CN109208066A - The method for preparing single crystal of ferroelectric ceramics class compound - Google Patents
The method for preparing single crystal of ferroelectric ceramics class compound Download PDFInfo
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- CN109208066A CN109208066A CN201810180001.7A CN201810180001A CN109208066A CN 109208066 A CN109208066 A CN 109208066A CN 201810180001 A CN201810180001 A CN 201810180001A CN 109208066 A CN109208066 A CN 109208066A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 54
- 239000013078 crystal Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000003980 solgel method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 7
- 239000012700 ceramic precursor Substances 0.000 claims abstract 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- -1 preferably Substances 0.000 claims 1
- 238000001238 wet grinding Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract 1
- 229910010252 TiO3 Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 235000015895 biscuits Nutrition 0.000 description 6
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 5
- 230000005621 ferroelectricity Effects 0.000 description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 3
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 3
- 229910003334 KNbO3 Inorganic materials 0.000 description 2
- 229910003781 PbTiO3 Inorganic materials 0.000 description 2
- 229910020698 PbZrO3 Inorganic materials 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910002938 (Ba,Sr)TiO3 Inorganic materials 0.000 description 1
- 230000005343 Curie-Weiss law Effects 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- STWHDNSRIOHYPG-UHFFFAOYSA-N acetic acid;2-methoxyethanol Chemical compound CC(O)=O.COCCO STWHDNSRIOHYPG-UHFFFAOYSA-N 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000991 transmission electron microscopy selected area electron diffraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B5/00—Single-crystal growth from gels
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/30—Niobates; Vanadates; Tantalates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/32—Titanates; Germanates; Molybdates; Tungstates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
本发明具体涉及一类铁电陶瓷类化合物的单晶制备方法。所述制备方法为：固相反应制备铁电陶瓷块体，进一步球磨成200～2000目以上的微米粉末；采用溶胶‑凝胶法制备铁电陶瓷前躯体溶胶，进一步烘干后获得无定形的铁电陶瓷干凝胶粉；和将微米粉体和干凝胶粉在溶剂中湿磨成浆料，制成素坯试样后在烧结炉中烧结。与现有技术相比，本发明具有如下优势：无液相参与下，较低的烧结温度，能够制备出高质量高纯度的摩尔比在0～100之间的所有固定组份的铁电陶瓷单晶体；工艺简单，成本低，复制性强，无需复杂的制备工艺过程和苛刻单晶生长条件。The invention specifically relates to a single crystal preparation method of a class of ferroelectric ceramic compounds. The preparation method is as follows: a ferroelectric ceramic block is prepared by a solid-phase reaction, and further ball-milled into a micron powder with a size of 200-2000 mesh or more; a sol-gel method is used to prepare a ferroelectric ceramic precursor sol, and after further drying, an amorphous powder is obtained. Ferroelectric ceramic xerogel powder; and wet grinding the micron powder and xerogel powder in a solvent to form a slurry, and then sintering in a sintering furnace after making a green sample. Compared with the prior art, the present invention has the following advantages: without the participation of the liquid phase, the sintering temperature is relatively low, and the ferroelectric ceramics of all fixed components with a molar ratio of high quality and high purity between 0 and 100 can be prepared Single crystal; simple process, low cost, strong reproducibility, no complicated preparation process and harsh single crystal growth conditions.
Description
Technical field
The invention belongs to single crystal preparation technical fields, and in particular to the single crystal preparation side of a kind of ferroelectric ceramics class compound
Method.
Background technique
Ferroelectric ceramics (ferroelectric ceramics) material, refers to a kind of material with ferroelectric effect.Ferroelectricity
The key property of ceramics are as follows:
(1) characteristic of ferroelectric material is also known as " ferroelectricity " or " ferroelectric effect ": referring to the crystal structure of material
Just there is spontaneous polarization phenomenon when external electric field is not added, the direction of spontaneous polarization can be inverted by extra electric field or determine again
To.
(2) for ferroelectric material when undergoing phase transition, dielectric constant will appear peak value, and there is Curie temperature (Tc)；Work as temperature
Higher than TcWhen, spontaneous polarization disappears, and ferroelectric phase transition is paraelectric phase, and dielectric properties obey Curie-Weiss law.
(3) ferroelectric material has except ferroelectricity, has piezoelectricity, dielectricity, pyroelectric, photoelectric effect, acousto-optic effect
It answers, numerous performances such as photorefractive effect and nonlinear optical effect.
