CN112707744A - Porous nitride ceramic and preparation method thereof - Google Patents
Porous nitride ceramic and preparation method thereof Download PDFInfo
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Abstract
The application provides a porous nitride ceramic and a preparation method thereof, belonging to the technical field of preparation of porous ceramics. The preparation method of the porous nitride ceramic comprises the following steps: mixing oxide powder, resin, amine organic compound and solvent to obtain slurry. And (4) soaking the porous organic template in the slurry, taking out and drying to obtain the soaked template. And placing the dipping template in an inert gas environment to carry out degreasing reaction on the organic matters so as to obtain the ceramic precursor. And placing the ceramic precursor in an inert gas environment for sintering to obtain the porous nitride ceramic. In the preparation process, the resin and the amine organic compound provide a carbon source and a nitrogen source through degreasing pyrolysis reaction, the resin and the amine organic compound react with oxide powder to obtain nitride ceramics, and the forming and the preparation of the ceramic material are completed in one step without adding other sintering aids.
Description
Technical Field
The application relates to the technical field of preparation of porous ceramics, in particular to porous nitride ceramics and a preparation method thereof.
Background
Various methods of preparing porous nitride ceramics are reported in the present disclosure, for example: the direct nitriding method mainly comprises the following steps: the porous nitride ceramic is prepared by using metal powder as main material and through the first making porous formed body and the subsequent nitriding reaction in nitrogen. The method has the following problems: in the nitriding process, a layer of nitride and oxide film can be formed on the surface of the metal powder to inhibit further nitriding reaction of the metal powder, so that the metal powder is difficult to nitride completely, and the prepared nitride porous ceramic has low purity and is not beneficial to industrial production.
The mold forming method mainly comprises the following steps: mixing oxide (such as metal oxide powder), sintering aid, carbon black and nitride to obtain granulated material, filling the granulated material into a mould, adopting a pressure forming process to obtain a formed blank, putting the formed blank into an atmosphere furnace, sintering under nitrogen, and obtaining the porous nitride ceramic by a carbothermic reduction nitridation method. The method has the following problems: the granulating material is solid, in order to fill the granulating material into a mould, the porosity of the mould is low generally, the porosity of the obtained porous ceramic is low, the adjustable range of the porosity is small, in addition, the nitride porous ceramic is prepared by a carbothermic reduction nitridation method, the problem that the nitride porous ceramic is difficult to completely nitridize still exists because the internal nitridation of metal powder is difficult, and the carbothermic reduction method uses metal oxide as a raw material, so that the metal powder does not exist, the purity of the nitride porous ceramic is reduced, and the ceramic performance is influenced.
The foam template method mainly comprises the following steps: and coating the ceramic slurry containing the nitride powder on an organic foam template with a porous structure, drying, and then burning off the organic foam template to obtain the porous ceramic. The method has the following problems: the nitride ceramic slurry is directly coated on the surface of the porous template, and the prepared porous ceramic is difficult to sinter due to the high melting point of the nitride, so that a sintering aid is generally required to be added, and the overall performance of the material is reduced.
Disclosure of Invention
The purpose of the application is to provide a porous nitride ceramic and a preparation method thereof, wherein an amine organic compound is used as a nitrogen source, other sintering aids are not required to be added, and the purity of the obtained porous nitride ceramic is higher.
In a first aspect, the present application provides a method of preparing a porous nitride ceramic, comprising: mixing oxide powder, resin, amine organic compound and solvent to obtain slurry. And (4) soaking the porous organic template in the slurry, taking out and drying to obtain the soaked template. And placing the dipping template in an inert gas environment to carry out degreasing reaction on the organic matters so as to obtain the ceramic precursor. And placing the ceramic precursor in an inert gas environment for sintering to obtain the porous nitride ceramic.
