CN115160023A - Method for preparing boron nitride nano material on porous ceramic pore surface - Google Patents
Method for preparing boron nitride nano material on porous ceramic pore surface Download PDFInfo
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Abstract
The invention discloses a method for preparing a boron nitride nano material on the surface of a porous ceramic pore, which comprises the following steps: 1. mixing boron source raw material powder with metal powder, and performing ball milling to obtain boron source precursor powder; 2. preparing a metal coating on the pore surface of the porous alumina ceramic; 3. and (3) preparing the boron nitride nano material on the pore surfaces of the porous ceramic with the deposited metal coating by high-temperature annealing. According to the invention, the boron nitride nano material grows on the surfaces of the pores of the porous ceramic, so that the specific surface area of the porous ceramic matrix is obviously increased, the porous ceramic matrix has good super-hydrophobic performance, and the characteristics of high temperature resistance and corrosion resistance of the ceramic material are maintained, so that the porous ceramic matrix can be used as a flue gas adsorption filter, sewage treatment, oil-water separation, catalyst carrier and drug carrier in a high-temperature corrosive environment.
Description
Technical Field
The invention belongs to the technical field of porous ceramic surface modification, and particularly relates to a method for preparing a boron nitride nano material on the surface of a porous ceramic pore.
Background
The ceramic material has unique application advantages under severe working conditions by virtue of corrosion resistance, high temperature resistance, high strength and other properties. The porous ceramic has wide practical application and development prospect in the fields of high-temperature (above 800 ℃) flue gas filtration, catalyst carriers, oil-water separation and the like due to the special properties of high porosity, high specific surface area and the like. In the above types of applications, the surface condition and specific surface area of the material are often the key factors affecting the performance. Generally, the rougher the surface of the material is, the stronger the capture or adsorption capacity for fine particles in high-temperature flue gas is; the larger the specific surface area of the material, the larger the amount of catalyst that can be supported; after hydrophobic or oil modification is carried out on the porous ceramic, the porous ceramic can also be used in the field of oil-water separation, and the larger the specific surface area is, the higher the separation efficiency is.
Nanomaterials also have high specific surface areas due to their small size characteristics. But it is usually in powder form and has some handling difficulties in practical use. If the material can be modified on the surface of the porous ceramic, the operation convenience can be solved, and the advantages of high specific surface area of the material and the porous ceramic can be exerted. Boron nitride is a graphite-like layered ceramic material in which nitrogen (N) atoms and boron (B) atoms exist in a covalent bond form, and has good high-temperature resistance, corrosion resistance, mechanical properties, chemical stability, neutron absorption, hydrogen storage performance and the like. The common shapes reported at present are nanospheres, nanoflowers, nanosheets, nanotubes, nanobelts, nano corals and the like. The boron nitride nanosheet is a petal-like boron nitride nanomaterial, is generally less than five nanometers in thickness, and has a very high specific surface area. The boron nitride nanosheet vertically grown on the surface of the material has excellent super-hydrophobic performance. The boron nitride nanotube is a fibrous hollow nano material, has a smooth surface, also has a higher specific surface area due to the nano-scale small size, can improve the specific surface area by vertically growing on the surface of the material, and has good hydrophobic property. The nano coral is a novel boron nitride nano material with thick nano sheets vertically grown on the surface of a nano tube. Compared with the nano tube, the nano coral has higher specific surface area due to the existence of a large number of nano sheets on the surface. And because of the existence of a large number of nano sheets on the surface, dense nano-scale small protrusions are formed, the surface roughness of the nano-scale small protrusions is increased, and the nano-scale small protrusions have excellent and stable super-hydrophobic performance. The boron nitride nano material grows on the surface of the porous ceramic, so that the specific surface area of the porous ceramic can be further improved on the basis of keeping the high temperature resistance and corrosion resistance of the ceramic material, the surface of the porous ceramic is changed from hydrophilic performance to hydrophobic performance, and the porous ceramic can be applied to impurity adsorption and oil-water separation and is particularly suitable for complex environments such as acid-base corrosion, high temperature and the like.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a boron nitride nanomaterial on the surface of a porous ceramic pore, aiming at the defects of the prior art. The method promotes the growth of the boron nitride nano material on the surface of the porous ceramic pore by depositing the metal coating on the surface of the porous ceramic pore, improves the bonding strength of the boron nitride nano material and the surface of the porous ceramic pore, avoids the boron nitride nano material from falling off in a flowing air flow or liquid flow environment, effectively improves the service performance of the porous ceramic with the boron nitride nano material growing on the surface, and widens the application range of the porous ceramic.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing a boron nitride nano material on the surface of a pore of porous ceramic is characterized by comprising the following steps:
