CN102515752A - Transparent ceramic material and preparation method thereof - Google Patents
Transparent ceramic material and preparation method thereof Download PDFInfo
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- CN102515752A CN102515752A CN2011104314396A CN201110431439A CN102515752A CN 102515752 A CN102515752 A CN 102515752A CN 2011104314396 A CN2011104314396 A CN 2011104314396A CN 201110431439 A CN201110431439 A CN 201110431439A CN 102515752 A CN102515752 A CN 102515752A
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Abstract
The invention discloses a transparent ceramic material and a preparation method thereof. The transparent ceramic material is lanthanum yttrium zirconate ceramic and has a chemical formula of LaYZr2O7. The preparation method for the material comprises the steps of preparation of powder, molding, sintering and annealing heat treatment, wherein, the powder is prepared by using a glycine-nitrate combustion method and the molding is realized by using a slip-casting molding process or a dry-pressing/cold isostatic pressing combined process. A sample with a thickness of 1 mm obtained after double-sided polishing of the lanthanum yttrium zirconate transparent ceramic material provided in the invention has maximal linear transmittance of more than 75% in visible bands, has high sintering density, has a relative density greater than 99.99% and can satisfy application requirements of the fields of information detection, laser mediums, high temperature windows, etc. Furthermore, the preparation method provided in the invention has the advantages of a simple process, good controllability, no need for sintering aids, simple sintering conditions, easy operation and production, etc.
Description
Technical field
The present invention relates to a kind of transparent ceramic material and preparation method thereof, specifically, relate to a kind of zirconic acid lanthanum yttrium transparent ceramic material and preparation method thereof, belong to technical field of ceramic material.
Background technology
Crystalline ceramics has the optical property of stupalith inherent HS, high insulation, characteristic such as high temperature resistant, corrosion-resistant and glass material concurrently, and its Application Areas is very extensive.
Compare monocrystalline, crystalline ceramics can require to realize the even doping of high concentration ion according to device application more conveniently, avoids because low, the pockety situation of doping content that the crystal growth technique restriction is caused.In addition, the preparation temperature of crystalline ceramics especially has practical significance far below the preparation temperature of monocrystalline for some dystectic materials.Research shows that the performance of some crystalline ceramics has has met or exceeded monocrystal material, and is expected in some specific occasions progressively substitute the monocrystalline optical material.With respect to glass material, high temperature resistant, advantages such as thermal conductivity is high, hardness is high, strong shock resistance that crystalline ceramics has have its unique using value at some special occasions.
Summary of the invention
The purpose of this invention is to provide a kind of novel transparent stupalith than high visible light transmissivity and preparation method thereof that has; For this area increases a kind of product innovation, to satisfy the performance requriements of fields such as information detection, laser medium, high temperature form to transparent ceramic material.
For realizing the foregoing invention purpose, the technical scheme that the present invention adopts is following:
A kind of transparent ceramic material is zirconic acid lanthanum yttrium pottery, and its chemical formula is LaYZr
2O
7
A kind of preparation method of described transparent ceramic material comprises: powder preparing, moulding, sintering and annealing heat treatment step is characterized in that: described powder preparing adopts glycocoll-nitrate salt combustion method; Described moulding adopts slip-casting shaping process or dry-pressing to combine cold isostatic compaction technology.
Further, it is following to adopt glycocoll-nitrate salt combustion method to prepare the step of powder: according to the mol ratio of Zr: La: Y is to take by weighing zirconium nitrate, Lanthanum trinitrate and Yttrium trinitrate at 2: 1: 1, is mixed with nitrate aqueous solution; Add the incendiary material glycocoll, stir and make dissolving fully; The pH value of regulator solution is 3～5; Heating makes the generation combustion reactions, obtains the presoma powder; The presoma powder is heat-treated; Ball milling, screening promptly get zirconic acid lanthanum yttrium powder.
The volumetric molar concentration of the nitrate ion in the said nitrate aqueous solution is recommended as 0.1～5mol/L, is preferably 0.1～2mol/L.
The mol ratio of said glycocoll and nitrate ion is preferably 0.3: 1～and 0.7: 1.
Said heat-treat condition was preferably: 1000～1200 ℃ of insulations 2～4 hours.