The resin has certain adhesive property, so that the slurry can be well impregnated with the organic template, and the slurry can be uniformly attached to the pore wall of the porous organic template. In the degreasing reaction process, resin, amine organic compounds and organic templates in the slurry are subjected to degreasing pyrolysis reaction to obtain a carbon source and a nitrogen source which are uniformly distributed and have high reactivity, so that a porous ceramic precursor is formed, in the sintering reaction process, oxide powder, the nitrogen source and the carbon source react, and active nitrogen elements (existing in amorphous CN) generated by pyrolysis have high chemical activity, so that the nitridation reaction process can be accelerated, no additional sintering aid is required, and the high-purity porous nitride ceramic is obtained.
In one possible embodiment, the oxide powder includes one or more of titanium oxide, aluminum oxide, silicon oxide, and zirconium oxide.
If the oxide powder is titanium oxide, titanium nitride porous ceramic is obtained; if the oxide powder is alumina, obtaining the aluminum nitride porous ceramic; if the oxide powder is silicon oxide, obtaining silicon nitride porous ceramic; if the oxide powder is zirconia, a zirconium nitride porous ceramic is obtained. The kind of the nitride ceramic may be adjusted according to the kind of nitride to be obtained, depending on the selection of the oxide powder.
In one possible embodiment, the resin comprises one or more of phenolic resin, epoxy resin, furan resin, and polyurethane. On one hand, the resin can be used as a binder, which is beneficial to the impregnation of slurry; on the other hand, the pyrolysis temperature is lower, and the carbon source can be used as a carbon source after subsequent degreasing reaction, so that the porous nitride ceramic can be obtained by subsequent sintering.
In one possible embodiment, the amine-based organic compound includes one or more of melamine, diamine, diethylamine, triethylamine, triethylenediamine, and monoethanolamine. The pyrolysis temperature of the amine organic compound is low, and a carbon source and a nitrogen source which are uniformly distributed can be obtained after pyrolysis, so that porous nitride ceramics can be obtained through subsequent sintering.
In one possible embodiment, the solvent comprises one or more of water, ethanol, isopropanol, acetone, diethyl ether, toluene, and xylene. So as to obtain the slurry with better dispersion effect.
In one possible embodiment, 120-160 parts by weight of oxide powder, 60-90 parts by weight of resin, 5-25 parts by weight of amine organic compound and 50-150 parts by weight of solvent are mixed to obtain a slurry. After the raw materials in parts by weight are mixed, the concentration of the slurry is moderate, and the purity of the obtained porous nitride ceramic is high.
In one possible embodiment, the slurry further comprises a dispersant and a binder. The addition of the dispersing agent and the binder can ensure that the slurry is dispersed more uniformly and can be more easily immersed on the template, so that the porous nitride ceramic can be obtained in the subsequent process.
Optionally, the dispersant is polyethylene glycol 200 or polyethylene glycol 400; optionally, the binder is polyvinyl butyral or polyvinyl alcohol.
In one possible embodiment, the porous organic template includes any one of a polyurethane template, an epoxy template, and a phenolic template. Optionally, the porous organic template is an SLS molding resin template or an FDM molding resin template. The porosity of the template is easy to adjust, the adjustment amplitude is large, the pore size of the prepared porous nitride ceramic is 10nm-10mm, and the porosity is 10% -80%.
In one possible embodiment, the method for preparing the impregnated template comprises: dipping the porous organic template in the slurry, blowing off the excess slurry and drying; the impregnation is repeated 3-10 times. More slurry can be attached to the pore walls of the template, so that the yield of the obtained porous nitride ceramic is higher.
In a possible embodiment, the porous organic template is soaked in the slurry, and the method further comprises the step of soaking the porous organic template in a sodium hydroxide solution and then drying the porous organic template. The template can be cleaned by soaking in a sodium hydroxide solution so that subsequent slurry can be more easily attached to the template.
In one possible embodiment, the degreasing reaction is carried out at a temperature of 450-. Under the conditions, the resin, the amine organic compound and the porous organic template can all undergo cracking reaction to obtain uniformly distributed carbon source and nitrogen source, and the carbon source and the nitrogen source are uniformly mixed with the oxide powder to obtain the high-purity porous nitride ceramic.