step one, preparing boron source precursor powder: mixing boron source raw material powder with metal powder and then carrying out ball milling to obtain boron source precursor powder;
step two, deposition of a metal coating: drying metal chloride to obtain metal chloride powder, laying the metal chloride powder on the surface of porous ceramic placed in a strip-shaped corundum crucible, vibrating until the metal chloride leaks from the pores of the porous ceramic, continuing to add the metal chloride powder, repeating the vibrating process and the adding process until the metal chloride powder completely fills the pores of the porous ceramic and covers the surface of the porous ceramic, transferring the porous ceramic to a tubular furnace, vacuumizing, and carrying out vibration treatment on the porous ceramic until the metal chloride powder completely covers the pores of the porous ceramic, wherein the metal chloride powder is obtained by the steps ofIntroduction of H 2 Heating to reduction temperature at the speed of 5 ℃/min, preserving heat for reduction treatment, cooling to room temperature, continuously transferring to a high-temperature tubular furnace, introducing NH at high temperature 3 Carrying out homogenization treatment to obtain porous ceramics with metal coatings uniformly distributed on the surfaces of pores;
or mixing the metal oxide and the thickening agent to prepare coating slurry, coating the coating slurry on the porous ceramic until the pores of the porous ceramic are completely filled and the surface of the porous ceramic is covered, transferring the porous ceramic to a tubular furnace after drying, vacuumizing the tubular furnace, and introducing H 2 Heating to a reduction temperature at the speed of 5 ℃/min, and carrying out reduction treatment by keeping the temperature to obtain porous ceramics with metal coatings uniformly distributed on the surfaces of pores;
step three, preparing the boron nitride nano material: placing the boron source precursor powder obtained in the step one in a square graphite boat, placing porous ceramics with metal coatings uniformly distributed on the surfaces of pores obtained in the step two at the central position of the upper part of the square graphite boat, covering graphite paper above the square graphite boat and ensuring smoothness of an air inlet and an air outlet, vacuumizing, heating to a reaction temperature at a speed of 10 ℃/min, keeping the temperature for more than 0.5 hour, and cooling to room temperature to obtain a white substance, namely a boron nitride nano material, on the surfaces of the pores of the porous ceramics; NH is introduced in the heating and cooling processes 3 。
Aiming at the problems that the common metal porous material has insufficient strength at high temperature (more than 800 ℃), poor strong acid/alkali corrosion resistance, low specific surface area of the porous ceramic material, difficult manipulation of the nano material and the like, the invention designs to prepare the boron nitride nano material on the surface of the pore of the porous ceramic. Specifically, the metal chloride powder is directly vibrated to fill the pores of the porous ceramic and cover the surface of the porous ceramic, and then the vibration is sequentially carried out through H 2 Reduction treatment and NH 3 Homogenizing to convert metal chloride into fine and uniform metal, and depositing on the surface of porous ceramic including pore surface to form metal coating, or coating the porous ceramic with coating slurry prepared from metal oxide, and subjecting to H 2 Reducing and depositing on the pore surface of the porous ceramic to form metalCoating; then placing boron source precursor powder obtained by mixing and ball-milling boron source raw material powder and metal powder into a square graphite boat, placing porous ceramics with metal coatings uniformly distributed on the surfaces of pores in the center of the upper part of the square graphite boat, enabling the boron source precursor powder and the porous ceramics to be in a non-contact state, covering graphite paper above the square graphite boat for gathering reaction gas and ensuring that a gas inlet and a gas outlet are unblocked, vacuumizing, heating and introducing ammonia gas from the gas inlet for reaction, sublimating the boron source precursor powder after heating to form gas, and reacting the gas with the introduced ammonia gas under the catalytic action of the metal powder: b 2 O 3 +2NH 3 →2BN+3H 2 O, or 2B +2NH 3 →2BN+3H 2 And boron nitride is generated, and meanwhile, the metal coating on the surface of the porous ceramic also plays a role in concerted catalysis, and the growth of the boron nitride on the surface of the porous ceramic is promoted to form the boron nitride nano material.
