CN117964364A - High-entropy rare earth silicate complex-phase ceramic and preparation method thereof - Google Patents
High-entropy rare earth silicate complex-phase ceramic and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 72
- -1 rare earth silicate Chemical class 0.000 title claims abstract description 67
- 239000000919 ceramic Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 41
- 239000011521 glass Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 9
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000002241 glass-ceramic Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- 239000001301 oxygen Substances 0.000 abstract description 18
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000011153 ceramic matrix composite Substances 0.000 abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 35
- 239000011651 chromium Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 2
- 238000000626 liquid-phase infiltration Methods 0.000 description 2
- 208000020442 loss of weight Diseases 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
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- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910008326 Si-Y Inorganic materials 0.000 description 1
- 229910006773 Si—Y Inorganic materials 0.000 description 1
- 229910009365 YSi2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 238000001784 detoxification Methods 0.000 description 1
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- 239000006112 glass ceramic composition Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a high-entropy rare earth silicate complex phase ceramic and a preparation method thereof, wherein the high-entropy rare earth silicate complex phase ceramic is prepared from high-entropy rare earth oxide and microcrystalline glass powder, the molecular formula of the high-entropy rare earth oxide is (RE 1RE2RE3RE4）2O3, the microcrystalline glass powder comprises the following components ：RE1 2O3、RE2 2O3、RE3 2O3、RE4 2O3、Al2O3, siO 2,RE1、RE2、RE3 and RE 4 which are different from each other and are selected from Y, yb, ho, er, dy, lu, gd, tm, and compared with the prior art, the high-entropy rare earth oxide introduced by the invention can react with silicon dioxide and aluminum oxide in microcrystalline glass to generate rare earth silicate and mullite with better anti-oxygen corrosion performance, and the anti-oxygen corrosion performance of a ceramic matrix composite material is further improved while the ceramic conversion rate is improved.
Description
Technical Field
The invention belongs to the technical field of rare earth silicate ceramics, and particularly relates to a high-entropy rare earth silicate complex-phase ceramic and a preparation method thereof.
Background
The development of the aviation field puts higher demands on the long service life of aero-engine materials, and the SiC f/SiC composite materials applied at present are easy to corrode in severe environments such as high-temperature oxygen, molten salt and the like, so that the SiC f/SiC composite materials fail. Therefore, it is desirable to introduce a water resistant modification to the SiC f/SiC composite. Although rare earth silicate has excellent resistance to oxygen corrosion, rare earth monosilicate and SiC matrix have mismatched coefficients of thermal expansion, rare earth disilicate has poor phase stability at high temperatures, and these problems limit the application of rare earth silicate to resistance to oxygen corrosion. In recent years, the high-entropy ceramics emerging from the recent years have improved the high-temperature stability of high-entropy rare earth silicates due to the high entropy effect. In addition, the cocktail effect expands the family of rare earth silicate, and introduces high-entropy rare earth silicate with different performances of different systems. Therefore, the high-entropy rare earth silicate is a potential ceramic matrix composite material water-resistant oxygen phase material.
The main methods for preparing the high-entropy rare earth silicate ceramic at present are a sol-gel method and a solid phase reaction method, and literature 1"High-entropy rare-earth disilicate (Lu0.2Yb0.2Er0.2Tm0.2Sc0.2)2Si2O7: A potential environmental barrier coating material. J. Eur. Ceram. Soc. 42 (2022): 3570-3578" adopts the solid phase reaction method, uniformly mixes the rare earth oxide with silicon dioxide in an equal molar ratio, and calcines the mixture at a high temperature to obtain the high-entropy rare earth silicate. The preparation temperature of the method is higher (1550 ℃) and the preparation time is long.
Literature 2"High-entropy environmental barrier coating for the ceramic matrix composites. J. Eur. Ceram. Soc. 39 (2019): 2574-2579" uses Tetraethoxysilane (TEOs) as a precursor, and the precursor is mixed with a plurality of rare earth nitrate solutions with equal molar ratio, and the high-entropy rare earth silicate is obtained through the steps of sol gelation, high-temperature heat treatment and the like. The method has the advantages of low preparation temperature, short preparation time and controllable reaction.
