CN104230364A - Preparation process of rod-like ZrB2 toughened ZrB2-SiC ultrahigh-temperature ceramic - Google Patents
Preparation process of rod-like ZrB2 toughened ZrB2-SiC ultrahigh-temperature ceramic Download PDFInfo
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- CN104230364A CN104230364A CN201410467238.5A CN201410467238A CN104230364A CN 104230364 A CN104230364 A CN 104230364A CN 201410467238 A CN201410467238 A CN 201410467238A CN 104230364 A CN104230364 A CN 104230364A
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- zirconium boride
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Abstract
The invention provides a preparation process of a rod-like ZrB2 toughened ZrB2-SiC ultrahigh-temperature ceramic. The preparation process is characterized by comprising the following steps: (1) adding zirconium boride ceramic powder into a solvent, uniformly stirring, adding a bonder and a plasticizer, and stirring for the second time to form uniform ceramic suspension, wherein the zirconium boride ceramic powder is formed by mixing rod-like zirconium boride powder with silicon carbide powder according to a volume percent ratio of (70%-90%) to (10%-30%); (2) drying the ceramic suspension in vacuum by adopting a rotary evaporator to form mixed powder; (3) degreasing the mixed powder in vacuum in a graphite grinding tool, and during degreasing, heating to 600-700 DEG C at the speed of 1-3 DEG C/min and preserving heat for 0.5-1 hour; and (4) performing hot pressed sintering in an argon gas atmosphere at 1,900-2,000 DEG C under the pressure of 20-40MPa for 0.5-2 hours to obtain the rod-like ZrB2 toughened ZrB2-SiC ultrahigh-temperature ceramic. The preparation process is simple; the obtained ceramic material is relatively good in oxidative ablation resistance, remarkably improved in fracture toughness and good in processability.
Description
Technical field
The invention provides bar-shaped ZrB
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics, belongs to the preparing technical field of structural ceramics.
Background technology
ZrB
2pottery has superior high temperature resistant and corrosion resistance nature and relatively low theoretical density, to be therefore considered in superhigh temperature ceramics (UHTCs) family one of material having application prospect most always.At present, ZrB
2pottery has been widely used as various thermal structure and functional materials, as: the turbine blade in aircraft industry, magnetohydrodynamic generator electrode etc.But ZrB
2ceramics strength and fracture toughness property lower, limit its application under harsh operating environment, as supersonic aircraft nose cone and forward position, scramjet engine hot-end component etc.Therefore, in order to ensure reliability in use procedure and security, ZrB must be improved
2the brittleness problems of pottery, thus improve its thermal shock resistance.
Patent CN101250061B " preparation method of Zirconia toughened boride ultra-temperature ceramic-based composite material ", adopt Zirconia toughened boride, fracture toughness property reaches 6.0 ~ 6.8 MPam
1/2.
Patent CN2009100721324 " zirconium boride-carborundum-carbon black ternary high-toughness ultra-temperature ceramic-based composite material and preparation method thereof ", adopt the toughness reinforcing zirconium boride ultrahigh-temperature ceramic of graphite, its critical temperature difference is 470 ~ 1000 DEG C, and fracture toughness property reaches 2.01 ~ 6.57 MPam
1/2, thermal-shock resistance is improved significantly.
Patent CN101250061B " a kind of SiC whisker toughened ZrC-based ultra-high temperature ceramic composite material and preparation method thereof ", adopt the crystal whisker toughened ZrC superhigh temperature ceramics of SiC, flexural strength is 300 ~ 600 MPa, and fracture toughness property is 2 ~ 6MPam
1/2.
Patent CN101891480A " preparation method of zirconium boride-carborundum based stratiform ultrahigh temperature ceramic composite ", first prepares ZrB respectively
2-20%volSiC powder and ZrB
2-30%volSiC powder, then be alternately stacked in graphite grinding tool, base substrate precompressed, hot pressed sintering, both zirconium boride-carborundum based stratiform superhigh temperature ceramics, the single-phase ZrB of bending strength ratio
2-20%volSiC improves 1.57 ~ 2.36 times, and fracture toughness property improves 17 ~ 46%.
Document 1 " Qilong Guo, Junguo Li, Qiang Shen. Toughening of ZrB
2-SiC ceramics with the microstructure ZrB
2/ Zr-Al-C fibrous monolith. Scripta Mater., 2012,66:296-299 ", prepare ZrB
2-20vol%SiC-30vol%Zr-Al-C pottery.Because the stratiform Zr-Al-C particle of fabricated in situ is to the deflection of crackle, bridge joint and bifurcated, make ZrB
2-SiC/Zr-Al-C pottery demonstrates excellent fracture toughness property, and fracture toughness property reaches 5.4MPam
1/2.
