CN116693287A - High-entropy perovskite zirconate ceramic and preparation method thereof - Google Patents
High-entropy perovskite zirconate ceramic and preparation method thereof Download PDFInfo
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- CN116693287A CN116693287A CN202310642576.7A CN202310642576A CN116693287A CN 116693287 A CN116693287 A CN 116693287A CN 202310642576 A CN202310642576 A CN 202310642576A CN 116693287 A CN116693287 A CN 116693287A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 49
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000498 ball milling Methods 0.000 claims abstract description 45
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 36
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 18
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims abstract description 18
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 239000003292 glue Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052727 yttrium Inorganic materials 0.000 claims description 14
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- 229910021523 barium zirconate Inorganic materials 0.000 description 3
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention relates to a high-entropy perovskite type zirconate ceramic and a preparation method thereof. The technical proposal is as follows: mixing materials according to the molar ratio of barium carbonate to strontium carbonate to calcium carbonate to lanthanum oxide to zirconium dioxide of 0.25 to (0.1-0.4) to (0.05-0.2) to 1, performing wet ball milling, drying and crushing to obtain powder I; calcining the powder I at 1100-1300 ℃ for 1-3 h, crushing and grinding to obtain powder II; mixing the powder II with 5wt% polyvinyl alcohol solution, granulating, standing, and performing mechanical press molding under the condition of 50-150 MPa; heating the formed green body to 500-650 ℃ at the speed of 4-5 ℃/min, discharging glue for 2-5 h at the temperature of 500-650 ℃, heating at the same speed, and sintering for 3-5 h at the temperature of 1400-1600 ℃ to obtain the high-entropy perovskite zirconate ceramic. The invention has the characteristics of low sintering temperature, short production period and simple process, and the prepared high-entropy perovskite zirconate ceramic has the characteristics of low heat conductivity, high density and excellent mechanical property.
Description
Technical Field
The invention belongs to the technical field of zirconate ceramics. In particular to a high-entropy perovskite type zirconate ceramic and a preparation method thereof.
Background
Among perovskite ceramics, perovskite zirconates generally have a relatively high melting point (2200 ℃ to 2700 ℃) and a relatively low chemical compositionThe reaction activation energy, the good thermal shock resistance and the excellent corrosion resistance are widely applied to the aspects of ceramics, refractory materials and the like. But has a relatively high thermal conductivity (2.1 to 5.3Wm -1 K -1 ) Limiting its application.
The literature (RostCM, sachetE, bormanT, et al, entry-stabilizerxides [ J ]. Nature communications,2015,6 (1): 8485.) successfully synthesized high entropy ceramic oxides having excellent electrical properties and having a single-phase rock salt structure, expanding a new direction for the preparation of inorganic nonmetallic ceramics.
The patent technology of 'preparation method of high-density barium zirconate ceramic' (CN 201410088274.0) discloses a preparation method of dense barium zirconate ceramic, which takes commercial barium zirconate powder as a raw material, and the preparation method is characterized in that the firing temperature in the preparation process is higher than 1600 ℃, the heat preservation time is longer than 12 hours, and the preparation period is longer.
The technology of the patent (CN 201910496315.2) is to prepare a solid solution ceramic material which is nearly single phase at the temperature exceeding 1600 ℃. But the compactness is only 94% -98% and the performance is not further described.
There is literature (Chen Guangyao, li Bao, same, gao Peng, et al, caO-doped vs. BaZrO 3 Crucible preparation and Effect of interfacial reaction with titanium alloy [ J]Silicate journal, 2017,45 (9): 1354-1359.) to produce BaZrO 3 The relative density of the crucible is 97.1%, and after CaO doping, the relative density of the crucible is increased to 98.5%. Although CaO is added to help BaZrO 3 Densification of the crucible is still not high enough.
The perovskite type zirconate ceramics have the problems that: high firing temperature, long heat preservation time, lower density and poorer mechanical property.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and aims to provide a preparation method of high-entropy perovskite zirconate ceramic with simple process, low sintering temperature, low cost and short heat preservation time.