According to the invention, the metal coating is deposited on the surface of the porous ceramic pore space, so that the boron nitride nano material stably grows on the porous ceramic matrix, and the boron nitride nano material is promoted to stably grow on the surface of the porous ceramic, so that the bonding strength of the boron nitride nano material and the surface of the porous ceramic pore space is improved, the boron nitride nano material is prevented from falling off in a flowing air flow or liquid flow environment, the service performance of the porous ceramic with the boron nitride nano material growing on the surface is effectively improved, and the application range of the porous ceramic is widened; meanwhile, the boron nitride nano material and the porous ceramic both have good high-temperature mechanical properties and corrosion resistance, and the boron nitride nano material and the porous ceramic are synergistic to exert the performance advantages of the boron nitride nano material and the porous ceramic, so that the porous ceramic with the boron nitride nano material grown on the surface can be applied to the conditions of higher temperature than that of a metal porous material and strong acid and alkali, and the application range of the porous ceramic is further expanded; in addition, the boron nitride nano material grows on the surface of the pore of the porous ceramic, and the advantages of small size, large specific surface area and excellent hydrophobic property of the boron nitride nano material are utilized, so that the disadvantage of low specific surface area of the porous ceramic is overcome, the problem that the nano material powder is difficult to control in the using process is solved, the porous ceramic with the boron nitride nano material growing on the surface has super-hydrophobic property and excellent adsorption and filtration properties, and the boron nitride nano material is applied to the fields of high-temperature flue gas filtration, oil-water separation, strong acid and alkali sewage treatment and catalyst carriers with high specific surface area under severe working conditions.
The method for preparing the boron nitride nano material on the porous ceramic pore surface is characterized in that in the step one, the molar ratio of the boron source raw material powder to the metal powder is 1.5-1. According to the invention, the boron source and the nitrogen source are provided for preparing the boron nitride nano material by controlling the types and the molar ratio of the boron source raw material powder to the metal powder in the boron source precursor powder, and the metal powder provides a catalytic action, so that the smooth operation of the subsequent preparation process is ensured.
The method for preparing the boron nitride nano material on the porous ceramic pore surface is characterized in that the ball milling time in the first step is more than 0.5h, and the particle size of the boron source precursor powder is 0.5-10 microns. The invention ensures the full and uniform mixing of the boron source raw material powder and the metal powder by controlling the ball milling time; meanwhile, because the reaction efficiency of different powders is different, the specific surface area of the boron source precursor powder is effectively improved by controlling the particle size of the boron source precursor powder, and the subsequent reaction efficiency is further improved.
The method for preparing the boron nitride nano material on the porous ceramic pore surface is characterized in that in the second step, the metal chloride is ferric chloride, ferrous chloride or nickel chloride, and the metal oxide is magnesium oxide. The corresponding metal iron, nickel or magnesium coating is generated by selecting the metal chloride or oxide, which is beneficial to the subsequent synergistic catalytic action.
The method for preparing the boron nitride nano material on the pore surfaces of the porous ceramics is characterized in that in the second step, the porous ceramics are porous alumina ceramics or porous zirconia ceramics. The invention adopts the porous ceramic with high temperature resistance, corrosion resistance and good chemical stability, and utilizes the characteristic of high porosity of the porous ceramic to increase the growth amount of the boron nitride nano material in the subsequent reaction process, thereby improving the adsorption and filtration performance of the porous ceramic with the boron nitride nano material growing on the surface. The porous ceramic of the invention can also adopt other high temperature resistant and corrosion resistant porous ceramics.
The method for preparing the boron nitride nano material on the porous ceramic pore surface is characterized in that the H in the step two 2 The flow rate of the gas is 50mL/min to 100mL/min, the reduction temperature of the reduction treatment is 600 ℃ to 800 ℃, and the homogenization temperature is 1100 ℃ to 1300 ℃. The invention controls H 2 The flow is introduced, the reduction temperature is controlled in a combined mode to ensure that a metal coating with proper thickness is obtained, the homogenization treatment temperature is controlled in a combined mode to enable the metal coating to be finer and more uniform, and the improvement of the binding force of the metal coating and the porous ceramic matrix is facilitated.
The method for preparing the boron nitride nano material on the porous ceramic pore surface is characterized in that in the third step, the reaction temperature is 1100-1600 ℃, the heat preservation time is 0.5-8h, NH is added 3 The flow rate of the gas is 10mL/min to 200mL/min. The invention ensures the smooth preparation and generation of the porous ceramic pore surface boron nitride nano material by controlling the reaction temperature and the heat preservation time range and simultaneously controls NH 3 The flow rate of the boron nitride nanometer material is ensured to fully react with the boron source raw material powder, and the phenomenon that the generated boron nitride product is thick due to overhigh flow rate of the boron nitride nanometer material is avoided, so that the boron nitride nanometer material is ensured to be generated.