ZrB conventional at present
2-SiC ceramic material method for toughening; One adds toughness reinforcing phase, namely in ceramic matrix, adds various mixture, as graphite, boron nitride, fiber and metastable state zirconium white etc.One changes SiC granule-morphology, as SiC whisker, nano SiC.
And by changing zirconium boride powder pattern, preparing zirconium boride-carborundum superhigh temperature ceramics and having no report.
Summary of the invention
The object of the invention is the problem in order to solve existing zirconium boride ultrahigh-temperature ceramic poor toughness, and bar-shaped ZrB is provided
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics.Its technical scheme is:
Bar-shaped ZrB
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics, is characterized in that adopting following steps:
1) first zirconium boride ceramic powder is added in solvent, zirconium boride ceramic powder by bar-shaped zirconium boride 99.5004323A8ure powder and silicon carbide powder by volume per-cent 70 ~ 90%:10 ~ 30% mix, add binding agent and softening agent after stirring, secondary stirring forms uniform ceramic suspension liquid;
2) adopt rotatory evaporator ceramic suspension liquid to be carried out vacuum-drying and form powder mix;
3) powder mix is put into graphite grinding tool, vacuum degreasing, during degreasing, heat-up rate is 1 ~ 3 DEG C/min, is warming up to 600 ~ 700 DEG C, insulation 0.5 ~ 1h;
4) hot pressed sintering under an argon atmosphere, sintering temperature is 1900 ~ 2000 DEG C, and insulation 0.5 ~ 2h, pressure is 20 ~ 40 MPa, obtains bar-shaped ZrB
2toughness reinforcing ZrB
2-SiC superhigh temperature ceramics.
Described bar-shaped ZrB
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics, in step 1), in zirconium boride ceramic powder, the diameter of bar-shaped zirconium boride 99.5004323A8ure powder is 0.5 ~ 2 μm, and length is 3 ~ 10 μm, and the particle diameter of silicon carbide powder is 0.5 ~ 2 μm.
Described bar-shaped ZrB
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics, calculates based on zirconium boride ceramic powder weight, takes binding agent 2 ~ 5%, softening agent 2 ~ 5% and solvent 100 ~ 300% by weight percentage.
Described bar-shaped ZrB
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics, binding agent adopts polyvinyl butyral acetal; Softening agent adopts one or both the mixing in polyoxyethylene glycol and polyvinyl alcohol; Solvent adopts dehydrated alcohol.
compared with prior art, tool has the following advantages in the present invention:
1, at the ZrB that the present invention obtains
2-SiC superhigh temperature ceramics, does not add the toughness reinforcing phases such as graphite, boron nitride, aluminium nitride, material is had good anti-oxidant ablative;
2, at the ZrB that the present invention obtains
2-SiC superhigh temperature ceramics, ZrB
2particle is bar-shaped, in hot pressing, has preferred orientation, bar-shapedly in pressurized process, is conducive to crack deflection perpendicular to hot pressing direction, improves fracture toughness property;
3, at the ZrB that the present invention obtains
2-SiC superhigh temperature ceramics, having can electroconductibility, and be conducive to linear cutter, workability is strong.
Embodiment
Embodiment 1
1) the bar-shaped zirconium boride 99.5004323A8ure powder of 425.6 grams and the silicon carbide powder of 96 grams is taken, i.e. bar-shaped zirconium boride 99.5004323A8ure powder and silicon carbide powder by volume per-cent 70%:30%, the diameter of bar-shaped zirconium boride 99.5004323A8ure powder is 0.5 μm, length is 3 μm, the particle diameter of silicon carbide powder is 0.5 μm, add 521.6 grams of dehydrated alcohols, add binding agent and softening agent after stirring, binding agent is 10.4 grams of polyvinyl butyral acetals; 10.4 grams of softening agent are polyoxyethylene glycol, and secondary stirring forms uniform ceramic suspension liquid;
2) adopt rotatory evaporator ceramic suspension liquid to be carried out vacuum-drying and form powder mix;
3) powder mix is put into graphite grinding tool, vacuum degreasing, during degreasing, heat-up rate is 1 DEG C/min, is warming up to 600 DEG C, insulation 1h;
4) hot pressed sintering under an argon atmosphere, sintering temperature is 1900 DEG C, and insulation 2h, pressure is 40 MPa, obtains bar-shaped ZrB
2toughness reinforcing ZrB
2-SiC superhigh temperature ceramics.