Optionally, the temperature rise rate of the degreasing reaction is 0.1-5 ℃/min. The resin and other organic matters can be cracked slowly, and other defects such as cracks and the like caused by rapid temperature rise are avoided.
In one possible embodiment, the sintering is carried out at a temperature of 1400 ℃ and 1900 ℃ for 4-8 h. Active nitrogen elements and active carbon elements are obtained after degreasing pyrolysis reaction, the nitridation reaction in the sintering process can be accelerated, the ceramic is densified, the sintering temperature is low and easy to achieve, and no additional sintering aid is needed to be added, so that the porous nitride ceramic with high purity can be obtained.
Optionally, the heating rate of sintering is 2-10 ℃/min.
In a second aspect, the present application provides a porous nitride ceramic prepared by the above method for preparing a porous nitride ceramic, the porous nitride ceramic including a nitride ceramic three-dimensionally connected and pores three-dimensionally connected. And preparing the porous nitride ceramics through a porous organic template so as to obtain the porous nitride ceramics with good continuity.
Alternatively, the purity of the porous nitride ceramic is not less than 96 wt%.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive efforts and also belong to the protection scope of the present application.
Fig. 1 is a flowchart of a method for preparing a porous nitride ceramic according to an embodiment of the present disclosure;
FIG. 2 is an XRD pattern of the porous titanium nitride ceramic provided in example 1;
FIG. 3 is a photograph of the porous titanium nitride ceramic provided in example 1;
FIG. 4 is an XRD pattern of the porous aluminum nitride ceramic provided in example 2;
FIG. 5 is a photograph of the porous aluminum nitride ceramic provided in example 2;
fig. 6 is an XRD pattern of the porous aluminum nitride ceramics provided in comparative example 1, comparative example 2 and comparative example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application.
Fig. 1 is a flowchart of a method for preparing a porous nitride ceramic according to an embodiment of the present disclosure. Referring to fig. 1, the method for preparing the porous nitride ceramic includes the steps of:
s10, mixing: mixing oxide powder, resin, amine organic compound and solvent to obtain slurry.
Optionally, the oxide powder comprises one or more of titania, alumina, silica, and zirconia. If it is desired to prepare a pure-phase porous nitride ceramic, the oxide powder is titanium oxide, aluminum oxide, silicon oxide, or zirconium oxide (that is, one of the oxide powders is selected); if it is desired to produce a multiphase nitride ceramic, the oxide powder is selected from two or more of titanium oxide, aluminum oxide, silicon oxide and zirconium oxide (that is, two or more of them are selected as the oxide powder).
Optionally, the resin comprises one or more of phenolic resin, epoxy resin, furan resin and polyurethane. For example: the resin is phenolic resin, epoxy resin, furan resin or polyurethane (one of the resins is selected); the resin is selected from two of phenolic resin, epoxy resin, furan resin and polyurethane (two of the resins are selected); the resin is selected from three of phenolic resin, epoxy resin, furan resin and polyurethane (three of the resins are selected); the resin is phenolic resin, epoxy resin, furan resin and polyurethane (four of the resins are selected).
Alternatively, the amine-based organic compound includes one or more of melamine, diamine, diethylamine, triethylamine, triethylenediamine, and monoethanolamine. For example: the amine organic compound is melamine, diamine, diethylamine, triethylamine, triethylene diamine or monoethanolamine (one of the amine organic compounds is selected); the amine organic compound is two of melamine, diamine, diethylamine, triethylamine, triethylene diamine and monoethanolamine (two of the amine organic compounds are selected); the amine organic compound is three of melamine, diamine, diethylamine, triethylamine, triethylene diamine and monoethanolamine (three of the amine organic compounds are selected), and the like.
Alternatively, the solvent comprises one or more of water, ethanol, isopropanol, acetone, diethyl ether, toluene and xylene. For example: the solvent is water, ethanol, isopropanol, acetone, diethyl ether, toluene or xylene (one of the solvents is selected); the solvent is two of water, ethanol, isopropanol, acetone, diethyl ether, toluene and xylene (two of the solvents are selected); the solvent is three of water, ethanol, isopropanol, acetone, diethyl ether, toluene and xylene (three of the solvents are selected); and so on.