The characteristic of ferroelectric ceramics determines its purposes.Using its high dielectric constant, can make large capacity capacitor,
High frequency button capacitor, high-voltage capacitor, stacked capacitor and semiconductor ceramic capacitor etc., using its polarization direction with outer
The ferroelectric hysteresis loop that the variation of electric field is formed can prepare the ferroelectric memory of high reserves；Using its dielectric constant with external electric field in non-
The electrooptic effect of linear change can make dielectric amplifier, waveguide and phase-shifter；It can be prepared using its photoelectric effect
Optical memory, light valve, optical modulator etc.；Using its pyroelectric, infrared detector etc. can be made.It can using its piezoelectricity
Make various piezoelectric devices, actuator and sensor etc..Currently, ferroelectric material is in novel energy research, mainly high storage
The exploitation of energy density and electric card effect.The electric card effect of ferroelectric material is current preparation solid-state refrigerator of new generation, instead of to ring
Border has the liquid refrigerator freon of destruction most to have to strive one of most promising material of power unexpectedly.
Currently, the annual value of production of global ferroelectric cell oneself reach tens billion of dollars.Ferroelectric material is a huger family,
The most preferably ceramics series of current application, is widely used to military and industrial circle.
Relatively common ferroelectric ceramics has Pb (Zr, Ti) O3(PZT) system, PbTiO3(PT) system, PbZrO3(PZ) system, (Pb,
Ba)(Zr,Ti)O3System, Pb (Zr, Sn, Ti) O3(PZST) system, Pb (Mg, Nb) O3(PMN) system, (Ba, Sr) TiO3(BST) system,
BaTiO3(BT) system, (Ba, Zr) TiO3(BZT)、KNbO3(KN) and K (Nb, Na) O3(KNN) ABO such as system3Perovskite structure.
Ceramics can be divided into polycrystalline and monocrystalline two major classes.Single-crystal ceramic is not because by grain size, crystal grain orientation, crystal boundary and gas
The influence of porosity etc. such as has more excellent dielectric, ferroelectricity and optics to possess more excellent performance than polycrystalline ceramics
Performance etc..
The main method for the monocrystal for preparing ferroelectric ceramics class compound at present has: floating zone method, flux method, lifting
Method, laser heating, Bridgman method etc..The purity requirement of the raw material of the above method is high, equipment is expensive, and process is complicated, work
Skill is not easy to control, crystallization temperature requirement is also higher, and the monocrystalline with fixed component of high quality hardly results in.
Summary of the invention
The present invention provides the method for preparing single crystal of a kind of ferroelectric ceramics class compound, tired to solve current single crystal preparation
Difficult problem.
In order to solve the above-mentioned technical problem, the technical scheme is that the monocrystalline system of the ferroelectric ceramics class compound
Preparation Method comprising following steps:
1) the ferroelectric ceramics block of solid phase reaction preparation setting component, further ball milling is at more than 200~2000 mesh micro-
Rice flour end；
2) ferroelectric ceramics precursor colloidal sol is prepared using sol-gel method, further obtains unbodied setting after drying
The ferroelectric ceramics dry gel powder of component；
3) by dry gel powder described in micro-powder described in step 1) and step 2), wet-milling is described at slurry in a solvent
It is pressed into biscuit sample after slurry drying, is then sintered the biscuit sample in sintering furnace, furnace cooling after the completion of sintering
The ferroelectric ceramic single crystal product of setting component is obtained to room temperature.
Optionally, the ferroelectric ceramics is ABO3Perovskite structure class, preferably PZT and BST system ferroelectric ceramics.
The ABO3Perovskite structure class ferroelectric ceramics it is relatively common have Pb (Zr, Ti) O3(PZT) system, PbTiO3(PT)
System, PbZrO3(PZ) system, (Pb, Ba) (Zr, Ti) O3System, Pb (Zr, Sn, Ti) O3(PZST) system, Pb (Mg, Nb) O3(PMN) system,
(Ba,Sr)TiO3(BST) system, BaTiO3(BT) system, (Ba, Zr) TiO3(BZT)、KNbO3(KN) or K (Nb, Na) O3(KNN) system
Compound.
Optionally, solid phase reaction process described in step 1) is to calcine in Muffle furnace after ball milling mixing, and calcination temperature is
Ferroelectric ceramic compound sintering temperature subtracts 100~300 DEG C, keeps the temperature 2~7 hours.
Optionally, in step 1), the process of the block micron powder in mortar specifically, first pound block
It is broken, 40~200 meshes are crossed, then using alcohols solvent as medium ball milling 24 hours, 200~2000 meshes are crossed in drying.
Optionally, complexing agent is high molecular material in the sol-gel method, it is preferable that polyvinylpyrrolidone (PVP)
Or citric acid.
Optionally, the solubility of step 2) the ferroelectric ceramics precursor colloidal sol is 0.1~1.0mol/L.
Optionally, in the sol-gel method, with deionized water, isopropanol, acetic acid, dehydrated alcohol or/and ethylene glycol
Methyl ether is
Optionally, in step 3), the mass ratio of the micro-powder and the dry gel powder is (3~20): 100.