The method for preparing the boron nitride nano material on the pore surface of the porous ceramic is characterized in that the boron nitride nano material obtained on the pore surface of the porous ceramic in the step three is a boron nitride nano sheet, a nano tube or a nano coral vertically growing on the pore surface of the porous ceramic. The invention controls the reaction temperature or NH in the reaction process 3 The shape of the product boron nitride nano material is controlled by introducing the flow, specifically, the boron nitride nanosheet, the nanotube and the nano coral are sequentially obtained along with the reaction temperature from low to high, and along with NH 3 The flow rate is from low to high to obtain the boron nitride nanosheet, the nanotube and the nano coral in sequence. The invention grows boron nitride nano materials with various appearances on the pore surfaces of the porous ceramics, and the boron nitride nano materials with different appearances are obtainedThe specific surface areas of the materials are different, so that the porous ceramics with the boron nitride nano materials growing on the surfaces have different super-hydrophobic properties and adsorption filtration properties, and the use requirements of different fields are met.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the metal coating is deposited on the surface of the porous ceramic pore, so that the growth of the boron nitride nano material on the surface of the porous ceramic pore is promoted, the bonding strength of the boron nitride nano material and the surface of the porous ceramic pore is improved, the boron nitride nano material is prevented from falling off in a flowing air flow or liquid flow environment, the service performance of the porous ceramic with the boron nitride nano material growing on the surface is effectively improved, and the application range of the porous ceramic is widened.
2. The porous ceramic matrix and the boron nitride nano material prepared on the surface of the pore of the porous ceramic matrix have good high-temperature mechanical property and corrosion resistance, so that the porous ceramic with the boron nitride nano material grown on the surface can be applied to the conditions of higher temperature than that of a metal porous material and strong acid and strong alkali, and the application range of the porous ceramic is expanded.
3. According to the invention, the boron nitride nano material grows on the surface of the porous ceramic pore space, and the advantages of small size, large specific surface area and excellent hydrophobic property of the boron nitride nano material are utilized, so that the disadvantage of low specific surface area of the porous ceramic is made up, the specific surface area of the porous ceramic is obviously increased, and the application in the fields of flue gas filtration, catalyst carriers and the like is facilitated.
4. Aiming at the defects that although the boron nitride nano material has excellent neutron absorption, adsorption performance and hydrophobic performance, the boron nitride nano material is inconvenient to use due to the powdery form, and impurities or oil substances are difficult to recover after being adsorbed, the boron nitride nano material is grown on the pore surface of the porous ceramic, the porous ceramic is used as a base material carried by the porous ceramic, the boron nitride nano material is convenient to use, the boron nitride nano material is favorable for exerting excellent superhydrophobicity and adsorption performance, and the boron nitride nano material and the porous ceramic are recovered simultaneously after being used, so that the operation is convenient, and the problem that the nano material powder is difficult to control in the using process is solved.
5. According to the invention, the boron source precursor powder is prepared by activating the ball mill, the reduction is carried out by adopting the tubular furnace, the target product is prepared by heating the annealing furnace under the protection of tubular atmosphere, the whole process adopts conventional equipment, no special equipment is needed, the preparation difficulty of the method is effectively reduced, and the industrial production and popularization are facilitated.
6. The boron source raw material powder, the metal chloride powder, the metal oxide, the porous ceramic, the hydrogen gas, the ammonia gas and the like adopted by the invention are all conventional common chemical raw materials, are easy to obtain, and further reduce the preparation difficulty of the invention from the raw materials.
7. The porous ceramic material with the boron nitride nano material grown on the pore surfaces, which is prepared by the invention, has the regeneration capacity which is simple, convenient and stable and durable to operate after adsorbing oil substances, and can be repeatedly used.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1a is a macroscopic view of the porous alumina ceramic with iron coating uniformly distributed on the surface of pores in example 1 of the present invention.
FIG. 1b is a micro-topography of the porous alumina ceramic with iron coating uniformly distributed on the pore surfaces in example 1 of the present invention.
FIG. 2a is a macro topography of the porous alumina ceramic in example 1 of the present invention.
FIG. 2b is a macro-topography of the porous alumina ceramic with boron nitride nano-coral on the surface of the pores in example 1 of the present invention.
FIG. 3a is a low magnification SEM image of a porous alumina ceramic with boron nitride nano coral on the pore surface in example 1 of the present invention.
FIG. 3b is an enlarged SEM image of the area indicated by the box in FIG. 3 a.
FIG. 3c is an enlarged SEM image of the area indicated by the box in FIG. 3 b.
FIG. 4 is an EDS energy spectrum of the porous alumina ceramic having boron nitride nano coral on the pore surface in example 1 of the present invention.
FIG. 5 is a graph showing the contact angle of a water droplet with a porous alumina ceramic having boron nitride nano-coral on the pore surface in example 1 of the present invention.
FIG. 6a is a low magnification SEM image of a porous alumina ceramic with boron nitride nanotubes on the pore surfaces in example 4 of the present invention.
FIG. 6b is an enlarged SEM image of the area indicated by the box in FIG. 6 a.
FIG. 6c is an enlarged SEM image of the area of the boron nitride nanotubes shown in box in FIG. 6 b.
FIG. 7 is an EDS energy spectrum of a porous alumina ceramic having boron nitride nanotubes on the pore surfaces in example 4 of the present invention.
