CN118186585A - Monocrystalline rare earth disilicate material with strong CMAS corrosion resistance and preparation method thereof - Google Patents
Monocrystalline rare earth disilicate material with strong CMAS corrosion resistance and preparation method thereof Download PDFInfo
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052681 coesite Inorganic materials 0.000 claims description 14
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- 229910052682 stishovite Inorganic materials 0.000 claims description 14
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- 239000011812 mixed powder Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
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- 238000003746 solid phase reaction Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
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- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 2
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- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 2
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
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- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 2
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention relates to the field of environmental barrier coatings or thermal barrier/environmental barrier integrated protective coatings, and discloses a single-crystal rare earth double silicate material with strong CMAS corrosion resistance and a preparation method thereof. Aiming at the rare earth disilicate with good thermal expansion matching property and excellent corrosion resistance, the single crystal rare earth disilicate material with strong CMAS corrosion resistance is obtained by improving the preparation method, and the requirement of an environmental barrier or a thermal barrier/environmental barrier integrated protective material is met. The specific procedures are as follows: the method is characterized in that rare earth oxide and silicon oxide are used as raw materials, and the raw materials are sequentially subjected to mechanical mixing, pressureless sintering, compression molding, cold isostatic pressing and optical suspension zone melting directional solidification to prepare the single-crystal rare earth double silicate material with compact internal combination, single grain orientation and excellent CMAS corrosion resistance.
Description
Technical Field
The invention relates to the field of environmental barrier coatings or thermal barrier/environmental barrier integrated protective coatings, in particular to a strong CMAS (CaO-MgO-Al 2O3-SiO2 low-melting-point environmental sediment) corrosion-resistant single-crystal rare earth double-silicate material RE 2Si2O7 and a preparation method thereof.
Background
The advanced aviation power system is known as "the pearl on the modern industrial crown", and represents the technological level, industrial foundation, economy and national defense strength of a country. With the development of aeroengines, higher requirements are put on the efficiency and thrust-weight ratio of the aeroengines, and the improvement of the temperature of the front air inlet of the turbine is a key measure for realizing high thrust-weight ratio and high efficiency. The silicon carbide fiber reinforced silicon carbide ceramic matrix composite (SiC f/SiC, CMC) has excellent performances of high temperature resistance, low density, high specific strength and the like, can meet the requirement of a hot end part of an aeroengine on high-temperature structural materials, and can be used for various thermal structural parts such as a turbine outer ring, turbine blades, a flame tube, a flame stabilizer and the like of the aeroengine. However, in a severe gas environment in actual service, the SiC f/SiC ceramic matrix composite is easily corroded by high-temperature steam, so that the oxide layer SiO 2 is failed and the structural member is damaged. In addition, in the actual service process, the molten oxide particles (such as dust, volcanic ash and desert sand) sucked into the engine can undergo eutectic reaction at about 1200 ℃ to form a low-melting-point glass phase CMAS (CaO-MgO-Al 2O3-SiO2 low-melting-point environmental sediment) to be adsorbed on the hot end part of the engine, and then react with the ceramic matrix composite material, so that the service life of the engine is reduced. Therefore, when the composite material is used as a structural component of an aeroengine, the surface of the SiC f/SiC ceramic matrix composite material is coated with a protective coating with excellent high-temperature resistance, abrasion resistance and high-temperature mechanical properties and excellent steam resistance and CMAS corrosion resistance.
