CN117902916A - Porous TaC ceramic material and preparation method thereof - Google Patents
Porous TaC ceramic material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 131
- 239000000843 powder Substances 0.000 claims abstract description 118
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 59
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- 239000011812 mixed powder Substances 0.000 claims abstract description 36
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 27
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- 238000000498 ball milling Methods 0.000 claims description 44
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- 239000002994 raw material Substances 0.000 claims description 21
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- 230000008569 process Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims description 6
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 6
- 125000001309 chloro group Chemical class Cl* 0.000 claims description 4
- 125000001153 fluoro group Chemical class F* 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 26
- 230000002349 favourable effect Effects 0.000 abstract description 2
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- 229910002804 graphite Inorganic materials 0.000 description 25
- 239000010439 graphite Substances 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a porous TaC ceramic material and a preparation method thereof, wherein a tantalum source A, fluoride salt and chloride salt are mixed to obtain molten salt powder, a part of molten salt powder is mixed with a tantalum source B and a carbon source to obtain mixed powder, the mixed powder is pressed and molded to obtain a preform, and then a part of molten salt powder is taken to embed the preform, and then the preform is sintered to obtain the porous TaC ceramic material; according to the preparation method, reaction sintering and a molten salt method are combined, wherein a molten salt system can convert tantalum into required tantalum ions and react with carbon source powder to generate TaC. In addition, the molten salt can volatilize at high temperature, and holes are formed in the matrix, so that the porous TaC ceramic is formed, the porosity of the porous TaC ceramic reaches 90-95%, the density of the porous TaC ceramic is 1.5-2.5g/cm 3, and meanwhile, the preparation process is simple, the period is short, the safety performance is high, and the porous TaC ceramic is favorable for industrial production.
Description
Technical Field
The invention belongs to the field of porous ceramic materials, and particularly relates to a porous TaC ceramic material and a preparation method thereof.
Background
Porous ceramics are a novel nonmetallic ceramic material. Compared with the traditional ceramic material, the ceramic material has the characteristics of high temperature and high pressure resistance, acid and alkali corrosion resistance, stable chemical property, large specific surface area, high porosity, controllable pore structure, long service life, good reproducibility and the like. Is favored in the fields of heat preservation and insulation materials, fuel cell electrode materials, gas-liquid filtering materials, highly sensitive sensor elements, biological medicament carriers and the like.
The performance and application field of the porous ceramic are closely related to the pore characteristics of the porous ceramic, and the selection of the preparation method is an important factor influencing the pore characteristics. The methods commonly used at present are as follows: a pore-forming agent adding method, a direct foaming method, an organic foam dipping method, a freeze drying method, a reaction sintering process, a sol-gel method, a biological template method, 3D printing and the like. The method has certain advantages and certain limitations, such as simple process and easy operation of the method for adding the pore-forming agent, but the prepared porous ceramic has uneven pore distribution and lower porosity; the freeze-drying method has the advantages of complete structure, high porosity and high mechanical strength of the product, but the production cost is too high, the requirements in the preparation process are strict, and the method is not suitable for industrial mass production; although the sol-gel method has the advantages of easy achievement of reaction conditions, mild and controllable reaction process, rich raw materials and the like, the prepared porous ceramic has low strength and higher cost, and is also unfavorable for industrialized mass production; the biological template method has the advantages of rich raw materials, low production cost, capability of re-engraving a pore structure similar to that of a biological template material and obtaining the performance similar to that of some used biological template materials, but the biological template is easy to break during sintering, can damage the product structure, has the defects of long production period and easy peeling of the outer layer of the product, and is not suitable for industrial production.
The porous TaC ceramic is a typical representative of porous ceramic, has the property advantages of the porous ceramic, and has more excellent high-temperature resistance and acid and alkali corrosion resistance, such as document Adsorption properties and preparation of porous TAC CERAMICS WITH regular steps, ning-NingYan and the like, volume 731 of Journal of Alloys and Compounds, pages 971-977, and discloses a preparation method of the porous TaC ceramic, which comprises the steps of mixing carbon powder and Ta 2O5 powder according to a molar ratio, injecting the mixture into a graphite mold, putting the graphite mold into a high-temperature sintering furnace, raising the temperature to 2100 ℃, keeping the temperature for 2 hours, and taking argon as a protective gas of a sample to prepare the porous TaC ceramic. The method can avoid the generation of defects such as cracks, fractures and the like caused by the shrinkage of the blank in the sintering process to a certain extent, so that the shape of the product is not changed, and meanwhile, the energy consumption and the production cost can be reduced. However, the method has the defects that the sintering temperature is still relatively high, the porosity of the prepared porous ceramic is low, and the porosity of the porous TaC ceramic obtained by reaction sintering is 65.321 percent.