In order to achieve the above purpose, the technical scheme adopted by the invention comprises the following specific steps:
firstly, weighing barium carbonate, strontium carbonate, calcium carbonate, lanthanum oxide and zirconium dioxide according to the molar ratio of 0.25:0.25:0.1-0.4:0.05-0.2:1 to obtain raw materials; and ball milling, drying and crushing the raw materials by adopting a wet method to obtain powder I.
Step two, heating the powder I to 1100-1300 ℃ at a speed of 4-7 ℃/min, calcining for 1-3 h, and cooling along with a furnace to obtain a block; crushing and grinding the block to obtain powder II.
And thirdly, mixing materials according to the mass ratio of the powder II to the polyvinyl alcohol solution of 5wt% of 1:0.02-0.05, granulating, and standing for 12-15 h to obtain the high-entropy perovskite zirconate ceramic powder.
And fourthly, mechanically pressing and forming the high-entropy perovskite type zirconate ceramic powder under the condition of 50-150 MPa to obtain a high-entropy perovskite type zirconate ceramic blank.
Step five, placing the high-entropy perovskite type zirconate ceramic blank in a high-temperature furnace under the air atmosphere and normal pressure, heating to 500-650 ℃ at the speed of 4-5 ℃/min, and discharging glue for 2-5 h under the condition of 500-650 ℃; and then continuously heating to 1400-1600 ℃ at the speed of 4-5 ℃/min under the air atmosphere and normal pressure condition, sintering for 3-5 h, and cooling along with the furnace to obtain the high-entropy perovskite zirconate ceramic.
The purity of the barium carbonate is more than 99.0 percent, and the particle size of the barium carbonate is less than 10 mu m.
The purity of the strontium carbonate is more than 99.0 percent, and the particle size of the strontium carbonate is less than 10 mu m.
The purity of the calcium carbonate is more than 99.0 percent, and the particle size of the calcium carbonate is less than 10 mu m.
The purity of the lanthanum oxide is more than 99.0 percent, and the particle size of the lanthanum oxide is less than 10 mu m.
The purity of the zirconium dioxide is more than 99.0 percent, and the grain size of the zirconium dioxide is less than 8 mu m.
The wet ball milling is as follows: the yttrium stable zirconia balls are used as ball milling media, deionized water is used as ball milling solvent, the mass ratio of the raw materials to the yttrium stable zirconia balls to the deionized water is 2:1:1 (1.9-2.1), and ball milling is carried out for 2-3 hours under the condition that the ball milling rotating speed is 200-400 rpm.
The drying is carried out for 12-15 h under the condition of 100-120 ℃.
By adopting the technical scheme, compared with the prior art, the invention has the following positive effects:
1. the invention takes barium carbonate, strontium carbonate, calcium carbonate, lanthanum oxide and zirconium dioxide as raw materials, and the raw materials are easy to obtain; uniformly mixing the raw materials through wet ball milling, and calcining to obtain high-entropy perovskite zirconate ceramic powder II; the high-entropy perovskite type zirconate ceramic is prepared by adopting a simple mechanical press forming and air atmosphere sintering process. The invention has lower requirements on equipment, does not need excessively high sintering temperature and excessively long heat preservation time, and has low cost, simple process and short production period; does not generate toxic and harmful gas, and is environment-friendly.
2. The invention adjusts the proportion of barium, strontium, calcium and lanthanum by dissolving barium, strontium, calcium and lanthanum, based on the high entropy effect, effectively reduces the firing temperature of the high entropy perovskite zirconate ceramic, forms a single solid solution, and reduces the thermal conductivity compared with the conventional perovskite zirconate material. The modification technology based on the solid solution system improves the density and mechanical property of the high-entropy perovskite zirconate ceramic product, and expands the application field of the high-entropy perovskite zirconate ceramic.
The high-entropy perovskite zirconate ceramic prepared by the invention is detected by the following steps: the density is 99.18 to 99.82 percent; the heat conductivity is 0.72-1.12 Wm -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the The flexural strength is 93.4-132.5 MPa.
Therefore, the invention has simple process, low requirements on equipment and low sintering temperature. The prepared high-entropy perovskite zirconate ceramic has high density, low heat conductivity and excellent mechanical property, and simultaneously expands the application field of the high-entropy perovskite zirconate ceramic.
