CN116514553A - Composite carbide ceramic powder material and preparation method and application thereof - Google Patents
Composite carbide ceramic powder material and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 127
- 239000000919 ceramic Substances 0.000 title claims abstract description 101
- 239000000463 material Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims description 54
- 239000002243 precursor Substances 0.000 claims description 44
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 43
- 238000001816 cooling Methods 0.000 claims description 33
- 239000007791 liquid phase Substances 0.000 claims description 27
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 26
- 239000000413 hydrolysate Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910007926 ZrCl Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
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- 238000000227 grinding Methods 0.000 description 7
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- 238000003763 carbonization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- ZRBFEDMQRDRUDG-UHFFFAOYSA-N silicon hexaboride Chemical compound B12B3[Si]45B3B2B4B51 ZRBFEDMQRDRUDG-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 238000002468 ceramisation Methods 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Abstract
The invention discloses a composite carbide ceramic powder material and a preparation method and application thereof, and belongs to the field of preparation of high-entropy ceramic materials.
Description
Technical Field
The invention belongs to the technical field of preparation of high-entropy ceramic materials, and particularly relates to a composite carbide ceramic powder material, and a preparation method and application thereof.
Background
Compared with the traditional ceramic material, the high-entropy ceramic material has the characteristics of excellent corrosion resistance, oxidation resistance, thermal stability, high hardness, low heat conduction and the like, and is widely applied to the fields of aerospace, new energy and the like.
The existing preparation method of the high-entropy carbide ceramic material mainly adopts a solid phase method, for example, metal carbide powder is used as a raw material, and the high-entropy carbide ceramic material is prepared by high-temperature and Spark Plasma Sintering (SPS); or preparing the graphite powder by using metal oxide and graphite powder through carbothermic reduction reaction; or adopting metal simple substance and graphite powder to prepare through ball milling; or adding ethanol into boride powder, ball milling, drying and vacuum sintering to obtain the ultra-high temperature ceramic material.
Patent CN 103833368A discloses a high temperature oxidation resistant ZrB 2 -SiB 6 The preparation method of the ultra-high temperature ceramic comprises the steps of preparing the ultra-high temperature ceramic raw materials, wherein the ultra-high temperature ceramic raw materials comprise zirconium boride powder and silicon hexaboride powder, the average grain diameter of the zirconium boride powder is 1-2 mu m, the purity of the zirconium boride powder is more than or equal to 99%, the average grain diameter of the silicon hexaboride powder is 1-5 mu m, and the purity of the zirconium boride powder is more than or equal to 99%; mixing silicon hexaboride powder and zirconium boride powder, dispersing in absolute ethyl alcohol, mixing in a ball mill, drying the obtained slurry after mixing to obtain mixed powder, grinding the mixed powder, sieving, performing hot-press sintering in vacuum or inert atmosphere, and naturally cooling to room temperature to obtain ZrB 2 -SiB 6 An ultra-high temperature ceramic material.
The high-entropy carbide ceramic material prepared in the prior art is mainly prepared from powdery raw materials, and is influenced by the size of the raw materials, so that the obtained ceramic powder is large in size and nonuniform in distribution, and nano ceramic powder cannot be obtained.
Prior Art (Ti) 0.2 Zr 0.2 Nb 0.2 Ta 0.2 Mo 0.2 ) Preparation and performance research of Cx-based high-entropy carbide ceramics (publication date 2022.05.01 of doctor's university of Guangdong Industrial university, paper Luo Sichun) discloses that a high-entropy ceramic material can be prepared by a solution method, the obtained material has uniform size and reaches the nanometer level, but the prepared high-entropy ceramic material does not have high-temperature oxidation resistance.
Therefore, there is a need in the art for a method for preparing nanoscale ceramic powders having uniform size distribution and high temperature oxidation resistance.
Disclosure of Invention
The invention aims to provide a composite carbide ceramic powder material, a preparation method and application thereof, so as to solve the problems in the prior art.
