor xerogel.
Step e1, grinding the hafnium boride precursor xerogel into powder by using a planetary ball mill, then placing the powder into a graphite crucible, placing the graphite crucible into a high-temperature tube furnace, taking high-purity argon (Ar is more than or equal to 99.999%) as protective gas, heating from room temperature to 1000 ℃ at the speed of 5 ℃/min, then heating to 1500 ℃ at the speed of 2 ℃/min, preserving heat for 120min, then cooling to 1000 ℃ at the speed of 2 ℃/min, then cooling to 300 ℃ at the speed of 5 ℃/min, and finally naturally cooling to room temperature to obtain the hafnium boride powder.
Purity detection and morphology observation
The hafnium boride ceramic powder prepared in examples 1 to 7 of the present invention was subjected to purity measurement and morphology observation, thereby obtaining the following results:
(1) Respectively carrying out substance detection on the hafnium boride ceramic powder prepared in the embodiments 1 to 7 of the present invention by using an X-ray diffraction analyzer, wherein XRD (X-ray diffraction) spectrums of the prepared hafnium boride ceramic powder are respectively shown in figures 1 (a) to (g); as can be seen from fig. 1: the hafnium boride ceramic powder prepared in examples 1 to 7 of the present invention has high purity and no impurity peak in XRD pattern.
(2) The morphology of the hafnium boride ceramic powder prepared in embodiments 1 to 7 of the present invention was detected by scanning electron microscopy, so as to obtain scanning electron micrographs as shown in fig. 2 and 3. Wherein, FIGS. 2 (a) - (f) are FESEM photographs of the hafnium boride powder prepared in examples 1-6 of the present invention at a magnification of 1k, respectively; FIGS. 3 (a) to (g) are FESEM photographs of the hafnium boride powders obtained in examples 1 to 7 of the present invention at a magnification of 5k, respectively.
As can be seen from fig. 2 and 3: each hafnium boride ceramic powder is in a micro-nano topological structure and has about several to dozens of branches, the length of each rod-shaped hafnium boride reaches dozens of micrometers, the average diameter is about 0.5-1 mu m, and the distribution range of included angles among the short rods is 10-60 degrees. The hafnium boride ceramic powder prepared in the embodiment 1 of the invention has an average length of 10.994 μm, an average diameter of 0.867 μm and a length-diameter ratio of 12.681; the hafnium boride ceramic powder prepared in the embodiment 2 of the invention has an average length of 10.103 μm, an average diameter of 0.910 μm and a length-diameter ratio of 11.10; the hafnium boride ceramic powder prepared in embodiment 3 of the invention has an average length of 11.469 μm, an average diameter of 0.975 μm, and a length-diameter ratio of 11.76; the hafnium boride ceramic powder prepared in the embodiment 4 of the invention has an average length of 9.163 μm, an average diameter of 0.872 μm and a length-diameter ratio of 10.51; the hafnium boride ceramic powder prepared in the embodiment 5 of the invention has an average length of 10.256 μm, an average diameter of 1.138 μm and a length-diameter ratio of 9.012; the hafnium boride ceramic powder prepared in embodiment 6 of the invention has an average length of 7.270 μm, an average diameter of 0.772 μm, and a length-diameter ratio of 9.417; the hafnium boride ceramic powder prepared in the embodiment 7 of the present invention has an average length of 6.503 μm, an average diameter of 0.760 μm, an aspect ratio of 8.557, and the aspect ratio of the embodiment 1 of the present invention is the largest. Each structural unit has about 8 branches, the number of the branches of the three-dimensional lattice unit cells can be regulated and controlled by properly prolonging the heat treatment time of the carbothermic reduction reaction in the synthesis process, when the heat preservation time is increased from 60min to 120min, the branches of the structural units for generating the hafnium boride ceramic powder are increased, and the roughness of the rod-shaped hafnium boride can be effectively increased by increasing the content of boric acid and sorbitol in the reaction.