Further, described slip-casting shaping process comprises the steps:
The solid content of the zirconic acid lanthanum yttrium powder that makes with 15～35vol% is scattered in the deionized water, under pH=8～10 or pH=3～5 conditions, adds dispersion agent, stir, ultra-sonic dispersion, ball milling, ageing handle, and makes slurry; Injection forming; Carry out the drying back demoulding, promptly get zirconic acid lanthanum yttrium biscuit of ceramics.
Said dispersion agent is recommended as polyacrylate or poly-methyl acrylate; Be preferably ammonium polyacrylate, ZX-I, ammonium polymethacrylate or sodium polymethacrylate.
The add-on of said dispersion agent is preferably and makes its content in solution is 0.5～1.5wt%.
The time of said ultra-sonic dispersion is preferably 15～30 minutes.
The said ball milling time is preferably 6～12 hours.
The said ageing treatment time is preferably 0.5～8 hour.
Said drying was preferably 15～35 ℃ of following dryings after 2～8 hours, and is following dry 2～8 hours at 40～70 ℃ again.
Further, described dry-pressing combines cold isostatic compaction technology to comprise the steps:
Earlier under 5～20MPa, be biscuit with the zirconic acid lanthanum yttrium powder that makes is dry-pressing formed, again the gained biscuit carried out isostatic cool pressing at 180～230MPa and handle, promptly get zirconic acid lanthanum yttrium biscuit of ceramics.
Said dry-pressing formed the processing with isostatic cool pressing all preferably at room temperature carried out.
The time that said isostatic cool pressing is handled is preferably 1～3 minute.
The median size of above-mentioned zirconic acid lanthanum yttrium powder is preferably 50～100nm.
Further, said agglomerating step is following: with the zirconic acid lanthanum yttrium biscuit of ceramics that makes earlier 1000～1200 ℃ of pre-burnings 2～4 hours, then under vacuum condition in 1800～1900 ℃ of sintering 4～10 hours.
The preferred vacuum tightness of said vacuum condition≤5.0 * 10
-3Pa.
Further, the heat treated step of said annealing is following: the sample behind the sintering is incubated 4～10 hours down in 1400～1600 ℃ in air atmosphere.
Compared with prior art; Zirconic acid lanthanum yttrium transparent ceramic material provided by the invention can reach more than 75% through the thick sample of 1mm of twin polishing in the maximum linear transmitance of visible light wave range; Sintered density is high simultaneously; Specific density can satisfy the application requiring in fields such as information detection, laser medium, high temperature forms greater than 99.99%.In addition, it is simple that preparation method of the present invention has technology, and controllability is good, need not sintering aid, and sintering condition is simpler relatively, advantages such as easy handling and production.
Description of drawings
The X ray diffracting spectrum of the zirconic acid lanthanum yttrium transparent ceramic material that Fig. 1 makes for embodiment 1;
The transmittance curve figure of the zirconic acid lanthanum yttrium transparent ceramic material that Fig. 2 makes for embodiment 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing to the present invention do further in detail, intactly explanation.
Embodiment 1
A) powder preparing: with 0.4 molar nitric acid zirconium (Zr (NO
3)
43H
2O, 99.9%), 0.2 molar nitric acid lanthanum (La (NO
3)
3, 99.99%) and 0.2 molar nitric acid yttrium (Y (NO
3)
3, 99.995%) be dissolved in the 1000mL deionized water, be mixed with nitrate aqueous solution; Add 1.6 moles of glycocoll, stir and make dissolving fully; Using the pH value of ammoniacal liquor regulator solution is 4; Heating makes the generation combustion reactions, obtains the presoma powder; The presoma powder is heat-treated: at 1000 ℃ of insulation 4h; Ball milling, screening, making median size is the zirconic acid lanthanum yttrium nano-powder of 50～100nm;
B) moulding: adopt dry-pressing to combine cold isostatic compaction technology; That is: earlier under room temperature, 5MPa, be biscuit with the zirconic acid lanthanum yttrium nano-powder that makes is dry-pressing formed; Again the gained biscuit is carried out isostatic cool pressing under room temperature, 180MPa and handle 3min, promptly get zirconic acid lanthanum yttrium biscuit of ceramics;
C) sintering: with the zirconic acid lanthanum yttrium biscuit of ceramics that makes earlier 1200 ℃ of pre-burnings 2 hours, then in vacuum tightness less than 5.0 * 10
-3Under the vacuum condition of Pa in 1800 ℃ of sintering 10 hours;
D) annealing thermal treatment: the sample behind the sintering is incubated 4 hours down in 1600 ℃ in air atmosphere, promptly gets zirconic acid lanthanum yttrium (LaYZr
2O
7) transparent ceramic material.