The sol-gel method is an excellent method for preparing the high-entropy rare earth silicate, but the problems of non-compactness, long period and the like existing in the preparation of the high-entropy rare earth silicate modified composite material are easy to occur. Thus, there is a need for a new approach to incorporate high entropy rare earth silicates into composite materials.
Currently, the processes for introducing rare earth materials into composite materials are mainly Chemical Vapor Infiltration (CVI), polymer impregnation cracking (PIP) and Reactive Melt Infiltration (RMI). The RMI has the advantages of short preparation period, high densification degree of the modified composite material, large-scale production and the like. Literature 3"Microstructure, thermophysical properties and oxidation resistance of SiCf/SiC-YSi2-Si composite fabricated through reactive melt infiltration. J. Eur. Ceram. Soc. 43(2023): 5950-5960." adopts an RMI method, selects Si-Y alloy as an infiltration material, prepares a SiC f/SiC-YSi2 -Si composite material, and has the advantages of only 4.83% of porosity, short preparation period and excellent oxidation resistance. However, the composite material modified by the Si alloy infiltration has more residual Si, which can have adverse effects on the high-temperature mechanical property and corrosion resistance of the composite material.
The result of the connection of the SiC f/SiC joint by the Y-Al-Si-O glass in the literature 4"Microstructure and properties of SiCf/SiC joint brazed by Y-Al-Si-O glass. Ceram. Int. 2018: 8656-8663." shows that the YAS glass can wet the SiC f/SiC composite material and can better maintain the shear strength of the SiC f/SiC composite material, which shows that the YAS glass can be used for the modification of the SiC f/SiC composite material matrix.
Patent number CN201510713666.6 proposes to mix Cr 2O3 with CaO-MgO-SiO 2-Al2O3 glass and to realize double fixation and detoxification of chromium by reaction at high temperature. The method successfully fixes Cr in the chromium slag by reacting Cr 2O3 with glass, and obtains the glass ceramic material containing Cr crystal phase. The patent shows that specific crystalline materials can be obtained after the specific oxide is mixed with glass for heat treatment, and the glass ceramization is promoted.
In summary, rare earth glass ceramics are expected to be used as a modifier of ceramic matrix composite materials, but how to further improve the ceramic conversion rate of glass and increase the high-entropy rare earth silicate phase ratio in glass ceramics is a problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the high-entropy rare earth silicate composite ceramic, the introduced high-entropy rare earth oxide reacts with silicon dioxide and aluminum oxide in microcrystalline glass to generate rare earth silicate and mullite with better water-oxygen corrosion resistance, and the water-oxygen corrosion resistance of the high-entropy rare earth silicate composite ceramic is further improved while the ceramic conversion rate is improved.
In order to achieve the aim, the invention provides high-entropy rare earth silicate composite ceramic, which is prepared from high-entropy rare earth oxide and microcrystalline glass powder, wherein the molecular formula of the high-entropy rare earth oxide is (RE 1RE2RE3RE4）2O3, the microcrystalline glass powder comprises the following components ：RE1 2O3、RE2 2O3、RE3 2O3、RE4 2O3、Al2O3 and SiO 2, the mass percentage of each component is as follows, the sum of the mass percentages of RE 1 2O3、RE2 2O3、RE3 2O3 and RE 4 2O3 is 0.1-45%, the mass percentage of Al 2O3 is 5-25%, the mass percentage of SiO 2 is 30-80%, and the RE 1、RE2、RE3 and RE 4 are different and are one selected from Y, yb, ho, er, dy, lu, gd, tm.
Preferably, the mass ratio of the high-entropy rare earth oxide to the microcrystalline glass powder is 1 (1-5). The invention adopts the high-entropy rare earth oxide and microcrystalline glass powder with the mass ratio, and can control the content of residual phase, thereby preparing the high-entropy rare earth silicate complex phase ceramic with excellent resistance to oxygen corrosion.