Figure 8a is a low power SEM image of a porous alumina ceramic with boron nitride nanosheets at the surface of the pores in example 5 of the present invention.
Figure 8b is a medium magnification SEM image of a porous alumina ceramic with boron nitride nanosheets at the surface of the pores in example 5 of the present invention.
Figure 8c is a high power SEM image of a porous alumina ceramic with boron nitride nanosheets at the surface of the pores in example 5 of the present invention.
FIG. 9 is an EDS energy spectrum of the porous alumina ceramic with boron nitride nanosheets on the surface of the pores in example 5 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, preparing boron source precursor powder: mixing boron oxide powder and iron powder according to a molar ratio of 1;
step two, deposition of a metal coating: drying ferrous chloride trihydrate in an oven at 120 ℃ for 8 hours to obtain ferrous chloride powder, then laying the ferrous chloride powder on the surface of porous alumina ceramic placed in a strip-shaped corundum crucible, vibrating until the ferrous chloride powder leaks from pores of the porous alumina ceramic, continuing adding the ferrous chloride powder, repeating the vibrating process and the adding process until the ferrous chloride powder completely fills the pores of the porous alumina ceramic and covers the surface of the porous alumina ceramic, transferring the porous alumina ceramic to a tubular furnace, vacuumizing, and introducing H 2 ，H 2 Is introduced intoThe flow is 50mL/min, the temperature is raised to 600 ℃ at the speed of 5 ℃/min and is kept for 1h for reduction treatment, the temperature is cooled to room temperature, the mixture is continuously transferred to a high-temperature tube furnace, NH is introduced at the temperature of 1100 DEG C 3 Carrying out homogenization treatment to obtain porous alumina ceramics with iron coatings uniformly distributed on the surfaces of pores;
step three, preparing the boron nitride nano material: placing the boron source precursor powder obtained in the step one in a square graphite boat, placing the porous alumina ceramics with the iron coatings uniformly distributed on the surfaces of the pores obtained in the step two at the central position of the upper part of the square graphite boat, covering graphite paper above the square graphite boat and ensuring the smoothness of an air inlet and an air outlet, vacuumizing and introducing NH 3 ，NH 3 The flow rate of the gas is 100mL/min, the temperature is raised to 1400 ℃ at the speed of 10 ℃/min and is kept for 1h, ammonia gas is continuously introduced to cool to the room temperature, and NH is added 3 The flow rate is 50mL/min, and the white substance obtained on the pore surface of the porous alumina ceramic is the boron nitride nano material, so that the porous alumina ceramic with the boron nitride nano material on the pore surface is formed.
Fig. 1a and 1b are a macro-topography and a micro-topography of the porous alumina ceramic with the iron coating uniformly distributed on the pore surface in this embodiment, respectively, and it can be seen from fig. 1a and 1b that the overall appearance of the porous alumina ceramic with the iron coating uniformly distributed on the pore surface is black and gray, and the pore surface of the porous alumina ceramic is covered with a large number of spherical iron particles.
Fig. 2a is a macro topography of the porous alumina ceramic of the present embodiment, and fig. 2b is a macro topography of the porous alumina ceramic of the present embodiment, wherein the pore surface of the porous alumina ceramic has boron nitride nano coral, and it can be known from fig. 1a and fig. 1b that a large amount of white fluffy substances appear on the surface of the porous alumina ceramic after the preparation method of the present embodiment.
Fig. 3a is a low-power SEM image of the porous alumina ceramic having boron nitride nanomaterial on the pore surface in this embodiment, fig. 3b is an enlarged SEM image of the area shown by the square frame in fig. 3a, fig. 3c is an enlarged SEM image of the area shown by the square frame in fig. 3b, fig. 4 is an EDS energy spectrum of the porous alumina ceramic having boron nitride nanocoral on the pore surface in this embodiment, as can be seen from fig. 3a to 3c and fig. 4, a large amount of white wool-like substances appearing on the surface of the porous alumina ceramic in this embodiment are boron nitride nanofiber structures, and a large amount of nanosheets are vertically present on the surface of the fiber structures, and the morphology is very similar to coral, which illustrates that in this embodiment, the boron nitride nanocoral vertically grown on the surface is prepared on the surface of the porous ceramic including the pore surface.
FIG. 5 is a graph of the contact angle between the porous alumina ceramic with boron nitride nano-coral on the pore surface and a water drop in the present example, and it can be seen from FIG. 5 that the contact angle is 139 °, which illustrates that the porous alumina ceramic with boron nitride nano-material on the pore surface in the present example exhibits excellent superhydrophobic performance.
The metal powder of this embodiment may be replaced with one or more of iron powder, nano iron powder, magnesium powder, and nickel powder other than iron powder.