In order to make the slurry disperse more uniformly and the template have better impregnation effect, the slurry also comprises a dispersant and a binder. The dispersant is polyethylene glycol 200 or polyethylene glycol 400; optionally, the binder is polyvinyl butyral or polyvinyl alcohol.
In the examples of the present application, 120-160 parts by weight of oxide powder, 60-90 parts by weight of resin, 5-25 parts by weight of amine organic compound, 50-150 parts by weight of solvent and 10-30 parts by weight of auxiliaries (dispersant and binder) are mixed to obtain a slurry.
S20, dipping: and (4) soaking the porous organic template in the slurry, taking out and drying to obtain the soaked template.
Optionally, soaking the porous organic template in the slurry, blowing off the excess slurry and then drying (drying at 80 ℃ for 1 h); the impregnation is repeated 3-10 times.
In the embodiment of the present application, the porous organic template includes any one of a polyurethane template, an epoxy resin template, and a phenolic resin template. For example: the porous organic template is a polyurethane template, an epoxy resin template or a phenolic resin template.
Alternatively, the porous organic template is an SLS (Selected Laser Sintering) molded resin template or an FDM (Fused Deposition Modeling) molded resin template. For example: the forming process of the porous organic template is SLS or FDM.
Further, before the porous organic template is soaked in the slurry, the method also comprises the step of soaking the porous organic template in a sodium hydroxide solution and then drying the porous organic template. For example: soaking the porous organic template in NaOH (0.5-1.5mol/L) solution for 20-30h, cleaning and drying for later use.
S30, degreasing: and placing the dipping template in an inert gas environment to carry out degreasing reaction on the organic matters so as to obtain the ceramic precursor.
Optionally, degreasing for 1-4h at the temperature of 450-850 ℃. The heating rate of the degreasing reaction is 0.1-5 ℃/min. Further, the inert gas atmosphere is an argon or nitrogen atmosphere.
In the embodiment of the application, the dipping template is placed in a degreasing furnace, the temperature is raised to 450-850 ℃ at the heating rate of 0.1-5 ℃/min in the inert gas atmosphere, and the temperature is maintained for 1-4h to obtain the ceramic precursor.
S40, sintering: and placing the ceramic precursor in an inert gas environment for sintering to obtain the porous nitride ceramic.
Optionally, the sintering reaction comprises: sintering at 1400-1900 deg.c for 4-8 hr. The heating rate of the sintering reaction is 2-10 ℃/min. Further, the inert gas atmosphere is an argon or nitrogen atmosphere.
In the embodiment of the application, the ceramic precursor is placed in a sintering furnace, the temperature is raised to 1400 ℃ and 1900 ℃ at the temperature raising rate of 2-10 ℃/min in the inert gas atmosphere, and the temperature is maintained for 4-8 h.
The porous nitride ceramic prepared by the preparation method of the porous nitride ceramic comprises three-dimensionally connected nitride ceramic and three-dimensionally communicated pores. Alternatively, the purity of the porous nitride ceramic is not less than 96 wt%.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
150g of titanium dioxide powder, 80g of phenolic resin, 10g of melamine, 75ml of ethanol, 1g of polyethylene glycol and 20g of polyvinyl butyral are mixed and stirred until the mixture is in an aqueous state to obtain slurry. Soaking polyurethane foam in NaOH (1mol/L) solution for 24 hours, cleaning and drying for later use, soaking the pretreated polyurethane foam in the slurry, blowing off the redundant slurry, drying (drying for 1 hour at the temperature of 80 ℃), and repeatedly soaking for 5 times to obtain the dipping template. And (3) placing the dipping template in a degreasing furnace, heating to 600 ℃ at the heating rate of 0.5 ℃/min in the nitrogen atmosphere, and preserving heat for 4 h. And (3) placing the degreased ceramic precursor into a pressureless sintering furnace, heating to 1700 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, and preserving heat for 2h to obtain the porous titanium nitride ceramic.
