CN110372378A - The potassium-sodium niobate photochromic transparent ceramics and preparation method thereof that europium/barium strontium titanate is modified altogether - Google Patents

The potassium-sodium niobate photochromic transparent ceramics and preparation method thereof that europium/barium strontium titanate is modified altogether Download PDF

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CN110372378A
CN110372378A CN201910660924.7A CN201910660924A CN110372378A CN 110372378 A CN110372378 A CN 110372378A CN 201910660924 A CN201910660924 A CN 201910660924A CN 110372378 A CN110372378 A CN 110372378A
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europium
potassium
strontium titanate
barium strontium
sodium niobate
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吴啸
周阳
林锦锋
鲁齐铃
林枞
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Fuzhou University
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Fuzhou University
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Abstract

The invention discloses a kind of preparation methods of potassium-sodium niobate photochromic transparent ceramics that europium/barium strontium titanate is modified altogether, xEu-KNN-yBST powder is prepared first, pass through dry-pressing compression molding, the sinter molding at 1200~1210 DEG C, obtain having pure tetragonal phase perovskite structure, consistency height, crystal grain tiny and uniform, light transmittance and has excellent luminescence generated by light/photochromic characteristic up to the 60% potassium-sodium niobate photochromic transparent ceramics that are modified altogether of europium/barium strontium titanate at 850 nm.The potassium-sodium niobate photochromic transparent ceramics that the europium/barium strontium titanate is modified altogether integrate high optical transmittance, excellent upper converting photoluminescent characteristic and photochromic characteristic, these multifunctional light electrical characteristics can further expand its corresponding application, be expected to the fields such as the optical switch applied to environment-friendly type, the storage of photoelectricity ferroelectricity image.

Description

The potassium-sodium niobate photochromic transparent ceramics and its preparation that europium/barium strontium titanate is modified altogether Method
Technical field
The present invention relates to multi-functional lead-free ferroelectric material field more particularly to a kind of niobic acids that europium/barium strontium titanate is modified altogether The preparation method of the photochromic crystalline ceramics of potassium sodium.
Background technique
Rare earth is valuable strategic resource, can be widely applied to the following important development such as electronics, new energy field, realizes The high-value-use and industrial chain extension of rare earth are the long-term strategies of sustainable development in China.Rare earth phosphor display, The fields such as optical communication and opto-electronic device are with a wide range of applications.Wherein, the inorganic up-conversion luminescent material of rare earth can incite somebody to action Near infrared light is converted into visible light, shines by force with narrowband and the feature of long lifetime of excited state, thus be applied to upper converting biological, The fields such as medicine fluorescent marker, solid-state laser, solar energy photoelectric conversion.Rare earth up-conversion luminescence host material can be divided into list Brilliant, polycrystalline and amorphous three classes material.Wherein non-crystalline material mainly includes glassy state and ceramic material.
Suitable host material is selected to be conducive to improve the pumping and the spectrum efficiency of Laser emission of rare earth.In recent years, K0.5Na0.5NbO3 (KNN) base ceramics are considered as most being hopeful to replace due to its high-curie temperature and big electromechanical coupling factor Traditional Pb (Zr, Ti) O3Best one of the candidate material of base ceramics.As rear-earth-doped host material, K0.5Na0.5NbO3 (KNN) base ceramics have small phonon energy, red sector Absorption edge other than excitation wavelength, blue area absorbs band edge and sends out in upper conversion The advantages that other than ejected wave is long.In recent years, people by ion doping (such as metal ion, transition metal ions or lanthanide ion) come Enhance its piezoelectric property, for example, Jia etc. reports rare earth ion Pr3+Adulterate K0.5Na0.5NbO3 (KNN) lead-free ceramics is photic Luminescent properties and ferroelectricity, piezoelectric polarization and between dual enhancing.Research based on forefathers, it is known that KNN base ceramics not only have High optical transmittance and consistency also has excellent upper converting photoluminescent characteristic and photochromic characteristic, utilizes these New multifunctional light electrical characteristics can further expand its corresponding application field, but in the application and development of KNN base transparent ceramic It needs to be studied.