The X ray diffracting spectrum of the zirconic acid lanthanum yttrium transparent ceramic material that Fig. 1 makes for present embodiment, visible by Fig. 1: prepared zirconic acid lanthanum yttrium transparent ceramic material is the defect state fluorite structure.
The transmittance curve figure of the zirconic acid lanthanum yttrium crystalline ceramics that Fig. 2 makes for present embodiment, visible by Fig. 2: prepared zirconic acid lanthanum yttrium transparent ceramic material reaches nearly 77% through the maximum linear transmitance of the thick sample of 1mm at the 1100nm place of twin polishing; Specific density is greater than 99.99%.
Embodiment 2
A) powder preparing: with 0.2 molar nitric acid zirconium (Zr (NO
3)
43H
2O, 99.9%), 0.1 molar nitric acid lanthanum (La (NO
3)
3, 99.99%) and 0.1 molar nitric acid yttrium (Y (NO
3)
3, 99.995%) be dissolved in the 500mL deionized water, be mixed with nitrate aqueous solution; Add 0.8 mole of glycocoll, stir and make dissolving fully; Using the pH value of ammoniacal liquor regulator solution is 4; Heating makes the generation combustion reactions, obtains the presoma powder; The presoma powder is heat-treated: at 1200 ℃ of insulation 2h; Ball milling, screening, making median size is the zirconic acid lanthanum yttrium nano-powder of 50～100nm;
B) moulding: adopt dry-pressing to combine cold isostatic compaction technology; That is: earlier under room temperature, 20MPa, be biscuit with the zirconic acid lanthanum yttrium nano-powder that makes is dry-pressing formed; Again the gained biscuit is carried out isostatic cool pressing under room temperature, 230MPa and handle 1min, promptly get zirconic acid lanthanum yttrium biscuit of ceramics;
C) sintering: with the zirconic acid lanthanum yttrium biscuit of ceramics that makes earlier 1000 ℃ of pre-burnings 4 hours, then in vacuum tightness less than 5.0 * 10
-3Under the vacuum condition of Pa in 1900 ℃ of sintering 4 hours;
D) annealing thermal treatment: the sample behind the sintering is incubated 10 hours down in 1400 ℃ in air atmosphere, promptly gets zirconic acid lanthanum yttrium (LaYZr
2O
7) transparent ceramic material.
The zirconic acid lanthanum yttrium transparent ceramic material that present embodiment makes reaches 75.7% through the maximum linear transmitance of the thick sample of 1mm at the 800nm place of twin polishing; Specific density is greater than 99.99%.
Embodiment 3
A) powder preparing: with 0.4 molar nitric acid zirconium (Zr (NO
3)
43H
2O, 99.9%), 0.2 molar nitric acid lanthanum (La (NO
3)
3, 99.99%) and 0.2 molar nitric acid yttrium (Y (NO
3)
3, 99.995%) be dissolved in the 800mL deionized water, be mixed with nitrate aqueous solution; Add 1.6 moles of glycocoll, stir and make dissolving fully; Using the pH value of ammoniacal liquor regulator solution is 4; Heating makes the generation combustion reactions, obtains the presoma powder; The presoma powder is heat-treated: at 1200 ℃ of insulation 2h; Ball milling, screening, making median size is the zirconic acid lanthanum yttrium nano-powder of 50～100nm;
B) moulding: adopt slip-casting shaping process, that is: the solid content of the zirconic acid lanthanum yttrium powder that makes with 15vol% is scattered in the deionized water, when pH=9, add the dispersion agent ammonium polyacrylate, it is 0.5wt% that the add-on of dispersion agent makes its content in solution; Stir, ultra-sonic dispersion 15 minutes, ball milling 12 hours, ageing 1 hour makes dispersiveness and flowability slurry preferably; Injection forming; After 5 hours, following dry 5 hours at 55 ℃ again 25 ℃ of following dryings; The demoulding promptly gets zirconic acid lanthanum yttrium biscuit of ceramics;
C) sintering: with the zirconic acid lanthanum yttrium biscuit of ceramics that makes earlier 1000 ℃ of pre-burnings 4 hours, then in vacuum tightness less than 5.0 * 10
-3Under the vacuum condition of Pa in 1900 ℃ of sintering 4 hours;
D) annealing thermal treatment: the sample behind the sintering is incubated 10 hours down in 1400 ℃ in air atmosphere, promptly gets zirconic acid lanthanum yttrium (LaYZr
2O
7) transparent ceramic material.