Rare earth disilicate (RE 2Si2O7) is considered as an environmental barrier or thermal barrier/environmental barrier integrated coating candidate material for SiC f/SiC ceramic matrix composites with the most promising application prospect due to its low density, high temperature stability, excellent chemical compatibility with the SiC f/SiC ceramic matrix composites and similar thermal expansion coefficients. However, due to the chemical attack of CMAS, the application of rare earth disilicates as environmental barrier or thermal/environmental barrier integrated coating materials is limited to below 1300 ℃ and cannot meet the service requirements of higher temperatures. When in service at 1300 ℃, the reaction between CMAS and rare earth disilicates can be divided into two different cases. The first case is that the rare earth disilicate reacts with CMAS to form a dense product layer, which delays the rate of CMAS further reaction, mainly in the larger ionic radius rare earth disilicates (e.g., gd 2Si2O7、Er2Si2O7 and Y 2Si2O7, etc.). In yet another case, no dense product layer is formed, while CMAS melt penetrates into the interior of the material through RE 2Si2O7 grain boundaries, predominantly in rare earth bissilicates of smaller ionic radius (such as Yb 2Si2O7 and Lu 2Si2O7). However, when RE 2Si2O7 is in service at higher temperatures (e.g., 1500 ℃), the thermal stability of the grain boundaries is further reduced, significant CMAS penetration of the RE 2Si2O7 material along the grain boundaries occurs, and swelling cracks or "holes" are created inside the material, resulting in material failure. Thus CMAS infiltration along grain boundaries is a main reason for preventing the service of rare earth disilicate materials at higher temperatures, and exploration for preparing rare earth disilicate materials with few grain boundaries or without grain boundaries is an effective measure for improving the service temperature of the environmental barrier or thermal barrier/environmental barrier integrated coating materials at present.
The light suspension zone-melting directional solidification technology uses a high-power halogen lamp as a heat source, and has the advantages of high smelting temperature, high temperature gradient, high solidification rate control precision, wide material and environment adaptability, no pollution and the like, and the prepared sample has uniform tissue distribution and excellent performance. Therefore, the invention selects the optical suspension zone-melting directional solidification technology to successfully prepare the single-crystal rare earth disilicate material, researches the CMAS corrosion resistance at a higher temperature of 1500 ℃, and results show that the single-crystal rare earth disilicate material prepared by the invention has compact structure and still maintains excellent CMAS corrosion resistance at 1500 ℃. The invention widens the application temperature of the rare earth disilicate material to 1500 ℃, and promotes the further improvement of the air inlet temperature and the working efficiency of the aeroengine.
Disclosure of Invention
The invention aims to provide a single-crystal rare earth double silicate material (RE 2Si2O7) with strong CMAS corrosion resistance and a preparation method thereof, and the rare earth double silicate material RE 2Si2O7 with compact structure, few grain boundaries or no grain boundaries is prepared by an optical suspension zone melting method, so that the aim of protecting a hot end part against CMAS corrosion at ultrahigh temperature is fulfilled, and the service life of an engine is prolonged.
The invention provides a single-crystal rare earth double silicate material with strong CMAS corrosion resistance, which is RE 2Si2O7, wherein RE is one of Y, sc, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu; the material has single orientation, no obvious grain boundary in the material, and still maintains excellent CMAS corrosion resistance in an ultra-high temperature environment.
The invention also provides a preparation method of the monocrystalline rare earth double silicate material with strong CMAS corrosion resistance, which takes rare earth oxide (RE 2O3) and silicon oxide (SiO 2) as raw materials, and sequentially carries out mechanical mixing, pressureless sintering, compression molding, cold isostatic pressing and optical suspension zone melting directional solidification to prepare the monocrystalline rare earth double silicate material RE 2Si2O7;
the specific method comprises the following steps:
(1) Mixing RE 2O3 oxide powder with SiO 2 powder, mixing the raw material mixed powder with a ball milling solvent, and sequentially performing ball milling, drying and screening to obtain uniformly mixed RE 2O3-SiO2 mixture powder; carrying out pressureless solid phase reaction on the RE 2O3-SiO2 mixture powder at the temperature of T 1 to obtain rare earth disilicate RE 2Si2O7 powder;
(2) Placing the uniformly dispersed RE 2Si2O7 powder into a mould, and preparing a prefabricated member blank under a certain pressure; and performing cold isostatic pressing treatment on the preform blank; carrying out pressureless sintering on the RE 2Si2O7 prefabricated part blank subjected to cold isostatic pressing treatment at the temperature of T 2 to obtain a prefabricated part with high density;
(3) And (3) directionally solidifying the pressureless sintered preform in optical suspension zone melting furnace equipment to prepare the single crystal rare earth double silicate RE 2Si2O7 sample rod.
