CN117383919A - High-entropy rare earth silicate ceramic coating material and preparation method thereof - Google Patents
High-entropy rare earth silicate ceramic coating material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 49
- -1 rare earth silicate Chemical class 0.000 title claims abstract description 39
- 238000005524 ceramic coating Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 74
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000011215 ultra-high-temperature ceramic Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000001276 controlling effect Effects 0.000 abstract description 8
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000012467 final product Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000000306 component Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000009694 cold isostatic pressing Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000012856 weighed raw material Substances 0.000 description 3
- 238000001238 wet grinding Methods 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- 241001675646 Panaceae Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—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
- C04B35/16—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 silicates other than clay
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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Abstract
The invention relates to a high-entropy rare earth silicate ceramic coating material and a preparation method thereof, belonging to the technical field of high-entropy ceramic materials. The phase composition of the coating material is A 2 Si 2 O 7 A is Yb 0.1 Lu 0.1 Ho x Y 0.1 Sc 0.7‑x Or Yb 0.2 Lu 0.2 Ho 0.2 Y 0.2 Sc 0.2 X=0.1 or 0.6. The preparation method comprises the steps of uniformly ball-milling and mixing raw material powder by a wet method to form slurry; and then drying, and heating to 1400-1500 ℃ and calcining for 6-10 hours at constant temperature to obtain the coating material. The coating material can achieve the purpose of regulating and controlling the thermal expansion coefficient by controlling different values of x, and five rare earth elements have equal molar ratios and are uniformly distributed. The coating material has extremely lowThe thermal conductivity of the ceramic has a thermal expansion coefficient matched with that of the silicon carbide substrate, so that the effective regulation and control of the thermal expansion coefficient can be realized, the service temperature of the ultra-high temperature ceramic is improved, and the service life of the coating is prolonged.
Description
Technical Field
The invention relates to a high-entropy rare earth silicate ceramic coating material and a preparation method thereof, belonging to the technical field of high-entropy ceramic materials.
Background
In the service process of the high-temperature component, a series of severe conditions such as ultrahigh temperature, corrosion, thermal shock and the like are faced, and a layer of thermal protection coating is required to be applied on the surface to improve the service environment of the high-temperature component and prolong the service life. The thermal protective coating material must have a low thermal conductivity to effectively block heat transfer and reduce the temperature of the core component. In addition, the thermal expansion coefficient is one of the most important factors influencing the service life of the coating, and the coating can be effectively prevented from cracking and failing by matching with the thermal expansion coefficient of the substrate. Therefore, the preparation of the coating material with controllable thermal expansion coefficient and thermal conductivity is of great significance.
The rare earth disilicate has a thermal expansion coefficient matched with that of silicon carbide (SiC), excellent high-temperature thermal stability and oxidation resistance, and becomes an ultra-high-temperature ceramic part thermal protection material with great potential. Rare earth bissilicates share seven types of crystal structures, which can be determined by the ionic radius of the rare earth element. Wherein, beta-RE 2 Si 2 O 7 Has a more stable structure and a lower thermal expansion coefficient. The research of atomic vibration modes of different crystal structures according to Density Functional Theory (DFT) shows that the low-frequency phonon is formed by beta-RE 2 Si 2 O 7 Translation of RE atoms plus SiO 4 The tetrahedral inter-tetrahedral rotation contributes to. This suggests that the thermal properties of rare earth disilicates can be controlled by varying the type of rare earth atoms. Therefore, the correlation between the thermal performance of the disilicate and the crystal structure difference caused by the ion type and quantity change is explored, and a new method is provided for improving the thermal performance of the disilicate.