The zirconic acid lanthanum yttrium transparent ceramic material that present embodiment makes reaches 75.5% through the maximum linear transmitance of the thick sample of 1mm at the 800nm place of twin polishing; Specific density is greater than 99.99%.
Embodiment 4
A) powder preparing: with 0.2 molar nitric acid zirconium (Zr (NO
3)
43H
2O, 99.9%), 0.1 molar nitric acid lanthanum (La (NO
3)
3, 99.99%) and 0.1 molar nitric acid yttrium (Y (NO
3)
3, 99.995%) be dissolved in the 500mL deionized water, be mixed with nitrate aqueous solution; Add 0.8 mole of glycocoll, stir and make dissolving fully; Using the pH value of ammoniacal liquor regulator solution is 4; Heating makes the generation combustion reactions, obtains the presoma powder; The presoma powder is heat-treated: at 1000 ℃ of insulation 4h; Ball milling, screening, making median size is the zirconic acid lanthanum yttrium nano-powder of 50～100nm;
B) moulding: adopt slip-casting shaping process; That is: the solid content of the zirconic acid lanthanum yttrium powder that makes with 35vol% is scattered in the deionized water; When pH=4, add the dispersion agent ammonium polymethacrylate, it is 1.5wt% that the add-on of dispersion agent makes its content in solution; Stir, ultra-sonic dispersion 30 minutes, ball milling 6 hours, ageing 8 hours makes dispersiveness and flowability slurry preferably; Injection forming; After 6 hours, following dry 6 hours at 50 ℃ again 20 ℃ of following dryings; The demoulding promptly gets zirconic acid lanthanum yttrium biscuit of ceramics;
C) sintering: with the zirconic acid lanthanum yttrium biscuit of ceramics that makes earlier 1200 ℃ of pre-burnings 2 hours, then in vacuum tightness less than 5.0 * 10
-3Under the vacuum condition of Pa in 1800 ℃ of sintering 10 hours;
D) annealing thermal treatment: the sample behind the sintering is incubated 4 hours down in 1600 ℃ in air atmosphere, promptly gets zirconic acid lanthanum yttrium (LaYZr
2O
7) transparent ceramic material.
The zirconic acid lanthanum yttrium transparent ceramic material that present embodiment makes reaches 75.3% through the maximum linear transmitance of the thick sample of 1mm at the 800nm place of twin polishing; Specific density is greater than 99.99%.
Be necessary at last to be pointed out that at this: above embodiment only is used for technical scheme of the present invention is done further detailed explanation; Can not be interpreted as the restriction to protection domain of the present invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (19)
1. transparent ceramic material is characterized in that: be zirconic acid lanthanum yttrium pottery, its chemical formula is LaYZr
2O
7
2. the preparation method of the described transparent ceramic material of claim 1, comprising: powder preparing, moulding, sintering and annealing heat treatment step is characterized in that: described powder preparing adopts glycocoll-nitrate salt combustion method; Described moulding adopts slip-casting shaping process or dry-pressing to combine cold isostatic compaction technology.
3. the preparation method of transparent ceramic material according to claim 2; It is characterized in that; It is following to adopt glycocoll-nitrate salt combustion method to prepare the step of powder: according to the mol ratio of Zr: La: Y is to take by weighing zirconium nitrate, Lanthanum trinitrate and Yttrium trinitrate at 2: 1: 1, is mixed with nitrate aqueous solution; Add the incendiary material glycocoll, stir and make dissolving fully; The pH value of regulator solution is 3～5; Heating makes the generation combustion reactions, obtains the presoma powder; The presoma powder is heat-treated; Ball milling, screening promptly get zirconic acid lanthanum yttrium powder.