The invention provides a preparation method of a high CMAS corrosion resistance single crystal rare earth double silicate material, wherein rare earth oxide RE 2O3 powder and silicon oxide SiO 2 powder in the step (1) are mixed according to the following (a 1) or (a 2):
(a1) Rare earth oxide RE 2O3 powder and silicon oxide SiO 2 powder are mixed according to a molar ratio of 1:2, the SiO 2 powder is slightly excessive, and the mass fraction of the slightly excessive SiO 2 powder is 0.1-10.0 wt%;
(a2) Rare earth oxide RE 2O3 powder and silicon oxide SiO 2 powder are firstly mixed according to a molar ratio of 1:1 to prepare rare earth monosilicate RE 2SiO5 powder, then RE 2SiO5 powder and SiO 2 powder are mixed according to a molar ratio of 1:1, siO 2 powder is slightly excessive, and the mass fraction of slightly excessive SiO 2 powder is 0.1-10.0 wt%.
According to the preparation method of the monocrystalline rare earth double silicate material with strong CMAS corrosion resistance, one of Y2O3,Sc2O3,La2O3,Ce2O3,Pr2O3,Nd2O3,Pm2O3,Sm2O3,Eu2O3,Gd2O3,Tb2O3,Dy2O3,Ho2O3,Er2O3,Tm2O3,Yb2O3 and Lu 2O3 can be selected from rare earth oxide RE 2O3.
The invention provides a preparation method of a high CMAS corrosion resistance single crystal rare earth double silicate material, wherein in the step (1), the mixing of rare earth oxide RE 2O3 powder and silicon oxide SiO 2 powder is carried out in a planetary ball mill; the ball milling solvent is absolute ethyl alcohol, wherein the mass ratio of the raw material mixed powder to the absolute ethyl alcohol is 1:2-2:1; ball-material ratio is 1:2-4:1, ball milling rotation speed is 120-350 rpm, mixing ball milling time is 2-24 h. In the step (1), T 1 is 1300-1600 ℃, and the heat preservation time is 2-24 h.
The invention provides a preparation method of a high CMAS corrosion resistance monocrystalline rare earth disilicate material, wherein a die in the step (2) is a stainless steel die or a rubber die; the size of the die is length, width and height= (10-200 mm) × (5-15 mm); the pressure value is 20-50 MPa, and the holding time is 5-50 min. The pressure value of the cold isostatic pressing in the step (2) is 200-350 MPa, and the holding time is 20-50 min. The temperature T 2 in the step (2) is 1300-1600 ℃, and the heat preservation time is 2-24 h.
The invention provides a preparation method of a high CMAS corrosion resistance monocrystalline rare earth double silicate material, wherein the heat source of an optical suspension zone melting furnace in the step (3) is a xenon lamp, the power of the xenon lamp is 2-4 kW, and the number of the xenon lamps is 2-4. The directional solidification seed crystal in the step (3) is alumina Al 2O3 or zirconia ZrO 2; the parameters of directional solidification growth are set as follows: the upper clamp and the lower clamp rotate in the same direction or in opposite directions, the rotation speed range is 5-30 rpm, the drawing speed range is 5-30 mm/h, argon is introduced in the directional solidification process, and the ventilation amount range is 1-5L/min.
The invention has the advantages and beneficial effects that:
1. The invention takes rare earth oxide and silicon oxide as raw materials, and the single crystal rare RE 2Si2O7 with single orientation, compact structure and no obvious grain boundary is prepared by mechanical mixing, pressureless sintering, compression molding, cold isostatic pressing of rare earth disilicate and directional solidification of light suspension zone melting in sequence.
