CN101767987A - Yttrium erbium aluminate powder for thermal barrier coating ceramic layer and preparation method thereof - Google Patents

Yttrium erbium aluminate powder for thermal barrier coating ceramic layer and preparation method thereof Download PDF

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Publication number
CN101767987A
CN101767987A CN201010103122A CN201010103122A CN101767987A CN 101767987 A CN101767987 A CN 101767987A CN 201010103122 A CN201010103122 A CN 201010103122A CN 201010103122 A CN201010103122 A CN 201010103122A CN 101767987 A CN101767987 A CN 101767987A
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powder
yttrium
ceramic layer
barrier coating
heat
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彭鹏
房明浩
冀新友
刘艳改
黄朝晖
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China University of Geosciences
China University of Geosciences Beijing
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China University of Geosciences Beijing
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Abstract

The invention relates to a yttrium erbium aluminate powder for a thermal barrier coating ceramic layer and a preparation method thereof; the yttrium erbium aluminate powder is formed chemically as follows: Y3-xErxAl5O12, wherein x is more than 0 and is less than or equal to 3; the intrinsic heat conduction coefficient of the material is lower than that of zirconium oxide stabilized by 7-8 percent of yttrium oxide, which is used generally at present. The phase is still stable at 1700 DEG C for 6 hours; the material can be used as the thermal barrier coating ceramic layer or the oxygen barrier layer material of YSZ ceramic layer, and the using temperature interval is from room temperature to 1700 DEG C; the yttrium erbium aluminate powder can be used for the thermal barrier coating ceramic layer, can be used for preparing yttrium erbium aluminate ceramics and can be used for preparing additives for other high-temperature materials.

Description

A kind of Yttrium erbium aluminate powder that is used for heat-barrier coating ceramic layer and preparation method thereof
Technical field
The present invention relates to a kind of Yttrium erbium aluminate powder that is used for heat-barrier coating ceramic layer and preparation method thereof, belong to the heat barrier coat material technical field.
Background technology
At present, the working temperature of hot machine constantly is enhanced, and its objective is in order to obtain higher working efficiency with save energy and reduction discharge amount of exhaust gas.To cause all multi-parts in the firing system to stand the influence of harsher high temperature and high thermal shocking, exhaust gas corrosion and particle erosion thus.For the reliability that improves the work of hot machine parts and increase the service life, need prepare one deck thermal insulation coating at the working-surface of parts, to reduce being heated of metallic matrix, guarantee the intensity and the corrosion resistance nature of these parts.These thermal insulation coatings just are called as thermal barrier coating (Thermal Barrier Coatings abbreviates TBCs as).Generally speaking, the TBCs of hot machine is by forming less than the ceramic surface and the melts combine bottom of 2W/ (mk) low heat conductivity.The synthetic more ceramic surface material of low heat conductivity is the developing direction of TBCs technology.
ZrO 2Characteristics such as pottery has fusing point height, hardness height, intensity and toughness is higher, thermal conductivity is low, thermal expansivity and superalloy are very approaching are to study and use one of maximum TBCs ceramic surface material over nearly more than 20 years.NASA (NASA) studies show that, with the Y of 6～8wt% 2O 3Stable ZrO 2The performance of (being called for short YSZ) is best, and this also is to use the most sophisticated at most ceramic heat insulating coating material among the present TBCs.For many years, to adding the ZrO of different stablizers 2The elevated temperature heat FATIGUE STABILITY of ceramic heat-barrier coating, and the heat-proof quality of the YSZ coating that (plasma spraying, CVD, EBPVD etc.) obtain under the different coating technology (thick-layer or thin layer) has been carried out a large amount of research work.But along with improving constantly of hot machine working temperature, the YSZ coating exposes following shortcomings gradually: 1, working temperature is not high enough, life-time service under high temperature (being higher than 1200 ℃), the YSZ coating still can exist phase transformation, grain growth, little pore to shrink phenomenons such as sintering, make thermal conductivity increase, the interface thermal stresses raises and causes disbonding, causes hot machine to reduce work-ing life; 2, thermal conductivity height limits its use range; 3, oxygen ion conduction hyperenergia, because YSZ is good oxygen ion conductor, under hot machine working conditions, oxygen is by the aluminium mutual diffusion mutually in ceramic layer and the tack coat, (main component is α-Al at ceramic layer and tie-layer interface place formation one deck thermal growth oxide layer 2O 3), cause the metal bonding coating under the ceramic layer to be easy to oxidized and corrosion, this causes the delamination of thermal barrier coating to a great extent and peels off.