(3) Respectively aiming at the invention by adopting a transmission electron microscopeThe hafnium boride ceramic powder prepared in example 1 was characterized to obtain a picture shown in fig. 4, and a High Resolution Transmission Electron Microscope (HRTEM) picture showing that the interplanar spacing was 0.265nm, corresponding to HfB 2 (100) crystal plane of (1).
The result shows that the high-purity single-phase HfB can be prepared under the condition of calcining at the low temperature (1500 ℃) by adopting a coprecipitation method through adjusting the formula and the preparation process of the sol 2 Ceramic powder. In addition, the embodiment of the invention has simple preparation process, does not relate to complex reaction process, can be prepared in short period, and the prepared HfB 2 The powder has higher purity and good micro-morphology, and can provide a technical basis and a commercial potential for toughening a large-scale synthesized ultrahigh-temperature ceramic material structure.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the scope of the invention as set forth in the claims should be deemed to be a part of the present invention.
Claims (7)
1. A preparation method of hafnium boride ceramic powder with a micro-nano topological structure is characterized by comprising the following steps:
step A, weighing boric acid and sorbitol with the weight ratio of 1 (1-3), adding the boric acid and sorbitol into acetic acid, stirring at constant temperature to completely dissolve the boric acid and sorbitol in the acetic acid to obtain a clear solution, and cooling to room temperature;
step B, uniformly and slowly dripping n-propyl hafnium into the clear solution, wherein the ratio of the added n-propyl hafnium to the boric acid substance in the step A is 1 (4-5), and continuously stirring to prepare yellow-brown hafnium boride precursor sol;
step C, sealing the hafnium boride precursor sol, and placing the sol at a constant temperature to ensure that the sol is fully gelatinized to prepare a hafnium boride precursor gel;
step D, fully drying the hafnium boride precursor gel, grinding the dried hafnium boride precursor gel into powder, and then calcining at high temperature, wherein the specific process of the high-temperature calcination is as follows: taking high-purity argon with Ar being more than or equal to 99.999wt% as protective gas, heating the high-temperature tube furnace from room temperature to 1000 ℃ at the speed of 1-5 ℃/min, then heating the high-temperature tube furnace to 1500-1800 ℃ at the speed of 0.5-2 ℃/min, preserving heat for 60-180min, then cooling the high-temperature tube furnace to 1000 ℃ at the speed of 0.5-2 ℃/min, then cooling the high-temperature tube furnace to 300 ℃ at the speed of 1-5 ℃/min, and finally naturally cooling the high-temperature tube furnace to room temperature to obtain the hafnium boride ceramic powder with the micro-nano topological structure.
2. The preparation method of the hafnium boride ceramic powder with the micro-nano topological structure according to claim 1, wherein the constant temperature stirring in the step A is 60-90 ℃, and the stirring mode is magnetic stirring.
3. The preparation method of the hafnium boride ceramic powder with the micro-nano topological structure according to claim 1, wherein in the step B, the hafnium n-propanol is uniformly and slowly added dropwise at a rate of 1-5 mL/min.
4. The preparation method of the hafnium boride ceramic powder with the micro-nano topological structure according to claim 1, wherein the specific process of placing under the constant temperature condition in the step C to fully gelatinize the hafnium boride ceramic powder is as follows: standing at 10-60 deg.C for 0.5-2h.
5. The preparation method of the hafnium boride ceramic powder with the micro-nano topological structure according to claim 1, wherein the temperature for fully drying the hafnium boride precursor gel in the step D is 60-120 ℃, and the time is 8-12h.
6. The preparation method of the hafnium boride ceramic powder with the micro-nano topological structure according to claim 1, wherein the grinding in the step D is ball milling, the rotation speed of the ball milling is 50-400rpm, and the time is 0.5-1h.
7. The hafnium boride ceramic powder with the micro-nano topological structure prepared by the preparation method of any one of claims 1 to 6.
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