2. When the rare earth double silicate RE 2Si2O7 preform blank is prepared, the cold isostatic pressing process is added after the compression molding step, so that the pressure inside the preform blank is uniformly distributed, the material combination is tight, and the success rate of preparing the single crystal rare earth double silicate RE 2Si2O7 with uniform structure and excellent performance by an optical suspension zone melting method is improved.
3. In the reaction of the prepared single-crystal rare earth double silicate RE 2Si2O7 and CMAS at 1500 ℃, no Ca and Si elements appear in the sample, no obvious CMAS permeates along grain boundaries, and internal swelling cracks are generated, which shows that the single-crystal rare earth double silicate RE 2Si2O7 has excellent CMAS corrosion resistance at 1500 ℃. The invention widens the application temperature of the rare earth disilicate material to 1500 ℃, and can promote the further improvement of the air inlet temperature of the aeroengine.
Drawings
FIG. 1 is an X-ray diffraction pattern of a single-crystal rare earth disilicate Lu 2Si2O7 sample in example 1;
FIG. 2 is a cross-sectional morphology of the single-crystal rare earth disilicate Lu 2Si2O7 sample of example 1 after reaction with CMAS at 1500℃for 50 h;
FIG. 3 shows electron back-scattering diffraction patterns (a), corresponding pole patterns (b), and corresponding counter pole patterns (c) of the single crystal rare earth disilicate Lu 2Si2O7 sample of example 2;
FIG. 4 is a plot of elemental surface scans of a sample of monocrystalline rare earth disilicate Lu 2Si2O7 of example 2 after reaction with CMAS at 1500℃for 50 hours;
wherein, (a) a partial cross-sectional profile, (b) Mg, (c) Al, (d) Si, (e) Ca, (f) Lu;
FIG. 5 is an X-ray diffraction pattern of a single-crystal rare earth disilicate Yb 2Si2O7 sample in example 3;
FIG. 6 is a cross-sectional morphology graph of a single-crystal rare-earth disilicate Yb 2Si2O7 sample of example 3 after 50h reaction with CMAS at 1500 ℃.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
The performance test information in the following examples is as follows:
1. Morphology observation:
Observing the morphology of the prepared sample after reaction with CMAS by using a field emission scanning electron microscope (SUPRA 35, zeiss, germany);
x-ray diffraction analysis:
The crystal structure of the sample was analyzed using an X-ray diffractometer (D/max-2400, rigaku, japan);
3. orientation analysis:
The crystal orientation of the samples was analyzed using an electron back-scattering diffractometer (NordlysNano, oxford Instruments, united Kingdom).
Example 1
1) Rare earth oxide Lu 2O3 powder and silicon oxide SiO 2 powder are used as raw materials,
2) Rare earth oxide Lu 2O3 powder and silicon oxide SiO 2 powder are prepared into rare earth disilicate Lu 2Si2O7 powder through a two-step method, the powder is mixed with a molar ratio of 1:1 to obtain Lu 2O3-SiO2 mixed powder, the obtained mixed powder is mixed with absolute ethyl alcohol in a planetary ball mill in a ratio of 1:1, the ball-material ratio is 1:1, the ball milling speed is 240rpm, and the mixing time is 12 hours. And (3) drying the mixed slurry at 80 ℃ and then sieving to obtain the uniformly mixed oxide raw material powder. And (3) carrying out pressureless solid phase reaction on the oxide raw material powder at 1550 ℃ for 10 hours to obtain Lu 2SiO5 powder. Weighing Lu 2SiO5 powder and SiO 2 powder in a molar ratio of 1:1 (5 wt% of SiO 2 powder excess), sequentially performing ball milling, drying and powder screening to obtain uniformly mixed Lu 2SiO5-SiO2 mixed powder, and performing pressureless solid phase reaction on the obtained powder at 1550 ℃ for 10 hours to obtain rare earth disilicate Lu 2Si2O7 powder;
3) The pressing process comprises two steps of mould dry pressing and cold isostatic pressing, namely, placing the Lu 2Si2O7 powder which is uniformly dispersed in a rubber mould for dry pressing, wherein the mould size is 100mm multiplied by 15mm, the pressure value is 30MPa, and the load retention time is 20min; and preparing a prefabricated member blank by cold isostatic pressing, wherein the pressure value of the cold isostatic pressing is 250MPa, and the holding time is 30min. Carrying out pressureless sintering on the Lu 2Si2O7 prefabricated part blank at 1550 ℃ for 20 hours to obtain a prefabricated part with high density;
