CN117209299A - High-temperature-resistant ceramic material based on hafnium boride and preparation method thereof - Google Patents
High-temperature-resistant ceramic material based on hafnium boride and preparation method thereof Download PDFInfo
- Publication number
- CN117209299A CN117209299A CN202311483855.XA CN202311483855A CN117209299A CN 117209299 A CN117209299 A CN 117209299A CN 202311483855 A CN202311483855 A CN 202311483855A CN 117209299 A CN117209299 A CN 117209299A
- Authority
- CN
- China
- Prior art keywords
- hafnium boride
- fiber
- ceramic
- ceramic material
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LRTTZMZPZHBOPO-UHFFFAOYSA-N [B].[B].[Hf] Chemical compound [B].[B].[Hf] LRTTZMZPZHBOPO-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 89
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 13
- 229910026551 ZrC Inorganic materials 0.000 claims abstract description 12
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000919 ceramic Substances 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 54
- 229920001709 polysilazane Polymers 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000009987 spinning Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- 238000000578 dry spinning Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- PYJRPLSURBGHSR-UHFFFAOYSA-N O.O.O.O.O.O.O.O.[Hf].ClOCl Chemical compound O.O.O.O.O.O.O.O.[Hf].ClOCl PYJRPLSURBGHSR-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011214 refractory ceramic Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 19
- 230000003647 oxidation Effects 0.000 abstract description 18
- 230000000052 comparative effect Effects 0.000 description 22
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- 230000004580 weight loss Effects 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000004584 weight gain Effects 0.000 description 5
- 235000019786 weight gain Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Abstract
The application discloses a high-temperature resistant ceramic material based on hafnium boride and a preparation method thereof, and the high-temperature resistant ceramic material comprises the following components in parts by weight: 70-90 parts of modified hafnium boride fiber, 4.5-13.5 parts of zirconium carbide, 5-15 parts of silicon powder and 0.5-1.5 parts of carbon powder. According to the application, the sintering performance of the ceramic material is improved by doping and modifying the hafnium boride fiber, so that the compactness and the high-temperature oxidation resistance of the high-temperature resistant material are improved.
Description
Technical Field
The application belongs to the technical field of ceramic materials, and particularly relates to a high-temperature-resistant ceramic material based on hafnium boride and a preparation method thereof.
Background
In hypersonic aircrafts and spacecrafts in extreme environments, an ultra-high temperature ceramic material is generally used as a protective material, and the melting point of the ultra-high temperature ceramic is generally above 3000 ℃, and mainly comprises boride, carbide and nitride of transition metal; the non-oxide ceramic material mainly exists in a covalent bond mode, has strong high-temperature deformation resistance, has the advantages of ultrahigh temperature resistance and outstanding oxidation resistance, can adapt to extreme conditions, has the advantages of high strength, high hardness, high conductivity, thermal shock resistance and the like, has strong covalent bonds in the hafnium boride, has low volume diffusion rate, is difficult to densify in the sintering process, needs to sinter the hafnium boride material at a temperature of more than 2000 ℃, has high energy consumption, and has difficult control of densification degree in sintering, so that the performance of the hafnium boride ceramic material is reduced.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the application provides the high-temperature-resistant ceramic material based on hafnium boride and the preparation method thereof, and in order to solve the problems of poor compactness and poor oxidation resistance of the ceramic material, the application provides a method for doping and modifying hafnium boride fibers to improve the sintering performance of the ceramic material, thereby improving the compactness and the high-temperature oxidation resistance of the high-temperature-resistant material.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows: the application provides a high-temperature-resistant ceramic material based on hafnium boride, which comprises the following components in parts by weight: 70-90 parts of modified hafnium boride fiber, 4.5-9 parts of zirconium carbide, 10-20 parts of silicon powder and 0.5-1 part of carbon powder.