Drawings
FIG. 1 is a phase composition diagram of a high entropy perovskite zirconate ceramic prepared by the invention.
Detailed Description
The invention is further described in connection with the drawings and the detailed description which follow, without limiting the scope of the invention.
A high-entropy perovskite zirconate ceramic and a preparation method thereof. The preparation method of the specific embodiment comprises the following steps:
firstly, weighing barium carbonate, strontium carbonate, calcium carbonate, lanthanum oxide and zirconium dioxide according to the molar ratio of 0.25:0.25:0.1-0.4:0.05-0.2:1 to obtain raw materials; and ball milling, drying and crushing the raw materials by adopting a wet method to obtain powder I.
Step two, heating the powder I to 1100-1300 ℃ at a speed of 4-7 ℃/min, calcining for 1-3 h, and cooling along with a furnace to obtain a block; crushing and grinding the block to obtain powder II.
And thirdly, mixing materials according to the mass ratio of the powder II to the polyvinyl alcohol solution of 5wt% of 1:0.02-0.05, granulating, and standing for 12-15 h to obtain the high-entropy perovskite zirconate ceramic powder.
And fourthly, mechanically pressing and forming the high-entropy perovskite type zirconate ceramic powder under the condition of 50-150 MPa to obtain a high-entropy perovskite type zirconate ceramic blank.
Step five, placing the high-entropy perovskite type zirconate ceramic blank in a high-temperature furnace under the air atmosphere and normal pressure, heating to 500-650 ℃ at the speed of 4-5 ℃/min, and discharging glue for 2-5 h under the condition of 500-650 ℃; and then continuously heating to 1400-1600 ℃ at the speed of 4-5 ℃/min under the air atmosphere and normal pressure condition, sintering for 3-5 h, and cooling along with the furnace to obtain the high-entropy perovskite zirconate ceramic.
The wet ball milling is as follows: the yttrium stable zirconia balls are used as ball milling media, deionized water is used as ball milling solvent, the mass ratio of the raw materials to the yttrium stable zirconia balls to the deionized water is 2:1:1 (1.9-2.1), and ball milling is carried out for 2-3 hours under the condition that the ball milling rotating speed is 200-400 rpm.
The drying is carried out for 12-15 h under the condition of 100-120 ℃.
In this embodiment:
the purity of the barium carbonate is more than 99.0%, and the particle size of the barium carbonate is less than 10 mu m;
the purity of the strontium carbonate is more than 99.0 percent, and the particle size of the strontium carbonate is less than 10 mu m;
the purity of the calcium carbonate is more than 99.0 percent, and the particle size of the calcium carbonate is less than 10 mu m;
the purity of the lanthanum oxide is more than 99.0%, and the particle size of the lanthanum oxide is less than 10 mu m;
the purity of the zirconium dioxide is more than 99.0 percent, and the grain size of the zirconium dioxide is less than 8 mu m.
The embodiments are not described in detail.
Example 1
A high-entropy perovskite zirconate ceramic and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, weighing barium carbonate, strontium carbonate, calcium carbonate, lanthanum oxide and zirconium dioxide according to the molar ratio of 0.25:0.25:0.30:0.10:1 of barium carbonate to strontium carbonate to calcium carbonate to lanthanum oxide to zirconium dioxide to obtain raw materials; and ball milling, drying and crushing the raw materials by adopting a wet method to obtain powder I.
Step two, heating the powder I to 1100 ℃ at a speed of 4 ℃/min, calcining for 1h, and cooling with a furnace to obtain a block; crushing and grinding the block to obtain powder II.
And thirdly, mixing materials according to the mass ratio of the powder II to the polyvinyl alcohol solution of 5wt% of 1:0.02, granulating, and standing for 12 hours to obtain the high-entropy perovskite zirconate ceramic powder.
And fourthly, mechanically pressing and forming the high-entropy perovskite type zirconate ceramic powder under the condition of 50MPa to obtain a high-entropy perovskite type zirconate ceramic blank.