Preferably, the grain diameter of the high-entropy rare earth oxide is 1-100 mu m, and the grain diameter of the microcrystalline glass powder is 1-100 mu m. The invention adopts the high-entropy rare earth oxide with the particle size and the microcrystalline glass powder, so that the reaction can be fully carried out, and the uniform high-entropy rare earth silicate complex-phase ceramic can be obtained.
Preferably, in the high-entropy rare earth silicate complex phase ceramic, the mass percentage content of each constituent phase is as follows: high entropy rare earth silicate: 50-75%, mullite: 15-35%, silicon dioxide 5-20% and rare earth oxide 5-15%.
The second aim of the invention is to provide a preparation method of high-entropy rare earth silicate complex phase ceramic, which specifically comprises the following steps:
s1, mixing raw materials: respectively weighing high-entropy rare earth oxide and microcrystalline glass powder, and uniformly mixing by ball milling to obtain mixed powder;
S2, press forming: compacting the mixed powder obtained in the step S1 to obtain a blank;
S3, calcining: and (3) placing the green body obtained in the step (S2) in a muffle furnace for calcination to obtain the high-entropy rare earth silicate complex-phase ceramic.
Preferably, in the step S1, the ball milling parameters are as follows: the ball-material ratio is 1 (2-6), the ball-milling medium is one of deionized water, absolute ethyl alcohol or toluene, the ball-milling rotating speed is 200-400 rpm, and the ball-milling time is 10-50h.
Preferably, in the step S2, the parameters of the press forming are as follows: the pressing pressure is 4-12Mpa, and the pressing time is 3-15min.
Preferably, in the step S3, the calcination parameters are as follows: the calcination temperature is 1200-1450 ℃, and the calcination time is 1-5h.
Compared with the prior art, the invention has the following advantages:
1. At high temperature, the glass crystallization is promoted by the reaction of the high-entropy rare earth oxide and silicon dioxide in the microcrystalline glass, so that the residual phase of the glass can be reduced, and the glass can be converted into rare earth silicate crystalline phase;
2. The introduced high-entropy rare earth oxide reacts with silicon dioxide and aluminum oxide in the microcrystalline glass to generate rare earth silicate and mullite with good anti-oxygen corrosion performance, so that the ceramic conversion rate is improved, and the anti-oxygen corrosion performance of the ceramic matrix composite is further improved.
Drawings
FIG. 1 is an XRD pattern of the high-entropy rare earth silicate composite ceramic prepared in the embodiment 1 of the invention after heat treatment at a high temperature of 1200-1450 ℃;
FIG. 2 is a water-oxygen weight loss curve of the high-entropy rare earth silicate complex phase ceramic prepared in the embodiment 1 of the invention at 1400 ℃.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
The embodiment of the invention provides a high-entropy rare earth silicate complex-phase ceramic, which is prepared from high-entropy rare earth oxide and microcrystalline glass powder, wherein the molecular formula of the high-entropy rare earth oxide is (RE 1RE2RE3RE4）2O3, the microcrystalline glass powder comprises the following components ：RE1 2O3、RE2 2O3、RE3 2O3、RE4 2O3、Al2O3 and SiO 2, the mass percentage of each component is as follows, the sum of the mass percentages of RE 1 2O3、RE2 2O3、RE3 2O3 and RE 4 2O3 is 0.1-45%, the mass percentage of Al 2O3 is 5-25%, the mass percentage of SiO 2 is 30-80%, and RE 1、RE2、RE3 and RE 4 are different and are one selected from Y, yb, ho, er, dy, lu, gd, tm.
In the specific embodiment, the mass ratio of the high-entropy rare earth oxide to the microcrystalline glass powder is 1 (1-5).
In a specific embodiment, the particle size of the high-entropy rare earth oxide is 1-100 mu m, and the particle size of the microcrystalline glass powder is 1-100 mu m.
In a specific embodiment, the high-entropy rare earth silicate complex phase ceramic comprises the following component phases in percentage by mass: high entropy rare earth silicate: 50-75%, mullite: 15-35%, silicon dioxide 5-20% and rare earth oxide 5-15%.