Preferably, the preparation method of the modified hafnium boride fiber comprises the following steps:
s1, preparing hafnium boride ceramic nascent fibers by adopting dry spinning;
s2, activating the primary hafnium boride ceramic fiber prepared in the step S1 by adopting an impregnation method to obtain an activated hafnium boride fiber;
s3, treating the activated hafnium boride fiber prepared in the step S2 with polysilazane solution to obtain a modified hafnium boride fiber
Preferably, the preparation method of the modified hafnium boride fiber specifically comprises the following steps:
s11, dissolving hafnium oxychloride octahydrate and boric acid in deionized water, and regulating the pH to 2-3 to obtain a ceramic fiber precursor solution;
s12, mixing the ceramic fiber precursor solution prepared in the step S11 with a polyvinyl alcohol solution, standing overnight for defoaming to obtain a ceramic fiber spinning solution;
s13, carrying out dry spinning on the ceramic fiber spinning solution prepared in the step S12 to obtain hafnium boride ceramic nascent fibers;
s21, soaking the hafnium boride ceramic nascent fiber prepared in the step S13 in a sodium hydroxide solution, heating in a water bath at 70-80 ℃ for 2-3 hours, naturally cooling to room temperature, filtering, washing with deionized water, and drying to obtain an activated hafnium boride fiber;
s31, dissolving polysilazane in n-butyl acetate to obtain polysilazane solution, soaking the activated hafnium boride fiber prepared in the step S21 in the polysilazane solution, carrying out ultrasonic treatment, filtering, removing redundant solution, placing in an oven for curing at 120-140 ℃ for 30-40min, and sintering after curing is completed to obtain modified hafnium boride fiber;
preferably, in step S11, the mass ratio of the hafnium oxychloride octahydrate to the boric acid is 1-2:10;
preferably, in step S11, the mass fraction of the hafnium oxychloride octahydrate in deionized water is 0.1-0.15g/mL;
preferably, in step S11, the mass fraction of the boric acid in the deionized water is 0.5-1.5g/mL;
preferably, in step S12, polyvinyl alcohol is dissolved in a mixed solution of ethanol and water to obtain a polyvinyl alcohol solution; the volume ratio of the ethanol to the water is 1-3:10;
preferably, in step S12, the mass fraction of the polyvinyl alcohol solution is 30-50%;
preferably, in step S12, the solid content of the ceramic fiber spinning solution is 30-35%;
preferably, in step S13, in dry spinning, the initial spinning temperature is 50-55 ℃, and the temperature is gradually increased to 160-190 ℃; the length of the channel is 6m, and the winding speed is 200-210m/min;
preferably, in step S21, the mass fraction of the sodium hydroxide solution is 25-35%;
preferably, in step S31, the polysilazane solution has a mass fraction of polysilazane of 3-7%;
preferably, in step S31, the ultrasonic power is 600-800W and the ultrasonic time is 10-20min during ultrasonic treatment;
preferably, in the step S31, the sintering temperature is 1600-1800 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h.
The application provides a preparation method of a high-temperature resistant ceramic material based on hafnium boride, which specifically comprises the following steps:
(1) mixing the modified hafnium boride fiber, zirconium carbide, silicon powder and carbon powder, adding absolute ethyl alcohol, performing wet mixing ball milling treatment by using zirconium oxide grinding balls, removing the absolute ethyl alcohol, and drying to obtain a ceramic mixture;
(2) sealing the ceramic mixture prepared in the step (1) in a reaction kettle, and sintering under an argon atmosphere to obtain a high-temperature-resistant ceramic material;
preferably, in the step (1), the mass ratio of the ball water to the material is 2:1.5:1;
preferably, in the step (1), the wet mixing ball milling time is 12 hours, and the ball milling rotating speed is 60rpm;
preferably, in the step (2), the sintering pressure is 40MPa, the sintering temperature is 1800-1900 ℃, the heating rate is 100 ℃/min, and the heat preservation time is 10-20min.
The beneficial effects obtained by the application are as follows:
the application provides a high-temperature resistant ceramic material based on hafnium boride and a preparation method thereof, which are characterized in that polysilazane is used for modifying the hafnium boride, so that the sintering property of the hafnium boride is improved, the compactness of the hafnium boride ceramic is improved, and the high-temperature resistant and oxidation resistant properties of the hafnium boride are improved; according to the preparation method, the hafnium boride fiber is activated and modified by sodium hydroxide, a large number of active groups are introduced into the surface of the hafnium boride fiber, and polysilazane is introduced into the surface of the hafnium boride fiber through a hydrogen bond or covalent bonding mode; the polysilazane is solidified on the surface of the hafnium boride fiber, in-situ doping of Si, C and N is realized through high-temperature sintering treatment, amorphous particles with smaller particle size can be formed on the hafnium boride ceramic material in a high-temperature environment, the effect of filling gaps is achieved, and the compactness of the hafnium boride material is improved in an ultrahigh-temperature environment, so that the high-temperature oxidation resistance is improved.