Example 2
The present embodiment differs from embodiment 1 in that: the reaction temperature in step three was 1600 ℃.
Through detection, in the embodiment, a large amount of dense boron nitride nano coral vertically growing on the pore surface of the porous alumina ceramic is prepared on the pore surface of the porous alumina ceramic, the morphology and the structure of the boron nitride nano coral are similar to those of the embodiment 1, but the diameter and the size of the boron nitride nano coral are increased.
Example 3
The present embodiment differs from embodiment 1 in that: the reaction temperature in step three was 1350 ℃.
Through detection, in the embodiment, a large amount of dense boron nitride nano coral vertically growing on the pore surface of the porous alumina ceramic is prepared on the pore surface of the porous alumina ceramic, the morphology and the structure of the boron nitride nano coral are similar to those of the embodiment 1, but the diameter and the size of the boron nitride nano coral are reduced.
Example 4
The present embodiment differs from embodiment 1 in that: the reaction temperature in step three was 1300 ℃.
Fig. 6a is a low-power SEM image of the porous alumina ceramic having boron nitride nanotubes on the pore surface in this example, fig. 6b is an enlarged SEM image of the region shown by the box in fig. 6a, fig. 6c is an enlarged SEM image of the boron nitride nanotubes in the region shown by the box in fig. 6b, fig. 7 is an EDS energy spectrum of the porous alumina ceramic having boron nitride nanotubes on the pore surface in this example, and it can be known from fig. 6a to 6c and fig. 7 that a large number of dense boron nitride nanotubes vertically grown on the pore surface of the porous ceramic are prepared on the pore surface of the porous ceramic in this example.
Example 5
The present embodiment differs from embodiment 1 in that: the reaction temperature in step three was 1200 ℃.
Fig. 8a is a low-power SEM image of the porous alumina ceramic of the present embodiment having boron nitride nanosheets on the pore surface, fig. 8b is a medium-power SEM image of the porous alumina ceramic of the present embodiment having boron nitride nanosheets on the pore surface, fig. 8c is a high-power SEM image of the porous alumina ceramic of the present embodiment having boron nitride nanosheets on the pore surface, fig. 9 is an EDS energy spectrum of the porous alumina ceramic of the present embodiment having boron nitride nanosheets on the pore surface, and as can be seen from fig. 8a to 8c and fig. 9, a large number of dense boron nitride nanosheets vertically grown on the pore surface of the porous ceramic are prepared on the pore surface of the porous ceramic in the present embodiment.
Example 6
The present embodiment differs from embodiment 1 in that: the reaction temperature in step three was 1100 ℃.
Through detection, a large number of dense boron nitride nanosheets vertically growing on the pore surfaces of the porous alumina ceramics are prepared on the pore surfaces of the porous alumina ceramics in the embodiment.
Example 7
The present embodiment differs from embodiment 1 in that: the flow rate of ammonia gas in the third step is 10mL/min.
Through detection, a large number of dense boron nitride nanosheets vertically growing on the pore surfaces of the porous alumina ceramics are prepared on the pore surfaces of the porous alumina ceramics in the embodiment.
Example 8
The present embodiment differs from embodiment 1 in that: the flow rate of ammonia gas in the third step is 200mL/min.
Through detection, in the embodiment, a large amount of dense boron nitride nano coral vertically growing on the pore surface of the porous alumina ceramic is prepared on the pore surface of the porous alumina ceramic, and the morphology and the structure of the boron nitride nano coral are the same as those of the embodiment 1, but the diameter and the size of the boron nitride nano coral are slightly larger.
Example 9
The present embodiment differs from embodiment 1 in that: the ball milling time is 0.5h.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the surfaces of the pores of the porous alumina ceramic is prepared on the surfaces of the pores of the porous alumina ceramic in the embodiment.
Example 10
The present embodiment differs from embodiment 1 in that: the ball milling time is 4h.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the pore surfaces of the porous alumina ceramics is prepared on the pore surfaces of the porous alumina ceramics in the embodiment.
Example 11
The present embodiment differs from embodiment 1 in that: the ball milling time is 12h.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the pore surfaces of the porous alumina ceramics is prepared on the pore surfaces of the porous alumina ceramics in the embodiment.
Example 12
The present embodiment differs from embodiment 1 in that: the reaction in step three was incubated for 0.5h.
Through detection, in the embodiment, a large number of boron nitride nanotubes with smooth surfaces are prepared on the pore surfaces of the porous alumina ceramic, and the diameters of the boron nitride nanotubes are smaller than those in embodiment 1, wherein a small number of nanosheets grow on the surfaces of a small number of boron nitride nanotubes, which indicates that most of the nanotubes do not completely grow into boron nitride nano coral with thick nanosheets growing on the surfaces due to the short reaction time in the embodiment.