4) And carrying out directional solidification on the pressureless sintered preform in an optical suspension zone melting device. The directional solidification seed crystal selects alumina Al 2O3, the heat source of the optical suspension zone melting furnace is a xenon lamp, the power of the xenon lamp is 3kW, and the number of the xenon lamps is 3; the parameters of directional solidification growth are set as follows: the upper and lower clamps rotate reversely, the rotation speed is 15rpm, the drawing speed is 15mm/h, argon is introduced in the directional solidification process, and the ventilation amount is 2L/min, so that the monocrystal rare earth double silicate Lu 2Si2O7 sample rod is prepared.
The prepared sample of the single crystal Lu 2Si2O7 is detected:
The prepared Lu 2Si2O7 sample bar was cut and CMAS corrosion experiments were performed after polishing the cross section. CMAS corrosion experiment parameter selection: CMAS has a composition of 33mol% CaO-6.5mol% Al 2O3-9 mol％MgO-45mol％SiO2, a reaction temperature of 1500 ℃, a reaction time of 50 hours, and a CMAS coating amount of 30mg/cm 2.
As shown in FIG. 1, in order to characterize the crystal structure of a sample prepared by the optical suspension zone melting method, X-ray diffraction analysis was performed on the obtained sample in this example, and the results show that the sample rods obtained in this example were simple in orientation, with the orientations of (001), (002),And (022).
As shown in fig. 2, in order to test CMAS corrosion resistance of the samples prepared in this example, cross sections of the samples after corrosion were observed using a scanning electron microscope. The results show that the samples showed no CMAS penetration along the grain boundaries after 50h reaction with CMAS at 1500 ℃ and exhibited excellent high temperature CMAS corrosion resistance.
Example 2
1) Rare earth oxide Lu 2O3 powder and silicon oxide SiO 2 powder are used as raw materials,
2) Rare earth oxide Lu 2O3 powder and silicon oxide SiO 2 powder are prepared into rare earth disilicate Lu 2Si2O7 powder through a one-step method, the powder is mixed according to a molar ratio of 1:2 to obtain Lu 2O3-SiO2 mixed powder (5 wt% of SiO 2 powder excess), the obtained mixed powder and absolute ethyl alcohol are mixed according to a ratio of 1:1 in a planetary ball mill, the ball-material ratio is 1:1, the ball milling speed is 240rpm, and the mixing time is 12h. And (3) drying the mixed slurry at 80 ℃ and then sieving to obtain the uniformly mixed oxide raw material powder. Carrying out non-pressure solid phase reaction on the oxide raw material powder at 1550 ℃ for 10 hours to obtain rare earth disilicate Lu 2Si2O7 powder;
3) The pressing process comprises two steps of mould dry pressing and cold isostatic pressing, namely, placing the Lu 2Si2O7 powder which is uniformly dispersed in a rubber mould for dry pressing, wherein the mould size is 100mm multiplied by 15mm, the pressure value is 30MPa, and the load retention time is 20min; and preparing a prefabricated member blank by cold isostatic pressing, wherein the pressure value of the cold isostatic pressing is 250MPa, and the holding time is 30min. Carrying out pressureless sintering on the Lu 2Si2O7 prefabricated part blank at 1550 ℃ for 20 hours to obtain a prefabricated part with high density;
4) And carrying out directional solidification on the pressureless sintered preform in an optical suspension zone melting device. The directional solidification seed crystal selects alumina Al 2O3, the heat source of the optical suspension zone melting furnace is a xenon lamp, the power of the xenon lamp is 3kW, and the number of the xenon lamps is 3; the parameters of directional solidification growth are set as follows: the upper and lower clamps rotate reversely, the rotation speed is 15rpm, the drawing speed is 15mm/h, argon is introduced in the directional solidification process, and the ventilation amount is 2L/min, so that the monocrystal rare earth double silicate Lu 2Si2O7 sample rod is prepared.