Fig. 2 is an XRD pattern of the porous titanium nitride ceramic provided in this example. As can be seen from FIG. 2, the porous titanium nitride ceramic is a pure-phase TiN ceramic, and the purity of the porous titanium nitride ceramic reaches more than 99%.
Fig. 3 is a photograph of the porous titanium nitride ceramic provided in this example. As can be seen from FIG. 3, the porous titanium nitride ceramic has a porous structure and relatively uniform pores.
Example 2
130g of aluminum oxide, 70g of epoxy resin, 20g of melamine, 100ml of ethanol, 1.5g of polyethylene glycol and 20g of polyvinyl butyral are mixed and stirred to be in an aqueous state to obtain slurry. Soaking polyurethane foam in NaOH (1mol/L) solution for 18h, cleaning and drying for later use, soaking the pretreated foam in the slurry, blowing off the excess slurry, drying (drying for 1h at 80 ℃), and repeatedly soaking for 8 times to obtain the impregnated template. And (3) placing the dipping template in a degreasing furnace, heating to 800 ℃ at the heating rate of 0.1 ℃/min in the nitrogen atmosphere, and preserving heat for 3h to obtain the ceramic precursor. And (3) placing the degreased ceramic precursor into a pressureless sintering furnace, heating to 1900 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, and preserving the temperature for 3h to obtain the porous aluminum nitride ceramic.
Fig. 4 is an XRD pattern of the porous aluminum nitride ceramic provided in the present example. As can be seen from FIG. 4, the porous aluminum nitride ceramic is a pure-phase AlN ceramic with a purity of 99% or more.
FIG. 5 is a photograph of the porous aluminum nitride ceramic provided in this example. As can be seen from FIG. 5, the porous aluminum nitride ceramic has a porous structure and uniform pores.
Comparative example 1
130g of aluminum oxide, 20g of melamine, 100ml of ethanol, 1.5g of polyethylene glycol and 20g of polyvinyl butyral are mixed and stirred to be in an aqueous state to obtain slurry. Soaking polyurethane foam in NaOH (1mol/L) solution for 18h, cleaning and drying for later use, soaking the pretreated foam in the slurry, blowing off the excess slurry, drying (drying for 1h at 80 ℃), and repeatedly soaking for 8 times to obtain the impregnated template. And (3) placing the dipping template in a degreasing furnace, heating to 800 ℃ at the heating rate of 0.1 ℃/min in the nitrogen atmosphere, and preserving heat for 3h to obtain the ceramic precursor. And (3) placing the degreased ceramic precursor into a pressureless sintering furnace, heating to 1900 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, and preserving the temperature for 3h to obtain the porous aluminum nitride ceramic with the purity of 95%.
Comparative example 2
130g of aluminum oxide, 70g of epoxy resin, 100ml of ethanol, 1.5g of polyethylene glycol and 20g of polyvinyl butyral are mixed and stirred to be in an aqueous state to obtain slurry. Soaking polyurethane foam in NaOH (1mol/L) solution for 18h, cleaning and drying for later use, soaking the pretreated foam in the slurry, blowing off the excess slurry, drying (drying for 1h at 80 ℃), and repeatedly soaking for 8 times to obtain the impregnated template. And (3) placing the dipping template in a degreasing furnace, heating to 800 ℃ at the heating rate of 0.1 ℃/min in the nitrogen atmosphere, and preserving heat for 3h to obtain the ceramic precursor. And (3) placing the degreased ceramic precursor into a pressureless sintering furnace, heating to 1900 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, and preserving the temperature for 3h to obtain the porous aluminum nitride ceramic with the purity of 90%.