Drawings
FIG. 1 is a graph of the relative density results of ceramic materials prepared in examples and comparative examples;
FIG. 2 is a graph showing the results of high-temperature oxidation resistance of the ceramic materials prepared in examples 1 to 3 and comparative examples 1 and 2 according to the present application;
FIG. 3 is a graph showing the results of corrosion resistance of the ceramic materials described in examples 1-3 and comparative examples 1, 2;
FIG. 4 is an XRD pattern of a hafnium boride-based refractory ceramic material prepared in example 1;
the accompanying drawings are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate the application and together with the embodiments of the application, serve to explain the application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application; all other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials and test strains used in the examples described below, unless otherwise specified, were commercially available.
The specific materials involved in the application are as follows:
polysilazane OPSZ, available from Merck, germany, model 1500RC, has the chemical structural formula shown below:
。
example 1
The application provides a hafnium boride-based high-temperature-resistant ceramic material, which comprises the following components in parts by weight: 80 parts of modified hafnium boride fiber, 9 parts of zirconium carbide, 10 parts of silicon powder and 1 part of carbon powder.
The preparation method of the modified hafnium boride fiber specifically comprises the following steps:
s11, accurately weighing 1g of hafnium oxychloride octahydrate, dissolving in 10mL of deionized water, adding 5g of boric acid after complete dissolution, stirring at 100rpm for 10 hours, uniformly mixing, and regulating the pH to 3 to obtain transparent and clear ceramic fiber precursor solution;
s12, accurately weighing 4g of polyvinyl alcohol, dissolving in 10mL of ethanol water solution (v: v=3:10), slowly adding the ceramic fiber precursor solution prepared in the step S11, mixing at 100rpm for 10 hours, standing overnight at room temperature, and defoaming to obtain a ceramic fiber spinning solution with 30% of solid content;
s13, carrying out fiber spinning on the ceramic fiber spinning solution prepared in the step S12 by adopting a dry spinning method, wherein the initial temperature of the dry spinning is 50 ℃, the channel is gradually heated to 160 ℃, the channel length is 6m, the winding speed is 200m/min, and the obtained hafnium boride ceramic nascent fiber is placed in a baking oven at 40 ℃ for standby;
s21, soaking the hafnium boride ceramic nascent fiber prepared in the step S13 in a 30% sodium hydroxide solution, heating to 70 ℃ in a water bath, soaking for 2 hours, cooling the reaction system to room temperature, filtering, washing the ceramic fiber with deionized water, removing a solvent, and drying to obtain an activated hafnium boride fiber;
s31, accurately weighing 0.5g of polysilazane, dissolving in 11.5mL of n-butyl acetate to obtain a polysilazane solution with the mass fraction of 5%, soaking the activated hafnium boride fiber prepared in the step S21 in the polysilazane solution, performing ultrasonic treatment at the ultrasonic power of 700W for 10min, filtering, removing the redundant solvent, placing in a 120 ℃ oven for curing for 40min, transferring to a high-pressure reaction load after curing is completed, heating up at the speed of 5 ℃/min under the nitrogen atmosphere, and preserving heat for 2h when the temperature is raised to 1600 ℃ to obtain the modified hafnium boride fiber.
The application also provides a preparation method of the hafnium boride-based high-temperature-resistant ceramic material, which specifically comprises the following steps:
(1) mixing modified hafnium boride fibers, zirconium carbide, silicon powder and carbon powder according to the weight ratio of 2:1.5:1, adding absolute ethyl alcohol and zirconia grinding balls, performing wet ball milling at 60rpm for 12 hours, removing the absolute ethyl alcohol, and drying to obtain a ceramic mixture;
(2) and (3) transferring the ceramic mixture prepared in the step (S11) into a reaction kettle, placing the reaction kettle in an environment of sealing, adjusting the pressure of the reaction kettle to 40MPa under the argon atmosphere, heating to 1800 ℃ according to 100 ℃/min, preserving heat for 10min, and naturally cooling to room temperature to obtain the high-temperature-resistant ceramic material.
Example 2
The application provides a hafnium boride-based high-temperature-resistant ceramic material, which comprises the following components in parts by weight: 90 parts of modified hafnium boride fiber, 4.5 parts of zirconium carbide, 5 parts of silicon powder and 0.5 part of carbon powder.