Example 13
The present embodiment differs from embodiment 1 in that: the reaction in the third step has the heat preservation time of 2 hours.
Through detection, in the embodiment, a large amount of dense boron nitride nano coral vertically growing on the pore surface of the porous alumina ceramic is prepared on the pore surface of the porous alumina ceramic, the morphology and the structure of the boron nitride nano coral are not obviously changed, but the diameter of the boron nitride nano coral is slightly larger than that of the boron nitride nano coral in the embodiment 1.
Example 14
The present embodiment differs from embodiment 1 in that: the reaction in the third step has the heat preservation time of 8h.
Through detection, in the embodiment, a large amount of dense boron nitride nano coral vertically growing on the pore surface of the porous alumina ceramic is prepared on the pore surface of the porous alumina ceramic, the morphology and the structure of the boron nitride nano coral are not obviously changed, but the diameter of the boron nitride nano coral is obviously larger than that of the boron nitride nano coral in the embodiment 1.
Example 15
The present embodiment differs from embodiment 1 in that: in the first step, the boron oxide powder and the iron powder are mixed according to a molar ratio of 1.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the pore surfaces of the porous alumina ceramics is prepared on the pore surfaces of the porous alumina ceramics in the embodiment.
Example 16
The present embodiment differs from embodiment 1 in that: in the first step, the boron oxide powder and the iron powder are mixed according to a molar ratio of 1.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the pore surfaces of the porous alumina ceramics is prepared on the pore surfaces of the porous alumina ceramics in the embodiment.
Example 17
The present embodiment differs from embodiment 1 in that: in the first step, the metal powder is magnesium powder and iron powder, and the boron oxide powder is mixed with the magnesium powder and the iron powder according to a molar ratio of 2.5.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the pore surfaces of the porous alumina ceramics is prepared on the pore surfaces of the porous alumina ceramics in the embodiment.
Example 18
The present embodiment differs from embodiment 1 in that: in the first step, the metal powder is magnesium powder and iron powder, and the boron oxide powder is mixed with the magnesium powder and the iron powder according to a molar ratio of 2.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the pore surfaces of the porous alumina ceramics is prepared on the pore surfaces of the porous alumina ceramics in the embodiment.
Example 19
The present embodiment differs from embodiment 1 in that: in the first step, the boron source raw material powder is boron powder, and the metal powder is nano iron powder.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the pore surfaces of the porous alumina ceramics is prepared on the pore surfaces of the porous alumina ceramics in the embodiment.
Example 20
The present embodiment differs from embodiment 1 in that: in the first step, the boron source raw material powder is boron powder, and the metal powder is nickel powder.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the surfaces of the pores of the porous alumina ceramic is prepared on the surfaces of the pores of the porous alumina ceramic in the embodiment.
Example 21
The present embodiment differs from embodiment 1 in that: in step two, H 2 The flow rate was 100mL/min.
Through detection, in the embodiment, a large amount of dense boron nitride nano coral vertically growing on the pore surface of the porous alumina ceramic is prepared on the pore surface of the porous alumina ceramic, and the morphology and the structure of the boron nitride nano coral are the same as those of the embodiment 1.
Example 22
The present embodiment differs from embodiment 1 in that: the metal chloride in the second step is ferric chloride, the temperature of the reduction treatment is 800 ℃, and the temperature of the homogenization treatment is 1300 ℃.
Through detection, in the second step of this embodiment, the spherical iron particles covered on the pore surfaces of the porous alumina ceramic are coarser, and in this embodiment, a large amount of dense boron nitride nano coral vertically grown on the pore surfaces of the porous alumina ceramic is prepared on the pore surfaces of the porous alumina ceramic.
Example 23
The present embodiment differs from embodiment 1 in that: and the metal chloride in the second step is nickel chloride.
Through detection, in the second step of this embodiment, the pore surfaces of the porous alumina ceramic are covered with the nickel coating with fine particles, and in this embodiment, a large amount of dense boron nitride nano coral vertically growing on the pore surfaces of the porous alumina ceramic is prepared on the pore surfaces of the porous alumina ceramic.
Example 24
The present embodiment differs from embodiment 1 in that: the deposition process of the metal coating in the second step is as follows: mixing the gold magnesium oxide with a thickening agent PVA to prepare coating slurry, coating the coating slurry on the porous alumina ceramic until the pores of the porous alumina ceramic are completely filled and the surface of the porous ceramic is covered, transferring the coating slurry to a tubular furnace after drying, vacuumizing the furnace and introducing H 2 ，H 2 The flow rate of the gas is 50mL/min, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, and the temperature is kept for 1h for reduction treatment, so that the porous alumina ceramic with the magnesium coating uniformly distributed on the pore surface is obtained.