High entropy rare earth silicates exhibit low thermal conductivity and have the potential to adjust the coefficient of thermal expansion, and atomic difference induced performance stacking and lattice distortion have received great attention. Currently, regarding (Yb 0.2 Y 0.2 Lu 0.2 Sc 0.2 Gd 0.2 ) 2 Si 2 O 7 、(Yb 0.2 Y 0.2 Lu 0.2 Ho 0.2 Er 0.2 ) 2 Si 2 O 7 、(Lu 0.2 Yb 0.2 Er 0.2 Tm 0.2 Sc 0.2 ) 2 Si 2 O 7 Research on the equal-high-entropy rare earth silicate shows that lattice distortion of the rare earth silicate enhances non-harmonic oscillation of a lattice, so that the heat conductivity coefficient is reduced, the volume thermal expansion coefficient is changed, but the influence of atomic species on the lattice thermal expansion coefficient and the enhancement mechanism thereof are not clear, so that the prepared rare earth high-entropy silicate has a fixed thermal expansion coefficient, can only be matched with a single matrix, and cannot effectively solve the fundamental problem that the thermal expansion coefficient is matched with the matrix.
Disclosure of Invention
In order to overcome the problem that the thermal expansion coefficient is fixed and can only be matched with a single matrix, so that the application range of the coating is limited, the invention aims to provide a high-entropy rare earth silicate ceramic coating material and a preparation method thereof, and the coating material has extremely low thermal conductivity and controllable thermal expansion coefficient.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A high-entropy rare-earth silicate ceramic coating material comprises the phase composition A 2 Si 2 O 7 Wherein A is Yb 0.1 Lu 0.1 Ho x Y 0.1 Sc 0.7-x Or Yb 0.2 Lu 0.2 Ho 0.2 Y 0.2 Sc 0.2 Wherein x=0.1 or0.6; i.e. the coating material is (Yb 0.1 Lu 0.1 Ho x Y 0.1 Sc 0.7-x ) 2 Si 2 O 7 Wherein x=0.1 or 0.6; or the coating material is (Yb 0.2 Lu 0.2 Ho 0.2 Y 0.2 Sc 0.2 ) 2 Si 2 O 7 。
The invention discloses a preparation method of a high-entropy rare earth silicate ceramic coating material, which comprises the following steps:
(1) Weighing all raw material powder according to the phase composition of the coating material by adopting a stoichiometric ratio, and uniformly mixing by adopting wet ball milling to form slurry;
in step (1):
the raw material powder is Yb 2 O 3 、Lu 2 O 3 、Ho 2 O 3 、Y 2 O 3 、Sc 2 O 3 And SiO 2 Is a powder of (a) a powder of (b).
Preferably, the particle size of the raw material powder is 1-5 mu m, and the purity is more than or equal to 99.9%.
Preferably, the mass ratio of the grinding balls of the ball mill to the raw material powder is 5:1.
Preferably, the ball milling medium of the ball milling is absolute ethyl alcohol.
Preferably, the ball milling rotating speed of the ball milling is 250r/min, and the ball milling time is 6h.
(2) Drying the slurry prepared in the step (1) to obtain powder, and heating the powder to 1400-1500 ℃ and calcining for 6-10 h at constant temperature to prepare the high-entropy rare earth silicate ceramic coating material.
In the step (2):
drying is preferably carried out by rotary evaporation.
Preferably, the slurry is ground after being dried, and is sieved to obtain sieved powder, and then the powder is heated and calcined.
The powder is preferably heated to 1400 to 1500 ℃ at a rate of 5 ℃/min.
The invention relates to a high-entropy rare earth silicate ceramic coating, which is prepared on a SiC-based ultrahigh-temperature ceramic matrix by adopting the high-entropy rare earth silicate ceramic coating material.
Advantageous effects
(1) The invention provides a high-entropy rare earth silicate ceramic coating material, when the phase composition of the coating material is (Yb 0.1 Lu 0.1 Ho x Y 0.1 Sc 0.7-x ) 2 Si 2 O 7 When, wherein x=0.1 or 0.6; by varying the value of x, different coefficients of thermal expansion can be obtained. Therefore, the purpose of regulating and controlling the thermal expansion coefficient can be achieved by controlling the size of x.