Summary of the invention
In order to improve the luminous efficiency of rare earth ion and realize the rear-earth-doped novel ceramic for obtaining multifunctional light electrical characteristics Ceramic material makes it in the base for improving luminous efficiency present invention aims at by finding suitable base material to rare earth ion On plinth, the method for the potassium-sodium niobate crystalline ceramics that there is luminescence generated by light/photochromic europium/barium strontium titanate to be modified altogether for acquisition.
The technical solution of the present invention is as follows:
The potassium-sodium niobate photochromic transparent ceramics and preparation method thereof that europium/barium strontium titanate is modified altogether, comprising the following steps:
(1) ingredient: raw material (Eu is weighed by the mass ratio of chemical composition general formula xEu-KNN-yBST2O3: Na2CO3 : K2CO3 : Nb2O5 : BaCO3 : SrCO3 : TiO2 =z: 0.1988: 0.2587: 1: u: v: w, wherein z= 0.0036 ~ 0.072, u=0.1183 ~ 0.1130, v=0.0891 ~ 0.1003, w=0.0479 ~ 0.0539), then It is uniformly mixed so as to obtain mixture;
(2) ball milling: being added ball-milling medium in mixture and is fitted into progress 9~12 h of ball milling in ball grinder, will after ball milling Mixture, is then put into mortar again and grinds by mixture drying;
(3) pre-burning: the mixture after above-mentioned grinding is added in crucible, after being compacted, is placed in Muffle furnace, is warming up to 800 ~850 DEG C and 3~6 h of heat preservation carry out pre-burning, then again take out crucible after cooled to room temperature;
(4) secondary ball milling: toward above-mentioned after ball-milling medium is added in the mixture of pre-burning, then being loaded into ball grinder, into 7~10 h of row secondary ball milling after secondary ball milling, mixture is dried, then again after sieve is sieved, can be prepared by powder Body, chemical composition general formula are xEu-KNN-yBST;
(5) be granulated: the poly-vinyl alcohol solution that 5~10 wt% are added toward above-mentioned powder is uniformly mixed, and is then placed in baking oven and is done again It is dry, then be sieved through sieve;
(6) tabletting: will by step (5) treated, powder is added in mold, depress to diameter in the pressure of 200~300MPa The green compact of 10~12 mm;
(7) dumping: being placed in above-mentioned green compact in pallet and cover, be then placed in Muffle furnace, 700~850 DEG C at a temperature of It keeps the temperature 1~3 h and carries out dumping, then again by it with furnace cooled to room temperature;
(8) it is sintered: will be placed in Muffle furnace by the green compact of step (7) processing, 2~6 h are sintered at 1200~1210 DEG C, so Cooled to room temperature afterwards can be prepared by the potassium-sodium niobate photochromic transparent ceramics that europium/barium strontium titanate is modified altogether.
As a preferred embodiment of the above technical solution, in the step (2), abrasive media is ethyl alcohol, the weight of mixture and ethyl alcohol Amount is than being 1: 2~1: 3.
As a preferred embodiment of the above technical solution, in the step (2) and (4), rotational speed of ball-mill is 150~280 rpm.
As a preferred embodiment of the above technical solution, in the step (3), heating rate is 3~5 in the temperature-rise period of pre-burning ℃/min。
As a preferred embodiment of the above technical solution, in the step (2) and (4), drying temperature is 80~85 DEG C.
As a preferred embodiment of the above technical solution, in the step (4) and (5), the aperture of the sieve is 80~100 mesh.
As a preferred embodiment of the above technical solution, in the step (5), (polyethylene after addition polyvinyl alcohol in the powder Alcohol will be uniformly mixed in powder), it is placed in baking oven and is dried with 90~130 DEG C of temperature.
As a preferred embodiment of the above technical solution, the raw material Eu2O3、Na2CO3、K2CO3、Nb2O5、BaCO3、SrCO3And TiO2It is that analysis is pure.
The present invention is by by rare earth ion Eu3+It mixes in KNN ceramics, in conjunction with Ba2+、 Sr2+、Ti4+The doping of plasma Effect, can obtain the xEu-KNN-yBST crystalline ceramics of high-compactness.Select KNN base ceramics as Eu3+The substrate material of ion Material, not only can be improved that its is infrared to visible up-conversion luminescence efficiency, can also obtain having the transparent pottery of photochromic ferroelectricity Porcelain can be very good the fluorescence intensity and transmitance of luminous KNN base transparent ceramic by changing colour.
