CN104098334A - Method for synthetizing leadless piezoelectric ceramic K0.65Na0.35NbO3 powder adopting two-step hydrothermal method - Google Patents
Method for synthetizing leadless piezoelectric ceramic K0.65Na0.35NbO3 powder adopting two-step hydrothermal method Download PDFInfo
- Publication number
- CN104098334A CN104098334A CN201410333443.2A CN201410333443A CN104098334A CN 104098334 A CN104098334 A CN 104098334A CN 201410333443 A CN201410333443 A CN 201410333443A CN 104098334 A CN104098334 A CN 104098334A
- Authority
- CN
- China
- Prior art keywords
- powder
- nbo
- nanbo
- knbo
- electric ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 110
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 71
- 239000000919 ceramic Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000003407 synthetizing effect Effects 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- 239000002243 precursor Substances 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 56
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 239000010955 niobium Substances 0.000 claims description 31
- 229910052758 niobium Inorganic materials 0.000 claims description 30
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 12
- 230000009514 concussion Effects 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 239000011734 sodium Substances 0.000 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 10
- 229910052700 potassium Inorganic materials 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011591 potassium Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000010355 oscillation Effects 0.000 abstract description 2
- 229910003334 KNbO3 Inorganic materials 0.000 abstract 2
- 229910003378 NaNbO3 Inorganic materials 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 2
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 abstract 2
- 239000013078 crystal Substances 0.000 abstract 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 14
- 238000007789 sealing Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 7
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a method for synthetizing leadless piezoelectric ceramic K0.65Na0.35NbO3 powder adopting a two-step hydrothermal method. Excess potassium hydroxide and excess sodium hydroxide are taken as a potassium source and a sodium source respectively and dissolved in deionized water; then niobium pentoxide is added into the solution respectively, and precursor solutions of KNbO3 and NaNbO3 can be synthesized respectively after even stirring; the precursor solutions are sealed in a hydrothermal kettle respectively, the hydrothermal kettle is placed in a thermostat for hydrothermal synthesis at a certain temperature, cooling to the room temperature is performed after the reaction, and powder obtained through the reaction is washed with deionized water for several times and dried finally. After a grinding process, KNbO3 powder and NaNbO3 powder are accurately weighed and mixed in the deionized water; microwave oscillation is performed after stirring; the mixture is poured into a hydrothermal reaction kettle and sealed for hydrothermal synthesis, cooling to the room temperature is performed after the reaction, and a mixed liquid obtained through the reaction is fully dried to obtain the powder. According to the method, the two-step hydrothermal method is adopted to synthetize the K0.65Na0.35NbO3 powder, the preparation technology is good in repeatability, the material component proportion is accurate, the powder is good in uniformity and high in purity, and crystal grains are complete in development and even in distribution.
Description
Technical field
The present invention relates to piezoelectric ceramic powder preparation field, especially a kind of two one-step hydrothermals synthesize leadless piezo-electric ceramic K
0.65na
0.35nbO
3the method of powder.
Background technology
The piezoceramic material using is at present with Pb-based lanthanumdoped zirconate titanates, and wherein in lead base piezoelectric ceramics, plumbous oxide accounts for 70% of starting material gross weight.Because plumbous oxide is a kind of volatile toxic substance, cause serious harm in the treating processes after using and discarding the mankind and ecotope; In preparation process, need sealed sintering, not only increased product cost, also caused the consistency of performance of product poor simultaneously.Along with the enhancing of social sustainable development implementation and people's environmental consciousness, the research of lead-free piezoceramic material and application cause people's concern more day by day.Than lead base piezoelectric ceramics such as PZT, for many years for valued base metal niobate pottery (KNbO
3, NaNbO
3, LiNbO
3) everyway has more excellent performance, specific inductivity is little, frequency constant is large, piezoelectricity is high and density is little etc.In addition, again because the metal ions such as Nb, Na, K all belong to non-toxic substance concerning human body and physical environment, and NaNbO
3-KNbO
3system is after improving conventional sintering technique, and properties can be better than the leadless piezoelectric ceramics of other system greatly; And with respect to PZT pottery, (K, Na) NbO
3pottery also has specific inductivity preferably, lower mechanical Qm value, low density and the high advantages such as acoustic propagation velocity, thereby also obtained application in high-frequency transducer field.Most important, (K, Na) NbO
3the Curie temperature of pottery up to 400 ℃, is expected to realize the application of the high performance device under hot conditions.The electrical property of the KNN base orientation leadless piezoelectric ceramics that the people such as SaitoY successfully develop can compare favourably with PZT, and then creates the researching value of KNN base piezoelectric ceramic.Certainly, NaNbO
3-KNbO
3system pottery becomes again the research object getting most of the attention.
The performance of potassium-sodium niobate is with its purity, particle shape, particle size and distribute relevant.Therefore, wish to obtain high purity, as far as possible little particle size and the particle of high-compactness.For this purpose, in succession adopted chemical precipitation method, sol-gel method, above method or complicated operation, or be exactly complex process, the cycle is long, poor repeatability.By contrast, hydrothermal method has the some superiority of synthetic potassium-sodium niobate, so be the method that most of researcher adopts, but traditional hydrothermal method cannot be avoided problem: because the binding ability of K, two kinds of ions of Na and Nb differs too large, if synthetic by traditional one step hydro thermal method, (K, Na) NbO often
3the not out existence of K of fundamental presentation in powder; But adopt NaNbO
3, KNbO
3separately synthetic remix, if mix in washing process, (K, Na) NbO
3potassium, sodium than at all, can not control accurately; If by the NaNbO preparing
3, KNbO
3powder metage mixes, although can also guarantee accurate potassium, sodium ratio, but after facing mixing, uniformity coefficient cannot ensure.