The coating material successfully achieves the purposes of reducing the heat conductivity and regulating and controlling the thermal expansion coefficient by changing the ion radius difference of an ion doping ratio control system and utilizing the change of a microstructure and an electronic structure caused by the ion radius difference. The thermal expansion coefficient of the disilicate is 4.57 multiplied by 10 by controlling the microstructure and the electronic structure -6 K -1 ～5.04×10 -6 K -1 Effective regulation and control are carried out, so that the reliability of the disilicate serving as the SiC-based coating is improved; the five rare earth elements are uniformly distributed, and the thermal conductivity is only 1.13W/m.K.
(2) The invention provides a high-entropy rare earth silicate ceramic coating material, when the phase composition of the coating material is (Yb 0.2 Lu 0.2 Ho 0.2 Y 0.2 Sc 0.2 ) 2 Si 2 O 7 When the rare earth elements are mixed, the molar ratio of the five rare earth elements is equal, and the distribution is uniform. The coating material has extremely low thermal conductivity, and the thermal conductivity of a sample at the room temperature to 1200 ℃ is measured by a laser thermal conductivity meter, and is 1.14W/m.K; coefficient of thermal expansion of 4.84×10 -6 K -1 Having a coefficient of thermal expansion that matches that of silicon carbide (SiC) provides more possibilities for the use of disilicates as silicon carbide-based coating materials.
(3) The invention provides a preparation method of a high-entropy rare earth silicate ceramic coating material, which not only provides a novel thermal protection coating material for a silicon carbide-based ultrahigh-temperature ceramic matrix, but also provides a novel technical idea of adjusting and controlling the thermal expansion coefficient to match different matrixes, and the method realizes effective adjustment and control of the thermal expansion coefficient by exploring the influence mechanism of element doping on the thermal performance on the electronic scale, finally achieves the purposes of improving the service temperature of the ultrahigh-temperature ceramic and prolonging the service life of the coating, and has important significance for the selection of the ultrahigh-temperature silicon carbide-based thermal protection coating material.
(4) The invention provides a preparation method of a high-entropy rare earth silicate ceramic coating material, wherein in the preparation method, raw material powder is fully and uniformly mixed by wet ball milling in the step (1), so that high-entropy rare earth silicate ceramic elements synthesized at high temperature can be uniformly distributed, and certain rare earth element agglomeration enrichment does not exist;
preferably, the particle size of the raw material powder is 1-5 mu m, and the purity is more than or equal to 99.9%. The uniformity of the composition of the synthesized product phase can be effectively improved due to the uniform particle size of the raw material powder. The higher purity ensures the synthesis effect, avoids the introduction of impurities and ensures the singleness of the phase composition of the product.
(5) The invention provides a preparation method of a high-entropy rare earth silicate ceramic coating material, which comprises the following steps of (2) calcining at a constant temperature of 1400-1500 ℃ for 6-10 h, and if the calcining is not satisfied, preparing a final product which contains SiO besides the coating material 2 Waiting for a second phase to affect the purity of the material, thereby affecting the thermophysical properties of the material;
preferably, the slurry is ground and sieved after being dried, so that the sieved powder is obtained, and the calcined powder particles are uniform, so that the high-entropy rare earth silicate ceramic coating material prepared by the method has uniform particle size distribution and good particle morphology.
(6) The invention provides a high-entropy rare earth silicate ceramic coating, which adopts the high-entropy rare earth silicate ceramic coating material; the SiC-based ultra-high temperature ceramic substrate is suitable for matching; the purpose of improving the service temperature of the ultra-high temperature ceramic and prolonging the service life of the coating is successfully realized; the method has wide application fields in the field of heat protection coatings of key high-end equipment.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the powder samples prepared in examples 1 and 2.
Fig. 2 is a graph of thermal conductivity of bulk samples prepared in examples 1 and 2.
Fig. 3 is a graph of the thermal expansion coefficients of the bulk samples prepared in examples 1 and 2.
Fig. 4 is an XRD pattern of the powder sample prepared in example 3.
FIG. 5 is an SEM-EDS image of a powder sample prepared in example 3.
Fig. 6 is a graph of thermal conductivity of bulk samples prepared in example 3.
FIG. 7 is a graph of the thermal expansion rate of the bulk sample prepared in example 3.