Based on the above shortcoming of the YSZ coating of generally using, existing the investigator of various countries has mainly carried out the work of two aspects in recent years in order to obtain more high performance TBCs material, is to the further modification of YSZ on the one hand, adds HfO in YSZ 2And Er 2O 3, NiO, Nd 2O 3, Gd 2O 3And Yb 2O 3Improve the high-temperature stability of material and the thermal conductivity of reduction material.Be to seek some to have the stable low heat conduction oxide ceramics of higher temperature and substitute YSZ on the other hand.Domestic aspect the research of TBCs ceramic coating material, also all concentrate on YSZ series or add on the zirconia coating material direction of other oxide stabilizer.
This class surrogate mainly contains: LaMgAl 11O 19Pottery, LaMgAl 11O 19Pottery have with the YSZ ceramic phase like heat physical properties, but its thermo-chemical stability and structural stability are better than YSZ pottery.R.Vassen finds La 2Zr 2O 7Pottery has the Young's modulus lower than YSZ pottery, lower thermal conductivity (700 ℃ thermal conductivity is 1.6W/mK), better high-temperature stability, and the fracture toughness property suitable with YSZ.In addition, the heat barrier coat material of the rare earth zirconate system that development in recent years is got up, have the thermal conductivity lower than YSZ material (1～1.6W/mK) and higher use temperature (more than 1600 ℃), be the novel heat barrier coat material that a class gets a good chance of.Another is to consist of Y 3Al xFe (5-x)O 12The garnet pottery of (x=0,0.7,1.4 and 5.0), it has excellent mechanical behavior under high temperature, (Y wherein before fusing 3Al 5O 12Fusing point is 2243K) can keep excellent phase stability and thermostability.While Y 3Al xFe (5-x)O 12The thermal conductivity of material is suitable with the YSZ material, but the oxygen diffusibility than low 10 orders of magnitude of YSZ about, Y 3Al xFe (5-x)O 12Being expected to provides better protection to tack coat.Prove absolutely all that below the rare earth ferro-aluminum hydrochlorate pottery through adulterated garnet structure is a kind of TBCs ceramic coating candidate material that gets a good chance of that has, particularly will have higher use temperature and longer work-ing life to the rare earth ferro-aluminum hydrochlorate pottery of garnet structure as the compound coating of the lower rare earth zirconate formation of oxygen barrier layers and thermal conductivity.
Garnet is a kind of oxide compound with complex crystals structure, and its structure cell has 160 ions and constitutes, and chemical formula is A 3B 2C 3O 12Cation A, B, C lay respectively at dodecahedron, octahedron and tetrahedral interstice, adopt heavier ion pair A, B, C position to mix, lattice is bigger to the phon scattering effect, can predict that the rare-earth garnet material after the doping has the thermal conductivity lower than YAG, has the better stability at elevated temperature than YSZ simultaneously.Though YAG has obtained extensive and deep research for many years as a kind of laser crystal material of excellent performance, but the research for the high temperature thermal property of YAG pottery is relative less with report, particularly just just begins for the research of mixing to the high-temperature behavior influence of the rare earth ferro-aluminum silicate material of garnet structure.People are also only to Y at present 3Al xFe (5-x)O 12Wait the heat conductivility of the rare earth ferro-aluminum hydrochlorate stupalith of a few garnet structure to study, and for a large amount of rear-earth-doped Y 3-xEr xAl 5O 12The heat conductivility and the stability at elevated temperature of series compound also be not very clear, and be also few as the data report of other important physical mechanical property of high temperature thermal barrier material.
The high oxygen diffusion rate of existing YSZ and rare earth zirconate system thermal barrier coating, and it is limited to cause thermal barrier coating to use.The rare earth aluminate of garnet structure has lower oxygen diffusion rate and Geng Gao use temperature, can remedy the deficiency of the high oxygen diffusion rate of YSZ and rare earth zirconate system material, improves its use temperature and efficient in heat barrier coat material.
The condition that the stupalith of screening thermal barrier coating need satisfy is: have high melt point, and stable mutually in room temperature to the interval thing of use temperature; Lower thermal conductivity and low oxygen permeability; Chemical property is stable and have a low sintering rate; Have and metallic matrix or tack coat bonding force and good heat resistanceheat resistant erosion property etc. preferably.