The preparation method of the modified hafnium boride fiber specifically comprises the following steps:
s11, accurately weighing 1.5g of hafnium oxychloride octahydrate, dissolving in 10mL of deionized water, adding 15g of boric acid after complete dissolution, stirring at 100rpm for 10 hours, uniformly mixing, and regulating the pH to 2 to obtain transparent and clear ceramic fiber precursor solution;
s12, accurately weighing 5g of polyvinyl alcohol, dissolving in 10mL of ethanol water solution (v: v=1:10), slowly adding the ceramic fiber precursor solution prepared in the step S11, mixing at 100rpm for 10 hours, standing overnight at room temperature, and defoaming to obtain a ceramic fiber spinning solution with the solid content of 35%;
s13, carrying out fiber spinning on the ceramic fiber spinning solution prepared in the step S12 by adopting a dry spinning method, wherein the initial temperature of the dry spinning is 55 ℃, the channel is gradually heated to 190 ℃, the channel length is 6m, the winding speed is 200m/min, and placing the obtained hafnium boride ceramic nascent fiber in a baking oven at 40 ℃ for standby;
s21, soaking the hafnium boride ceramic nascent fiber prepared in the step S13 in a sodium hydroxide solution with the mass fraction of 25%, heating to 80 ℃ in a water bath, soaking for 3 hours, waiting for the reaction system to cool to room temperature, filtering, washing the ceramic fiber with deionized water, removing the solvent, and drying to obtain an activated hafnium boride fiber;
s31, accurately weighing 0.3g of polysilazane, dissolving in 11.5mL of n-butyl acetate to obtain a polysilazane solution with the mass fraction of 3%, soaking the activated hafnium boride fiber prepared in the step S21 in the polysilazane solution, performing ultrasonic treatment for 20min at the ultrasonic power of 600W, filtering, removing the redundant solvent, placing in a 140 ℃ oven for curing for 30min, transferring to a high-pressure reaction load after curing is completed, heating up at the speed of 5 ℃/min under the nitrogen atmosphere, and preserving heat for 2h when the temperature is raised to 1800 ℃ to obtain the modified hafnium boride fiber.
The application also provides a preparation method of the hafnium boride-based high-temperature-resistant ceramic material, which specifically comprises the following steps:
(1) mixing modified hafnium boride fibers, zirconium carbide, silicon powder and carbon powder according to the weight ratio of 2:1.5:1, adding absolute ethyl alcohol and zirconia grinding balls, performing wet ball milling at 60rpm for 12 hours, removing the absolute ethyl alcohol, and drying to obtain a ceramic mixture;
(2) and (3) transferring the ceramic mixture prepared in the step (S11) into a reaction kettle, placing the reaction kettle in an environment of sealing, adjusting the pressure of the reaction kettle to 40MPa under the argon atmosphere, heating to 1900 ℃ according to 100 ℃/min, preserving heat for 20min, and naturally cooling to room temperature to obtain the high-temperature-resistant ceramic material.
Example 3
The application provides a hafnium boride-based high-temperature-resistant ceramic material, which comprises the following components in parts by weight: 70 parts of modified hafnium boride fiber, 13.5 parts of zirconium carbide, 15 parts of silicon powder and 1.5 parts of carbon powder.
The preparation method of the modified hafnium boride fiber specifically comprises the following steps:
s11, accurately weighing 1g of hafnium oxychloride octahydrate, dissolving in 10mL of deionized water, adding 10g of boric acid after complete dissolution, stirring at 100rpm for 10 hours, uniformly mixing, and regulating the pH to 3 to obtain transparent and clear ceramic fiber precursor solution;
s12, accurately weighing 3g of polyvinyl alcohol, dissolving in 10mL of ethanol water solution (v: v=2:10), slowly adding the ceramic fiber precursor solution prepared in the step S11, mixing at 100rpm for 10 hours, standing overnight at room temperature, and defoaming to obtain a ceramic fiber spinning solution with 30% of solid content;
s13, carrying out fiber spinning on the ceramic fiber spinning solution prepared in the step S12 by adopting a dry spinning method, wherein the initial temperature of the dry spinning is 55 ℃, the channel is gradually heated to 180 ℃, the channel length is 6m, the winding speed is 200m/min, and the obtained hafnium boride ceramic nascent fiber is placed in a baking oven at 40 ℃ for standby;
s21, soaking the hafnium boride ceramic nascent fiber prepared in the step S13 in a 30% sodium hydroxide solution, heating to 75 ℃ in a water bath, soaking for 3 hours, cooling the reaction system to room temperature, filtering, washing the ceramic fiber with deionized water, removing a solvent, and drying to obtain an activated hafnium boride fiber;
s31, accurately weighing 0.7g of polysilazane, dissolving in 113mL of n-butyl acetate to obtain a polysilazane solution with the mass fraction of 7%, soaking the activated hafnium boride fiber prepared in the step S21 in the polysilazane solution, performing ultrasonic treatment for 10min with ultrasonic power of 700W, filtering, removing excessive solvent, placing in a 130 ℃ oven for curing for 30min, transferring to a high-pressure reaction load after curing is completed, heating up in a nitrogen atmosphere according to 5 ℃/min, and preserving heat for 2h when heating up to 1700 ℃ to obtain the modified hafnium boride fiber.