Optionally, in step 3), the preparation process of slurry is specially the micro-powder and the dry gel powder with alcohols
Solvent is that medium wet-milling forms slurry, and slurry is dried in drying box after taking out, and drying temperature is 100~300 DEG C；The slurry of drying
Feed powder is pressed into biscuit sample under the pressure of 1~10MPa, and biscuit sample is placed in sintering furnace and is sintered, and keeps the temperature 2~10 hours
Complete sintering.
Optionally, the alcohols solvent is methanol, ethyl alcohol or isopropanol.
Optionally, in step 3), sintering temperature is at 1350 DEG C or less in the sintering furnace.
Compared with prior art, technical solution provided by the invention has the advantage that
1) high quality high-purity monocrystal: proposed by the invention prepares micron seed crystal using conventional solid reaction process,
Induction is prepared with sol-gel and sees the monocrystal that crystal grain is brilliant source preparation high quality with being situated between for component, in crystal growing process,
Aneroid mutually participates in.The ferroelectric ceramics of all fixed components of the molar ratio of high quality high-purity between 0~100 can be prepared
Monocrystal.
2) sintering temperature is low: being grown up as seed crystal, unbodied dry gel powder as seed crystal using the powder and micron of calcining
Brilliant source just looks like that " clone " seed crystal is the same, be may be implemented under the sintering temperature not higher than 1350 DEG C, different required for preparing
The monocrystalline of crystal orientation.
3) method and process provided by the invention is simple, at low cost, and technique is repeatable, without complicated preparation process and
Harsh crystal growth condition；Without expensive and high-energy equipment, the easily preparation of the ferro-electricity single crystal of realization high quality high-purity.
Detailed description of the invention
Fig. 1 is the Ba prepared in embodiment 10.60Sr0.40TiO3The XRD spectrum of sintered body ceramics；
Fig. 2 a, Fig. 2 b are the Ba prepared in embodiment 10.60Sr0.40TiO3Sintered body ceramics natural surface amplifies 100 times
SEM photograph；
Fig. 3 a is the Ba prepared in embodiment 10.60Sr0.40TiO3The TEM-SAED figure of sintered body ceramics big crystal grain slice,
Wherein upper right corner illustration is the 3D figure of big crystal grain slice in Fig. 2 b；
Fig. 3 b is the Ba prepared in embodiment 10.60Sr0.40TiO3The HRTEM figure of sintered body ceramics big crystal grain slice.
Specific embodiment
In order to make it easy to understand, illustrating the method for preparing single crystal of ferroelectric ceramics class compound below with reference to embodiment, it should be appreciated that
These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Agents useful for same is such as non-specifically indicated with raw material in the present embodiment, is commercially available general goods, wherein PVP uses K
It is worth the PVP-K30 of range 30 or so.
Embodiment 1: barium strontium ratio is the BST of 60:40 (mol%)
1) solid phase reaction: with BaTiO3、SrTiO3For raw material, according to chemical formula: Ba0.60Sr0.40TiO3Ingredient is carried out, with nothing
Water-ethanol is medium wet-milling 2 hours, and bulk Φ 15*15mm is pressed after drying2, it is put into Muffle furnace and is forged within 7 hours in 1175 DEG C of heat preservations
It burns；The block of calcining crushed 40 meshes ball milling 24 hours again, and 200 meshes are crossed after drying, prepared micron-sized 1175 DEG C of calcinings
Ba0.60Sr0.40TiO3Powder；
2) sol-gel process: being dissolved completely in PVP in isopropanol in room temperature, and it is different to PVP- that butyl titanate is added dropwise
In the solution of propyl alcohol, with magnetic stirrer stirring at normal temperature 2 hours, the solution of butyl titanate-PVP- isopropanol is prepared；It will rub
You are added in glacial acetic acid than the barium acetate and strontium acetate for being 60:40, are heated with stirring to 110 DEG C with magnetic stirrer and are kept for 10 points
Clock to barium acetate and strontium acetate is completely dissolved, and is cooled to 80 DEG C, is slowly added dropwise into above-mentioned tetra-n-butyl titanate-PVP- isopropanol
It is stirred in solution, after completion of dropwise addition 15~30 minutes, obtains barium strontium titanate precursor colloidal sol, concentration 0.4mol/L；Will before
Body colloidal sol, which is put into drying box, dries, drying box temperature be 120 DEG C, dry prepare within 24 hours it is unbodied
(Ba0.60Sr0.40TiO3) dry gel powder；
3) crystal growth: micron order Ba in step 1)0.60Sr0.40TiO3Powder is as doped raw material, that is, seed crystal, in step 2)
Unbodied Ba0.60Sr0.40TiO3Raw material is as brilliant source, the micro-powder and the dry gel powder based on dry gel powder
Mass ratio be 10:100；Using isopropanol as ball-milling medium, after mixed powder is carried out wet-milling 2 hours, drying is taken out, without
It is granulated, compression moulding is Φ 10*10mm under the pressure of 2MPa2Biscuit sample；Biscuit sample is placed horizontally at Muffle furnace
In, directly heating keeps the temperature 7 hours acquisition sintered body ceramics at 1350 DEG C.