The invention provides a preparation method of a composite carbide ceramic powder material, which comprises the following steps:
step one, preparing a carbide liquid phase precursor
TiCl is added to the mixture 4 、ZrCl 4 、HfCl 4 、TaCl 5 And NbCl 5 Adding the mixture into a mixed solution of absolute ethyl alcohol and acetylacetone, adding a carbon source after the reaction, and continuing the reaction to obtain a carbide liquid phase precursor;
step two, preparing tetraethoxysilane hydrolysate
Adding ethyl orthosilicate into oxalic acid aqueous solution, and reacting to obtain ethyl orthosilicate hydrolysate;
step three, preparing a composite carbide ceramic powder material;
and adding the tetraethoxysilane hydrolysate into the carbide liquid phase precursor, reacting, and cooling to obtain the composite carbide ceramic powder material.
Further, in the first step, the carbon source is one of furfuryl alcohol, phenolic resin, glucose or salicylic acid;
the volume ratio of the absolute ethyl alcohol to the acetylacetone is 30:5-10;
the molecular weight of the phenolic resin is 122g/mol.
The TiCl is 4 、ZrCl 4 、HfCl 4 、TaCl 5 And NbCl 5 The dosage ratio is equal molar ratio;
the TiCl is 4 、ZrCl 4 、HfCl 4 、TaCl 5 And NbCl 5 The molar ratio of the total amount of (C) to the carbon source is 2:1-10:1.
Further, the mixing temperature of the absolute ethyl alcohol and the acetylacetone in the first step is 30-40 ℃ and the time is 30-60min;
the reaction temperature is 40-60 ℃ and the reaction time is 30-60min;
the temperature of the continuous reaction is 160-200 ℃ and the reaction time is 1-3h.
Further, tiCl described in step one 4 、ZrCl 4 、HfCl 4 、TaCl 5 And the molar ratio of the total amount of NbCl to the ethyl orthosilicate in the second step is 1:4-4:1; in the second step, the reaction temperature is 40 ℃; the time is 24 hours;
further, the temperature of the reaction in the step three is 180-200 ℃, and the reaction time is 2-3h.
The invention also provides the composite carbide ceramic powder material prepared by the preparation method.
The invention also provides a preparation method of the ceramic powder, which comprises the following steps:
the method comprises the following steps of firstly, drying the composite carbide ceramic powder material to be sticky, cooling, and continuing to dry to obtain dry precursor powder;
secondly, heating and cooling the dry precursor powder in an argon atmosphere to obtain an intermediate;
and thirdly, calcining and cooling the intermediate to obtain ceramic powder.
Further, in the first step, the drying temperature is 120-140 ℃, the temperature is reduced to 40-60 ℃, and the continuous drying time is 6-8; in the second step, the heating temperature is 800-1000 ℃ and the time is 2 hours; in the third step, the calcining temperature is 1800-2000 ℃ and the calcining time is 2h.
The invention also provides ceramic powder prepared by the preparation method and application of the ceramic powder in preparation of multi-carbide ceramic.
The invention has the beneficial effects that:
1) Under the combined action of absolute ethyl alcohol and acetylacetone, the transition metal chloride (TiCl 4 、ZrCl 4 、HfCl 4 、TaCl 5 And NbCl 5 ) The chloride ions of (2) are completely substituted to obtain metal alkoxide, and the metal alkoxide and active functional groups on a carbon source undergo substitution condensation reaction to obtain a carbide liquid phase precursor; the polyhydroxy silicon source formed after the catalytic hydrolysis of the tetraethoxysilane and the carbide liquid phase precursor further undergo a crosslinking complexing reaction, the introduced silicon source is converted into SiC through subsequent heat treatment, so that the antioxidation temperature range of the material is improved, the composite carbide ceramic powder material is obtained, the prepared composite carbide ceramic powder material is dried and solidified to obtain an intermediate, and finally the intermediate is subjected to high-temperature heat treatment to obtain the ceramic powder.