The application also provides a preparation method of the hafnium boride-based high-temperature-resistant ceramic material, which specifically comprises the following steps:
(1) mixing modified hafnium boride fibers, zirconium carbide, silicon powder and carbon powder according to the weight ratio of 2:1.5:1, adding absolute ethyl alcohol and zirconia grinding balls, performing wet ball milling at 60rpm for 12 hours, removing the absolute ethyl alcohol, and drying to obtain a ceramic mixture;
(2) and (3) transferring the ceramic mixture prepared in the step (S11) into a reaction kettle, placing the reaction kettle in an environment of sealing, adjusting the pressure of the reaction kettle to 40MPa under the argon atmosphere, heating to 1850 ℃ according to 100 ℃/min, preserving heat for 20min, and naturally cooling to room temperature to obtain the high-temperature-resistant ceramic material.
Comparative example 1
This comparative example provides a hafnium boride ceramic material that differs from example 1 only in that: the preparation method of the hafnium boride fiber does not comprise the steps S21 and S31; the remaining components and the content of the components were the same as in example 1.
Comparative example 2
This comparative example provides a hafnium boride ceramic material, which differs from example 1 in that: the ceramic material does not include Si powder and C powder.
Experimental example 1
The present experimental example was conducted to determine the relative densities of the ceramic materials prepared in the examples and comparative examples by measuring the actual sintered density of the sample density by the archimedes' drainage method, calculating the theoretical density of the ceramic material by the law of mixing, and calculating the relative density of the ceramic material by the following formula:
；
FIG. 1 is a graph showing the relative density results of the ceramic materials prepared in examples and comparative examples, wherein the ceramic materials have a relative density of 93.36-95.22%, the ceramic materials prepared in comparative example 1 have a relative density of 81.58%, and the ceramic materials prepared in comparative example 2 have a relative density of 83.86%; in the ceramic material prepared in the example, hafnium boride fiber was modified by forming a surfaceThe polysilazane is combined, and in the subsequent sintering process, the polysilazane is converted into SiC and Si3N4, and simultaneously ZrC, si powder and C powder are matched, so that the polysilazane can be used in HfB 2 Forming smaller sized particles on the substrate, filling the HfB 2 And the sintering density is improved.
Experimental example 2
Experimental example the high temperature oxidation resistance of the ceramic materials prepared in examples 1 to 3 and comparative examples 1 and 2 was measured, and the ceramic materials prepared in examples 1 to 3 and comparative examples 1 and 2 were prepared into test pieces having parameters of 2 mm. Times.3 mm. Times.16 mm, and were placed in Al burned to constant weight 2 O 3 In the crucible, after the furnace temperature is raised to the target temperature, pushing the crucible into the furnace, keeping for 1h, taking out a sample, naturally cooling to room temperature in a dryer, weighing, and representing the oxidation resistance of the ceramic material by the oxidation weight loss rate of the sample, wherein the oxidation weight loss rate of the sample is calculated according to the following formula:
oxidation weight gain (%) = (mt-m 0)/m0×100%;
wherein m0 is the initial weight; mt is the weight at the time of sampling.
FIG. 2 is a graph showing the results of high-temperature oxidation resistance of the ceramic materials prepared in examples 1 to 3 and comparative examples 1 and 2 according to the present application, in which the oxidation weight gain of the ceramic materials prepared in examples 1 to 3 was maintained between 0.4% and 0.5% at 1500℃and the oxidation weight gain of the ceramic materials prepared in comparative example 1 was 1.86% at 1500℃and the oxidation weight gain of the ceramic materials prepared in comparative example 2 was 1.32% at 1500℃and the ceramic materials HfB capable of being filled were absent in comparative examples 1 and 2 2 The compactness of the ceramic material is poor due to the particles in the gaps, oxygen in the ceramic material is rapidly diffused in the high-temperature oxidation process, a large amount of oxide is generated, and the oxidation weight gain rate is obviously increased.