FIG. 8 is a graph of the thermal expansion coefficients of bulk samples prepared in example 3.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples, but is not intended to limit the scope of the patent.
In the following examples:
raw material powder Yb 2 O 3 ，Lu 2 O 3 ，Ho 2 O 3 ，Y 2 O 3 ，Sc 2 O 3 With SiO 2 The grain diameter of the product is 1 mu m-5 mu m, and the purity is more than or equal to 99.9 percent.
The following tests were performed on the powder samples and the bulk samples prepared:
(1) X-ray diffraction (XRD)
The manufacturer: pamalytical, netherlands, instrument model: empyrean of the Panaceae. The test is carried out by adopting a Cu target, the working voltage is 45KV, the current is 40mA, the scanning speed of each step is 10.2/s, and the step length is 0.013.
(2) Field emission scanning electron microscope
The manufacturer: calzeiss, instrument model: empyreanZeiss/Auriba of the Panaceae family. And polishing the sample to be tested until the thickness is less than 0.5mm, polishing the surface to a mirror surface without obvious effect, and performing metal spraying treatment on the surface to be tested and then performing surface appearance test. And (3) carrying out component analysis on the sample to be detected by using an energy spectrometer equipped with a scanning electron microscope.
(3) Thermal conductivity
The manufacturer: german relaxation-resistant instruments, instrument model: LFA-457. And testing the heat conductivity coefficient of the prepared high-entropy rare earth silicate ceramic block at the room temperature to 1200 ℃ by adopting a laser thermal conductivity meter. Preparing a sample into a wafer with the diameter of 12.7mm, polishing the cut wafer until the thickness is less than 3mm, and polishing the surface until the surface is bright.
(4) Thermal expansion rate and coefficient
Measuring the thermal expansion rate of the sample by adopting a high-temperature thermal expansion instrument, and obtaining the thermal expansion coefficients of the sample at different temperatures by adopting a conventional calculation method
The manufacturer: german relaxation-resistant instruments, instrument model: DIL402PC. Cutting the block to be tested into blocks with the length of 3mm multiplied by 30mm, polishing to be parallel at two ends, and placing the blocks into an instrument for testing.
The experimental materials described in the present invention can be obtained commercially, unless otherwise specified, and the experimental methods described herein are conventional.
Example 1
(1) According to the phase composition (Yb 0.1 Lu 0.1 Ho 0.1 Y 0.1 Sc 0.6 ) 2 Si 2 O 7 Weighing each raw material powder by adopting a stoichiometric ratio:
yb is processed into 2 O 3 、Lu 2 O 3 、Ho 2 O 3 、Y 2 O 3 、Sc 2 O 3 With SiO 2 Weighing according to the molar ratio of 1:1:1:1:6:20;
the weighed raw material powder and zirconia grinding balls are placed into a ball milling tank according to the mass ratio of 1:5, absolute ethyl alcohol is added to soak the grinding balls and the raw material powder as a ball milling medium to carry out wet milling and mixing, and the mixture is ball milled on a planetary ball mill for 6 hours at the rotating speed of 250r/min and uniformly mixed to form slurry.
(2) Drying the slurry prepared in the step (1) at 55 ℃ by using a rotary evaporator, grinding the dried powder by using an agate mortar, and respectively sieving with 100-mesh and 300-mesh screens; obtaining sieved powder; placing the sieved powder into an alumina crucible, placing the alumina crucible into a pressureless box-type sintering furnace, heating to 1400 ℃ at a speed of 5 ℃/min, and calcining for 10 hours at constant temperature to obtain the final product powder; and then cooling to room temperature along with the furnace, taking out, and grinding by using a mortar until no obvious particles exist, so as to be used as a powder sample for testing.