2) The liquid phase polymer precursor method is adopted to obtain the composite carbide ceramic powder material with uniformly dispersed element molecular level in a metal-containing monomer polymerization mode, the uniform distribution of each component can be kept in the high-temperature ceramization process, and the atomic migration is promoted to a greater extent, so that the generation of solid solution is facilitated, and finally the high-temperature oxidation-resistant ceramic powder with submicron size and uniformly distributed elements is obtained.
3) The preparation method of the ceramic powder has the advantages of simple operation, low operation temperature, short reaction time, low equipment requirement and the like, and is suitable for large-scale industrial production.
4) The invention has important reference value for preparing other high-entropy ceramic powder, and the prepared composite carbide ceramic powder material can be applied to the preparation of ceramic matrix composite materials and ceramic fibers.
5) In the preparation process, the solvent, byproducts and unreacted small molecules are removed by heating and drying to obtain dry precursor powder, so that the problem of corrosion of HCl generated by decomposition in a high-temperature environment to equipment is solved, the service life of the equipment is prolonged, and the production cost is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a ceramic powder obtained in example 1 of the present invention;
FIG. 2 is an SEM image of the ceramic powder obtained in example 1 of the invention;
FIG. 3 is a thermogravimetric graph of the ceramic powder obtained in example 1 of the present invention under an air atmosphere, wherein the black curve is a thermogravimetric curve, the blue curve is a differential thermogravimetric analysis curve, and the red curve is an absorption-heat release curve;
FIG. 4 is an XRD pattern of the ceramic powder obtained in the comparative example of the present invention;
FIG. 5 is an SEM image of a ceramic powder obtained according to a comparative example of the invention;
FIG. 6 is a graph showing the thermogravimetric curve of the ceramic powder obtained in the comparative example of the present invention under an air atmosphere, wherein the black curve is a thermogravimetric curve, the blue curve is a differential thermogravimetric analysis curve, and the red curve is an absorption-heat release curve.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The room temperature of the present invention means 25.+ -. 2 ℃.
Example 1
Preparation method of composite carbide ceramic powder material
1. Preparation of carbide liquid phase precursor
Respectively weighing 30mL of absolute ethyl alcohol and 5mL of acetylacetone, adding into a 250mL three-neck flask, uniformly mixing, heating and stirring by an oil bath type magnetic stirrer, heating to 40 ℃, reacting for 30min, and respectively weighing 0.275mL (0.0025 mol) of TiCl 4 、0.58g(0.0025mol)ZrCl 4 、0.8g(0.0025mol)HfCl 4 、0.9g(0.0025mol)TaCl 5 And 0.675g (0.0025 mol) NbCl 5 Adding into a three-neck flask, heating to 60 ℃, reacting for 1h, adding 0.26g (0.0019 mol) of waterHeating salicylic acid to 180 ℃, and reacting for 120min to obtain a carbide liquid phase precursor;
2. preparation of Ethyl orthosilicate hydrolysate
5.6mL of tetraethyl orthosilicate (TEOS) is measured, added into 5mL of oxalic acid water solution with pH of 6, and hydrolyzed for 24 hours at 40 ℃ to obtain tetraethyl orthosilicate hydrolysate.
3. Preparation of composite carbide ceramic powder material
Adding the tetraethoxysilane hydrolysate into the carbide liquid phase precursor, heating to 180 ℃, reacting for 2 hours, and cooling along with room temperature to obtain the brown yellow composite carbide ceramic powder material.
In this embodiment, the ceramic powder is prepared by continuously using the obtained composite carbide ceramic powder material.
S1: heating the obtained composite carbide ceramic powder material to 120 ℃, drying to be sticky, cooling to 40 ℃, and continuously drying for 6 hours to obtain brown yellow dry precursor powder;
s2, grinding the obtained brown yellow dry precursor powder, placing the powder into a tube furnace, heating to 1000 ℃ at 10 ℃/min under the argon atmosphere, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain an intermediate;
s3, placing the intermediate powder into a high-temperature carbonization furnace, heating to 1800 ℃ at 10 ℃/min, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain ceramic powder.