Therefore, the existing porous TaC ceramic preparation method is relatively single by integrating the analysis, and has the problems of higher reaction temperature, lower porosity and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the first aim of the invention is to provide a preparation method of a porous TaC ceramic material. The preparation method combines the reaction sintering and the molten salt method to prepare the porous TaC ceramic, and the porous TaC ceramic material with the porosity of more than or equal to 90% can be prepared at a lower sintering temperature.
The second object of the invention is to provide a porous TaC ceramic material prepared by the preparation method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention provides a preparation method of a porous TaC ceramic material, which comprises the steps of mixing a tantalum source A, fluoride salt and chloride salt to obtain molten salt powder, mixing a part of molten salt powder with reactive sintering raw material powder to obtain mixed powder, compacting the mixed powder to obtain a preform, embedding a part of molten salt powder into the preform, and sintering at 1300-1500 ℃ to obtain the porous TaC ceramic material; the reaction sintering raw material powder consists of a tantalum source B and a carbon source.
The preparation method provided by the invention combines reaction sintering and a molten salt method, and a blocky preform is obtained by pressing and forming mixed powder of molten salt powder and reaction sintering raw material powder, and is further wrapped by the molten salt powder, wherein salt substances in the preform gradually become a molten state along with the rise of temperature in the reaction process, and then become gas to volatilize, so that gas holes are formed on the surface and inside of the preform, and a porous TaC ceramic material is formed; meanwhile, as the fused salt powder is wrapped by the prefabricated body, the fused salt is adopted for assistance, and the diffusion of reactants in the liquid fused salt can be accelerated mainly through the liquid medium environment provided by the fused salt. The diffusion rate of the reactant in the liquid molten salt is high, because the surface energy is improved under the polarization effect of the molten salt, the reaction barrier required by the reaction is broken through more easily, the reaction temperature can be obviously reduced, the reaction time is shortened, the reaction is carried out in the liquid molten salt, the reaction medium has fluidity, the reactant can be dispersed more uniformly, and a liquid-phase salt environment is provided for the prefabricated block, so that Ta ions are more active, and the generated porous tantalum carbide is more uniform and has higher porosity.
The preparation method effectively combines the advantages of reaction sintering and a molten salt method, has simple reaction sintering operation and shorter reaction time, and ensures that the prepared tantalum carbide has low porosity; the molten salt method is simple to operate, can reduce the reaction temperature, improve the reaction rate, further shorten the reaction time, meanwhile, molten salt in the prefabricated body can react with carbon elements to generate tantalum carbide, the molten salt can be converted into a gaseous state, pores are reserved in the prefabricated body, the porosity is improved, the molten salt and the gaseous state can be combined to better show advantages, the reaction sintering is easy to generate non-uniformity in the reaction process, the reaction products are unevenly distributed, the defect can be overcome by the molten salt method, and the wrapped salt substances can be changed into a molten state at a high temperature and uniformly distributed in the prefabricated body to react with residual carbon in the prefabricated body.
The inventors found that only the preparation of molten salt powder for encapsulation and mixed powder according to the method of the present invention eventually results in a porous TaC ceramic material having high purity and high porosity, and even if the total composition ratio is unchanged, adding a tantalum source only to the mixed powder or only to the molten salt powder for encapsulation affects the final molding, and even if the molding is possible, the porous TaC ceramic material has low purity due to incomplete reaction with carbon.
In addition, if the molten salt powder is wrapped, the reactive molten salt is simply used, and the equipment is damaged due to the fact that the content of the molten salt is increased.
In the preferable scheme, in the molten salt powder, according to mass ratio, chlorine salt: fluorine salt: tantalum source a=50-120: 3-10:4-10.