For scanning electron microscope observation, thermal conductivity and thermal expansion coefficient test, the powder sieved in step (2) of this example is prepared into a block sample for test, and the specific method is as follows:
carrying out primary pressing on the sieved powder by using a manual tablet press, wherein the used die is a round grinding tool with the diameter of 20mm and a strip-shaped die with the diameter of 5mm multiplied by 50mm, the pressure is 8MPa, and the pressure maintaining time is 1min; then carrying out secondary pressing by utilizing cold isostatic pressing, wherein the pressure is 250MPa, and the pressure maintaining time is 5min, so as to obtain a blank;
placing the blank into an alumina crucible, placing the alumina crucible into a pressureless box-type sintering furnace, heating to 1400 ℃ at a speed of 5 ℃/min, and calcining for 10 hours at constant temperature to prepare a block sample for testing; cooling to room temperature along with the furnace.
The powder sample and the block sample prepared in this example were tested as follows:
(1) X-ray diffraction (XRD)
The test results are shown in fig. 1, and the powder sample is a typical disilicate structure, has no impurity peak, and proves that the final product is single-phase high-entropy disilicate.
(2) Scanning electron microscope-energy spectrum (SEM-EDS)
The microstructure structure and the element distribution condition of the powder sample are observed by adopting SEM-EDS, and the result shows that all elements are uniformly distributed without obvious segregation.
From the above, it can be seen that the final product prepared in this example is a high-entropy rare earth silicate ceramic coating material (Yb) 0.1 Lu 0.1 Ho 0.1 Y 0.1 Sc 0.6 ) 2 Si 2 O 7 。
(3) Thermal conductivity
The thermal conductivity test result of the cooled block sample is shown in FIG. 2, and the thermal conductivity is 1.13W/mK at the lowest, so that the block sample has good heat insulation performance.
(4) Coefficient of thermal expansion
The results of the thermal expansion coefficient test of the cooled block sample are shown in FIG. 3, and it is found that the thermal expansion coefficient is 5.04×10 -6 K -1 。
Example 2
(1) According to the phase composition (Yb 0.1 Lu 0.1 Ho 0.6 Y 0.1 Sc 0.1 ) 2 Si 2 O 7 Weighing each raw material powder by adopting a stoichiometric ratio:
yb is processed into 2 O 3 、Lu 2 O 3 、Ho 2 O 3 、Y 2 O 3 、Sc 2 O 3 With SiO 2 Weighing according to the molar ratio of 1:1:6:1:1:20;
the weighed raw material powder and zirconia grinding balls are placed into a ball milling tank according to the mass ratio of 1:5, absolute ethyl alcohol is added to soak the grinding balls and the raw material powder as a ball milling medium to carry out wet milling and mixing, and the mixture is ball milled on a planetary ball mill for 6 hours at the rotating speed of 250r/min and uniformly mixed to form slurry.
(2) Calcining at a constant temperature of 1500 ℃ for 6 hours, wherein the rest is the same as in the step (2) of the example 1.
For scanning electron microscope observation, thermal conductivity and thermal expansion coefficient test, the powder sieved in step (2) of this example is prepared into a block sample for test, and the specific method is as follows:
carrying out primary pressing on the sieved powder by using a manual tablet press, wherein the used die is a round grinding tool with the diameter of 20mm and a strip-shaped die with the diameter of 5mm multiplied by 50mm, the pressure is 8MPa, and the pressure maintaining time is 1min; then carrying out secondary pressing by utilizing cold isostatic pressing, wherein the pressure is 250MPa, and the pressure maintaining time is 5min, so as to obtain a blank;
placing the blank into an alumina crucible, placing the alumina crucible into a pressureless box-type sintering furnace, heating to 1500 ℃ at a speed of 5 ℃/min, and calcining for 6 hours at constant temperature to prepare a block sample for testing; cooling to room temperature along with the furnace.
The powder sample and the block sample prepared in this example were tested as follows:
(1) X-ray diffraction (XRD)
The test results are shown in fig. 1, and the powder sample is a typical disilicate structure, has no impurity peak, and proves that the final product is single-phase high-entropy disilicate.
(2) Scanning electron microscope-energy spectrum (SEM-EDS)
The microstructure structure and the element distribution condition of the powder sample are observed by adopting SEM-EDS, and the result shows that all elements are uniformly distributed without obvious segregation.