FIGS. 1-3 are graphs of XRD spectrum, SEM spectrum and thermal gravimetric graph under air atmosphere of ceramic powder obtained in this example, and we can see from FIG. 1 that we obtain ceramic composite material; as can be seen from FIG. 2, the ceramic powder obtained by us has a layered structure with uniform size and consistent structure, which shows that the prepared SiC-doped high-entropy ceramic powder has the characteristics of good uniformity and high purity; from FIG. 3, it is seen that the ceramic powder starts to oxidize at 500+ -20deg.C and has good oxidation resistance at a temperature lower than 500 deg.C.
Example 2
Preparation method of composite carbide ceramic powder material
1. Preparation of carbide liquid phase precursor
30mL of the solution is measured separatelyAdding ethanol and 5mL of acetylacetone into a 250mL three-neck flask, uniformly mixing, heating and stirring by an oil bath type magnetic stirrer, heating to 60 ℃, reacting for 30min, and taking 0.275mL (0.0025 mol) of TiCl respectively 4 、0.58g(0.0025mol)ZrCl 4 、0.8g(0.0025mol)HfCl 4 、0.9g(0.0025mol)TaCl 5 And 0.675g (0.0025 mol) NbCl 5 Adding the mixture into a three-neck flask, heating to 60 ℃, reacting for 1h, adding 0.43g (0.0031 mol) of salicylic acid, heating to 190 ℃, and reacting for 120min to obtain a carbide liquid phase precursor;
2. preparation of Ethyl orthosilicate hydrolysate
2.8mL of tetraethyl orthosilicate (TEOS) is measured, added into 2mL of oxalic acid water solution with pH of 6, and hydrolyzed for 24 hours at 40 ℃ to obtain tetraethyl orthosilicate hydrolysate.
3. Preparation of composite carbide ceramic powder material
Adding the tetraethoxysilane hydrolysate into the obtained carbide liquid phase precursor, heating to 190 ℃, reacting for 2 hours, and cooling along with room temperature to obtain the brown-yellow composite carbide ceramic powder material.
In this embodiment, the ceramic powder is prepared by continuously using the obtained composite carbide ceramic powder material
S1: heating the obtained composite carbide ceramic powder material to 140 ℃, drying to be sticky, cooling to 40 ℃, and continuously drying for 8 hours to obtain brown yellow dry precursor powder;
s2, grinding the obtained brown yellow dry precursor powder, placing the powder in a tubular furnace for pretreatment, heating to 900 ℃ at 10 ℃/min under the argon atmosphere, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain an intermediate;
s3, placing the intermediate in a high-temperature carbonization furnace, heating to 1800 ℃ at 10 ℃/min, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain ceramic powder.
Example 3
Preparation method of composite carbide ceramic powder material
1. Preparation of carbide liquid phase precursor
Respectively weighing 30mL of absolute ethyl alcohol and 5mL of acetylacetone, adding into a 250mL three-neck flask, and uniformly mixingHeating and stirring with oil bath type magnetic stirrer, heating to 50deg.C, reacting for 30min, and collecting 0.275mL (0.0025 mol) TiCl respectively 4 、0.58g(0.0025mol)ZrCl 4 、0.8g(0.0025mol)HfCl 4 、0.9g(0.0025mol)TaCl 5 And 0.675g (0.0025 mol) NbCl 5 Adding a three-neck flask, heating to 60 ℃, reacting for 1h, adding 0.38g (0.0081 mol) of phenolic resin with the molecular weight of 122g/mol, heating to 180 ℃, and reacting for 120min to obtain a carbide liquid phase precursor;
2. preparation of Ethyl orthosilicate hydrolysate
5.6mL of tetraethyl orthosilicate (TEOS) is measured, added into 5mL of oxalic acid water solution with pH of 6, and hydrolyzed for 24 hours at 40 ℃ to obtain tetraethyl orthosilicate hydrolysate.