Through detection, in the second step of this embodiment, the pore surfaces of the porous alumina ceramic are covered with the magnesium coating with fine particles, and in this embodiment, a large amount of dense boron nitride nano coral vertically growing on the pore surfaces of the porous alumina ceramic is prepared on the pore surfaces of the porous alumina ceramic.
Example 25
The present embodiment differs from embodiment 1 in that: the porous ceramic is porous zirconia ceramic.
Through detection, a large amount of dense boron nitride nano coral vertically growing on the surfaces of the pores of the porous ceramic is prepared on the surfaces of the pores of the porous zirconia ceramic in the embodiment.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (8)
1. A method for preparing a boron nitride nano material on the surface of a pore of porous ceramic is characterized by comprising the following steps:
step one, preparing boron source precursor powder: mixing boron source raw material powder with metal powder and then carrying out ball milling to obtain boron source precursor powder;
step two, deposition of a metal coating: drying metal chloride to obtain metal chloride powder, laying the metal chloride powder on the surface of porous ceramic placed in a strip-shaped corundum crucible, vibrating until the metal chloride leaks from pores of the porous ceramic, continuing to add the metal chloride powder, repeating the vibrating process and the adding process until the metal chloride powder is completely filled in the pores of the porous ceramic and covers the surface of the porous ceramic, transferring the porous ceramic to a tubular furnace, vacuumizing, and introducing H 2 Heating to reduction temperature at the speed of 5 ℃/min, preserving heat for reduction treatment, cooling to room temperature, continuously transferring to a high-temperature tubular furnace, introducing NH at high temperature 3 Carrying out homogenization treatment to obtain porous ceramic with metal coatings uniformly distributed on the surfaces of pores;
or mixing the metal oxide and the thickening agent to prepare coating slurry, coating the coating slurry on the porous ceramic until the pores of the porous ceramic are completely filled and the surface of the porous ceramic is covered, transferring the porous ceramic to a tubular furnace after drying, vacuumizing the tubular furnace, and introducing H 2 Heating to a reduction temperature at the speed of 5 ℃/min, and carrying out reduction treatment by heat preservation to obtain porous ceramic with metal coatings uniformly distributed on the surfaces of pores;
step three, preparing the boron nitride nano material: placing the boron source precursor powder obtained in the step one in a square graphite boat, placing porous ceramics with metal coatings uniformly distributed on the surfaces of pores obtained in the step two at the central position of the upper part of the square graphite boat, covering graphite paper above the square graphite boat and ensuring the smoothness of an air inlet and an air outlet, vacuumizing, heating to reaction temperature at the speed of 10 ℃/min, preserving heat for more than 0.5h, cooling to room temperature, and obtaining a white substance on the surfaces of the pores of the porous ceramics, namely the boron nitride nano material; NH is introduced in the heating and cooling processes 3 。
2. The method for preparing boron nitride nano-materials on the surfaces of the pores of the porous ceramic according to claim 1, wherein in the step one, the molar ratio of the boron source raw material powder to the metal powder is 1.5-1, the boron source raw material powder is boron oxide or boron powder, and the metal powder is one or more than two of iron powder, nano-iron powder, magnesium powder and nickel powder.
3. The method for preparing boron nitride nano-materials on the surfaces of the pores of the porous ceramic according to claim 1, wherein the ball milling time in the first step is more than 0.5h, and the particle size of the boron source precursor powder is 0.5 μm to 10 μm.
4. The method for preparing boron nitride nano-materials on the pore surfaces of porous ceramics according to claim 1, wherein in the second step, the metal chloride is ferric chloride, ferrous chloride or nickel chloride, and the metal oxide is magnesium oxide.
5. The method for preparing the boron nitride nano-material on the pore surfaces of the porous ceramic according to claim 1, wherein the porous ceramic in the second step is porous alumina ceramic or porous zirconia ceramic.
6. The method for preparing boron nitride nano-materials on the pore surfaces of porous ceramics according to claim 1, wherein the H in the second step 2 The flow rate of the gas is 50mL/min to 100mL/min, the reduction temperature of the reduction treatment is 600 ℃ to 800 ℃, and the homogenization temperature is 1100 ℃ to 1300 ℃.
7. The method for preparing the boron nitride nano material on the pore surface of the porous ceramic as claimed in claim 1, wherein the reaction temperature in the third step is 1100-1600 ℃, the holding time is 0.5-8h, NH 3 The flow rate of the gas is 10mL/min to 200mL/min.
8. The method for preparing boron nitride nano-materials on the pore surfaces of porous ceramics as claimed in claim 1, wherein the morphology of the boron nitride nano-materials obtained on the pore surfaces of porous ceramics in step three is boron nitride nano-sheets, nano-tubes or nano-corals vertically grown on the pore surfaces of porous ceramics.
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