The second aim of the specific embodiment of the invention is to provide a preparation method of high-entropy rare earth silicate complex phase ceramic, which comprises the following steps:
s1, mixing raw materials: respectively weighing high-entropy rare earth oxide and microcrystalline glass powder, and uniformly mixing by ball milling to obtain mixed powder;
S2, press forming: compacting the mixed powder obtained in the step S1 to obtain a blank;
S3, calcining: and (3) placing the green body obtained in the step (S2) in a muffle furnace for calcination to obtain the high-entropy rare earth silicate complex-phase ceramic.
In specific embodiments, in step S1, the ball milling parameters are as follows: ball-material ratio is 1 (2-6), ball-milling medium is selected from one of deionized water, absolute ethyl alcohol or toluene, ball-milling rotating speed is 200-400 rpm, and ball-milling time is 10-50h;
In specific embodiments, in step S2, the parameters of the press forming are as follows: the pressing pressure is 4-12Mpa, and the pressing time is 3-15min.
In a specific embodiment, in step S2, the diameter of the blank is 1-10cm.
In a specific embodiment, in step S3, the calcination parameters are as follows: the calcination temperature is 1200-1450 ℃, and the calcination time is 1-5h.
The technical effects of the present invention will be described below with reference to specific examples.
Example 1: the embodiment provides a high-entropy rare earth silicate complex phase ceramic, which is prepared from a high-entropy rare earth oxide and glass ceramic powder, wherein the molecular formula of the high-entropy rare earth oxide is (Y 0.25Yb0.25Er0.25Ho0.25)2O3, the glass ceramic powder comprises the following components ：Y2O3、Yb2O3、Er2O3、Ho2O3、Al2O3 and SiO 2, the mass percentage of each component is ：4.8wt% Y2O3、8.2wt%Yb2O3、8.1wt%Er2O3、7.9wt%Ho2O3、16wt%Al2O3、55wt%SiO2,, the mass of the high-entropy rare earth oxide is 2g, and the mass of the glass ceramic powder is 2g.
The high-entropy rare earth silicate complex phase ceramic is prepared by the following method:
S1, mixing raw materials: respectively weighing high-entropy rare earth oxide and microcrystalline glass powder, and uniformly mixing by ball milling to obtain mixed powder, wherein the ball milling parameters are as follows: ball-material ratio is 1:5, ball-milling medium is deionized water, rotating speed is 300rpm, and ball-milling time is 10h;
S2, press forming: weighing 1.5g of the mixed powder obtained in the step S1, and compacting to obtain a green body, wherein the compacting parameters are as follows: the pressing pressure is 4Mpa, the pressing time is 3min, and the diameter of a pressed blank is 13mm;
S3, calcining: and (2) placing the green body obtained in the step (S2) in a muffle furnace for calcination to obtain the high-entropy rare earth silicate complex-phase ceramic, wherein the calcination parameters are as follows: the calcination temperature was 1200℃and the calcination time was 2 hours.
The applicant carries out further analysis, wherein fig. 1 is an XRD pattern of the high-entropy rare earth silicate composite ceramic prepared in embodiment 1 of the present invention after heat treatment at a high temperature of 1200-1450 ℃, and as can be seen from fig. 1, the high-entropy rare earth silicate composite ceramic prepared in this embodiment contains high-entropy rare earth silicate, mullite, silica, rare earth oxide and other structures, and contains only trace amounts of SiO 2 residual glass phase; fig. 2 is a water-oxygen weight loss curve of the high-entropy rare earth silicate composite ceramic prepared in the embodiment 1 of the invention at 1400 ℃, and as can be seen from fig. 2, the water-oxygen environment of 1400 ℃ and 50% H 2O-50%O2 keeps 100h to lose weight only by 0.022%.
Example 2: the embodiment provides a high-entropy rare earth silicate complex phase ceramic, which is prepared from high-entropy rare earth oxide and glass ceramic powder, wherein the molecular formula of the high-entropy rare earth oxide is (Y 0.25Yb0.25Er0.25Ho0.25)2O3, the glass ceramic powder comprises the following components ：Y2O3、Yb2O3、Er2O3、Ho2O3、Al2O3 and SiO 2, the mass percentage of each component is ：4.6wt% Y2O3、8wt%Yb2O3、7.8wt%Er2O3、7.6wt%Ho2O3、18wt%Al2O3 and 54wt% of SiO 2, the mass of the high-entropy rare earth oxide is 0.6g, and the mass of the glass ceramic powder is 1.2g.