From the above, it can be seen that the final product prepared in this example is a high-entropy rare earth silicate ceramic coating material (Yb) 0.1 Lu 0.1 Ho 0.6 Y 0.1 Sc 0.1 ) 2 Si 2 O 7 。
(3) Thermal conductivity
The thermal conductivity test result of the cooled block sample is shown in FIG. 2, and the thermal conductivity is 1.59W/mK at the lowest, and the block sample has good heat insulation performance.
(4) Coefficient of thermal expansion
The results of the thermal expansion coefficient test of the cooled block sample are shown in FIG. 3, and it is found that the thermal expansion coefficient is 4.08X10 -6 K -1 。
As can be seen from the results of the thermal expansion coefficient test of examples 1 and 2, the thermal expansion coefficient of the high-entropy rare earth silicate ceramic coating material of the invention can be effectively realized in a range of 4.08X10 by changing the element ratio -6 K -1 ～5.04×10 -6 K -1 And (3) regulating and controlling the components.
Example 3
(1) According to the phase composition (Yb 0.2 Lu 0.2 Ho 0.2 Y 0.2 Sc 0.2 ) 2 Si 2 O 7 Weighing each raw material powder by adopting a stoichiometric ratio:
yb is processed into 2 O 3 、Lu 2 O 3 、Ho 2 O 3 、Y 2 O 3 、Sc 2 O 3 With SiO 2 According to moleWeighing the materials according to the ratio of 1:1:1:1:1:10;
the weighed raw material powder and zirconia grinding balls are placed into a ball milling tank according to the mass ratio of 1:5, absolute ethyl alcohol is added to soak the grinding balls and the raw material powder as a ball milling medium to carry out wet milling and mixing, and the mixture is ball milled on a planetary ball mill for 6 hours at the rotating speed of 250r/min and uniformly mixed to form slurry.
(2) Drying the slurry prepared in the step (1) at 65 ℃ by using a rotary evaporator, grinding the dried powder by using an agate mortar, and respectively sieving with 100-mesh and 300-mesh screens; obtaining sieved powder; placing the sieved powder into an alumina crucible, placing the alumina crucible into a pressureless box-type sintering furnace, heating up to 1450 ℃ at a speed of 5 ℃/min, and calcining for 8 hours at constant temperature to obtain the final product powder; and then cooling to room temperature along with the furnace, taking out, and grinding by using a mortar until no obvious particles exist, so as to be used as a powder sample for testing.
For scanning electron microscope observation, thermal conductivity and thermal expansion coefficient test, the powder sieved in step (2) of this example is prepared into a block sample for test, and the specific method is as follows:
carrying out primary pressing on the sieved powder by using a manual tablet press, wherein the used die is a round grinding tool with the diameter of 20mm and a strip-shaped die with the diameter of 5mm multiplied by 50mm, the pressure is 8MPa, and the pressure maintaining time is 1min; then carrying out secondary pressing by utilizing cold isostatic pressing, wherein the pressure is 250MPa, and the pressure maintaining time is 5min, so as to obtain a blank;
placing the blank into an alumina crucible, placing the alumina crucible into a pressureless box-type sintering furnace, heating to 1450 ℃ at a speed of 5 ℃/min, and calcining for 8 hours at constant temperature to prepare a block sample for testing; cooling to room temperature along with the furnace.
The powder sample and the block sample prepared in this example were tested as follows:
(1) X-ray diffraction (XRD)
The test results are shown in fig. 4, and the powder sample is a typical disilicate structure, and has no impurity peak, so that the final product is proved to be single-phase high-entropy disilicate.
(2) Scanning electron microscope-energy spectrum (SEM-EDS)
The microstructure and element distribution of the powder sample are observed by adopting SEM-EDS, and the result is that all elements are uniformly distributed without obvious segregation as shown in figure 5.