Step five, placing the high-entropy perovskite type zirconate ceramic blank in a high-temperature furnace under the air atmosphere and normal pressure, heating to 500 ℃ at the speed of 4 ℃/min, and discharging glue for 2 hours under the condition of 500 ℃; and then continuously heating to 1400 ℃ at the speed of 4 ℃/min under the air atmosphere and normal pressure condition, sintering for 3 hours, and cooling along with the furnace to obtain the high-entropy perovskite zirconate ceramic.
The wet ball milling is as follows: the yttrium stable zirconia balls are used as ball milling media, deionized water is used as ball milling solvent, the mass ratio of the raw materials to the yttrium stable zirconia balls to the deionized water is 2:1:1.9, and ball milling is carried out for 2 hours under the condition of 200rpm of ball milling rotating speed.
The drying is carried out at a temperature of 100 ℃ for 12 hours.
The high-entropy perovskite zirconate ceramic prepared by the invention is detected by the following steps: the density is 99.18%; thermal conductivity of 0.72Wm -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the The flexural strength is 93.4MPa.
Example 2
A high-entropy perovskite zirconate ceramic and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, weighing barium carbonate, strontium carbonate, calcium carbonate, lanthanum oxide and zirconium dioxide according to the molar ratio of 0.25:0.25:0.25:0.125:1 to obtain raw materials; and ball milling, drying and crushing the raw materials by adopting a wet method to obtain powder I.
Step two, heating the powder I to 1200 ℃ at a speed of 5 ℃/min, calcining for 2 hours, and cooling along with a furnace to obtain a block; crushing and grinding the block to obtain powder II.
And thirdly, mixing materials according to the mass ratio of the powder II to the polyvinyl alcohol solution of 5wt% of 1:0.03, granulating, and standing for 13 hours to obtain the high-entropy perovskite zirconate ceramic powder.
And fourthly, mechanically pressing and forming the high-entropy perovskite type zirconate ceramic powder under the condition of 80MPa to obtain a high-entropy perovskite type zirconate ceramic blank.
Step five, placing the high-entropy perovskite type zirconate ceramic blank in a high-temperature furnace under the air atmosphere and normal pressure, heating to 550 ℃ at the speed of 4 ℃/min, and discharging glue for 3 hours under the condition of 550 ℃; and then continuously heating to 1500 ℃ at the speed of 4 ℃/min under the air atmosphere and normal pressure condition, sintering for 3 hours, and cooling along with the furnace to obtain the high-entropy perovskite zirconate ceramic.
The wet ball milling is as follows: the yttrium stable zirconia balls are used as ball milling media, deionized water is used as ball milling solvent, the mass ratio of the raw materials to the yttrium stable zirconia balls to the deionized water is 2:1:1.95, and ball milling is carried out for 3 hours under the condition of 300rpm of ball milling rotating speed.
The drying is carried out at 110 ℃ for 13 hours.
The high-entropy perovskite zirconate ceramic prepared by the invention is detected by the following steps: the density is 99.26%; thermal conductivity of 0.84Wm -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the The flexural strength is 132.5MPa.
Example 3
A high-entropy perovskite zirconate ceramic and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, weighing barium carbonate, strontium carbonate, calcium carbonate, lanthanum oxide and zirconium dioxide according to the molar ratio of 0.25:0.25:0.1:0.2:1 to obtain raw materials; and ball milling, drying and crushing the raw materials by adopting a wet method to obtain powder I.
Step two, heating the powder I to 1250 ℃ at a speed of 6 ℃/min, calcining for 2.5h, and cooling with a furnace to obtain a block; crushing and grinding the block to obtain powder II.
And thirdly, mixing materials according to the mass ratio of the powder II to the polyvinyl alcohol solution of 5wt% of 1:0.04, granulating, and standing for 14 hours to obtain the high-entropy perovskite zirconate ceramic powder.
And fourthly, mechanically pressing and forming the high-entropy perovskite type zirconate ceramic powder under the condition of 100MPa to obtain a high-entropy perovskite type zirconate ceramic blank.