The high-entropy rare earth silicate complex phase ceramic is prepared by the following method:
S1, mixing raw materials: respectively weighing high-entropy rare earth oxide and microcrystalline glass powder, and uniformly mixing by ball milling to obtain mixed powder, wherein the ball milling parameters are as follows: ball-material ratio is 1:4, ball-milling medium is absolute ethyl alcohol, rotating speed is 250 rpm, ball-milling time is 20h;
S2, press forming: weighing 1.5g of the mixed powder obtained in the step S1, and compacting to obtain a green body, wherein the compacting parameters are as follows: the pressing pressure is 6Mpa, the pressing time is 6min, and the diameter of a pressed blank body is 13mm;
s3, calcining: and (2) placing the green body obtained in the step (S2) in a muffle furnace for calcination to obtain the high-entropy rare earth silicate complex-phase ceramic, wherein the calcination parameters are as follows: the calcination temperature was 1300℃and the calcination time was 1h.
The high-entropy rare earth silicate complex phase ceramic obtained by SEM detection contains only trace SiO 2 residual glass phase, and the loss of weight of 100 h is kept to be only 0.05% in a water-oxygen environment of 1400 ℃ and 50% H 2O-50%O2.
Example 3: the embodiment provides a high-entropy rare earth silicate complex phase ceramic, which is prepared from a high-entropy rare earth oxide and glass ceramic powder, wherein the molecular formula of the high-entropy rare earth oxide is (Y 0.25Er0.25Lu0.25Tm0.25)2O3, the glass ceramic powder comprises the following components ：Y2O3、Lu2O3、Er2O3、Tm2O3、Al2O3 and SiO 2, the mass percentage of each component is ：7.3 wt%Y2O3、12.9 wt%Lu2O3、12.5 wt%Er2O3、12.3 wt%Tm2O3、22wt%Al2O3、33wt%SiO2,, the mass of the high-entropy rare earth oxide is 1.2g, and the mass of the glass ceramic powder is 3.6g.
The high-entropy rare earth silicate complex phase ceramic is prepared by the following method:
S1, mixing raw materials: respectively weighing high-entropy rare earth oxide and microcrystalline glass powder, and uniformly mixing by ball milling to obtain mixed powder, wherein the ball milling parameters are as follows: ball-material ratio is 1:4, ball-milling medium is selected from one of deionized water, absolute ethyl alcohol or toluene, rotating speed is 300 rpm, and ball-milling time is 24 hours;
S2, press forming: weighing 1.5g of the mixed powder obtained in the step S1, and compacting to obtain a green body, wherein the compacting parameters are as follows: the pressing pressure is 10Mpa, the pressing time is 10min, and the diameter of a pressed blank is 13mm;
S3, calcining: and (2) placing the green body obtained in the step (S2) in a muffle furnace for calcination to obtain the high-entropy rare earth silicate complex-phase ceramic, wherein the calcination parameters are as follows: the calcination temperature was 1450℃and the calcination time was 3 hours.
The high-entropy rare earth silicate complex phase ceramic obtained by SEM detection contains only trace SiO 2 residual glass phase, and the loss of weight of 100 h is kept to be only 0.01% in a water-oxygen environment of 1400 ℃ and 50% H 2O-50%O2.
From the results, the introduced high-entropy rare earth oxide reacts with silicon dioxide and aluminum oxide in the microcrystalline glass to generate rare earth silicate and mullite with good anti-oxygen corrosion performance, so that the ceramic conversion rate is improved, and the anti-oxygen corrosion performance of the ceramic matrix composite is further improved.
Although the present disclosure is disclosed above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the disclosure.