Summary of the invention
One of purpose of the present invention is the high oxygen diffusion rate at existing YSZ and rare earth zirconate system thermal barrier coating, and cause thermal barrier coating to use limited problem, a kind of more rare earth modified Yttrium erbium aluminate heat-barrier coating ceramic layer material of low heat conductivity, lower oxygen diffusion rate and Geng Gao use temperature that has has been proposed, by a large amount of rare earth elements that in oxide matrix, mix, reduced the thermal conductivity of heat barrier coat material effectively.
Another object of the present invention is to have proposed a kind of Yttrium erbium aluminate powder that is used for heat-barrier coating ceramic layer and preparation method thereof, adopts solid state reaction synthetic.Can adopt in high-temperature reaction process and control heat-up rate and insulation stage by stage, make reaction be more prone to carry out, preparation cost is lower.
The present invention is a kind of Yttrium erbium aluminate powder that is used for heat-barrier coating ceramic layer, and the chemical constitution of compound is Y 3-xEr xAl 5O 12, wherein the scope of x value is 0＜x≤3.
A kind of preparation is used for the Yttrium erbium aluminate powder of heat-barrier coating ceramic layer, yttrium oxide powder, Erbium trioxide powder, aluminum oxide powder or aluminium hydrate powder are as main preparation raw material, wherein to account for total mass percentage ratio be 0.1～60% to the yttrium oxide quality, and yttrium oxide purity is greater than 97%, and particle diameter is less than 1 millimeter; It is 0.1～70% that the Erbium trioxide quality accounts for total mass percentage ratio, and Erbium trioxide purity is greater than 97%, and particle diameter is less than 1 millimeter; Aluminum oxide or aluminium hydroxide quality account for total mass percentage ratio and are respectively 30～40% or 40%～55%, and aluminum oxide or aluminium hydroxide purity are respectively greater than 97%, and particle diameter is less than 1 millimeter.
A kind of preparation is used for the method for the Yttrium erbium aluminate powder of heat-barrier coating ceramic layer, and following preparation steps is arranged:
1) (yttrium oxide purity is greater than 97% with the yttrium oxide powder, particle diameter is less than 1 millimeter), (Erbium trioxide purity is greater than 97% for the Erbium trioxide powder, particle diameter is less than 1 millimeter), (aluminum oxide or aluminium hydroxide purity are respectively greater than 97% for aluminum oxide powder or aluminium hydrate powder, particle diameter is less than 1 millimeter) as raw material, raw material is prepared burden by stoichiometric ratio after pre-treatment and is mixed, and with the precursor of this mixture as preparation powder of the present invention.
2) this precursor is placed High Temperature Furnaces Heating Apparatus, insulation is 1 minute～20 hours under 1400 ℃～1950 ℃ temperature condition, can adopt in high-temperature reaction process and control heat-up rate and insulation stage by stage, finishes the back furnace cooling to room temperature in final insulation; Taking-up is ground to 1～10 micron or needed granular size, promptly gets the Yttrium erbium aluminate powder that is used for heat-barrier coating ceramic layer.
A kind of advantage that is used for the Yttrium erbium aluminate material of heat-barrier coating ceramic layer of the present invention is: compare with the zirconium white of 7～8% stabilized with yttrium oxide and have lower thermal conductivity, thermal conductivity (1000 ℃) is 2.90～1.77Wm -1K -1In the powder crystal diffraction interpretation of result of powder, this material is single garnet phase, and powder is still keeping phase stability after 1700 ℃ of long heat treatment, does not take place to change mutually; This material is non-oxygen ion conductor simultaneously, has the oxygen permeability lower than YSZ, can solve the problem of oxidation of tack coat and superalloy effectively.As YEr 2Al 5O 12Can be under 1700 ℃ of conditions life-time service, therefore can replace YSZ and become the stupalith of hot machine thermal barrier coating of new generation.
Preparation method's advantage of the present invention is: the technology of solid state reaction is simple relatively, and preparation cost is lower; Can control reaction by gradient increased temperature, make reaction be more prone to complete.
Resources advantage of the present invention has been to make full use of the rare earth resources of China, makes it to become the material of high-performance high added value, is national defense industry and civilian service.
Embodiment
Embodiment 1:
Preparation Y 2ErAl 5O 12The method of ceramic layer powder.