The prepared sample of the single crystal Lu 2Si2O7 is detected:
The prepared Lu 2Si2O7 sample bar was cut and CMAS corrosion experiments were performed after polishing the cross section. CMAS corrosion experiment parameter selection: CMAS has a composition of 33mol% CaO-6.5mol% Al 2O3-9 mol％MgO-45mol％SiO2, a reaction temperature of 1500 ℃, a reaction time of 50 hours, and a CMAS coating amount of 30mg/cm 2.
As shown in FIG. 3, in order to characterize the grain orientation of the samples prepared by the optical suspension zone melting method, the electron back scattering diffraction analysis was performed on the obtained samples in this example, and the results show that the sample rods obtained in this example were single in orientation, have no distinct grain boundaries, and have a grain orientation of (001) in the selected region.
As shown in fig. 4, in order to test CMAS corrosion resistance of the samples prepared in this example, cross sections of the corroded samples were observed using an energy dispersive X-ray spectrometer. The results show that the sample has no phenomenon that Ca and Si elements permeate into the sample along grain boundaries after the sample reacts with CMAS for 50 hours at 1500 ℃, and shows excellent high-temperature CMAS corrosion resistance.
Example 3
1) Rare earth oxide Yb 2O3 powder and silicon oxide SiO 2 powder are taken as raw materials,
2) The rare earth oxide Yb 2O3 powder and the silicon oxide SiO 2 powder are prepared into rare earth disilicate Yb 2Si2O7 powder through a two-step method, the mixed powder of Yb 2O3-SiO2 is obtained by mixing the powder with a molar ratio of 1:1, the obtained mixed powder is mixed with absolute ethyl alcohol in a planetary ball mill with a ball-material ratio of 1:1, the ball-milling rotating speed is 240rpm, and the mixing time is 12 hours. And (3) drying the mixed slurry at 80 ℃ and then sieving to obtain the uniformly mixed oxide raw material powder. And (3) carrying out pressureless solid phase reaction on the oxide raw material powder at 1550 ℃ for 10 hours to obtain Yb 2SiO5 powder. Weighing Yb 2SiO5 powder and SiO 2 powder in a molar ratio of 1:1 (5 wt% of SiO 2 powder excess), sequentially performing ball milling, drying and powder screening to obtain uniformly mixed Yb 2SiO5-SiO2 mixed powder, and performing pressureless solid phase reaction on the obtained powder at 1550 ℃ for 10 hours to obtain rare earth disilicate Yb 2Si2O7 powder;
3) The pressing process comprises two steps of mould dry pressing and cold isostatic pressing, wherein uniformly dispersed Yb 2Si2O7 powder is placed in a rubber mould for dry pressing, the mould size is 100mm multiplied by 15mm, the pressure value is 30MPa, and the holding time is 20min; and preparing a prefabricated member blank by cold isostatic pressing, wherein the pressure value of the cold isostatic pressing is 250MPa, and the holding time is 30min. Carrying out pressureless sintering on the Yb 2Si2O7 prefabricated member blank at 1550 ℃ for 20 hours to obtain a prefabricated member with high density;
4) And carrying out directional solidification on the pressureless sintered preform in an optical suspension zone melting device. The directional solidification seed crystal selects alumina Al 2O3, the heat source of the optical suspension zone melting furnace is a xenon lamp, the power of the xenon lamp is 3kW, and the number of the xenon lamps is 3; the parameters of directional solidification growth are set as follows: the upper and lower clamps rotate positively, the rotation speed is 15rpm, the drawing speed is 15mm/h, argon is introduced in the directional solidification process, and the ventilation amount is 2L/min, so that the single crystal rare earth double silicate Yb 2Si2O7 sample rod is prepared.