Embodiment 2
1) the bar-shaped zirconium boride 99.5004323A8ure powder of 547.2 grams and the silicon carbide powder of 32 grams is taken, namely bar-shaped zirconium boride 99.5004323A8ure powder and silicon carbide powder by volume per-cent 90%:10% mix, the diameter of bar-shaped zirconium boride 99.5004323A8ure powder is 2 μm, length is 10 μm, the particle diameter of silicon carbide powder is 2 μm, add 1737.6 grams of dehydrated alcohols, add binding agent and softening agent after stirring, binding agent is 29 grams of polyvinyl butyral acetals; Softening agent is 29 grams of polyvinyl alcohol, and secondary stirring forms uniform ceramic suspension liquid;
2) adopt rotatory evaporator ceramic suspension liquid to be carried out vacuum-drying and form powder mix;
3) powder mix is put into graphite grinding tool, vacuum degreasing, during degreasing, heat-up rate is 3 DEG C/min, is warming up to 700 DEG C, insulation 0.5h;
4) hot pressed sintering under an argon atmosphere, sintering temperature is 2000 DEG C, and insulation 0.5h, pressure is 20MPa, obtains bar-shaped ZrB
2toughness reinforcing ZrB
2-SiC superhigh temperature ceramics.
Embodiment 3
1) the bar-shaped zirconium boride 99.5004323A8ure powder of 486.4 grams and the silicon carbide powder of 64 grams is taken, namely bar-shaped zirconium boride 99.5004323A8ure powder and silicon carbide powder by volume per-cent 80%:20% mix, the diameter of bar-shaped zirconium boride 99.5004323A8ure powder is 1 μm, length is 5 μm, the particle diameter of silicon carbide powder is 1 μm, add the dehydrated alcohol of 1100.8 grams, add binding agent and softening agent after stirring, binding agent is polyvinyl butyral acetal; Softening agent is the mixing of polyoxyethylene glycol and polyvinyl alcohol, and take the polyvinyl butyral acetal of 22 grams, the polyoxyethylene glycol of 11 grams, the polyvinyl alcohol of 11 grams, secondary stirring forms uniform ceramic suspension liquid;
2) adopt rotatory evaporator ceramic suspension liquid to be carried out vacuum-drying and form powder mix;
3) powder mix is put into graphite grinding tool, vacuum degreasing, during degreasing, heat-up rate is 2 DEG C/min, is warming up to 650 DEG C, insulation 1h;
4) hot pressed sintering under an argon atmosphere, sintering temperature is 1950 DEG C, and insulation 1h, pressure is 30 MPa, obtains bar-shaped ZrB
2toughness reinforcing ZrB
2-SiC superhigh temperature ceramics.
Embodiment 4
1) the bar-shaped zirconium boride 99.5004323A8ure powder of 486.4 grams and the silicon carbide powder of 64 grams is taken, namely bar-shaped zirconium boride 99.5004323A8ure powder and silicon carbide powder by volume per-cent 80%:20% mix, the diameter of bar-shaped zirconium boride 99.5004323A8ure powder is 1 μm, length is 10 μm, the particle diameter of silicon carbide powder is 0.5 μm, add the dehydrated alcohol of 825.6 grams, add binding agent and softening agent after stirring, binding agent adopts polyvinyl butyral acetal; Softening agent adopts the mixing in polyoxyethylene glycol and polyvinyl alcohol, calculates based on zirconium boride ceramic powder weight, and take 27.5 grams of polyvinyl butyral acetals, the polyoxyethylene glycol of 11 grams, 11 grams of polyvinyl alcohol, secondary stirring forms uniform ceramic suspension liquid;
2) adopt rotatory evaporator ceramic suspension liquid to be carried out vacuum-drying and form powder mix;
3) powder mix is put into graphite grinding tool, vacuum degreasing, during degreasing, heat-up rate is 2 DEG C/min, is warming up to 700 DEG C, insulation 0.7h;
4) hot pressed sintering under an argon atmosphere, sintering temperature is 2000 DEG C, and insulation 1h, pressure is 40MPa, obtains bar-shaped ZrB
2toughness reinforcing ZrB
2-SiC superhigh temperature ceramics.