As shown in Figs. 1-2, microstructure analysis shows that ceramics have big crystal grain of the apparent size at 100 to 300 μm,
Complete crystal form, it is clear in structure.As shown in figure 3, being dot chart rather than concentric loop figure, may indicate that acquisition is single barium strontium ratio
Barium strontium titanate monocrystal, in figure it is identified go out lattice constant, which is cubic system, space group Pm-3m
(221), cell parameter are as follows: α=β=γ=90 °,Unit cell volume are as follows:
Embodiment 2: barium strontium ratio is the BST of 75:25 (mol%)
Referring to embodiment 1, difference is preparation method, according to chemical formula in step 1: Ba0.75Sr0.25TiO3Ingredient is carried out,
The molar ratio of barium acetate and strontium acetate is 75:25 in step 2).
Embodiment 3: zirconium titanium ratio is the PZT of 53:47mol%
1) solid phase reaction: with Pb3O4、ZrO2And TiO2For raw material, according to chemical formula: Pb (Zr0.53Ti0.47)O3Matched
Material presses bulk Φ 15*15mm using dehydrated alcohol as medium wet-milling 2 hours after drying2, it is put into Muffle furnace and keeps the temperature 7 at 1000 DEG C
Hour calcining；The block of calcining crushed 40 meshes ball milling 24 hours again, and 200 meshes are crossed after drying, prepare micron-sized 1000
DEG C calcining Pb (Zr0.53Ti0.47)O3Powder；
2) sol-gel process: being dissolved completely in PVP in isopropanol in room temperature, and it is different to PVP- that butyl titanate is added dropwise
In the solution of propyl alcohol, it is then added tetrabutyl zirconate, the molar ratio of tetrabutyl zirconate and butyl titanate is 53:47, uses magnetic force
Blender stirring at normal temperature 2 hours, prepare butyl titanate-tetrabutyl zirconate-PVP- isopropanol solution；Lead acetate is added
Into ethylene glycol monomethyl ether, 120 DEG C are heated with stirring to magnetic stirrer and keeps being completely dissolved to lead acetate for 30 minutes, is cooled to 80
DEG C, butyl titanate-tetrabutyl zirconate-PVP- isopropanol solution is slowly added dropwise into lead acetate-ethylene glycol monomethyl ether solution
In, it is stirred for after completion of dropwise addition 15~30 minutes, obtains lead zirconate titanate precursor colloidal sol, concentration 0.4mol/L；By precursor
Colloidal sol is put into drying box and dries, and drying box temperature is 120 DEG C, dries and prepares within 24 hours unbodied (Pb (Zr0.53Ti0.47)O3)
Dry gel powder；
3) crystal growth: micron order Pb (Zr in step 1)0.53Ti0.47)O3Powder is as doped raw material, that is, seed crystal, step 2)
In unbodied Pb (Zr0.53Ti0.47)O3Raw material is as brilliant source, the quality and xerogel of micro-powder based on dry gel powder
The mass ratio of powder is 10:100；Using isopropanol as ball-milling medium, after mixed powder is carried out wet-milling 2 hours, drying is taken out, without
Granulation is crossed, compression moulding is Φ 10*10mm under the pressure of 2MPa2Biscuit sample；Biscuit sample is placed horizontally at Muffle furnace
In, directly heating keeps the temperature 7 hours acquisition sintered body ceramics at 1200 DEG C.It is apparent to show that ceramics have through microstructure analysis
For size in the big crystal grain monocrystalline of 1mm or more, complete crystal form is clear in structure.
4 zirconium titanium ratio of embodiment is 10:90mol%
Referring to embodiment 1, difference is preparation method, according to chemical formula in step 1): Pb (Zr0.10Ti0.90)O3Matched
Expect, the molar ratio of tetrabutyl zirconate and butyl titanate is 10:90 in step 2).
Embodiment 5
Difference with embodiment 3 is, first, micron powder crosses 1000 meshes in step 1)；Second, in step 2), institute
The solubility for stating lead zirconate titanate precursor colloidal sol is 0.1mol/L；Third, sintering temperature is 650 DEG C, monocrystalline after sintering in step 3)
Partial size is 0.5-1 μm.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations.Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment, or some or all of the technical features are equal
Replacement, and these modifications or substitutions, the model for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (10)
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