In summary: the invention has the following advantages:
Present invention process step is simple, reproducible, easily operated, and greatly enhances the optics storage of ferroelectric material Energy density is expected to the fields such as the optical switch applied to environment-friendly type, the storage of photoelectricity ferroelectricity image.
Detailed description of the invention
The present invention is further elaborated with reference to the accompanying drawings and detailed description:
Fig. 1 is the XRD diagram for the 0.5Eu-KNN-9BST crystalline ceramics sample that embodiment 2 obtains;
Fig. 2 is the light transmittance figure for the 0.5Eu-KNN-9BST crystalline ceramics sample that embodiment 2 obtains and the entity for polishing sample Figure;
Fig. 3 is the SEM figure for the 0.5Eu-KNN-9BST crystalline ceramics sample that embodiment 2 obtains;
Fig. 4 is the sterogram for the xEu-KNN-yBST crystalline ceramics sample discoloration front and back that embodiment 2 obtains;
Fig. 5 is the figure that the 0.5Eu-KNN-9BST crystalline ceramics fluorescent quenching that embodiment 2 obtains changes with light application time.
Specific embodiment
The present invention is further detailed below in conjunction with attached drawing.
Present embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art Any change for being made after having read specification of the invention of member, as long as within the scope of the claims, it all will be by The protection of Patent Law.
Embodiment 1
A kind of potassium-sodium niobate photochromic transparent ceramics and preparation method thereof that europium/barium strontium titanate is modified altogether, comprising the following steps:
(1) ingredient: raw material (Eu is weighed by the mass ratio of chemical composition general formula xEu-KNN-yBST2O3 : Na2CO3 : K2CO3 : Nb2O5 : BaCO3 : SrCO3 : TiO2 =z: 0.1988: 0.2587: 1: u: v: w, wherein z= 0.0036 ~ 0.072, u=0.1183 ~ 0.1130, v=0.0891 ~ 0.1003, w=0.0479 ~ 0.0539), then It is uniformly mixed so as to obtain mixture;
(2) ball milling: being added ball-milling medium in mixture and is fitted into progress 9 h of ball milling in ball grinder, after ball milling, will mix Mixture, is then put into mortar again and grinds by material drying;
(3) pre-burning: the mixture after above-mentioned grinding is added in crucible, after being compacted, is placed in Muffle furnace, is warming up to 800 DEG C and keep the temperature 3 h carry out pre-burning, then crucible is taken out after cooled to room temperature again;
(4) secondary ball milling: toward above-mentioned after ball-milling medium is added in the mixture of pre-burning, then being loaded into ball grinder, into 7 h of row ball milling after ball milling, mixture is dried, then again after sieve is sieved, can be prepared by powder, chemical composition General formula is 0.25Eu-KNN-9BST;
(5) be granulated: the poly-vinyl alcohol solution for being added 5% toward above-mentioned powder is uniformly mixed, and is then placed in drying in baking oven again, then pass through Sieve sieving;
(6) tabletting: will by step (5) treated, powder is added in mold, depress to diameter 10 in the pressure of 200 MPa The green compact of mm;
(7) dumping: being placed in above-mentioned green compact in pallet and cover, be then placed in Muffle furnace, 700 DEG C at a temperature of keep the temperature 1 H carries out dumping, then again by it with furnace cooled to room temperature;
(8) it is sintered: will be placed in Muffle furnace by the green compact of step (7) processing, 2 h are sintered at 1200 DEG C, it is then naturally cold But to room temperature, the potassium-sodium niobate photochromic transparent ceramics that europium/barium strontium titanate is modified altogether be can be prepared by.
Performance test
By ceramics sample wear down and it is polished to 0.3 mm, surveys its light transmittance, test result shows saturating when wavelength is about 850 nm Light rate is 50%, and the sample has good photochromic characteristic.