Detecting the prepared sample of the single crystal Yb 2Si2O7:
The prepared Yb 2Si2O7 sample bar was cut, and CMAS corrosion experiments were performed after polishing the cross section. CMAS corrosion experiment parameter selection: CMAS has a composition of 33mol% CaO-6.5mol% Al 2O3-9mol％MgO-45mol％SiO2, a reaction temperature of 1500 ℃, a reaction time of 50 hours, and a CMAS coating amount of 30mg/cm 2.
As shown in FIG. 5, in order to characterize the crystal structure of the sample prepared by the optical suspension zone melting method, the X-ray diffraction analysis was performed on the obtained sample in this example, and the results show that the sample rods obtained in this example were simple in orientation, namely (022), (400) and (023).
As shown in fig. 6, in order to test CMAS corrosion resistance of the samples prepared in this example, cross sections of the samples after corrosion were observed using a scanning electron microscope. The results show that the samples showed no CMAS penetration along the grain boundaries after 50h reaction with CMAS at 1500 ℃ and exhibited excellent high temperature CMAS corrosion resistance.
The embodiment results show that the RE 2Si2O7 sample prepared and obtained by adopting the optical suspension zone melting method has single orientation and small number of grain boundaries, can still maintain good CMAS corrosion resistance at 1500 ℃, and meets the service requirements of environmental barriers or thermal barrier/environmental barrier integrated coatings at high temperature.
Although the present invention has been described in some embodiments, it should be understood that the invention is not limited to the embodiments, and that any person skilled in the art may make any possible variations and modifications to the technical solution of the present invention by using the methods and technical matters disclosed in the foregoing description without departing from the spirit and scope of the present invention, and therefore any simple modifications, equivalent variations and modifications to the embodiments described above according to the technical matters of the present invention fall within the scope of the technical matters of the present invention.
Claims (12)
1. A strong CMAS corrosion resistant single crystal rare earth disilicate material characterized by: the material is RE 2Si2O7, wherein RE is one of Y, sc, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu; the material has single orientation, no obvious grain boundary in the material, and excellent CMAS corrosion resistance in an ultra-high temperature environment.
2. A method for preparing the single-crystal rare earth disilicate material with strong CMAS corrosion resistance according to claim 1, which is characterized in that: the preparation method comprises the steps of taking rare earth oxide (RE 2O3) and silicon oxide (SiO 2) as raw materials, sequentially carrying out mechanical mixing, pressureless sintering, compression molding, cold isostatic pressing and optical suspension zone melting directional solidification to prepare the single-crystal rare earth double silicate material RE 2Si2O7.
3. The method for preparing the single-crystal rare earth disilicate material with strong CMAS corrosion resistance according to claim 2, wherein:
(1) Mixing RE 2O3 oxide powder with SiO 2 powder, mixing the raw material mixed powder with a ball milling solvent, and sequentially performing ball milling, drying and screening to obtain uniformly mixed RE 2O3-SiO2 mixture powder; carrying out pressureless solid phase reaction on the RE 2O3-SiO2 mixture powder at the temperature of T 1 to obtain rare earth disilicate RE 2Si2O7 powder;
(2) Placing the uniformly dispersed RE 2Si2O7 powder into a mould, and preparing a prefabricated member blank under a certain pressure; and performing cold isostatic pressing treatment on the preform blank; carrying out pressureless sintering on the RE 2Si2O7 prefabricated part blank subjected to cold isostatic pressing treatment at the temperature of T 2 to obtain a prefabricated part with high density;
(3) And (3) directionally solidifying the pressureless sintered preform in optical suspension zone melting furnace equipment to prepare the single crystal rare earth double silicate RE 2Si2O7 sample rod.