Experimental example 3
The ceramic materials prepared in examples 1 to 3 and comparative examples 1 and 2 were subjected to a water-oxygen corrosion treatment at 1200 ℃ for 100 hours according to water vapor: introducing oxygen into a tubular furnace at a flow rate of 85mL/min at an oxygen volume ratio of 1:1, maintaining the temperature of the tubular furnace at 1200 ℃, sampling at a temperature lower than that of the tubular furnace by 10h, 20h, 50h and 100h respectively, measuring the weight of a dried sample by using a high-precision analytical balance, and calculating the corrosion weight loss rate of the sample;
corrosion weight loss (%) = (M0-Mt)/m0×100%;
wherein M0 is the initial weight; mt is the weight at the time of sampling.
FIG. 3 is a graph showing the results of corrosion resistance of the ceramic materials of examples 1-3 and comparative examples 1 and 2, wherein the ceramic materials prepared in examples 1-3 have significantly higher resistance to water and oxygen corrosion than those of comparative examples 1 and 2, and the ceramic materials undergo oxidation reaction under high temperature and oxygen conditions to form SiO 2 ，SiO 2 React with water vapor to form Si (OH) which is a highly volatile material 4 Under the conditions of this experimental example, due to SiO 2 May cause an increase in the weight of the ceramic, with a decrease in weight as volatiles are formed; in the embodiment, the ceramic weight loss rate is low within 0-10 h, the corrosion weight loss rate is low within 10-20 h, and a large amount of SiO is generated 2 Forming volatile substances, so that the corrosion weight loss rate of the ceramic is rapidly improved, and the corrosion weight loss rate tends to be balanced after 20 hours, and is 11% -13% at 100 hours; the ceramic material in comparative example 1 has a rapid increase in corrosion weight loss rate within the initial 20 hours, reaching about 33% at 100 hours; the corrosion weight loss rate reaches about 21% at 100h in comparative example 2; in the embodiment, the refractory metal is used for doping silazane, and the Si loss in the ceramic matrix is less due to higher crosslinking degree, so that the corrosion resistance of the hafnium boride ceramic material is improved.
Experimental example 4
In this experimental example, the phase composition of the hafnium boride ceramic material prepared in example 1 was measured, and fig. 4 is an XRD pattern of the hafnium boride ceramic material prepared in example 1.
Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
The application and its embodiments have been described above with no limitation, and the application is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the application can be practiced without the specific details disclosed herein.
Claims (9)
1. A preparation method of a high-temperature resistant ceramic material based on hafnium boride is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) mixing the modified hafnium boride fiber, zirconium carbide, silicon powder and carbon powder, adding absolute ethyl alcohol, performing wet mixing ball milling treatment by using zirconium oxide grinding balls, removing the absolute ethyl alcohol, and drying to obtain a ceramic mixture;
(2) sealing the ceramic mixture prepared in the step (1) in a reaction kettle, and sintering under an argon atmosphere to obtain a high-temperature-resistant ceramic material;
in the step (1), the ceramic mixture comprises the following raw materials in parts by weight: 70-90 parts of modified hafnium boride fiber, 4.5-9 parts of zirconium carbide, 10-20 parts of silicon powder and 0.5-1 part of carbon powder;
in the step (1), the preparation method of the modified hafnium boride fiber comprises the following steps:
s1, preparing hafnium boride ceramic nascent fibers by adopting dry spinning;
s2, activating the primary hafnium boride ceramic fiber prepared in the step S1 by adopting an impregnation method to obtain an activated hafnium boride fiber;
s3, treating the activated hafnium boride fiber prepared in the step S2 with polysilazane solution to obtain the modified hafnium boride fiber.
2. The method for preparing a hafnium boride-based high temperature resistant ceramic material according to claim 1, wherein: in the step (1), the mass ratio of the ball water to the material is 2:1.5:1; the wet mixing ball milling time is 12 hours, and the ball milling rotating speed is 60rpm.