Embodiment 2
A kind of potassium-sodium niobate photochromic transparent ceramics and preparation method thereof that europium/barium strontium titanate is modified altogether, comprising the following steps:
(1) ingredient: raw material (Eu is weighed by the mass ratio of chemical composition general formula xEu-KNN-yBST2O3 : Na2CO3 : K2CO3 : Nb2O5 : BaCO3 : SrCO3 : TiO2 =z: 0.1988: 0.2587: 1: u: v: w, wherein z= 0.072, u=0.1130, v=0.1003, w=0.0539), then it is uniformly mixed so as to obtain mixture;
(2) ball milling: being added ball-milling medium in mixture and is fitted into progress 12 h of ball milling in ball grinder, after ball milling, will mix Material drying is closed, then mixture is put into mortar again and is ground;
(3) pre-burning: the mixture after above-mentioned grinding is added in crucible, after being compacted, is placed in Muffle furnace, is warming up to 850 DEG C and keep the temperature 4 h carry out pre-burning, then crucible is taken out after cooled to room temperature again;
(4) secondary ball milling: toward above-mentioned after ball-milling medium is added in the mixture of pre-burning, then being loaded into ball grinder, into 10 h of row ball milling after ball milling, mixture is dried, then again after sieve is sieved, can be prepared by powder, chemical composition General formula is 0.5Eu-KNN-9BST;
(5) be granulated: the poly-vinyl alcohol solution for being added 6% toward above-mentioned powder is uniformly mixed, and is then placed in drying in baking oven again, then pass through Sieve sieving;
(6) tabletting: will by step (5) treated, powder is added in mold, depress to diameter 12 in the pressure of 300 MPa The green compact of mm;
(7) dumping: being placed in above-mentioned green compact in pallet and cover, be then placed in Muffle furnace, 800 DEG C at a temperature of keep the temperature 2 H carries out dumping, then again by it with furnace cooled to room temperature;
(8) it is sintered: will be placed in Muffle furnace by the green compact of step (7) processing, 4 h are sintered at 1205 DEG C, it is then naturally cold But to room temperature, the potassium-sodium niobate photochromic transparent ceramics that europium/barium strontium titanate is modified altogether be can be prepared by.
Performance test
By ceramics sample wear down and it is polished to 0.3 mm, is then tested.
XRD diagram, SEM figure, light transmittance figure and the sample for the 0.5Eu-KNN-9BST crystalline ceramics sample that embodiment 2 obtains The sterogram of product, the sterogram of discoloration front and back and discoloration regulation fluorescence intensity figure difference are as shown in Figs. 1-5.Fig. 1 shows, gained The ceramics sample arrived is pure tetragonal phase perovskite structure, almost without miscellaneous phase appearance, illustrates that the ion of doping incorporates well Into KNN matrix;Fig. 2 shows that the grain crystalline of the sample is good, compact structure, crystal grain tiny (~137 nm) and distribution is equal It is even, facilitate it and keeps higher light transmittance;The potsherd light transmittance figure obtained after Fig. 3 display sintering, it can be seen that it 850 Light transmittance at nm reaches 60%, reaches transparent level;The sterogram of Fig. 4 display discoloration front and back, can understand before non-illumination See beneath middle text, darken after illumination and light transmittance reduce, show photochromic to regulate and control its transmitance; Fig. 5 shows the fluorescent quenching degree (Δ with the increase of the light application time sampleR t ) it is gradually increased until saturation, show light Mutagens color can regulate and control the fluorescence intensity of the sample well.
Embodiment 3
A kind of potassium-sodium niobate photochromic transparent ceramics and preparation method thereof that europium/barium strontium titanate is modified altogether, comprising the following steps:
(1) ingredient: raw material (Eu is weighed by the mass ratio of chemical composition general formula xEu-KNN-yBST2O3 : Na2CO3 : K2CO3 : Nb2O5 : BaCO3 : SrCO3 : TiO2 =z: 0.1988: 0.2587: 1: u: v: w, wherein z= 0.0036, u=0.1183, v=0.0891, w=0.0479), then it is uniformly mixed so as to obtain mixture;
(2) ball milling: being added ball-milling medium in mixture and is fitted into progress 10 h of ball milling in ball grinder, after ball milling, will mix Material drying is closed, then mixture is put into mortar again and is ground;
(3) pre-burning: the mixture after above-mentioned grinding is added in crucible, after being compacted, is placed in Muffle furnace, is warming up to 820 DEG C and keep the temperature 6 h carry out pre-burning, then crucible is taken out after cooled to room temperature again;
(4) secondary ball milling: toward above-mentioned after ball-milling medium is added in the mixture of pre-burning, then being loaded into ball grinder, into 8 h of row ball milling after ball milling, mixture is dried, then again after sieve is sieved, can be prepared by powder, chemical composition General formula is 0.25Eu-KNN-8BST;
(5) be granulated: the poly-vinyl alcohol solution that 10 wt% are added toward above-mentioned powder is uniformly mixed, and is then placed in drying in baking oven again, It is sieved again through sieve;
(6) tabletting: will by step (5) treated, powder is added in mold, depress to diameter 11 in the pressure of 200 MPa The green compact of mm;
(7) dumping: being placed in above-mentioned green compact in pallet and cover, be then placed in Muffle furnace, 850 DEG C at a temperature of keep the temperature 3 H carries out dumping, then again by it with furnace cooled to room temperature;
(8) it is sintered: will be placed in Muffle furnace by the green compact of step (7) processing, 6 h are sintered at 1210 DEG C, it is then naturally cold But to room temperature, the potassium-sodium niobate photochromic transparent ceramics that europium/barium strontium titanate is modified altogether be can be prepared by.
Performance test
By ceramics sample wear down and it is polished to 0.3 mm, surveys its light transmittance, test result shows saturating when wavelength is about 850 nm Light rate is 50%, and the sample has good photochromic characteristic.
Embodiment 4
A kind of potassium-sodium niobate photochromic transparent ceramics and preparation method thereof that europium/barium strontium titanate is modified altogether, comprising the following steps:
(1) ingredient: raw material (Eu is weighed by the mass ratio of chemical composition general formula xEu-KNN-yBST2O3 : Na2CO3 : K2CO3 : Nb2O5 : BaCO3 : SrCO3 : TiO2 =z: 0.1988: 0.2587: 1: u: v: w, wherein z= 0.072, u=0.1183, v=0.0891, w=0.0479), then it is uniformly mixed so as to obtain mixture;
(2) ball milling: being added ball-milling medium in mixture and is fitted into progress 10 h of ball milling in ball grinder, after ball milling, will mix Material drying is closed, then mixture is put into mortar again and is ground;
(3) pre-burning: the mixture after above-mentioned grinding is added in crucible, after being compacted, is placed in Muffle furnace, is warming up to 800 DEG C and keep the temperature 3 h carry out pre-burning, then crucible is taken out after cooled to room temperature again;
(4) secondary ball milling: toward above-mentioned after ball-milling medium is added in the mixture of pre-burning, then being loaded into ball grinder, into 7 h of row ball milling after ball milling, mixture is dried, then again after sieve is sieved, can be prepared by powder, chemical composition General formula is 0.5Eu-KNN-8BST;
(5) be granulated: the poly-vinyl alcohol solution that 10 wt% are added toward above-mentioned powder is uniformly mixed, and is then placed in drying in baking oven again, It is sieved again through sieve;
(6) tabletting: will by step (5) treated, powder is added in mold, depress to diameter 10 in the pressure of 250 MPa The green compact of mm;
(7) dumping: being placed in above-mentioned green compact in pallet and cover, be then placed in Muffle furnace, 700~850 DEG C at a temperature of It keeps the temperature 1 h and carries out dumping, then again by it with furnace cooled to room temperature;
(8) it is sintered: will be placed in Muffle furnace by the green compact of step (7) processing, 5 h are sintered at 1205 DEG C, it is then naturally cold But to room temperature, the potassium-sodium niobate photochromic transparent ceramics that europium/barium strontium titanate is modified altogether be can be prepared by.
Performance test
By ceramics sample wear down and it is polished to 0.3 mm, surveys its light transmittance, test result shows saturating when wavelength is about 850 nm Light rate is 50%, and the sample has good photochromic characteristic.

Claims (8)

1. a kind of potassium-sodium niobate photochromic transparent ceramics and preparation method thereof that europium/barium strontium titanate is modified altogether, it is characterised in that: Itself the following steps are included:
(1) ingredient: weighing raw material by following mass ratio, mixes, obtains mixture;Eu2O3: Na2CO3 : K2CO3 : Nb2O5 : BaCO3 : SrCO3 : TiO2 =z: 0.1988: 0.2587: 1: u: v: w, wherein z=0.0036 ~ 0.072, u=0.1183 ~ 0.1130, v=0.0891 ~ 0.1003, w=0.0479 ~ 0.0539;
(2) ball milling: being added ball-milling medium in mixture and is fitted into progress 9~12 h of ball milling in ball grinder, will after ball milling Mixture, is then put into mortar again and grinds by mixture drying;
(3) pre-burning: the mixture after above-mentioned grinding is added in crucible, after being compacted, is placed in Muffle furnace, is warming up to 800 ~850 DEG C and 3~6h of heat preservation carry out pre-burning, then again take out crucible after cooled to room temperature;
(4) secondary ball milling: toward above-mentioned after ball-milling medium is added in the mixture of pre-burning, then being loaded into ball grinder, into After secondary ball milling, mixture is dried by row 7~10h of secondary ball milling, and then again after sieve is sieved, powder is made, changes Learning composition general formula is xEu-KNN-yBST;
(5) be granulated: the poly-vinyl alcohol solution that 5~10wt% is added toward above-mentioned powder is uniformly mixed, and is then placed in baking oven and is done again It is dry, then be sieved through sieve;
(6) tabletting: will by step (5) treated, powder is added in mold, depressed to directly in the pressure of 200~300 MPa The green compact of 10~12 mm of diameter;
(7) dumping: being placed in above-mentioned green compact in pallet and cover, be then placed in Muffle furnace, 700~850 DEG C at a temperature of It keeps the temperature 1~3 h and carries out dumping, then again by it with furnace cooled to room temperature;
(8) it is sintered: will be placed in Muffle furnace by the green compact of step (7) processing, 2~6h is sintered at 1200~1210 DEG C, so The potassium-sodium niobate photochromic transparent ceramics that europium/barium strontium titanate is modified altogether are made in cooled to room temperature afterwards.
2. potassium-sodium niobate photochromic transparent ceramics that a kind of europium/barium strontium titanate according to claim 1 is modified altogether and its Preparation method, it is characterised in that: in the step (2), abrasive media is ethyl alcohol, and the weight ratio of mixture and ethyl alcohol is 1: 2 ~1: 3.
3. potassium-sodium niobate photochromic transparent ceramics that a kind of europium/barium strontium titanate according to claim 1 is modified altogether and its Preparation method, it is characterised in that: in the step (2) and (4), rotational speed of ball-mill is 150~280 rpm.
4. potassium-sodium niobate photochromic transparent ceramics that a kind of europium/barium strontium titanate according to claim 1 is modified altogether and its Preparation method, it is characterised in that: in the step (3), heating rate is 3~5 DEG C/min in the temperature-rise period of pre-burning.
5. potassium-sodium niobate photochromic transparent ceramics that a kind of europium/barium strontium titanate according to claim 1 is modified altogether and its Preparation method, it is characterised in that: in the step (2) and (4), drying temperature is 80~85 DEG C.
6. potassium-sodium niobate photochromic transparent ceramics that a kind of europium/barium strontium titanate according to claim 1 is modified altogether and its Preparation method, it is characterised in that: in the step (4) and (5), the aperture of the sieve is 80~100 mesh.
7. potassium-sodium niobate photochromic transparent ceramics that a kind of europium/barium strontium titanate according to claim 1 is modified altogether and its Preparation method, it is characterised in that: in the step (5), after polyvinyl alcohol is added in the powder, be placed in baking oven with 90~ 130 DEG C of temperature is dried.
8. potassium-sodium niobate photochromic transparent ceramics that a kind of europium/barium strontium titanate according to claim 1 is modified altogether and its Preparation method, it is characterised in that: the raw material Eu2O3、Na2CO3、K2CO3、Nb2O5、BaCO3、SrCO3And TiO2It is analysis It is pure.
CN201910660924.7A 2019-07-22 2019-07-22 The potassium-sodium niobate photochromic transparent ceramics and preparation method thereof that europium/barium strontium titanate is modified altogether Pending CN110372378A (en)

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CN108863360A (en) * 2018-07-27 2018-11-23 福州大学 A kind of preparation method of Er ions potassium-sodium niobate-strontium titanates crystalline ceramics
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* Cited by examiner, † Cited by third party
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