Step five, placing the high-entropy perovskite type zirconate ceramic blank in a high-temperature furnace under the air atmosphere and normal pressure, heating to 600 ℃ at a speed of 5 ℃/min, and discharging glue for 4 hours under the condition of 600 ℃; and then continuously heating to 1550 ℃ at a speed of 5 ℃/min under the air atmosphere and normal pressure, sintering for 4 hours, and cooling along with a furnace to obtain the high-entropy perovskite zirconate ceramic.
The wet ball milling is as follows: the yttrium stable zirconia balls are used as ball milling media, deionized water is used as ball milling solvent, the mass ratio of the raw materials to the yttrium stable zirconia balls to the deionized water is 2:1:2, and ball milling is carried out for 2 hours under the condition of 300rpm of ball milling rotating speed.
The drying is carried out at 110 ℃ for 14 hours.
The high-entropy perovskite zirconate ceramic prepared by the invention is detected by the following steps: the density is 99.46%; thermal conductivity of 0.74Wm -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the The flexural strength is 110.5MPa.
Example 4
A high-entropy perovskite zirconate ceramic and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, weighing barium carbonate, strontium carbonate, calcium carbonate, lanthanum oxide and zirconium dioxide according to the molar ratio of 0.25:0.25:0.4:0.05:1 of barium carbonate to strontium carbonate to calcium carbonate to lanthanum oxide to zirconium dioxide to obtain raw materials; and ball milling, drying and crushing the raw materials by adopting a wet method to obtain powder I.
Step two, heating the powder I to 1300 ℃ at a speed of 7 ℃/min, calcining for 3 hours, and cooling along with a furnace to obtain a block; crushing and grinding the block to obtain powder II.
And thirdly, mixing materials according to the mass ratio of the powder II to the polyvinyl alcohol solution of 5wt% of 1:0.05, granulating, and standing for 15 hours to obtain the high-entropy perovskite zirconate ceramic powder.
And fourthly, mechanically pressing and forming the high-entropy perovskite type zirconate ceramic powder under the condition of 150MPa to obtain a high-entropy perovskite type zirconate ceramic blank.
Step five, placing the high-entropy perovskite type zirconate ceramic blank in a high-temperature furnace under the air atmosphere and normal pressure, heating to 650 ℃ at a speed of 5 ℃/min, and discharging glue for 5 hours under the condition of 650 ℃; and then continuously heating to 1600 ℃ at a speed of 5 ℃/min under the air atmosphere and normal pressure condition, sintering for 5 hours, and cooling along with a furnace to obtain the high-entropy perovskite zirconate ceramic.
The wet ball milling is as follows: the yttrium stable zirconia balls are used as ball milling media, deionized water is used as ball milling solvent, the mass ratio of the raw materials to the yttrium stable zirconia balls to the deionized water is 2:1:2.1, and ball milling is carried out for 3 hours under the condition of 400rpm of ball milling rotating speed.
The drying is carried out at 120 ℃ for 15 hours.
The high-entropy perovskite zirconate ceramic prepared by the invention is detected by the following steps: the density is 99.82%; thermal conductivity of 1.12Wm -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the The flexural strength is 108.4MPa.
Compared with the prior art, the specific embodiment has the following positive effects:
1. the method takes barium carbonate, strontium carbonate, calcium carbonate, lanthanum oxide and zirconium dioxide as raw materials, the raw materials are easy to obtain, the raw materials are uniformly mixed by ball milling, and the high-entropy perovskite zirconate ceramic powder II is prepared after calcination; the simple mechanical press forming and air atmosphere sintering process is adopted, so that the requirements on equipment are low; the method does not need too high sintering temperature and too long heat preservation time, and has simple process and short production period; does not generate toxic and harmful gas, and is environment-friendly.
2. The invention adjusts the proportion of barium, strontium, calcium and lanthanum by dissolving barium, strontium, calcium and lanthanum, based on the high entropy effect, effectively reduces the firing temperature of the high entropy perovskite zirconate ceramic, forms a single solid solution, and reduces the thermal conductivity compared with the conventional perovskite zirconate material. The density and mechanical property of the zirconate ceramic product are improved based on the material preparation modification technology related to the solid solution system, and the application field of the high-entropy perovskite type zirconate ceramic is expanded. The high-entropy perovskite zirconate ceramic prepared by the invention is shown in the accompanying drawing, and fig. 1 is a phase composition diagram of the high-entropy perovskite zirconate ceramic prepared in example 2. As can be seen from fig. 1: the prepared high-entropy perovskite type zirconate ceramic presents a single-phase structure and has no other substances.