4. the preparation method of transparent ceramic material according to claim 3, it is characterized in that: the volumetric molar concentration of the nitrate ion in the said nitrate aqueous solution is 0.1～5mol/L.
5. the preparation method of transparent ceramic material according to claim 3, it is characterized in that: the mol ratio of said glycocoll and nitrate ion is 0.3: 1～0.7: 1.
6. the preparation method of transparent ceramic material according to claim 3, it is characterized in that: said heat-treat condition was: 1000～1200 ℃ of insulations 2～4 hours.
7. the preparation method of transparent ceramic material according to claim 2; It is characterized in that; Described slip-casting shaping process comprises the steps: the solid content of the zirconic acid lanthanum yttrium powder that makes with 15～35vol% is scattered in the deionized water; Under pH=8～10 or pH=3～5 conditions, add dispersion agent, stir, ultra-sonic dispersion, ball milling, ageing handle, and makes slurry; Injection forming; Carry out the drying back demoulding, promptly get zirconic acid lanthanum yttrium biscuit of ceramics.
8. the preparation method of transparent ceramic material according to claim 7, it is characterized in that: said dispersion agent is polyacrylate or poly-methyl acrylate.
9. the preparation method of transparent ceramic material according to claim 8, it is characterized in that: said dispersion agent is ammonium polyacrylate, ZX-I, ammonium polymethacrylate or sodium polymethacrylate.
10. the preparation method of transparent ceramic material according to claim 7, it is characterized in that: it is 0.5～1.5wt% that the add-on of said dispersion agent will make its content in solution.
11. the preparation method of transparent ceramic material according to claim 7 is characterized in that: the time of said ultra-sonic dispersion is 15～30 minutes, and the said ball milling time is 6～12 hours, and the said ageing treatment time is 0.5～8 hour.
12. the preparation method of transparent ceramic material according to claim 7 is characterized in that: said drying be earlier 15～35 ℃ dry 2～8 hours down, then 40～70 ℃ dry 2～8 hours down.
13. the preparation method of transparent ceramic material according to claim 2; It is characterized in that; Described dry-pressing combines cold isostatic compaction technology to comprise the steps: earlier under 5～20MPa to be biscuit with the zirconic acid lanthanum yttrium powder that makes is dry-pressing formed; Again the gained biscuit is carried out isostatic cool pressing at 180～230MPa and handle, promptly get zirconic acid lanthanum yttrium biscuit of ceramics.
14. the preparation method of transparent ceramic material according to claim 13 is characterized in that: said dry-pressing formed the processing with isostatic cool pressing all at room temperature carried out.
15. the preparation method of transparent ceramic material according to claim 13 is characterized in that: the time that said isostatic cool pressing is handled is 1～3 minute.
16. the preparation method according to claim 3,7 or 13 described transparent ceramic materials is characterized in that: the median size of described zirconic acid lanthanum yttrium powder is 50～100nm.
17. the preparation method of transparent ceramic material according to claim 2; It is characterized in that; Said agglomerating step is following: with the zirconic acid lanthanum yttrium biscuit of ceramics that makes earlier 1000～1200 ℃ of pre-burnings 2～4 hours, then under vacuum condition in 1800～1900 ℃ of sintering 4～10 hours.
18. the preparation method of transparent ceramic material according to claim 17 is characterized in that: said vacuum condition is vacuum tightness≤5.0 * 10
-3Pa.