Raw material: commercially available analytical pure yttrium oxide powder (middle particle diameter is 2 microns), high-purity Erbium trioxide powder (middle particle diameter is 2 microns), pure alpha-aluminum oxide powder (middle particle diameter is 2 microns).
The first step: with oxidate powder Y 2O 3, Er 2O 3, α-Al 2O 3Respectively wet ball grinding ground after 180 minutes, sieved to obtain particle diameter less than 2 microns fine powder; In 75 ℃ loft drier, take out after dry 600 minutes, make dried fine powder; Dried fine powder is prepared burden Y by stoichiometric ratio 2O 3Dried fine powder account for total batching quality 33.60%, Er 2O 3Dried fine powder account for total batching quality 28.46%, α-Al 2O 3Dried fine powder accounts for 37.94% of total batching quality; Mixed 3 hours through wet ball grinding, mixture is preliminarily dried in Rotary Evaporators earlier, in 100 ℃ loft drier, take out after dry 180 minutes then, and with the precursor of this mixture as preparation powder of the present invention.
Second step: with the precursor that the first step makes, placing High Temperature Furnaces Heating Apparatus is 1600 ℃ of following sintering in final sintering temperature, and soaking time is 12 hours.Sintering finishes the back furnace cooling to room temperature; Take out below reactant and the ball milling to 5 micron or needed granular size; Place 150 ℃ loft drier to take out after dry 150 minutes with grinding the back powder, promptly get Y of the present invention 2ErAl 5O 12Yttrium erbium aluminate powder.
At the above-mentioned Y that makes 2ErAl 5O 12In the powder crystal diffraction analysis of Yttrium erbium aluminate powder, this powder thing is single Y mutually 2ErAl 5O 12The garnet phase; Adopting the laser method that shines to measure thermal conductivity is 2.01Wm -1K -1(1000 ℃); Adopting high temperature dilatometer to record thermal expansivity is 9.0 * 10 -6K -1(1200 ℃).This material is compared with the YSZ of widespread use, has lower thermal conductivity; This material is non-oxygen ion conductor, has lower oxygen permeability, can solve the problem of oxidation of tack coat and superalloy effectively; This material long heat treatment under 1700 ℃ of high temperature still keeps phase stability, can use under room temperature to 1700 ℃ condition.This Yttrium erbium aluminate powder can be used for heat-barrier coating ceramic layer, also can be used to prepare the Yttrium erbium aluminate pottery, can be as the additive of other high temperature material of preparation.
Embodiment 2:
Preparation YEr 2Al 5O 12The method of ceramic layer powder.
Raw material: commercially available analytical pure yttrium oxide powder (middle particle diameter is 2 microns), Erbium trioxide powder (middle particle diameter is 2 microns), alpha-aluminium oxide powder (middle particle diameter is 2 microns).
The first step: with oxidate powder Y 2O 3, Er 2O 3, α-Al 2O 3Respectively wet ball grinding ground after 60 minutes, sieved to obtain particle diameter less than 1.5 microns fine powder; In 150 ℃ loft drier, take out after dry 150 minutes, make dried fine powder; Dried fine powder is prepared burden Y by stoichiometric ratio 2O 3Dried fine powder account for total batching quality 15.05%, Er 2O 3Dried fine powder account for total batching quality 50.98%, α-Al 2O 3Dried fine powder accounts for 33.97% of total batching quality; Mixed 4 hours through wet ball grinding, mixture is preliminarily dried in Rotary Evaporators earlier, in 100 ℃ loft drier, take out after dry 200 minutes then, and with the precursor of this mixture as preparation powder of the present invention.
Second step: with the precursor that the first step makes, placing High Temperature Furnaces Heating Apparatus is 1650 ℃ of following sintering in final sintering temperature, and soaking time is 4.5 hours, and sintering finishes the back furnace cooling to room temperature; Take out below reactant and the ball milling to 5 micron or needed granular size; Place 150 ℃ loft drier to take out after dry 150 minutes with grinding the back powder, promptly get YEr of the present invention 2Al 5O 12Yttrium erbium aluminate powder.