The high-entropy perovskite zirconate ceramic prepared by the invention is detected by the following steps: the density is 99.18-99.82%: the heat conductivity is 0.72-1.12 Wm -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the The flexural strength is 93.4-132.5 MPa.
Therefore, the invention has simple process, low requirements on equipment, low firing temperature and short heat preservation time, and the prepared high-entropy perovskite zirconate ceramic has high density, low heat conductivity and excellent mechanical property, and simultaneously expands the application field of the high-entropy perovskite zirconate ceramic.
Claims (9)
1. The preparation method of the high-entropy perovskite zirconate ceramic is characterized by comprising the following steps of:
firstly, weighing barium carbonate, strontium carbonate, calcium carbonate, lanthanum oxide and zirconium dioxide according to the molar ratio of 0.25:0.25:0.1-0.4:0.05-0.2:1 to obtain raw materials; carrying out wet ball milling, drying and crushing on the raw materials to obtain powder I;
step two, heating the powder I to 1100-1300 ℃ at a speed of 4-7 ℃/min, calcining for 1-3 h, and cooling along with a furnace to obtain a block; crushing and grinding the block to obtain powder II;
step three, mixing materials according to the mass ratio of the powder II to the polyvinyl alcohol solution of 5wt% of 1:0.02-0.05, granulating, and standing for 12-15 h to obtain high-entropy perovskite zirconate ceramic powder;
fourthly, mechanically pressing and forming the high-entropy perovskite zirconate ceramic powder under the condition of 50-150 MPa to obtain a high-entropy perovskite zirconate ceramic blank;
step five, placing the high-entropy perovskite type zirconate ceramic blank in a high-temperature furnace under the air atmosphere and normal pressure, heating to 500-650 ℃ at the speed of 4-5 ℃/min, and discharging glue for 2-5 h under the condition of 500-650 ℃; and then continuously heating to 1400-1600 ℃ at the speed of 4-5 ℃/min under the air atmosphere and normal pressure condition, sintering for 3-5 h, and cooling along with the furnace to obtain the high-entropy perovskite zirconate ceramic.
2. The method for preparing high-entropy perovskite zirconate ceramic according to claim 1, wherein the purity of the barium carbonate is more than 99.0%, and the particle size of the barium carbonate is less than 10 μm.
3. The method for preparing high-entropy perovskite zirconate ceramic according to claim 1, wherein the purity of the strontium carbonate is more than 99.0%, and the particle size of the strontium carbonate is less than 10 μm.
4. The method for preparing high-entropy perovskite zirconate ceramic according to claim 1, wherein the purity of the calcium carbonate is more than 99.0%, and the particle size of the calcium carbonate is less than 10 μm.
5. The method for preparing the high-entropy perovskite zirconate ceramic according to claim 1, wherein the purity of the lanthanum oxide is more than 99.0%, and the particle size of the lanthanum oxide is less than 10 μm.
6. The method for preparing high-entropy perovskite zirconate ceramic according to claim 1, wherein the purity of the zirconium dioxide is more than 99.0%, and the particle size of the zirconium dioxide is less than 8 μm.
7. The method for preparing the high-entropy perovskite zirconate ceramic according to claim 1, wherein the wet ball milling is: the yttrium stable zirconia balls are used as ball milling media, deionized water is used as ball milling solvent, the mass ratio of the raw materials to the yttrium stable zirconia balls to the deionized water is 2:1:1 (1.9-2.1), and ball milling is carried out for 2-3 hours under the condition that the ball milling rotating speed is 200-400 rpm.
8. The method for preparing high-entropy perovskite zirconate ceramic according to claim 1, wherein the drying is performed at a temperature of 100 to 120 ℃ for 12 to 15 hours.
9. A high-entropy perovskite zirconate ceramic, characterized in that the high-entropy perovskite zirconate ceramic is prepared according to the preparation method of the high-entropy perovskite zirconate ceramic according to any one of claims 1 to 8.
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