Comparative example 3
130g of aluminum oxide, 70g of epoxy resin, 100ml of ethanol, 1.5g of polyethylene glycol and 20g of polyvinyl butyral are mixed and stirred to be in an aqueous state to obtain slurry. Soaking polyurethane foam in NaOH (1mol/L) solution for 18h, cleaning and drying for later use, soaking the pretreated foam in the slurry, blowing off the excess slurry, drying (drying for 1h at 80 ℃), and repeatedly soaking for 8 times to obtain the impregnated template. And (3) placing the dipping template in a pressureless sintering furnace, heating to 1900 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, and preserving heat for 3h to obtain the porous aluminum nitride ceramic with the purity of 85%.
FIG. 6 is XRD patterns of the porous aluminum nitride ceramics provided in comparative examples 1, 2 and 3 (wherein the uppermost one is an XRD pattern of the porous aluminum nitride ceramic provided in comparative example 1, the middle one is an XRD pattern of the porous aluminum nitride ceramic provided in comparative example 2, and the lowermost one is an XRD pattern of the porous aluminum nitride ceramic provided in comparative example 3). As can be seen from FIG. 6, the porous aluminum nitride ceramic is a hetero-phase AlN ceramic containing cubic-phase alumina and hexagonal-phase alumina.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (10)
1. A method for producing a porous nitride ceramic, comprising:
mixing oxide powder, resin, amine organic compound and solvent to obtain slurry;
dipping the porous organic template in the slurry, taking out and drying to obtain a dipped template;
placing the dipping template in an inert gas environment to carry out degreasing reaction on organic matters so as to obtain a ceramic precursor;
and placing the ceramic precursor in an inert gas environment for sintering to obtain the porous nitride ceramic.
2. The production method according to claim 1, wherein the oxide powder includes one or more of titanium oxide, aluminum oxide, silicon oxide, and zirconium oxide;
optionally, the resin comprises one or more of phenolic resin, epoxy resin, furan resin, and polyurethane;
optionally, the amine organic compound comprises one or more of melamine, diamine, diethylamine, triethylamine, triethylenediamine and monoethanolamine;
optionally, the solvent comprises one or more of water, ethanol, isopropanol, acetone, diethyl ether, toluene, and xylene.
3. The production method according to claim 1 or 2, characterized in that the slurry is obtained by mixing, in parts by weight, 120-160 parts of the oxide powder, 60-90 parts of the resin, 5-25 parts of the amine-based organic compound, and 50-150 parts of the solvent.
4. The production method according to claim 3, wherein the slurry further comprises a dispersant and a binder;
optionally, the dispersant is polyethylene glycol 200 or polyethylene glycol 400;
optionally, the binder is polyvinyl butyral or polyvinyl alcohol.
5. The method according to claim 1, wherein the porous organic template comprises any one of a polyurethane template, an epoxy resin template, and a phenolic resin template;
optionally, the porous organic template is an SLS molding resin template or an FDM molding resin template.
6. The method according to claim 1, wherein the method for preparing the impregnation template comprises: dipping the porous organic template in the slurry, blowing off the excess slurry and then drying; repeatedly soaking for 3-10 times;
optionally, before the porous organic template is immersed in the slurry, the method further includes a step of immersing the porous organic template in a sodium hydroxide solution and then drying the porous organic template.
7. The method as claimed in claim 1, wherein the degreasing reaction is carried out at a temperature of 450-850 ℃ for 1-4 h;
optionally, the temperature rise rate of the degreasing reaction is 0.1-5 ℃/min.
8. The method as claimed in claim 1, wherein the sintering is carried out at 1400-1900 ℃ for 4-8 h;
optionally, the temperature rise rate of the sintering is 2-10 ℃/min.
9. A porous nitride ceramic produced by the method for producing a porous nitride ceramic according to any one of claims 1 to 8, comprising a nitride ceramic three-dimensionally connected and three-dimensionally connected pores.
10. The porous nitride ceramic of claim 9, wherein the purity of the porous nitride ceramic is not less than 96 wt%.
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| FR3134334A1 (en) * | 2022-04-08 | 2023-10-13 | Safran | Waterproof part obtained by additive manufacturing |
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