At the above-mentioned YEr that makes 2Al 5O 12In the powder crystal diffraction analysis of Yttrium erbium aluminate powder, this material thing is single Y Er mutually 2Al 5O 12The garnet phase; Adopting the laser method that shines to measure the thermal conductivity that thermal conductivity (German Netzsch LFA 427) obtains is 1.97Wm -1K -1(1000 ℃); Adopting German Netzsch DIL 402 type high temperature dilatometers to record thermal expansivity is 8.6 * 10 -6K -1(1200 ℃).This material is compared with the YSZ of widespread use, has lower thermal conductivity (7～8%YSZ, ≈ 2.4Wm -1K -1, 1000 ℃); This material is non-oxygen ion conductor, has lower oxygen permeability, can solve the problem of oxidation of tack coat and superalloy effectively; This material long time treatment under 1700 ℃ of high temperature still keeps phase stability, can be in room temperature to 1700 ℃ use.This Yttrium erbium aluminate powder can be used for heat-barrier coating ceramic layer, also can be used to prepare the Yttrium erbium aluminate pottery, can be as the additive of other high temperature material of preparation.
Embodiment 3:
Preparation Er 3Al 5O 12The method of ceramic layer powder.
Raw material: high-purity Erbium trioxide (Erbium trioxide content 〉=99%, middle particle diameter are 3 microns); Aluminium hydroxide (aluminium hydroxide content 〉=99%, middle particle diameter are 3 microns).
The first step: with oxidate powder Er 2O 3, Al (OH) 3Respectively wet ball grinding ground after 60 minutes, sieved to obtain particle diameter less than 2.5 microns fine powder; In 70 ℃ loft drier, take out after dry 300 minutes, make dried fine powder; Dried fine powder is prepared burden Er by stoichiometric ratio 2O 3Dried fine powder account for total batching quality 59.54%, Al (OH) 3Dried fine powder accounts for 40.46% of total batching quality; Mixed 5 hours through wet ball grinding, mixture is preliminarily dried in Rotary Evaporators earlier, in 100 ℃ loft drier, take out after dry 240 minutes then, and with the precursor of this mixture as preparation powder of the present invention.
Second step: with the precursor that the first step makes, placing High Temperature Furnaces Heating Apparatus is 1700 ℃ of following sintering in final sintering temperature, and soaking time is 6 hours.Sintering finishes the back furnace cooling to room temperature; Take out below reactant and the ball milling to 10 micron or needed granular size; Place 150 ℃ loft drier to take out after dry 150 minutes with grinding the back powder, promptly get Er of the present invention 3Al 5O 12Yttrium erbium aluminate powder.
In above-mentioned preparation method's second step, temperature of reaction can be a graded, and regulating the reaction in furnace temperature is 1700 ℃, and wherein when room temperature rose to 350 ℃ of temperature, temperature rise rate was 5 ℃/min; At 350 ℃ of insulation 30min; When 350 ℃ to 1100 ℃ temperature, temperature rise rate is 10 ℃/min; In the time of 1100 ℃ to 1450 ℃, temperature rise rate is 8 ℃/min; At 1450 ℃ of insulation 30min; In the time of 1450 ℃ to 1700 ℃, temperature rise rate is 5 ℃/min.
With the above-mentioned Er that makes 3Al 5O 12The ceramic layer powder adopts the powder crystal diffraction analysis to be Er 3Al 5O 12The garnet phase material; Adopting the laser method that shines to measure the thermal conductivity that thermal conductivity (German Netzsch LFA427) obtains is 1.77Wm -1K -1(1000 ℃); Adopting German Netzsch DIL 402 type high temperature dilatometers to record thermal expansivity is 8.5 * 10 -6K -1(1200 ℃).This material is compared with the YSZ of widespread use, has lower thermal conductivity; This material is non-oxygen ion conductor, has lower oxygen permeability, can solve the problem of oxidation of tack coat and superalloy effectively; This material long time treatment under 1700 ℃ of high temperature still keeps phase stability, can be in room temperature to 1700 ℃ use.This Yttrium erbium aluminate powder can be used for heat-barrier coating ceramic layer, also can be used to prepare the Yttrium erbium aluminate pottery, can be as the additive of other high temperature material of preparation.

Claims (4)

1. a Yttrium erbium aluminate powder that is used for heat-barrier coating ceramic layer is characterized in that having following chemical constitution: Y 3-xEr xAl 5O 12, wherein the scope of x value is 0＜x≤3.