From the above, it can be seen that the final product prepared in this example is a high-entropy rare earth silicate ceramic coating material (Yb) 0.2 Lu 0.2 Ho 0.2 Y 0.2 Sc 0.2 ) 2 Si 2 O 7 。
(3) Thermal conductivity
The thermal conductivity test results of the cooled bulk sample are shown in FIG. 6, and it is known that the coating material has extremely low thermal conductivity, only 1.14W/mK.
(4) Thermal expansion rate and coefficient
The thermal expansion rate of the cooled bulk sample is shown in fig. 7, and shows typical linear thermal expansion, indicating that the coating material has good thermal stability.
The coefficient of thermal expansion of the cooled block sample is shown in FIG. 8, and the coefficient of thermal expansion of the coating material is 4.84X10 -6 K -1 Close to silicon carbide.
Claims (10)
1. A high-entropy rare earth silicate ceramic coating material is characterized in that: the phase composition of the coating material is A 2 Si 2 O 7 Wherein A is Yb 0.1 Lu 0.1 Ho x Y 0.1 Sc 0.7-x Or Yb 0.2 Lu 0.2 Ho 0.2 Y 0.2 Sc 0.2 X=0.1 or 0.6.
2. A method for preparing the high-entropy rare earth silicate ceramic coating material according to claim 1, wherein: the method comprises the following steps:
(1) Weighing all raw material powder according to the phase composition of the coating material by adopting a stoichiometric ratio, and uniformly mixing by adopting wet ball milling to form slurry;
the raw material powder is Yb 2 O 3 、Lu 2 O 3 、Ho 2 O 3 、Y 2 O 3 、Sc 2 O 3 And SiO 2 Is a powder of (1);
(2) Drying the slurry to obtain powder, heating the powder to 1400-1500 ℃ and calcining for 6-10 h at constant temperature to prepare the high-entropy rare earth silicate ceramic coating material.
3. The method for preparing the high-entropy rare earth silicate ceramic coating material according to claim 2, which is characterized in that: in the step (1), the particle size of the raw material powder is 1-5 mu m, and the purity is more than or equal to 99.9%.
4. A method for preparing a high entropy rare earth silicate ceramic coating material according to claim 2 or 3, characterized in that: in the step (1), the mass ratio of the ball-milled grinding balls to the raw material powder is 5:1; the ball milling medium of the ball milling is absolute ethyl alcohol; the ball milling rotating speed of the ball milling is 250r/min, and the ball milling time is 6h.
5. The method for preparing the high-entropy rare earth silicate ceramic coating material according to claim 2, which is characterized in that: in step (2), drying is performed by rotary evaporation.
6. The method for preparing the high-entropy rare earth silicate ceramic coating material according to claim 2, which is characterized in that: in the step (2), the slurry is ground after being dried, and is sieved to obtain sieved powder, and then the powder is heated and calcined.
7. The method for preparing the high-entropy rare earth silicate ceramic coating material according to claim 2, which is characterized in that: in the step (2), the temperature of the powder is raised at a rate of 5 ℃/min.
8. The method for preparing the high-entropy rare earth silicate ceramic coating material according to claim 2, which is characterized in that: in the step (2), rotary evaporation is adopted for drying; grinding and sieving the slurry after drying to obtain sieved powder, and heating and calcining the powder; the powder was warmed up at a rate of 5 ℃/min.
9. The method for preparing the high-entropy rare earth silicate ceramic coating material according to claim 2, which is characterized in that: in the step (1), the particle size of the raw material powder is 1-5 mu m, and the purity is more than or equal to 99.9%; the mass ratio of the ball-milling balls to the raw material powder is 5:1; the ball milling medium of the ball milling is absolute ethyl alcohol; the ball milling rotating speed of the ball milling is 250r/min, and the ball milling time is 6h;
in the step (2), rotary evaporation is adopted for drying; grinding and sieving the slurry after drying to obtain sieved powder, and heating and calcining the powder; the powder was warmed up at a rate of 5 ℃/min.
10. A high-entropy rare earth silicate ceramic coating is characterized in that: the coating is prepared on a SiC-based ultrahigh-temperature ceramic matrix by adopting the high-entropy rare earth silicate ceramic coating material as claimed in claim 1.
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