19. the preparation method of transparent ceramic material according to claim 2 is characterized in that, the heat treated step of said annealing is following: the sample behind the sintering is incubated 4～10 hours down in 1400～1600 ℃ in air atmosphere.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815945A (en) * | 2012-09-13 | 2012-12-12 | 中国科学院上海硅酸盐研究所 | Lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
| CN102815941A (en) * | 2012-09-13 | 2012-12-12 | 中国科学院上海硅酸盐研究所 | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
| CN103113106A (en) * | 2013-01-25 | 2013-05-22 | 福建福晶科技股份有限公司 | Preparation method of pyrochlore-type A2B2O7 transparent ceramics |
| CN104478434A (en) * | 2014-12-08 | 2015-04-01 | 上海大学 | Transparent ceramic Eu<2+>/Eu3+>: Y1.8-xLa0.2ZrxO3 and preparation method thereof |
| CN104478432A (en) * | 2014-12-26 | 2015-04-01 | 合肥创想能源环境科技有限公司 | Preparation method of high-strength composite ceramic body with low sintering temperature |
| CN106927502A (en) * | 2017-04-11 | 2017-07-07 | 陕西科技大学 | A kind of method that combustion method of citric acid prepares zirconic acid yttrium |
| CN107010662A (en) * | 2017-04-11 | 2017-08-04 | 陕西科技大学 | A kind of method that nitrate urea combustion prepares zirconic acid yttrium powder body |
| CN107082449A (en) * | 2017-04-11 | 2017-08-22 | 陕西科技大学 | A kind of method that careless acid dihydrazide combustion method prepares zirconic acid yttrium |
| TWI660933B (en) * | 2018-06-29 | 2019-06-01 | 中國鋼鐵股份有限公司 | Method for fabricating transparent ceramic material |
| CN111646504A (en) * | 2020-05-29 | 2020-09-11 | 厦门理工学院 | Nano lanthanum zirconate and preparation method thereof |
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| CN101343173A (en) * | 2007-05-08 | 2009-01-14 | 肖特公开股份有限公司 | Optoceramics, optical elements manufactured thereof and their use as imaging optics |
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| CN101343173A (en) * | 2007-05-08 | 2009-01-14 | 肖特公开股份有限公司 | Optoceramics, optical elements manufactured thereof and their use as imaging optics |
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| CN102815945A (en) * | 2012-09-13 | 2012-12-12 | 中国科学院上海硅酸盐研究所 | Lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
| CN102815941A (en) * | 2012-09-13 | 2012-12-12 | 中国科学院上海硅酸盐研究所 | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
| CN102815945B (en) * | 2012-09-13 | 2014-09-10 | 中国科学院上海硅酸盐研究所 | Lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
| CN103113106A (en) * | 2013-01-25 | 2013-05-22 | 福建福晶科技股份有限公司 | Preparation method of pyrochlore-type A2B2O7 transparent ceramics |
| CN104478434A (en) * | 2014-12-08 | 2015-04-01 | 上海大学 | Transparent ceramic Eu<2+>/Eu3+>: Y1.8-xLa0.2ZrxO3 and preparation method thereof |
| CN104478432A (en) * | 2014-12-26 | 2015-04-01 | 合肥创想能源环境科技有限公司 | Preparation method of high-strength composite ceramic body with low sintering temperature |
| CN106927502A (en) * | 2017-04-11 | 2017-07-07 | 陕西科技大学 | A kind of method that combustion method of citric acid prepares zirconic acid yttrium |
| CN107010662A (en) * | 2017-04-11 | 2017-08-04 | 陕西科技大学 | A kind of method that nitrate urea combustion prepares zirconic acid yttrium powder body |
| CN107082449A (en) * | 2017-04-11 | 2017-08-22 | 陕西科技大学 | A kind of method that careless acid dihydrazide combustion method prepares zirconic acid yttrium |
| CN107082449B (en) * | 2017-04-11 | 2018-06-22 | 陕西科技大学 | A kind of method that grass acid dihydrazide combustion method prepares zirconic acid yttrium |
| CN107010662B (en) * | 2017-04-11 | 2019-01-25 | 陕西科技大学 | A kind of method that nitrate-urea combustion prepares zirconic acid yttrium powder body |
| CN106927502B (en) * | 2017-04-11 | 2019-01-25 | 陕西科技大学 | A kind of method that citric acid-combustion method prepares zirconic acid yttrium |
| TWI660933B (en) * | 2018-06-29 | 2019-06-01 | 中國鋼鐵股份有限公司 | Method for fabricating transparent ceramic material |
| CN111646504A (en) * | 2020-05-29 | 2020-09-11 | 厦门理工学院 | Nano lanthanum zirconate and preparation method thereof |
| CN111646504B (en) * | 2020-05-29 | 2022-08-12 | 厦门理工学院 | Nano lanthanum zirconate and preparation method thereof |
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Application publication date: 20120627 |