In the molten salt powder, the mass ratio of the chlorine salt to the fluorine salt is controlled within the proportion range of the molten salt slurry, and the finally obtained molten salt system has lower viscosity and lower melting point, because the fluidity of reaction components in a liquid phase is enhanced in a molten state, the diffusion rate of reaction substances is obviously improved, and the molten salt penetrates between powder particles to prevent the interconnection between the particles, so that the powder prepared by the molten salt method has no agglomeration or only has weak agglomeration, and the synthesis temperature can be greatly reduced and the reaction time can be shortened by using the molten salt method.
Of course, the adding amount of the tantalum source needs to be effectively controlled, if the adding amount of the tantalum source is too large, powder waste is easily caused, and if the adding amount of the tantalum source is too small, the residual carbon reaction in the prefabricated body is incomplete, so that the purity of the obtained porous tantalum carbide is not high.
Further preferably, in the molten salt powder, the chlorine salt comprises the following components in percentage by mass: fluorine salt: tantalum source a=90-110: 3-7:4-7.
Preferably, the chloride salt is at least one selected from potassium chloride, sodium chloride, calcium chloride and tantalum chloride, preferably sodium chloride and/or potassium chloride. When the chloride salt is sodium chloride and potassium chloride low-melting-point molten salt, the sodium chloride and the potassium chloride do not react with the crystal, so that the solid solubility in the crystal is smaller, the compound which is not easy to form a solid solution with the crystal has small viscosity, and is favorable for the transportation of solute and energy, thereby improving the dissolution rate and the diffusion rate, achieving the effect of reducing the reaction temperature, and the sodium chloride and the potassium chloride are easy to obtain and have lower cost.
Preferably, the fluoride salt is at least one selected from lithium fluoride, potassium fluoride, calcium fluoride, sodium fluoride, potassium fluorotantalate and tantalum pentafluoride, preferably potassium fluorotantalate and/or tantalum pentafluoride. The inventors found that potassium fluorotantalate and/or tantalum pentafluoride are preferable as reactive molten salts, and that the tantalum ion generated by potassium fluorotantalate or tantalum pentafluoride is large in activity and further reacts with residual carbon element to generate tantalum carbide. Meanwhile, molten salt powder, tantalum source and carbon source powder are uniformly mixed, and reactive molten salt is filled between the powder, so that in the sintering process, along with the rising of temperature, salts gradually become molten state, so that the surface energy and interface energy between reactants and the molten salt are continuously reduced in the molten state, the contact area between the reactants and the molten salt is increased, and the reaction is more sufficient, therefore, the purity of the finally synthesized substance by a molten salt method is high, and when potassium fluotantalate and/or tantalum pentafluoride are adopted, the purity of the prepared porous tantalum carbide is higher, and the porosity of the porous tantalum carbide is higher.
In a preferred embodiment, the tantalum source a is selected from one of tantalum powder, tantalum oxide and tantalum chloride, and is preferably tantalum powder.
The inventors found that when the tantalum source in the molten salt powder is preferably tantalum powder, on the one hand, the purity is high and, on the other hand, sintering is easier.
In the preferred scheme, the purity of the tantalum source A is more than or equal to 99.9%, and the granularity of the tantalum source A is less than or equal to 2500 meshes.
In the preferred scheme, a tantalum source A, fluoride salt and chloride salt are placed in a mortar for grinding and mixing, and then are sieved by a sieve with 80-120 meshes, and the undersize is taken to obtain molten salt powder.
In a preferred embodiment, in the reaction sintering raw material powder, the molar ratio of the tantalum source B to the carbon source is 1:7-10.
In a preferred embodiment, the tantalum source B is selected from one of tantalum powder, tantalum oxide and tantalum chloride, and is preferably tantalum oxide.
The carbothermic reduction of metal oxides is one of the most widely used methods from an industrial point of view, but since its reduction temperature is above 1500 ℃, the reaction rate is very slow, and the TaC particles tend to grow up at higher temperatures, degrading its mechanical properties. The method of using molten salt can increase the contact area between powders and the diffusion rate, thereby accelerating the reaction rate and reducing the reaction temperature.
Preferably, the carbon source is at least one selected from graphite powder, carbon powder and phenolic resin.
In a preferred scheme, the purity of the carbon source is more than or equal to 99.9%, and the particle size is 300-500 meshes.
In the preferable scheme, in the mixed powder, the mass ratio of the reaction sintering raw material powder to the molten salt powder is 1-3:1.