4. A method for preparing a strong CMAS corrosion resistant single crystal rare earth disilicate material according to claim 2 or 3, characterized by: the rare earth oxide RE 2O3 is one of Y2O3,Sc2O3,La2O3,Ce2O3,Pr2O3,Nd2O3,Pm2O3,Sm2O3,Eu2O3,Gd2O3,Tb2O3,Dy2O3,Ho2O3,Er2O3,Tm2O3,Yb2O3 and Lu 2O3.
5. A method for preparing a strong CMAS corrosion resistant single crystal rare earth disilicate material according to claim 3, wherein: the rare earth oxide RE 2O3 powder and the silicon oxide SiO 2 powder in the step (1) are mixed according to the following mode (a 1) or (a 2):
(a1) Rare earth oxide RE 2O3 powder and silicon oxide SiO 2 powder are mixed according to a molar ratio of 1:2, the SiO 2 powder is slightly excessive, and the mass fraction of the slightly excessive SiO 2 powder is 0.1-10.0 wt%;
(a2) Rare earth oxide RE 2O3 powder and silicon oxide SiO 2 powder are firstly mixed according to a molar ratio of 1:1 to prepare rare earth monosilicate RE 2SiO5 powder, then RE 2SiO5 powder and SiO 2 powder are mixed according to a molar ratio of 1:1, siO 2 powder is slightly excessive, and the mass fraction of slightly excessive SiO 2 powder is 0.1-10.0 wt%.
6. A method for preparing a strong CMAS corrosion resistant single crystal rare earth disilicate material according to claim 3, wherein: the rare earth oxide RE 2O3 powder and the silicon oxide SiO 2 powder in the step (1) are mixed in a planetary ball mill;
The ball milling solvent is absolute ethyl alcohol, wherein the mass ratio of the raw material mixed powder to the absolute ethyl alcohol is 1:2-2:1;
Ball-material ratio is 1:2-4:1, ball milling rotation speed is 120-350 rpm, mixing ball milling time is 2-24h.
7. A method for preparing a strong CMAS corrosion resistant single crystal rare earth disilicate material according to claim 3, wherein: in the step (1), T 1 is 1300-1600 ℃, and the heat preservation time is 2-24 h.
8. A method for preparing a strong CMAS corrosion resistant single crystal rare earth disilicate material according to claim 3, wherein: the die in the step (2) is a stainless steel die or a rubber die; the size of the die is length, width and height= (10-200 mm) × (5-15 mm); the pressure value is 20-50 MPa, and the holding time is 5-50 min.
9. A method for preparing a strong CMAS corrosion resistant single crystal rare earth disilicate material according to claim 3, wherein: the pressure value of the cold isostatic pressing in the step (2) is 200-350 MPa, and the holding time is 20-50 min.
10. A method for preparing a strong CMAS corrosion resistant single crystal rare earth disilicate material according to claim 3, wherein: the temperature T 2 in the step (2) is 1300-1600 ℃, and the heat preservation time is 2-24 h.
11. A method for preparing a strong CMAS corrosion resistant single crystal rare earth disilicate material according to claim 3, wherein: the heat source of the light suspension zone furnace in the step (3) is a xenon lamp, the power of the xenon lamp is 2-4 kW, and the number of the xenon lamps is 2-4.
12. A method for preparing a strong CMAS corrosion resistant single crystal rare earth disilicate material according to claim 3, wherein: the directional solidification seed crystal in the step (3) is alumina Al 2O3 or zirconia ZrO 2; the parameters of directional solidification growth are set as follows: the upper clamp and the lower clamp rotate in the same direction or in opposite directions, the rotation speed range is 5-30 rpm, the drawing speed range is 5-30 mm/h, argon is introduced in the directional solidification process, and the ventilation amount range is 1-5L/min.
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