Claims (4)
1. bar-shaped ZrB
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics, is characterized in that adopting following steps:
1) first zirconium boride ceramic powder is added in solvent, zirconium boride ceramic powder by bar-shaped zirconium boride 99.5004323A8ure powder and silicon carbide powder by volume per-cent 70 ~ 90%:10 ~ 30% mix, add binding agent and softening agent after stirring, secondary stirring forms uniform ceramic suspension liquid;
2) adopt rotatory evaporator ceramic suspension liquid to be carried out vacuum-drying and form powder mix;
3) powder mix is put into graphite grinding tool, vacuum degreasing, during degreasing, heat-up rate is 1 ~ 3 DEG C/min, is warming up to 600 ~ 700 DEG C, insulation 0.5 ~ 1h;
4) hot pressed sintering under an argon atmosphere, sintering temperature is 1900 ~ 2000 DEG C, and insulation 0.5 ~ 2h, pressure is 20 ~ 40 MPa, obtains bar-shaped ZrB
2toughness reinforcing ZrB
2-SiC superhigh temperature ceramics.
2. bar-shaped ZrB as claimed in claim 1
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics, is characterized in that: in step 1), and in zirconium boride ceramic powder, the diameter of bar-shaped zirconium boride 99.5004323A8ure powder is 0.5 ~ 2 μm, and length is 3 ~ 10 μm, and the particle diameter of silicon carbide powder is 0.5 ~ 2 μm.
3. bar-shaped ZrB as claimed in claim 1
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics, is characterized in that: in step 1), calculates based on zirconium boride ceramic powder weight, takes binding agent 2 ~ 5%, softening agent 2 ~ 5% and solvent 100 ~ 300% by weight percentage.
4. the bar-shaped ZrB as described in claim 1 and 3
2toughness reinforcing ZrB
2the preparation technology of-SiC superhigh temperature ceramics, is characterized in that: binding agent adopts polyvinyl butyral acetal; Softening agent adopts one or both the mixing in polyoxyethylene glycol and polyvinyl alcohol; Solvent adopts dehydrated alcohol.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272267A (en) * | 2015-10-19 | 2016-01-27 | 山东理工大学 | Preparation technology of intragranular ZrB2 based UHTCs (ultra-high temperature ceramics) |
| CN106478110A (en) * | 2016-10-12 | 2017-03-08 | 黑龙江科技大学 | A kind of ZrB2The preparation method of SiC composite ceramicses |
| CN106830954A (en) * | 2017-02-20 | 2017-06-13 | 南通美铭锦纶有限公司 | Superhigh temperature anti-yaw damper C/C SiC ZrB2 intelligent composites |
| CN108585889A (en) * | 2018-04-28 | 2018-09-28 | 武汉科技大学 | A kind of rodlike zirconium boride-sheet-shaped silicon carbide monocrystalline composite granule and preparation method thereof |
| CN109369190A (en) * | 2018-11-13 | 2019-02-22 | 广东工业大学 | A kind of high-fracture toughness ZrB2SiC ceramic and its preparation method and application |
| CN113880583A (en) * | 2021-10-15 | 2022-01-04 | 山东鹏程陶瓷新材料科技有限公司 | Preparation method of high-performance zirconium boride-silicon carbide composite ceramic electrode |
| CN114933484A (en) * | 2022-06-14 | 2022-08-23 | 武汉科技大学 | Toughened SiC-based high-temperature ceramic composite material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272267A (en) * | 2015-10-19 | 2016-01-27 | 山东理工大学 | Preparation technology of intragranular ZrB2 based UHTCs (ultra-high temperature ceramics) |
| CN106478110A (en) * | 2016-10-12 | 2017-03-08 | 黑龙江科技大学 | A kind of ZrB2The preparation method of SiC composite ceramicses |
| CN106830954A (en) * | 2017-02-20 | 2017-06-13 | 南通美铭锦纶有限公司 | Superhigh temperature anti-yaw damper C/C SiC ZrB2 intelligent composites |
| CN108585889A (en) * | 2018-04-28 | 2018-09-28 | 武汉科技大学 | A kind of rodlike zirconium boride-sheet-shaped silicon carbide monocrystalline composite granule and preparation method thereof |
| CN109369190A (en) * | 2018-11-13 | 2019-02-22 | 广东工业大学 | A kind of high-fracture toughness ZrB2SiC ceramic and its preparation method and application |
| CN109369190B (en) * | 2018-11-13 | 2021-11-19 | 广东工业大学 | High-fracture toughness ZrB2-SiC ceramic and preparation method and application thereof |
| CN113880583A (en) * | 2021-10-15 | 2022-01-04 | 山东鹏程陶瓷新材料科技有限公司 | Preparation method of high-performance zirconium boride-silicon carbide composite ceramic electrode |
| CN114933484A (en) * | 2022-06-14 | 2022-08-23 | 武汉科技大学 | Toughened SiC-based high-temperature ceramic composite material and preparation method thereof |
| CN114933484B (en) * | 2022-06-14 | 2023-08-18 | 武汉科技大学 | Toughened SiC-based high-temperature ceramic composite material and preparation method thereof |
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