In the invention, the proportion of the reactive sintering raw material powder to the molten salt powder is controlled within the range, the obtained porous TaC ceramic material has high strength and high porosity, and if the salt powder is too much, the formed gas holes are too many, so that the internal binding force of the material is not strong, and the sintering molding is not facilitated; and too little molten salt powder material causes too few holes and low porosity.
In the preferred scheme, the mode of mixing a part of molten salt powder and reactive sintering raw material powder is ball milling, the ball milling mode is dry ball milling, air is used as a ball milling medium, the ball milling speed is 40-60r/min, and the ball milling time is 12-24h. In the actual operation process, after ball milling is completed, drying is carried out in a blast drying oven for 5-10 hours, and mixed powder is obtained.
Further preferably, the ball-milling ratio is 0.2-0.7:1.
By adopting the conditions, the mixed powder is obtained, so that powder particles can be thinned, fully and uniformly mixed, and sintering is promoted. In the actual operation process, the grinding balls can be adopted or not, the reason of the adoption is that the grinding balls are convenient and fast, the operation is simple, the cleaning is easy, and the grinding balls are mixed with molten salt, so that the dry ball milling is adopted, and if the grinding balls are adopted, the ball-to-material ratio is controlled to be 0.2-0.7: and 1, the ball milling effect is optimal.
Preferably, the pressure of the compression molding is 10-25MPa. In the actual operation process, the mixed powder is pressed on a molding press, and the pressure is controlled within the range of the invention, so that a firm prefabricated body can be obtained, the strength of the material obtained after sintering can be ensured to be high, and the material does not warp.
Preferably, the molten salt powder for embedding the preform is 30-50% of which is placed at the bottom of the preform and the remainder is placed at the upper portion of the preform.
Preferably, the mass ratio of the prefabricated body to the fused salt powder for embedding the prefabricated body is 1:1-1.5.
The mass ratio of the preform to the fused salt powder for embedding the preform is controlled within the range, the reaction is most complete, and the obtained porous TaC ceramic material has high purity and high porosity.
Preferably, the sintering process is as follows: heating to 1000-1200deg.C at 3-5deg.C/min, maintaining for 30-60min, heating to 1300-1500deg.C at 3-5deg.C/min, and maintaining for 30-60min.
In the sintering process, firstly, the temperature is raised to 1000-1200 ℃ for heat preservation, and at the moment, the salt is in a molten state, so that the reactivity is high, the molten salt in the preform and the coated molten salt are more easily reacted with carbon, and the reaction is complete; then heating to 1300-1500 ℃ to remove salts, and finally sintering and forming.
In the actual operation process, a graphite tank carrying a preform is placed in a sintering furnace, the furnace is vacuumized to be less than 50pa, ar gas is filled into the tubular furnace to enable the furnace to reach atmospheric pressure, then the furnace is heated, insulated and sintered, and finally cooled along with the furnace after the sintering is finished, the voltage of the furnace body is reduced, the furnace body is gradually cooled instead of naturally cooled, and the cooling rate is 2-6 ℃/min.
The invention also provides the porous TaC ceramic material prepared by the preparation method.
In a preferred embodiment, the porous TaC ceramic material has a porosity of 90-95% and a density of 1.5-2.5g/cm 3.
The porosity of the prepared porous TaC ceramic material is as high as 90-95%, and at the moment, the porous TaC ceramic material has multiple open pores and closed pores, and the open pores have the functions of filtering, absorbing, adsorbing, eliminating echoes and the like; the closed mouth is beneficial to preventing heat, sound and liquid and solid particles from being transferred, and is beneficial to expanding the application of the porous ceramic.
Principle and advantages
The preparation method provided by the invention combines reaction sintering and a molten salt method, and a blocky preform is obtained by pressing and forming mixed powder containing molten salt powder and reaction sintering raw material powder, and is further wrapped by the molten salt powder, wherein salt substances in the preform gradually become a molten state along with the rise of temperature in the reaction process, and then become gas to volatilize, so that gas holes are formed on the surface and inside of the preform, and a porous TaC ceramic material is formed; meanwhile, as the fused salt powder is wrapped by the prefabricated body, the fused salt is adopted for assistance, and the diffusion of reactants in the liquid fused salt can be accelerated mainly through the liquid medium environment provided by the fused salt. The diffusion rate of the reactant in the liquid molten salt is high, because the surface energy is improved under the polarization effect of the molten salt, the reaction barrier required by the reaction is broken through more easily, the reaction temperature can be obviously reduced, the reaction time is shortened, the reaction is carried out in the liquid molten salt, the reaction medium has fluidity, the reactant can be dispersed more uniformly, and a liquid-phase salt environment is provided for the prefabricated block, so that Ta ions are more active, and the generated porous tantalum carbide is more uniform and has higher porosity.