3. The method for preparing a hafnium boride-based high temperature resistant ceramic material according to claim 2, wherein: in the step (1), the preparation method of the modified hafnium boride fiber specifically comprises the following steps:
s11, dissolving hafnium oxychloride octahydrate and boric acid in deionized water, and regulating the pH to 2-3 to obtain a ceramic fiber precursor solution;
s12, mixing the ceramic fiber precursor solution prepared in the step S11 with a polyvinyl alcohol solution, standing overnight for defoaming to obtain a ceramic fiber spinning solution;
s13, carrying out dry spinning on the ceramic fiber spinning solution prepared in the step S12 to obtain hafnium boride ceramic nascent fibers;
s21, soaking the hafnium boride ceramic nascent fiber prepared in the step S13 in a sodium hydroxide solution, heating in a water bath at 70-80 ℃ for 2-3 hours, naturally cooling to room temperature, filtering, washing with deionized water, and drying to obtain an activated hafnium boride fiber;
s31, dissolving polysilazane in n-butyl acetate to obtain polysilazane solution, soaking the activated hafnium boride fiber prepared in the step S21 in the polysilazane solution, carrying out ultrasonic treatment, filtering, removing redundant solution, placing in an oven for curing at 120-140 ℃ for 30-40min, and sintering after curing is completed to obtain the modified hafnium boride fiber.
4. A method for preparing a hafnium boride-based refractory ceramic material according to claim 3, wherein: in the step S11, the mass ratio of the hafnium oxychloride octahydrate to the boric acid is 1-2:10; the mass fraction of the hafnium oxychloride octahydrate in deionized water is 0.1-0.15g/mL; the mass fraction of the boric acid in the deionized water is 0.5-1.5g/mL.
5. The method for producing a hafnium boride-based high temperature resistant ceramic material according to claim 4, wherein: in step S12, polyvinyl alcohol is dissolved in a mixed solution of ethanol and water to obtain a polyvinyl alcohol solution; the volume ratio of the ethanol to the water is 1-3:10; the mass fraction of the polyvinyl alcohol solution is 30-50%; the solid content of the ceramic fiber spinning solution is 30-35%.
6. The method for producing a hafnium boride-based high temperature resistant ceramic material according to claim 5, wherein: in the step S13, in dry spinning, the initial temperature of spinning is 50-55 ℃, and the temperature is gradually increased to 160-190 ℃; the length of the channel is 6m, and the winding speed is 200-210m/min.
7. The method for preparing a hafnium boride-based high temperature ceramic material according to claim 6, wherein: in step S21, the mass fraction of the sodium hydroxide solution is 25-35%.
8. The method for preparing a hafnium boride-based high temperature ceramic material according to claim 7, wherein: in step S31, the mass fraction of polysilazane in the polysilazane solution is 3-7%; during ultrasonic treatment, the ultrasonic power is 600-800W, and the ultrasonic time is 10-20min; in the sintering treatment, the sintering temperature is 1600-1800 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2h.
9. A hafnium boride-based high temperature ceramic material prepared by the method for preparing a hafnium boride-based high temperature ceramic material according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311483855.XA CN117209299B (en) | 2023-11-09 | 2023-11-09 | High-temperature-resistant ceramic material based on hafnium boride and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311483855.XA CN117209299B (en) | 2023-11-09 | 2023-11-09 | High-temperature-resistant ceramic material based on hafnium boride and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117209299A true CN117209299A (en) | 2023-12-12 |
| CN117209299B CN117209299B (en) | 2024-01-16 |
Family
ID=89051483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311483855.XA Active CN117209299B (en) | 2023-11-09 | 2023-11-09 | High-temperature-resistant ceramic material based on hafnium boride and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117209299B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117466662A (en) * | 2023-12-27 | 2024-01-30 | 之江实验室 | Preparation method of ultrahigh-temperature ceramic material with high bending strength and fracture toughness |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2140495A1 (en) * | 1994-01-21 | 1995-07-22 | Sankar Dasgupta | Ceramic Fibre and Process Therefor |
| US5443771A (en) * | 1992-09-15 | 1995-08-22 | Gupta; Sankar D. | Ceramic fibre and process therefor |
| US8409491B1 (en) * | 2007-09-28 | 2013-04-02 | The United States of America as represented by the Administrator of the National Aeronautics & Space Administration (NASA) | In-situ formation of reinforcement phases in ultra high temperature ceramic composites |