3. Preparation of composite carbide ceramic powder material
Adding the tetraethoxysilane hydrolysate into the obtained carbide liquid phase precursor, heating to 200 ℃, reacting for 3 hours, and cooling along with room temperature to obtain the brown-yellow composite carbide ceramic powder material.
In this embodiment, the ceramic powder is prepared by continuously using the obtained composite carbide ceramic powder material
S1: heating the obtained composite carbide ceramic powder material to 130 ℃, drying to be sticky, cooling to 70 ℃, and continuously drying for 7 hours to obtain brown yellow dry precursor powder;
s2, grinding the obtained brown yellow dry precursor powder, placing the powder in a tubular furnace for pretreatment, heating to 900 ℃ at 10 ℃/min under the argon atmosphere, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain an intermediate;
s3, placing the intermediate in a high-temperature carbonization furnace, heating to 2000 ℃ at 10 ℃/min, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain ceramic powder.
The ceramic powder obtained in this example has better crystallinity due to a longer time of heat treatment, but has a sintering phenomenon to some extent.
Example 4
Preparation method of composite carbide ceramic powder material
1. Preparation of carbide liquid phase precursor
Respectively weighing 30mL of absolute ethyl alcohol and 5mL of acetylacetone, adding into a 250mL three-neck flask, uniformly mixing, heating and stirring by an oil bath type magnetic stirrer, heating to 40 ℃, reacting for 30min, and respectively weighing 0.275mL (0.0025 mol) of TiCl 4 、0.58g(0.0025mol)ZrCl 4 、0.8g(0.0025mol)HfCl 4 、0.9g(0.0025mol)TaCl 5 And 0.675g (0.0025 mol) NbCl 5 Adding a three-neck flask, heating to 60 ℃, reacting for 1h, adding 0.5g (0.004 mol) of phenolic resin with the molecular weight of 122g/mol, heating to 200 ℃, and reacting for 150min to obtain a carbide liquid phase precursor;
2. preparation of Ethyl orthosilicate hydrolysate
2.8mL of tetraethyl orthosilicate (TEOS) is measured, added into 2mL of oxalic acid water solution with pH of 6, and hydrolyzed for 24 hours at 40 ℃ to obtain tetraethyl orthosilicate hydrolysate.
3. Preparation of composite carbide ceramic powder material
Adding the tetraethoxysilane hydrolysate into the obtained carbide liquid phase precursor, heating to 200 ℃, reacting for 1h, and cooling along with room temperature to obtain the brown-yellow composite carbide ceramic powder material.
In this embodiment, the ceramic powder is prepared by continuously using the obtained composite carbide ceramic powder material
S1: heating the obtained composite carbide ceramic powder material to 130 ℃, drying to be sticky, cooling to 50 ℃, and continuously drying for 6 hours to obtain brown yellow dry precursor powder;
s2, grinding the obtained brown yellow dry precursor powder, placing the powder in a tubular furnace for pretreatment, heating to 900 ℃ at 10 ℃/min under the argon atmosphere, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain an intermediate;
s3, placing the intermediate in a high-temperature carbonization furnace, heating to 1900 ℃ at 10 ℃/min, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain ceramic powder.
Example 5
Preparation method of composite carbide ceramic powder material
1. Preparation of carbide liquid phase precursor
Respectively weighing 30mL of absolute ethyl alcohol and 5mL of acetylacetone, adding into a 250mL three-neck flask, uniformly mixing, heating and stirring by an oil bath type magnetic stirrer, heating to 40 ℃, reacting for 30min, and respectively weighing 0.275mL (0.0025 mol) of TiCl 4 、0.58g(0.0025mol)ZrCl 4 、0.8g(0.0025mol)HfCl 4 、0.9g(0.0025mol)TaCl 5 And 0.675g (0.0025 mol) NbCl 5 Adding the mixture into a three-neck flask, heating to 60 ℃, reacting for 1h, adding 0.6g (0.0033 mol) of glucose, heating to 200 ℃, and reacting for 180min to obtain a carbide liquid phase precursor;
2. preparation of Ethyl orthosilicate hydrolysate
5.6mL of tetraethyl orthosilicate (TEOS) is measured, added into 5mL of oxalic acid water solution with pH of 6, and hydrolyzed for 24 hours at 40 ℃ to obtain tetraethyl orthosilicate hydrolysate.