Claims (8)
1. The high-entropy rare earth silicate composite ceramic is characterized by being prepared from high-entropy rare earth oxide and microcrystalline glass powder, wherein the molecular formula of the high-entropy rare earth oxide is (RE 1RE2RE3RE4）2O3, the microcrystalline glass powder comprises the following components ：RE1 2O3、RE2 2O3、RE3 2O3、RE4 2O3、Al2O3 and SiO 2, the mass percentage of each component is as follows, the sum of the mass percentages of RE 1 2O3、RE2 2O3、RE3 2O3 and RE 4 2O3 is 0.1-45%, the mass percentage of Al 2O3 is 5-25%, the mass percentage of SiO 2 is 30-80%, and RE 1、RE2、RE3 and RE 4 are different from each other and are one selected from Y, yb, ho, er, dy, lu, gd, tm.
2. The high-entropy rare earth silicate composite ceramic according to claim 1, wherein the mass ratio of the high-entropy rare earth oxide to the glass ceramic powder is 1 (1-5).
3. The high-entropy rare earth silicate composite ceramic according to claim 1, wherein the particle size of the high-entropy rare earth oxide is 1-100 μm and the particle size of the glass ceramic powder is 1-100 μm.
4. The high-entropy rare earth silicate complex phase ceramic according to claim 1, wherein the mass percentage of each constituent phase in the high-entropy rare earth silicate complex phase ceramic is as follows: high entropy rare earth silicate: 50-75%, mullite: 15-35%, silicon dioxide 5-20% and rare earth oxide 5-15%.
5. A method for preparing the high-entropy rare earth silicate composite ceramic according to any one of claims 1 to 4, comprising the following steps:
s1, mixing raw materials: respectively weighing high-entropy rare earth oxide and microcrystalline glass powder, and uniformly mixing by ball milling to obtain mixed powder;
S2, press forming: compacting the mixed powder obtained in the step S1 to obtain a blank;
S3, calcining: and (3) placing the green body obtained in the step (S2) in a muffle furnace for calcination to obtain the high-entropy rare earth silicate complex-phase ceramic.
6. The method for preparing high-entropy rare earth silicate composite ceramic according to claim 5, wherein in the step S1, the ball milling parameters are as follows: the ball-material ratio is 1 (2-6), the ball-milling medium is one of deionized water, absolute ethyl alcohol or toluene, the ball-milling rotating speed is 200-400 rpm, and the ball-milling time is 10-50h.
7. The method for preparing high-entropy rare earth silicate composite ceramic according to claim 5, wherein in the step S2, the parameters of the press forming are as follows: the pressing pressure is 4-12MPa, and the pressing time is 3-15min.
8. The method for preparing high-entropy rare earth silicate composite ceramic according to claim 5, wherein in the step S3, the parameters of calcination are as follows: the calcination temperature is 1200-1450 ℃, and the calcination time is 1-5h.
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| WO2023174159A1 (en) * | 2022-03-14 | 2023-09-21 | 中国科学院宁波材料技术与工程研究所 | Metal-based composite material, and preparation method therefor and use thereof |
| CN117362035A (en) * | 2023-09-27 | 2024-01-09 | 西北工业大学 | High-entropy rare earth silicate ceramic powder resistant to high-temperature water oxygen corrosion and preparation method thereof |
| CN117383919A (en) * | 2023-08-30 | 2024-01-12 | 郑州大学 | High-entropy rare earth silicate ceramic coating material and preparation method thereof |
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| WO2023174159A1 (en) * | 2022-03-14 | 2023-09-21 | 中国科学院宁波材料技术与工程研究所 | Metal-based composite material, and preparation method therefor and use thereof |
| CN117383919A (en) * | 2023-08-30 | 2024-01-12 | 郑州大学 | High-entropy rare earth silicate ceramic coating material and preparation method thereof |
| CN117362035A (en) * | 2023-09-27 | 2024-01-09 | 西北工业大学 | High-entropy rare earth silicate ceramic powder resistant to high-temperature water oxygen corrosion and preparation method thereof |
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| 李刘媛等: "RE-Si-Al-O玻璃相对高熵稀土双硅酸盐微结构及耐CMAS腐蚀性能的影响", 《无机材料学报》, 27 March 2024 (2024-03-27), pages 1 - 12 * |
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