The preparation method effectively combines the advantages of reaction sintering and a molten salt method, has simple reaction sintering operation and shorter reaction time, and ensures that the prepared tantalum carbide has low porosity; the molten salt method is simple to operate, can reduce the reaction temperature, improve the reaction rate, further shorten the reaction time, meanwhile, molten salt in the prefabricated body can react with carbon elements to generate tantalum carbide, the molten salt can be converted into a gaseous state, pores are reserved in the prefabricated body, the porosity is improved, the molten salt and the gaseous state can be combined to better show advantages, the reaction sintering is easy to generate non-uniformity in the reaction process, the reaction products are unevenly distributed, the defect can be overcome by the molten salt method, and the wrapped salt substances can be changed into a molten state at a high temperature and uniformly distributed in the prefabricated body to react with residual carbon in the prefabricated body. Meanwhile, after the reaction is finished, deionized water with higher temperature is used for cleaning for a plurality of times, so that salt in the reactant can be diluted, and the reactant with higher purity can be formed by using a molten salt method.
Compared with the prior art, the invention has the advantages and positive effects that:
The porous ceramic prepared by combining the reaction sintering and the molten salt method has low preparation temperature which is 600-750 ℃ lower than the preparation temperature of the existing tantalum carbide ceramic prepared by using the tantalum oxide through the reaction sintering method;
The preparation process is simple and one-step, and can be industrially produced;
the preparation method combining the reaction sintering and the molten salt method can be used for preparing the porous tantalum carbide, and can be used for preparing other carbide porous ceramics (such as porous silicon carbide, porous zirconium carbide and the like), so that a new thought is provided for preparing the porous ceramics, and a new route is expanded.
Drawings
FIG. 1 is an SEM image of a porous TaC ceramic material obtained by the preparation method of the invention in example 1.
FIG. 2 is an enlarged SEM image of a porous TaC ceramic material obtained by the preparation method of the invention in example 1.
Fig. 3 is an XRD analysis pattern of the phase composition of the porous TaC ceramic material obtained by the preparation method of the present invention of example 1.
Detailed Description
The invention will be further described with reference to examples and figures:
example 1
The mass ratio is 4:5:0.3: weighing NaCl, KCl, K 2TaF6 and Ta powder in a proportion of 0.7, performing ball milling and dry mixing to obtain required molten salt powder, and then mixing tantalum oxide powder and carbon powder in a molar ratio of 1: and 7, preparing a reaction sintering raw material, wherein the mass ratio of a part of molten salt powder to the reaction sintering raw material powder is 3: and 1, preparing mixed powder for ball milling, wherein air is used as a ball milling medium, the ball milling rotating speed is 40r/min, and the ball milling time is 24 hours. In the actual operation process, after ball milling is completed, the mixture is dried in a blast drying oven for 10 hours to obtain mixed powder. And (3) performing compression molding on the mixed powder at 20MPa to obtain a preform, wherein the preform is 5.693g, then placing the preform in a graphite tank, wherein graphite paper is paved on the upper part and the lower part of the graphite tank, and then performing molten salt powder embedding on the preform. Wherein, the fused salt powder is 6g, firstly, 30% of powder is paved at the bottom of a graphite tank, then, the prefabricated body made of the mixed powder is placed on the fused salt powder, and finally, the remaining fused salt powder is wrapped on the prefabricated body. Then placing the furnace in an alumina ark, and then placing the furnace in a tube furnace for vacuumizing treatment, so that the air pressure in the furnace is lower than 50Pa. Then, argon is injected into the tubular furnace for protection, so that the air pressure in the furnace is balanced with the external atmospheric pressure, the temperature is raised to 1200 ℃ at the temperature rising rate of 5 ℃/min and is kept for 60min, and the temperature is raised to 1500 ℃ at the temperature rising rate of 3 ℃/min and is kept for 3h. Cooling to 500 ℃ at 5 ℃/min after heat preservation, cooling to room temperature along with a furnace, taking out a square boat, cleaning a sample with deionized water, and drying to obtain the porous TaC ceramic material.
FIG. 1 shows a photograph of microscopic morphology of the porous TaC ceramic material produced in example 1, as measured using a scanning electron microscope.
Fig. 2 is a photomicrograph of the porous TaC ceramic material at a magnification, and as can be seen from fig. 2, the porous TaC ceramic material has a plurality of pores, and the pore size is about 60-150 μm. FIG. 3 shows the phase composition of the porous TaC ceramic material produced in example 1 as measured by X-ray diffraction. From fig. 3, it can be seen that the porous TaC ceramic material is composed of TaC, and the peak of TaC is high and sharp, which indicates that Ta and C react completely, and that there is no residual salt in the ceramic, and the ceramic phase content is high and the crystallinity is good.
Example 2
The mass ratio is 4:6:0.6: weighing NaCl, caCl, K 2TaF6 and Ta powder in a ratio of 0.4, performing ball milling and dry mixing to obtain required molten salt powder, and then mixing tantalum oxide powder and carbon powder in a molar ratio of 1:8, preparing a reaction sintering raw material, wherein the mass ratio of a part of molten salt powder to the reaction sintering raw material powder is 2: and 1, preparing mixed powder for ball milling, wherein zirconia balls are used as ball milling media for ball milling, the rotating speed of the ball milling is 50r/min, and the ball milling time is 24 hours. In the actual operation process, after ball milling is completed, drying is carried out in a blast drying oven for 8 hours, and mixed powder is obtained. The preform was obtained by press molding the mixed powder at 10MPa, wherein the weight of the preform was 6.763g. And then placing the preform in a graphite tank, wherein graphite paper is paved on the upper part and the lower part of the graphite tank, and then embedding molten salt powder into the preform. Wherein, the fused salt powder is 8g, firstly, 30% of powder is paved at the bottom of a graphite tank, then, the prefabricated body made of the mixed powder is placed on the fused salt powder, and finally, the remaining fused salt powder is wrapped on the prefabricated body. Then placing the furnace in an alumina ark, and then placing the furnace in a tube furnace for vacuumizing treatment, so that the air pressure in the furnace is lower than 50Pa. Then, argon is filled into the tubular furnace for protection, so that the air pressure in the furnace is balanced with the external atmospheric pressure, the temperature is raised to 1000 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 60min, and the temperature is raised to 1350 ℃ and the temperature is kept for 3h. Cooling to 500 ℃ at 3 ℃/min after heat preservation, cooling to room temperature along with a furnace, taking out a square boat, cleaning a sample with deionized water, and drying to obtain the porous TaC ceramic material.
Example 3
The mass ratio is 4:6:0.6: weighing NaCl, KCl, K 2TaF6 and Ta powder in a proportion of 0.4, performing ball milling and dry mixing to obtain required molten salt powder, and then mixing tantalum powder and phenolic resin powder in a molar ratio of 1: and 7, configuring powder, wherein the mass ratio of the obtained powder to molten salt powder is 1:1, preparing mixed powder. The preform was obtained by press molding the mixed powder at 25MPa, wherein the weight of the preform was 5.397g. And then placing the preform in a graphite tank, wherein graphite paper is paved on the upper part and the lower part of the graphite tank, and then embedding molten salt powder into the preform. Wherein, the fused salt powder is 6g, firstly, 30% of powder is paved at the bottom of a graphite tank, then, the prefabricated body made of the mixed powder is placed on the fused salt powder, and finally, the remaining fused salt powder is wrapped on the prefabricated body. Then placing the furnace in an alumina ark, and then placing the furnace in a tube furnace for vacuumizing treatment, so that the air pressure in the furnace is lower than 50Pa. Then, argon is filled into the tubular furnace for protection, so that the air pressure in the furnace is balanced with the external atmospheric pressure, the temperature is increased to 1200 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 30min, and the temperature is increased to 1500 ℃ and the temperature is kept for 5h. Cooling to 500 ℃ at 5 ℃/min after heat preservation, cooling to room temperature along with a furnace, taking out a square boat, cleaning a sample with deionized water, and drying to obtain the porous TaC ceramic material.
Comparative example 1
The molar ratio is 1:7, carrying out ball milling and dry grinding on tantalum oxide powder and carbon powder to obtain mixed powder, then carrying out compression molding to obtain a preform, then placing the preform in a graphite tank, placing the graphite tank in an alumina ark, placing the alumina ark in a tubular furnace, and carrying out vacuumizing treatment to ensure that the air pressure in the furnace is lower than 50Pa. Then, argon is filled into the tubular furnace for protection, so that the air pressure in the furnace is balanced with the external atmospheric pressure, the temperature is increased to 1200 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 60min, and the temperature is increased to 1500 ℃ and the temperature is kept for 3h. Cooling to 500 ℃ at 5 ℃/min after heat preservation, cooling to room temperature along with a furnace, taking out a square boat, cleaning a sample with deionized water, and drying to obtain the porous TaC ceramic material.
The density of the samples obtained in examples 1 to 3 and comparative example 1 was measured according to the archimedes' drainage method by first thoroughly drying the sample, weighing the dry weight m 1 of the sample in air with an electronic balance, then placing the sample in a closed container filled with distilled water, evacuating until no bubbles are generated, taking out the sample, placing it on a tray suspended below the electronic balance, completely immersing the sample in a beaker filled with distilled water without contact with the balance, measuring the floating weight m 2 of the sample in water, finally taking out the sample, wiping the moisture on the surface of the sample with a wet towel, and measuring the wet weight m 3 with an electronic balance. Finally, the porosity is calculated by the formula 1:
The calculation results are shown in Table 1.
Comparative example 2
The mass ratio is 4:5:0.3: weighing NaCl, KCl, K 2TaF6 and Ta powder in a proportion of 0.7, performing ball milling and dry mixing to obtain required molten salt powder, and then mixing a part of molten salt powder with carbon powder in a mass ratio of 3: and 1, preparing mixed powder for ball milling, wherein air is used as a ball milling medium, the ball milling rotating speed is 40r/min, and the ball milling time is 24 hours. In the actual operation process, after ball milling is completed, the mixture is dried in a blast drying oven for 10 hours to obtain mixed powder. And (3) performing compression molding on the mixed powder to obtain a preform, wherein the preform is 5.461g, then placing the preform in a graphite tank, wherein graphite paper is paved on the upper part and the lower part of the graphite tank, and then embedding molten salt powder into the preform. Wherein, the fused salt powder is 6g, firstly, 30% of powder is paved at the bottom of a graphite tank, then, the prefabricated body made of the mixed powder is placed on the fused salt powder, and finally, the remaining fused salt powder is wrapped on the prefabricated body. Then placing the furnace in an alumina ark, and then placing the furnace in a tube furnace for vacuumizing treatment, so that the air pressure in the furnace is lower than 50Pa. Then, argon is filled into the tubular furnace for protection, so that the air pressure in the furnace is balanced with the external atmospheric pressure, the temperature is increased to 1200 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 60min, and the temperature is increased to 1500 ℃ and the temperature is kept for 3h. Cooling to 500 ℃ at 5 ℃/min after heat preservation, cooling to room temperature along with a furnace, taking out the ark, and obtaining black powder which is not molded.
Comparative example 3
The mass ratio is 4:5: weighing NaCl, KCl, K 2TaF6 powder according to the proportion of 0.3, performing ball milling and dry mixing to obtain required molten salt powder, and then mixing tantalum oxide powder and carbon powder according to the mole ratio of 1: and 7, preparing a reaction sintering raw material, wherein the mass ratio of a part of molten salt powder to the reaction sintering raw material powder is 3: and 1, preparing mixed powder for ball milling, wherein air is used as a ball milling medium, the ball milling rotating speed is 50r/min, and the ball milling time is 24h. In the actual operation process, after ball milling is completed, the mixture is dried in a blast drying oven for 10 hours to obtain mixed powder. And (3) performing compression molding on the mixed powder to obtain a preform, wherein the preform is 5.983g, then placing the preform in a graphite tank, wherein graphite paper is paved on the upper part and the lower part of the graphite tank, and then embedding molten salt powder into the preform. Wherein, the fused salt powder is 6g, firstly, 30% of powder is paved at the bottom of a graphite tank, then, the prefabricated body made of the mixed powder is placed on the fused salt powder, and finally, the remaining fused salt powder is wrapped on the prefabricated body. Then placing the furnace in an alumina ark, and then placing the furnace in a tube furnace for vacuumizing treatment, so that the air pressure in the furnace is lower than 50Pa. Then, argon is filled into the tubular furnace for protection, so that the air pressure in the furnace is balanced with the external atmospheric pressure, the temperature is increased to 1200 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 60min, and the temperature is increased to 1500 ℃ and the temperature is kept for 3h. Cooling to 500 ℃ at 3 ℃/min after heat preservation, cooling to room temperature along with a furnace, taking out the ark, and obtaining powder which is dark yellow in color and is not molded.
Comparative example 4
Other conditions were the same as in the examples except that the Ta powder was added to the mixed powder in proportion, but the Ta powder was not added to the powder for wrapping the preform, and as a result, the product was still powder, black in color, and the product was not molded.
Claims (10)
1. A preparation method of a porous TaC ceramic material is characterized by comprising the following steps: mixing tantalum source A, fluoride salt and chloride salt to obtain molten salt powder, mixing a part of molten salt powder with reactive sintering raw material powder to obtain mixed powder, compacting the mixed powder to obtain a preform, embedding a part of molten salt powder into the preform, and sintering at 1300-1500 ℃ to obtain the porous TaC ceramic material; the reaction sintering raw material powder consists of a tantalum source B and a carbon source.
2. The method for preparing the porous TaC ceramic material according to claim 1, wherein the method comprises the following steps: in the molten salt powder, the mass ratio of chlorine salt: fluorine salt: tantalum source a=50-120: 3-10:4-10.
3. The method for preparing a porous TaC ceramic material according to claim 1 or 2, wherein:
the chloride salt is at least one selected from potassium chloride, sodium chloride, calcium chloride and tantalum chloride,
The fluoride salt is at least one selected from lithium fluoride, potassium fluoride, calcium fluoride, sodium fluoride, potassium fluorotantalate and tantalum pentafluoride,
The tantalum source A is selected from one of tantalum powder, tantalum oxide and tantalum chloride,
And (3) putting the tantalum source A, the fluoride salt and the chloride salt into a mortar for grinding and mixing, sieving with a 80-120 mesh sieve, and taking the undersize to obtain molten salt powder.
4. The method for preparing a porous TaC ceramic material according to claim 1 or 2, wherein:
in the reaction sintering raw material powder, the mole ratio of the tantalum source B to the carbon source is 1:7-10;
The tantalum source B is selected from one of tantalum powder, tantalum oxide and tantalum chloride,
The carbon source is at least one selected from graphite powder, carbon powder and phenolic resin,
The purity of the carbon source is more than or equal to 99.9 percent, and the grain diameter is 300-500 meshes.
5. The method for preparing a porous TaC ceramic material according to claim 1 or 2, wherein:
In the mixed powder, the mass ratio of the reaction sintering raw material powder to the molten salt powder is 1-3:1.
6. The method for preparing a porous TaC ceramic material according to claim 1 or 2, wherein:
the method for mixing a part of molten salt powder and reaction sintering raw material powder is ball milling, wherein the ball milling method is dry ball milling, air is used as a ball milling medium, the ball milling rotating speed is 40-60r/min, and the ball milling time is 12-24h;
during ball milling, the ball-material ratio is 0.2-0.7:1.
7. The method for preparing a porous TaC ceramic material according to claim 1 or 2, wherein:
The pressure of the compression molding is 10-25MPa.
8. The method for preparing a porous TaC ceramic material according to claim 1 or 2, wherein: molten salt powder for embedding the preform, wherein 30-50% of the molten salt powder is arranged at the bottom of the preform, and the rest of the molten salt powder is arranged at the upper part of the preform;
The mass ratio of the preform to the molten salt powder for embedding the preform is 1:1-1.5.
9. The method for preparing a porous TaC ceramic material according to claim 1 or 2, wherein: the sintering process comprises the following steps: heating to 1000-1200deg.C at 3-5deg.C/min, maintaining for 30-60min, heating to 1300-1500deg.C at 3-5deg.C/min, and maintaining for 30-60min.
10. A porous TaC ceramic material prepared by the preparation method of any one of claims 1-9, characterized in that: the porosity of the porous TaC ceramic material is 90-95%, and the density is 1.5-2.5g/cm 3.
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