3. Preparation of composite carbide ceramic powder material
Adding the tetraethoxysilane hydrolysate into the obtained carbide liquid phase precursor, heating to 200 ℃, reacting for 1h, and cooling along with room temperature to obtain the brown-yellow composite carbide ceramic powder material.
In this embodiment, the ceramic powder is prepared by continuously using the obtained composite carbide ceramic powder material
S1: heating the obtained composite carbide ceramic powder material to 120 ℃, drying to be sticky, cooling to 40 ℃, and continuously drying for 8 hours to obtain brown yellow dry precursor powder;
s2, grinding the obtained brown yellow dry precursor powder, placing the powder in a tubular furnace for pretreatment, heating to 1000 ℃ at 10 ℃/min under the argon atmosphere, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain an intermediate;
s3, placing the intermediate in a high-temperature carbonization furnace, heating to 1800 ℃ at 10 ℃/min, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain ceramic powder.
Example 6
Preparation method of composite carbide ceramic powder material
1. Preparation of carbide liquid phase precursor
30mL of absolute ethyl alcohol and 10mL of acetylacetone are respectively measured,adding into a 250mL three-neck flask, mixing, heating and stirring with an oil bath type magnetic stirrer, heating to 50deg.C, reacting for 60min, and collecting 0.275mL (0.0025 mol) TiCl respectively 4 、0.58g(0.0025mol)ZrCl 4 、0.8g(0.0025mol)HfCl 4 、0.9g(0.0025mol)TaCl 5 And 0.675g (0.0025 mol) NbCl 5 Adding the mixture into a three-neck flask, heating to 50 ℃, reacting for 1h, adding 0.56g (0.0031 mol) of glucose, heating to 200 ℃, and reacting for 120min to obtain a carbide liquid phase precursor;
2. preparation of Ethyl orthosilicate hydrolysate
2.8mL of tetraethyl orthosilicate (TEOS) is measured, added into 5mL of oxalic acid water solution with pH of 6, and hydrolyzed for 24 hours at 40 ℃ to obtain tetraethyl orthosilicate hydrolysate.
3. Preparation of composite carbide ceramic powder material
Adding the tetraethoxysilane hydrolysate into the obtained carbide liquid phase precursor, heating to 200 ℃, reacting for 2 hours, and cooling to obtain the brown-yellow composite carbide ceramic powder material.
In this embodiment, the ceramic powder is prepared by continuously using the obtained composite carbide ceramic powder material
S1: heating the obtained ceramic composite carbide ceramic powder material to 130 ℃, drying to be sticky, then cooling to 50 ℃, and continuously distilling for 6 hours to obtain brown yellow dry precursor powder;
s2, grinding the obtained brown yellow dry precursor powder, placing the powder in a tubular furnace for pretreatment, heating to 1000 ℃ at 10 ℃/min under the argon atmosphere, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain an intermediate;
s3, placing the intermediate in a high-temperature carbonization furnace, heating to 1800 ℃ at 10 ℃/min, preserving heat for 2 hours, and cooling along with the furnace temperature to obtain ceramic powder.
Comparative example
Preparation method of composite carbide ceramic powder material
The difference is that no hydrolyzed ethyl orthosilicate was added as in example 1.
In this comparative example, the ceramic powder was prepared by continuing to use the obtained composite carbide ceramic powder material, and the preparation method was the same as in example 1.