| US8562901B1 (en) * | 2008-08-25 | 2013-10-22 | The United States Of America As Represented By The Secretary Of The Air Force | Method of making crack-free ceramic matrix composites |
-
2023
- 2023-11-09 CN CN202311483855.XA patent/CN117209299B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5443771A (en) * | 1992-09-15 | 1995-08-22 | Gupta; Sankar D. | Ceramic fibre and process therefor |
| CA2140495A1 (en) * | 1994-01-21 | 1995-07-22 | Sankar Dasgupta | Ceramic Fibre and Process Therefor |
| US8409491B1 (en) * | 2007-09-28 | 2013-04-02 | The United States of America as represented by the Administrator of the National Aeronautics & Space Administration (NASA) | In-situ formation of reinforcement phases in ultra high temperature ceramic composites |
| US8562901B1 (en) * | 2008-08-25 | 2013-10-22 | The United States Of America As Represented By The Secretary Of The Air Force | Method of making crack-free ceramic matrix composites |
Non-Patent Citations (4)
| Title |
|---|
| AYASEELAN, D. D.等: "Microstructural evolution of HfB2 based ceramics during oxidation at 1600-2000°C", ADVANCES IN APPLIED CERAMICS, vol. 114, no. 5, pages 277 - 295 * |
| YUAN, JIA等: "Single-Source-Precursor Synthesis of Hafnium-Containing Ultrahigh-Temperature Ceramic Nanocomposites (UHTC-NCs)", INORGANIC CHEMISTRY, vol. 53, no. 19, pages 10443 - 10455 * |
| 孟祥利;崔红;闫联生;张强;宋麦丽;朱阳;: "基体改性C/C-HfC-HfB_2-SiC复合材料抗烧蚀性能研究", 中国材料进展, no. 11 * |
| 贾坤乐;张鑫;张思源;王彦军;: "硼化铪粉末制备研究", 热喷涂技术, no. 02 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117466662A (en) * | 2023-12-27 | 2024-01-30 | 之江实验室 | Preparation method of ultrahigh-temperature ceramic material with high bending strength and fracture toughness |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117209299B (en) | 2024-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117209299B (en) | High-temperature-resistant ceramic material based on hafnium boride and preparation method thereof | |
| CN106478105B (en) | A kind of method that multistep reaction sintering process prepares the thyrite of low residual silicon | |
| CN109437943B (en) | Cf/C-SiC-ZrB2Composite material and preparation method thereof | |
| JP4014254B2 (en) | Si concentration step-variable Si-SiC material, Si concentration step change-type SiC fiber reinforced Si-SiC composite material, and production method thereof | |
| CN112250450B (en) | Preparation method of heat insulation tile blank capable of resisting high temperature of 2000 DEG C | |
| CN112374917B (en) | High-temperature ceramic coating and preparation method thereof | |
| CN115124339B (en) | Multielement high entropy doped zirconia-based ceramic material and preparation method and application thereof | |
| CN106810285A (en) | A kind of preparation method of the carbon fiber-reinforced aluminium oxide ceramics of in-situ preparation | |
| CN106673708B (en) | A kind of method that surface of carbon/carbon composite prepares silicon carbide nanometer line porous layer | |
| WO2023103209A1 (en) | Preparation method for modified carbon fiber-toughened alumina self-healing ceramic | |
| CN106957179A (en) | A kind of SiBN fiber reinforcements SiO2‑BN‑Al2O3The preparation method of wave-penetrating composite material | |
| CN106220213A (en) | A kind of preparation method of carbon/ceramic composite material | |
| CN103755352B (en) | Preparation method of porous BN/Si3N4 composite ceramic hole sealing layer | |
| CN101734925B (en) | Silicon nitride porous ceramics with controllable porosity and preparation method thereof | |
| JPS63144172A (en) | Silicon nitride powder composition, preparation and manufacture of sintered products | |
| CN112279650A (en) | Preparation method of high-density silicon carbide ceramic composite material | |
| CN114956828B (en) | Silicon carbide ceramic and preparation method and application thereof | |
| JP2657838B2 (en) | Manufacturing method of silicon nitride products | |
| CN114656275B (en) | SiC preparation by vacuum impregnation combined with reaction melt infiltration f Method for preparing/Si-Y-B-C composite material | |
| CN108530104A (en) | PIP combinations growth in situ graphene/boron nitride nano-tube ceramic matric composite densifying method | |
| CN101734920B (en) | Titanium nitride porous ceramics and preparation method thereof | |
| JP4484004B2 (en) | Method for producing ceramic matrix composite member | |
| CN108774072B (en) | Rigid heat insulation tile and preparation method thereof | |
| CN108456004B (en) | Preparation method of carbon/carbon composite material surface composite ceramic coating | |
| CN115894085B (en) | Composite ceramic coating material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |