CN110342934A - A kind of micron-stage sheet-like niobic acid sodium crystal and its preparation method and application - Google Patents

A kind of micron-stage sheet-like niobic acid sodium crystal and its preparation method and application Download PDF

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CN110342934A
CN110342934A CN201910533195.9A CN201910533195A CN110342934A CN 110342934 A CN110342934 A CN 110342934A CN 201910533195 A CN201910533195 A CN 201910533195A CN 110342934 A CN110342934 A CN 110342934A
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powder
micron
acid sodium
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niobic acid
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靳立
乔俊
徐卓
魏晓勇
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Xian Jiaotong University
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Abstract

The invention discloses a kind of micron-stage sheet-like niobic acid sodium crystals and its preparation method and application, belong to piezoelectric ceramic technology field.It is characterized in that preparing flaky sodium niobate crystal, Bi using molten-salt growth method2.5Na3.5Nb5O18As presoma, the presoma crystal and Na are made by ion-exchange reactions2CO3Mixing, while NaCl powder and KCl powder being mixed；Aforementioned two kinds of mixtures are mixed again, keep the temperature 3~10 hours at 900~1000 DEG C；Then NaCl, KCl in burned material are removed by ultrasonic cleaning, the Bi removed in burned material is cleaned using dust technology2O3, obtain micron-stage sheet-like niobic acid sodium crystal.Niobic acid sodium crystal of the invention has cubic phase perovskite structure, and square flake-like shape, size is about 10 × 10 × 1 μm, and size distribution is uniform.The crystal is extremely suitable for preparing the seed crystal of high-performance textured piezoelectric ceramic as template grain growth (Templated Grain Grouth).

Description

A kind of micron-stage sheet-like niobic acid sodium crystal and its preparation method and application
Technical field
The invention belongs to piezoelectric ceramic technology field, be related to a kind of micron-stage sheet-like niobic acid sodium crystal and preparation method thereof and Using.
Background technique
Piezoelectric material is widely used in the technical grades national defence such as ultrasonic device, sonar, SAW filter, piezo-electric motor neck Domain.Most commonly used currently on the market is lead base piezoelectric ceramics such as lead zirconate titanate (PZT) and lead magnesio-niobate (PMNT), but lead is to people Body and environment have biggish harm, therefore unleaded ceramics are the development trends of the following piezoelectric ceramics.Sodium niobate base (NN) and niobium Sour potassium sodium base (KNN) ceramics have excellent ferroelectricity, piezoelectric property and higher residence as the substitute of the following lead base ceramics In temperature.But crystal grain random orientation makes its performance fail to reach current use standard.Monocrystal material performance is high but prepares skill Art is complicated and expense is high limits use scope.
Templated grain growth (Temlated Grain Growth) is that a kind of polycrystalline material performance that improves has efficacious prescriptions Method.This method improves the performance in crystal direction and making polycrystalline material form preferred orientation (texture).Template is made in advance It is standby to have provided anisotropy shape (sheet, needle-shaped etc.) small crystals, then seed crystal is mixed with ceramic powder, by being cast legal system At film.Seed crystal is aligned in casting processes by the shearing force of casting machine scraper.After sintering, ceramic powder is along seed Brilliant surface epitaxial growth, to form textured ceramic.Principle is as shown in Figure 1.
From the description above as it can be seen that the seed crystal of preparation high quality is one of key technology of template, the quality of seed crystal is straight Connect the growth and final texture degree for determining matrix grain.Seed crystal should meet claimed below:
(1) anisotropic shape.Seed crystal is necessary for sheet or needles shape, can be oriented and be arranged by casting technique Column.
(2) suitably sized.The size of seed crystal is at least 4~5 times of matrix powder, matrix can be guided to grow, because This seed size cannot be too small.But size can not be excessive simultaneously, and seed size is excessive to be easy to be scraped in casting processes by scraper It is disconnected.In summary consider, seed size is 10 × 10 × 1 μm of optimum.
(3) suitable crystal structure.Seed crystal must have the structure to match with matrix ceramic powders, just be able to guide matrix Crystal grain is in seed crystal face epitaxial growth.Such as the lattice constant of lead magnesio-niobate piezoelectric ceramics is 4.044nm, the seed crystal of selection is also answered With similar lattice constant.
(4) good thermal stability.Seed crystal must keep stable during the sintering process, not react with matrix.
Therefore, it is prepared in textured piezoelectric ceramic field in template grain growth at present, preparation height preferred orientation Sodium niobate base (NN) ceramics are research hotspots.Seed crystal used at present is using K2CO3Sodium niobate (the NaNbO of preparation3) and use Sodium niobate (the NaNbO of single fused salt NaCl preparation3).But both crystal all limit due to there are unavoidable defect suitable With range: using K2CO3Sodium niobate (the NaNbO of preparation3) seed size is larger (30~40 μm), excessive size is easy flowing It is scraped by scraper disconnected during prolonging, seed crystal pattern is damaged, follow-up sintering process is influenced.Use single fused salt NaCl preparation Sodium niobate (NaNbO3) seed crystal face is coarse, and easily mutually bonds between generation seed crystal, it can not be separated in later period cleaning process, So that part seed crystal thickness is thicker, draw ratio is reduced, and can not be guided matrix powder oriented growth during the sintering process, be made texture degree It reduces.
Therefore, finding a kind of better seed crystal technology of preparing is current template grain growth preparation texturing sodium niobate base The breach of ceramic technology.
Summary of the invention
In order to overcome the disadvantages of the above prior art, it is brilliant that the purpose of the present invention is to provide a kind of micron-stage sheet-like sodium niobates Body and its preparation method and application, this method is easy to operate, is suitble to large-scale production；The micron-stage sheet-like niobium prepared through this method Sour sodium crystalline substance has cubic phase perovskite structure, and particle size distribution is uniform.
In order to achieve the above object, the present invention is achieved by the following scheme:
The invention discloses a kind of preparation methods of micron-stage sheet-like niobic acid sodium crystal, comprising the following steps:
1) by Bi2O3Powder, Na2CO3Powder and Nb2O5Powder is uniformly mixed obtained mixture；
2) mixture made from NaCl powder and step 1) is sufficiently mixed uniformly, then at 1050~1200 DEG C at heat preservation 4~10h is managed, burned material is obtained, cleaning removes the NaCl in burned material, obtains sheet Bi2.5Na3.5Nb5O18Presoma；
3) by sheet Bi made from step 2)2.5Na3.5Nb5O18Presoma and Na2CO3Powder is mixed to get mixture A；It will NaCl powder and KCl powder are mixed to get mixture B；
4) after mixing by mixture A and mixture B, 3~10h of isothermal holding, is burnt at 900~1000 DEG C Object, cleaning remove NaCl, KCl and Bi in burned material2O3, the micron-stage sheet-like niobic acid sodium crystal of sheet is made.
Preferably, in step 1), Bi2O3Powder, Na2CO3Powder and Nb2O5The molar ratio of powder is 1:(1~2): (2~4).
Preferably, in step 2), the mass ratio of mixture made from NaCl powder and step 1) is (1~2.5): 1.
Preferably, in step 3), sheet Bi2.5Na3.5Nb5O18Presoma and Na2CO3The molar ratio of powder is 1:(1~4).
Preferably, in step 3), the molar ratio of NaCl powder and KCl powder is (6~11): 1.
Preferably, in step 4), the mass ratio of mixture A and mixture B are 1:(1~2.5).
Preferably, in step 1), it is to be carried out using the deionized water of heat by ultrasound that cleaning, which removes the NaCl in burned material, Cleaning.
Preferably, in step 4), cleaning is the NaCl and KCl successively removed using the deionized water of heat in burned material, is made The Bi removed in burned material is cleaned with dust technology2O3, finally using deionized water clean, entire cleaning process by ultrasonic method into Row.
The invention also discloses using micron-stage sheet-like niobic acid sodium crystal made from above-mentioned preparation method, the micron order piece Shape niobic acid sodium crystal have cubic phase perovskite structure, square flake-like shape, a length of 8~15 μm of square flake-like shape, with a thickness of 0.8 ~1.5 μm, size distribution is uniform.
The invention also discloses above-mentioned micron-stage sheet-like niobic acid sodium crystals in preparation high-performance textured piezoelectric ceramic Application in seed crystal.
Compared with prior art, the invention has the following advantages:
The intermediate for meeting flake-like shape condition is prepared using molten-salt growth method by this method, then passes through ion-exchange reactions, It is required element by component permutation under conditions of not changing shape.Each step operation of this method is simple, is suitble to extensive raw It produces, prepares textured piezoelectric ceramic for template batch and open road.
Through micron-stage sheet-like niobic acid sodium crystal made from the method for the present invention, there is cubic phase perovskite structure, be regular Square flake-like shape, size distribution is uniform, and 10 × 10 × 1 μm of average grain diameter, therefore can fully meet as preparing piezoelectric ceramics Seed crystal requirement.
Detailed description of the invention
Fig. 1 is the schematic illustration that template grain growth prepares textured ceramics；
Fig. 2 is Bi prepared by the present invention2.5Na3.5Nb5O18The scanning electron microscope of (NaCl: oxide=1.5:1) is shone Piece；
Fig. 3 is Bi prepared by the present invention2.5Na3.5Nb5O18The electron scanning micrograph of (NaCl: oxide=1:1)；
Fig. 4 is Bi prepared by the present invention2.5Na3.5Nb5O18The scanning electron microscope of (NaCl: oxide=2.5:1) is shone Piece；
Fig. 5 is NaNbO of the invention3Electron scanning micrograph.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work It encloses.
In addition, term " includes " and " having " and their any deformation, it is intended that covering non-exclusive includes example Such as, the process, method, system, product or equipment for containing a series of steps or units those of are not necessarily limited to be clearly listed Step or unit, but may include being not clearly listed or intrinsic for these process, methods, product or equipment other Step or unit.
The invention will be described in further detail with reference to the accompanying drawing:
High quality seed crystal of the invention has cubic phase perovskite structure, square flake-like shape, 10 × 10 × 1 μ of average grain diameter M, the uniform crystal of size distribution, the crystal be cubic phase, perovskite structure sodium niobate monocrystal outer dimension a length of 8~ 15 μm, with a thickness of 0.8~1.5 μm.
The method disclosed by the invention for preparing above-mentioned micron-stage sheet-like niobic acid sodium crystal, using molten-salt growth method and ion exchange Method preparation, the specific steps are that:
Step 1: by molten-salt growth method in NaCl molten salt system synthesizing flaky Bi2.5Na3.5Nb5O18Crystal
1) mixing: first by Bi2O3Powder and Na2CO3Powder and Nb2O5Powder 1:(1~2 in molar ratio): (2~4) mixing；Again will NaCl powder is with aforementioned mixture (1~2.5) in mass ratio: 1 mixes, and the above mixed process uses nylon ball grinder, zirconium oxide (ZrO2) abrading-ball, anhydrous ethanol medium is ball milling mixing 8 hours, stand-by in 75 DEG C of drying.
2) it is sintered: mixture made from step 1) is placed in the alumina crucible of capping, it is Celsius at 1050~1200 DEG C Degree heat preservation 4~10 hours, near room temperature.
3) clean: this step purpose is to remove the NaCl in burned material.It is clear that burned material is placed in ultrasound in deionized water It washes, removes supernatant liquor, be repeated several times, product is dried to get pure sheet Bi is arrived2.5Na3.5Nb5O18Crystal.
Step 2: Bi is used2.5Na3.5Nb5O18Crystal, by molten-salt growth method in NaCl-KCl molten salt system synthesizing flaky NaNbO3Crystal
1) mixing: by Bi2.5Na3.5Nb5O18Crystal and Na2CO3Powder 1:(1~4 in molar ratio) mixing；By NaCl powder and KCl Powder is in molar ratio (6~11): 1 mixing；By two kinds of front mixture 1:(1~2.5 in mass ratio) mixing.
2) be sintered: mixture is placed in the alumina crucible of capping, be warming up to 900~1000 DEG C degrees Celsius heat preservation 4~ 10 hours, it is down to room temperature.
3) it cleans: after ion-exchange reactions, precursor B i2.5Na3.5Nb5O18In Bi displaced by Na, and formed It is insoluble in the yellow Bi that water is soluble in nitric acid2O3.Cleaning method is first place the product in the deionized water boiled, and using super Sound cleaning, stands and removes supernatant.It so carries out several times, NaCl soluble easily in water and KCl being removed.Then to product Middle addition dust technology, and be cleaned by ultrasonic, stand and remove supernatant.It so carries out that several times, the Bi of nitric acid can will be soluble in2O3 It is dissolved as Bi (NO3)3.Dehydrated alcohol is finally added into product, and is cleaned by ultrasonic, stand and removes supernatant liquor.By this step After rapid, Bi (NO3)3It is completely removed, obtains pure sheet NaNbO3Final product.
Embodiment 1
1) Bi is prepared2.5Na3.5Nb5O18Flat crystal:
Take Bi2O34g, Na2CO34.88g Nb2O513.35g, the NaCl33g (mass ratio of NaCl powder and aforementioned mixture For 1.5:1), ball milling mixing is dried after 8 hours.It is warming up to 1125 DEG C and keeps the temperature 5 hours, be down to room temperature.5 DEG C/min of heating rate, 5 DEG C/min of cooling rate.Obtain square piece shape Bi2.5Na3.5Nb5O18Crystal, length are about 10 μm, and thickness is about 0.5~1 μm, ruler Very little to be evenly distributed, favorable dispersibility, the presoma has the square flake-like shape of standard, and the results are shown in attached figure 2 for sem analysis.
2) NaNbO is prepared using NaCl-KCl molten salt system3Flat crystal
The Bi prepared using step 1)2.5Na3.5Nb5O1810g is as reaction raw materials, then takes Na2CO31.17g NaCl19.57g, KCl2.77g are dried after magnetic agitation 60min using anhydrous ethanol medium.Mixture is placed in the oxygen of capping Change in aluminium crucible, is warming up to 1130 DEG C and keeps the temperature 5 hours, 5 DEG C/min of heating rate, 5 DEG C/min of cooling rate.Rule is obtained Square piece shape NaNbO3Crystal, length are about 10 μm, and thickness is about 1 μm, and seed crystal is evenly distributed, without mutually bonding.NaNbO3With side Flake-like shape, about 10 × 10 × 1 μm of size, the results are shown in attached figure 5 for sem analysis.
3) it cleans
Take NaNbO3Crystal is several, is first cleaned by ultrasonic using hot deionized water, reuses dust technology ultrasonic cleaning, finally makes It is cleaned by ultrasonic with deionized water.As a result pure NaNbO is obtained3Crystal, length are about 10 μm, and thickness is about 1 μm, and are distributed Uniformly, favorable dispersibility.The effect of three cleaning steps is: hot deionized water dissolves NaCl and KCl；Dust technology is by Bi2O3Dissolution For Bi (NO3)3, deionized water washes away Bi (NO3)3。
Embodiment 2
Take Bi2O34g, Na2CO34.88g Nb2O513.35g, the NaCl22.2g (quality of NaCl powder and aforementioned mixture Than for 1:1), ball milling mixing is dried after 8 hours.It is warming up to 1125 DEG C and keeps the temperature 5 hours, be down to room temperature.5 DEG C/min of heating rate, 5 DEG C/min of cooling rate.Obtain square piece shape Bi2.5Na3.5Nb5O18Crystal, length are about 10-15 μm, and thickness is about 0.5~1 μm, Even size distribution, favorable dispersibility.Unlike the first embodiment, the presoma template under the ratio is compared with 1 Pattern plate ruler of embodiment It is very little bigger, the reason is that fused salt ratio is reduced, it is not enough to separate the small-size grains of nucleation, some crystal grain can swallow small crystalline substance around Grain, thus size increased.The presoma has the square flake-like shape of standard, and the results are shown in attached figure 3 for sem analysis.
Embodiment 3
Take Bi2O34g, Na2CO34.88g Nb2O513.35g, the NaCl55.5g (quality of NaCl powder and aforementioned mixture Than for 2.5:1), ball milling mixing is dried after 8 hours.It is warming up to 1125 DEG C and keeps the temperature 5 hours, be down to room temperature.5 DEG C of heating rate/ Min, 5 DEG C/min of cooling rate.Obtain square piece shape Bi2.5Na3.5Nb5O18Crystal, length are about 8-12 μm, and thickness is about 0.5~1 μm, even size distribution, favorable dispersibility.The presoma has the square flake-like shape of standard, and the results are shown in attached figure 4 for sem analysis.
Comparative example 1: K is used2CO3Prepare NaNbO3Flat crystal
Raw material uses Bi2.5Na3.5Nb5O18And K2CO3, molar ratio 1:1.73 the NaCl of quality such as uses as molten salt body System.It is warming up to 900 DEG C and keeps the temperature 2 hours, room temperature is down to 5 DEG C/min.
NaNbO obtained3Although crystal is square piece shape, the size of template is larger (30~40 μm).The reason is that K2CO3 Reactivity is high in fused salt, and ionic mobility is high, therefore NaNbO3The speed of growth is very fast, but reduces reaction temperature or reduce and protect The warm time cannot obtain crystallizing preferable seed crystal again.
Comparative example 2: NaNbO is individually prepared using NaCl fused salt3Flat crystal
Raw material uses Bi2.5Na3.5Nb5O18And Na2CO3, molar ratio 1:1.5 the NaCl of quality such as uses as molten salt body System.975 DEG C are warming up to, 5 hours is kept the temperature, room temperature is down to 5 DEG C/min.
Sodium niobate (the NaNbO of preparation3) seed crystal face is coarse, and easily mutually bonds between generation seed crystal, it can not be in the later period It is separated in cleaning process, so that part seed crystal thickness is thicker, draw ratio is reduced.
Comparative example 3: NaNbO is individually prepared using KCl fused salt3Flat crystal
Raw material uses Bi2.5Na3.5Nb5O18And Na2CO3, molar ratio 1:1.5 the KCl of quality such as uses as molten salt body System.975 DEG C are warming up to, 5 hours is kept the temperature, room temperature is down to 5 DEG C/min.Sodium niobate (the NaNbO of preparation3) seed crystal be square piece shape, Surface is smooth, and length is 8 μm, with a thickness of 0.5 μm, but is found by X-ray diffraction, there are miscellaneous peaks in diffraction maximum, cannot obtain Pure phase sodium niobate (NaNbO3) seed crystal.
Comparative example 4: sintering temperature (low temperature) is to preparation Bi2.5Na3.5Nb5O18The influence of flat crystal
Sintering temperature is to be warming up to 1080 DEG C to keep the temperature 5 hours, other are the same as embodiment 3.The square piece shape of acquisition Bi2.5Na3.5Nb5O18Crystal length is about 8 μm, and thickness is about 0.3 μm, and the crystal morphology of acquisition is similar, but undersized, and table There are some defects in face, the reason is that reaction temperature reduction, causes crystal growth slow, and grain crystalline is deteriorated.
Comparative example 5: sintering temperature (high temperature) is to preparation Bi2.5Na3.5Nb5O18The influence of flat crystal
Sintering temperature is to be warming up to 1200 DEG C to keep the temperature 3 hours, other are the same as embodiment 3.Obtain larger square piece shape Bi2.5Na3.5Nb5O18Crystal.Length is about 20 μm, and with a thickness of 1~1.5 μm, the crystal morphology of acquisition is similar, but size is larger, And bonded between partial crystals, the reason is that reaction temperature improves, cause crystal growth rapider.
Comparative example 6: NaNbO is prepared using NaCl-KCl molten salt system3Flat crystal (reaction temperature reduction)
Reaction condition is to be warming up to 1050 DEG C to keep the temperature 5 hours, other are the same as embodiment 1.Compared with Example 1, the crystalline substance of acquisition Bodily form looks are similar, but are found by X-ray diffraction analysis, and there are a small amount of Bi in product2.5Na3.5Nb5O18Impurity, the reason is that reaction Temperature reduces, and particle migration rate reduces, and leads to Bi2.5Na3.5Nb5O18In Bi element do not replaced completely by Na element.
Comparative example 7: NaNbO is prepared using NaCl-KCl molten salt system3Flat crystal (reaction temperature raising)
Reaction condition is to be warming up to 1200 DEG C to keep the temperature 5 hours, other are the same as embodiment 1.Compared with Example 1, the crystalline substance of acquisition Bodily form looks are similar, but product and crucible portion bond, and the product of once purged acquisition is less, the reason is that reaction temperature increases, melt Salt volatilization is more, causes mutually to bond between product.
Comparative example 8: separation NaNbO3The selection of cleaning solvent when crystal
Take the NaNbO of 1 preparation3Crystal is several, is cleaned by ultrasonic 30min, compared with Example 1, nothing using hot deionized water Method is by NaNbO3Crystal is separated from other sintered products.The reason is that containing NaNbO in sintered product3Crystal, NaCl- KCl fused salt and Bi2O3, wherein NaCl-KCl fused salt can be washed away with the deionized water of heat, but Bi2O3It is not soluble in water, thus can not Removal.
Comparative example 9: separation NaNbO3The selection of cleaning solvent when crystal
NaNbO prepared by Example 13Crystal is several, is cleaned by ultrasonic using dust technology, compared with Example 1, can not incite somebody to action NaNbO3Crystal is separated from other sintered products.The reason is that dust technology can dissolve Bi2O3, generate Bi (NO3)3If It is cleaned without deionized water, then can not completely remove Bi (NO3)3。
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention Protection scope within.

Claims (10)

1. a kind of preparation method of micron-stage sheet-like niobic acid sodium crystal, which comprises the following steps:
1) by Bi2O3Powder, Na2CO3Powder and Nb2O5Powder is uniformly mixed obtained mixture；
2) mixture made from NaCl powder and step 1) is sufficiently mixed uniformly, then the isothermal holding 4 at 1050~1200 DEG C ~10h, obtains burned material, and cleaning removes the NaCl in burned material, obtains sheet Bi2.5Na3.5Nb5O18Presoma；
3) by sheet Bi made from step 2)2.5Na3.5Nb5O18Presoma and Na2CO3Powder is mixed to get mixture A；By NaCl powder Mixture B is mixed to get with KCl powder；
4) after mixing by mixture A and mixture B, 3~10h of isothermal holding, obtains burned material at 900~1000 DEG C, Cleaning removes NaCl, KCl and Bi in burned material2O3, the micron-stage sheet-like niobic acid sodium crystal of sheet is made.
2. the preparation method of micron-stage sheet-like niobic acid sodium crystal according to claim 1, which is characterized in that in step 1), Bi2O3Powder, Na2CO3Powder and Nb2O5The molar ratio of powder is 1:(1~2): (2~4).
3. the preparation method of micron-stage sheet-like niobic acid sodium crystal according to claim 1, which is characterized in that in step 2), The mass ratio of mixture made from NaCl powder and step 1) is (1~2.5): 1.
4. the preparation method of micron-stage sheet-like niobic acid sodium crystal according to claim 1, which is characterized in that in step 3), Sheet Bi2.5Na3.5Nb5O18Presoma and Na2CO3The molar ratio of powder is 1:(1~4).
5. the preparation method of micron-stage sheet-like niobic acid sodium crystal according to claim 1, which is characterized in that in step 3), The molar ratio of NaCl powder and KCl powder is (6~11): 1.
6. the preparation method of micron-stage sheet-like niobic acid sodium crystal according to claim 1, which is characterized in that in step 4), The mass ratio of mixture A and mixture B are 1:(1~2.5).
7. the preparation method of micron-stage sheet-like niobic acid sodium crystal according to claim 1, which is characterized in that in step 1), It is to be cleaned using the deionized water of heat by ultrasound that cleaning, which removes the NaCl in burned material,.
8. the preparation method of micron-stage sheet-like niobic acid sodium crystal according to claim 1, which is characterized in that in step 4), Cleaning is the NaCl and KCl successively removed using the deionized water of heat in burned material, is cleaned and is removed in burned material using dust technology Bi2O3, finally cleaned using deionized water, entire cleaning process is carried out by ultrasonic method.
9. special using micron-stage sheet-like niobic acid sodium crystal made from preparation method described in any one of claim 1~8 Sign is, which has a cubic phase perovskite structure, square flake-like shape, and square piece shape outer dimension is long It is 8~15 μm, with a thickness of 0.8~1.5 μm, size distribution is uniform.
10. micron-stage sheet-like niobic acid sodium crystal as claimed in claim 9 is in the seed crystal of preparation high-performance textured piezoelectric ceramic Application.
CN201910533195.9A 2019-06-19 2019-06-19 A kind of micron-stage sheet-like niobic acid sodium crystal and its preparation method and application Pending CN110342934A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112792350A (en) * 2019-10-25 2021-05-14 中国科学院福建物质结构研究所 Antimony and/or bismuth nanosheet, stibene and/or bislimonene and preparation method and application thereof
CN115520898A (en) * 2022-09-30 2022-12-27 上海应用技术大学 Preparation method and application of flaky microcrystalline powder

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271409A (en) * 2014-07-25 2016-01-27 同济大学 Preparation method of sheet shaped potassium-sodium niobate powder
CN110357625A (en) * 2019-07-22 2019-10-22 福州大学 A method of potassium-sodium niobate texture crystalline ceramics is prepared based on the tape casting

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271409A (en) * 2014-07-25 2016-01-27 同济大学 Preparation method of sheet shaped potassium-sodium niobate powder
CN110357625A (en) * 2019-07-22 2019-10-22 福州大学 A method of potassium-sodium niobate texture crystalline ceramics is prepared based on the tape casting

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GAO FENG等: "Effect of different templates on microstructure of textured Na0.5Bi0.5TiO3–BaTiO3 ceramics with RTGG method", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 *
GAO FENG等: "Phase transition and piezoelectric properties of K0.48Na0.52NbO3–LiTa0.5Nb0.5O3–NaNbO3 lead-free ceramics", 《JOURNAL OF ALLOYS AND COMPOUND》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112792350A (en) * 2019-10-25 2021-05-14 中国科学院福建物质结构研究所 Antimony and/or bismuth nanosheet, stibene and/or bislimonene and preparation method and application thereof
CN112792350B (en) * 2019-10-25 2022-04-19 中国科学院福建物质结构研究所 Antimony and/or bismuth nanosheet, stibene and/or bislimonene and preparation method and application thereof
CN115520898A (en) * 2022-09-30 2022-12-27 上海应用技术大学 Preparation method and application of flaky microcrystalline powder
CN115520898B (en) * 2022-09-30 2024-04-30 上海应用技术大学 Preparation method and application of flaky microcrystalline powder

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Application publication date: 20191018