FIGS. 4 to 6 are XRD patterns, SEM patterns and thermogravimetric patterns of the ceramic powders obtained in the comparative example, and the ceramic phases obtained in the case of no doping of SiC are high-entropy ceramic and amorphous pyrolytic carbon as shown in FIG. 4; as can be seen from fig. 5, under the condition of not doping SiC, we obtain ceramic powder with a particle morphology of about 500nm, more pores exist between particles, and the larger specific surface area can cause poor oxidation resistance; from FIG. 6, it is known that the ceramic powder without Si source has a low initial temperature for oxidation weight increase, and the oxidation weight increase is started at 300+ -20deg.C, with poor oxidation resistance.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. The preparation method of the composite carbide ceramic powder material is characterized by comprising the following steps of:
step one, preparing a carbide liquid phase precursor
TiCl is added to the mixture 4 、ZrCl 4 、HfCl 4 、TaCl 5 And NbCl 5 Adding the mixture into a mixed solution of absolute ethyl alcohol and acetylacetone, adding a carbon source after the reaction, and continuing the reaction to obtain a carbide liquid phase precursor;
step two, preparing tetraethoxysilane hydrolysate
Adding ethyl orthosilicate into oxalic acid aqueous solution, and reacting to obtain ethyl orthosilicate hydrolysate;
step three, preparing composite carbide ceramic powder material
And adding the tetraethoxysilane hydrolysate into the carbide liquid phase precursor, reacting, and cooling to obtain the composite carbide ceramic powder material.
2. The method according to claim 1, wherein the carbon source in the first step is one of furfuryl alcohol, phenolic resin, glucose or salicylic acid;
the volume ratio of the absolute ethyl alcohol to the acetylacetone is 30:5-10;
the TiCl is 4 、ZrCl 4 、HfCl 4 、TaCl 5 And NbCl 5 The dosage ratio is equal molar ratio;
the TiCl is 4 、ZrCl 4 、HfCl 4 、TaCl 5 And NbCl 5 The molar ratio of the total amount of (C) to the carbon source is 2:1-10:1.
3. The method according to claim 1, wherein the mixing temperature of the anhydrous ethanol and the acetylacetone in the first step is 30 to 40 ℃;
the reaction temperature is 40-60 ℃ and the reaction time is 30-60min;
the temperature of the continuous reaction is 160-200 ℃ and the reaction time is 1-3h.
4. The process according to claim 1, wherein TiCl is fed to the first step 4 、ZrCl 4 、HfCl 4 、TaCl 5 And the molar ratio of the total amount of NbCl to the ethyl orthosilicate in the second step is 1:4-4:1;
in the second step, the pH value of the oxalic acid aqueous solution is 6, and the volume ratio of the tetraethoxysilane to the oxalic acid aqueous solution is as follows: the reaction temperature is 40 ℃ in the range of 1:1 to 2:1; the time was 24h.
5. The method according to claim 1, wherein the temperature of the reaction in the third step is 180 to 200 ℃ and the reaction time is 2 to 3 hours.
6. A composite carbide ceramic powder material prepared by the method of any one of claims 1-5.
7. The preparation method of the ceramic powder is characterized by comprising the following steps:
the method comprises the steps of firstly, drying the composite carbide ceramic powder material of claim 6 to be sticky, cooling, and continuing to dry to obtain dry precursor powder;
secondly, heating and cooling the dry precursor powder in an argon atmosphere to obtain an intermediate;
and thirdly, calcining and cooling the intermediate to obtain ceramic powder.
8. The preparation method according to claim 7, wherein the drying temperature in the first step is 120-140 ℃, the temperature is reduced to 40-60 ℃, and the continuous drying time is 6-8 hours;
in the second step, the heating temperature is 800-1000 ℃ and the time is 2 hours;
in the third step, the calcining temperature is 1800-2000 ℃ and the calcining time is 2h.
9. A ceramic powder prepared by the preparation method of claim 7 or 8.
10. Use of the ceramic powder of claim 9 in the preparation of a multi-carbide ceramic.
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