2. Yttrium erbium aluminate powder that is used for heat-barrier coating ceramic layer as claimed in claim 1, it is characterized in that: described Yttrium erbium aluminate has Y 2ErAl 5O 12Or YEr 2Al 5O 12Erbium aluminate has Er 3Al 5O 12
3. Yttrium erbium aluminate powder that is used for heat-barrier coating ceramic layer as claimed in claim 1, it is characterized in that: adopt yttrium oxide powder, Erbium trioxide powder, aluminum oxide powder or aluminium hydrate powder as main preparation raw material, wherein to account for total mass percentage ratio be 0.1～60% to the yttrium oxide quality; It is 0.1～70% that the Erbium trioxide quality accounts for total mass percentage ratio; Aluminum oxide or aluminium hydroxide quality account for total mass percentage ratio and are respectively 30～40% or 40%～55%.
4. preparation method who is used for the Yttrium erbium aluminate powder of heat-barrier coating ceramic layer as claimed in claim 1, it is characterized in that following preparation steps is arranged: 1) will prepare burden by stoichiometric ratio after each raw materials pretreatment and mix, and with the precursor of this mixture as preparation powder of the present invention; 2) this precursor is placed High Temperature Furnaces Heating Apparatus, insulation is 1 minute～20 hours under 1400 ℃～1950 ℃ temperature condition, can adopt in high-temperature reaction process and control heat-up rate and insulation stage by stage, finishes the back furnace cooling to room temperature in final insulation; Take out reaction product and be ground to 1～10 micron or needed granular size, can obtain Yttrium erbium aluminate powder, this Yttrium erbium aluminate powder can be used for heat-barrier coating ceramic layer, also can be used to prepare the Yttrium erbium aluminate pottery, can be as the additive of other high temperature material of preparation.
CN201010103122A 2010-02-01 2010-02-01 Yttrium erbium aluminate powder for thermal barrier coating ceramic layer and preparation method thereof Pending CN101767987A (en)

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Cited By (7)

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CN103215535A (en) * 2013-04-16 2013-07-24 中国科学院金属研究所 Method for preparing protective coating layer for surface of plasma etched cavity
CN104988454A (en) * 2015-07-09 2015-10-21 北京航空航天大学 Melted CMAS-corrosion resistant rare-earth aluminate thermal barrier coating and preparation method thereof
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CN106588042A (en) * 2016-11-18 2017-04-26 北京理工大学 Ternary rare earth doped YSZ thermal barrier coating material and preparation method thereof
CN109626994A (en) * 2018-11-23 2019-04-16 昆明理工大学 A kind of heat barrier coat material and preparation method thereof of low infrared transmittivity
CN110627495A (en) * 2019-09-23 2019-12-31 航天材料及工艺研究所 Low-thermal-conductivity high-entropy aluminate ceramic and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103215535A (en) * 2013-04-16 2013-07-24 中国科学院金属研究所 Method for preparing protective coating layer for surface of plasma etched cavity
CN103215535B (en) * 2013-04-16 2014-10-22 中国科学院金属研究所 Method for preparing protective coating layer for surface of plasma etched cavity
CN104988454A (en) * 2015-07-09 2015-10-21 北京航空航天大学 Melted CMAS-corrosion resistant rare-earth aluminate thermal barrier coating and preparation method thereof
CN105152688A (en) * 2015-08-11 2015-12-16 南京理工大学 Wavelength selective radiator coating applied to thermophotovoltaic power generation device and preparation method
CN106588042A (en) * 2016-11-18 2017-04-26 北京理工大学 Ternary rare earth doped YSZ thermal barrier coating material and preparation method thereof
CN109626994A (en) * 2018-11-23 2019-04-16 昆明理工大学 A kind of heat barrier coat material and preparation method thereof of low infrared transmittivity
CN109626994B (en) * 2018-11-23 2021-12-28 昆明理工大学 Thermal barrier coating material with low infrared transmittance and preparation method thereof
CN110627495A (en) * 2019-09-23 2019-12-31 航天材料及工艺研究所 Low-thermal-conductivity high-entropy aluminate ceramic and preparation method thereof
CN110627495B (en) * 2019-09-23 2021-09-03 航天材料及工艺研究所 Low-thermal-conductivity high-entropy aluminate ceramic and preparation method thereof
CN117466635A (en) * 2023-12-28 2024-01-30 天津包钢稀土研究院有限责任公司 Method for preparing dense mullite from rare earth modified gangue
CN117466635B (en) * 2023-12-28 2024-03-08 天津包钢稀土研究院有限责任公司 Method for preparing dense mullite from rare earth modified gangue

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