Summary of the invention
The object of the invention is to solve problems of the prior art, provide a kind of material composition proportion speed, grain-size is little and the synthetic leadless piezo-electric ceramic K of even, purity is high two one-step hydrothermals
0.65na
0.35nbO
3the method of powder.
Technical scheme of the present invention is:
Comprise the following steps:
The first step: add Niobium Pentxoxide respectively in potassium hydroxide solution and sodium hydroxide solution, wherein the mol ratio of potassium hydroxide and Niobium Pentxoxide, sodium hydroxide and Niobium Pentxoxide is (2～24): 1, stir and form uniform KNbO
3precursor liquid and NaNbO
3precursor liquid, by KNbO
3precursor liquid and NaNbO
3precursor liquid seals respectively and carries out Hydrothermal Synthesis, after having reacted, obtains powder, finally powder is washed respectively, dries and obtain KNbO
3powder and NaNbO
3powder;
Second step: through grinding technics, get KNbO by the required stoichiometric ratio of preparing powder
3, NaNbO
3powder mixes and seals and carries out Hydrothermal Synthesis in water, after having reacted, obtains mixing solutions, is dried and both obtains leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder.
The concentration of described potassium hydroxide solution and sodium hydroxide solution is 3～12mol/L.
In the described the first step, stir is to use magnetic stirring apparatus to stir 30～70min.
Hydrothermal synthesis reaction in the described the first step is by KNbO
3precursor liquid and NaNbO
3precursor liquid is sealed in respectively in hydrothermal reaction kettle, at the temperature of 180～220 ℃, is incubated 6～10h, has reacted cool to room temperature.
The compactedness of described hydrothermal reaction kettle is 65～90%.
KNbO in described second step
3, NaNbO
3powder mixes and refers in water, uses magnetic stirrer 30～80min, re-uses microwave concussion 30～80min.
Described second step hydrothermal synthesis reaction is by KNbO
3, NaNbO
3powder is sealed in hydrothermal reaction kettle after mixing in water, at the temperature of 180～220 ℃, is incubated 2～6h, has reacted cool to room temperature.
The leadless piezo-electric ceramic K that described second step obtains
0.65na
0.35nbO
3powder is through washing and oven dry.
Described washing, for using deionized water rinsing to neutral, is dried as being incubated 20～26h at 70～110 ℃.
In described hydrothermal synthesis reaction, hydrothermal reaction kettle is placed in to thermostat container.
Compared with prior art, the present invention has following useful technique effect:
Leadless piezo-electric ceramic K prepared by the present invention
0.65na
0.35nbO
3powder, by usining excessive potassium hydroxide solution and sodium hydroxide solution as potassium source, sodium source, forms precursor liquid with Niobium Pentxoxide respectively, through hydrothermal synthesis reaction, obtains KNbO
3powder and NaNbO
3powder, effectively avoids K, two kinds of ions of Na inaccurate from the different composition proportion that cause of binding ability of Nb; And through washing and dry, make powder purity high, inclusion-free impact; According to required material, can adjust got KNbO again
3, NaNbO
3powder mol ratio, gets two kinds and is dissolved in distilled water through the powder grinding, and can accurately control the mol ratio of powder, and through grinding, diameter of particle is less, is convenient to mix in liquor, makes it carry out hydrothermal synthesis reaction and obtains leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder, the present invention at least has the following advantages: have preparation technology reproducible; Material composition proportion speed; Through grinding physically, and intermediate water thermal response makes mixed powder effectively ensure uniformity coefficient, and prepared powder has very high purity, grain-size is little and even; Not containing hazardous compounds such as Pb, meet the requirement that environment-friendly electronic material is manufactured.
Further, in second step, use magnetic agitation and microwave oscillation that powder is mixed more fully in water, make the leadless piezo-electric ceramic K obtaining
0.65na
0.35nbO
3powder is more even.
Accompanying drawing explanation
Fig. 1 is the leadless piezo-electric ceramic K of being prepared by the embodiment of the present invention 3
0.65na
0.35nbO
3the X-ray diffraction of powder (XRD) figure;
Fig. 2 is the leadless piezo-electric ceramic K of being prepared by the embodiment of the present invention 3
0.65na
0.35nbO
3the SEM figure of powder.
Embodiment
The present invention includes following steps:
The first step, KNbO
3, NaNbO
3synthesizing of powder
(1) get the potassium hydroxide solution that 20mL concentration is 3～12mol/L, get the sodium hydroxide solution that 20mL concentration is 3～12mol/L;
(2) in potassium hydroxide solution, sodium hydroxide solution, add separately 0.01～0.03mol Niobium Pentxoxide, the mol ratio of potassium hydroxide and Niobium Pentxoxide, sodium hydroxide and Niobium Pentxoxide is (2～24): 1; Use magnetic stirring apparatus, stir 30～70min, form uniform KNbO
3precursor liquid, NaNbO
3precursor liquid; By KNbO
3precursor liquid, NaNbO
3precursor liquid is poured into respectively in different hydrothermal reaction kettles, and controlling compactedness is 65～90%, puts into thermostat container and at 180～220 ℃, be incubated 6～10h and carry out Hydrothermal Synthesis after sealing;
(3) question response completes and is cooled to room temperature, and the material in taking-up hydrothermal reaction kettle, is dried at 70～110 ℃ of insulation 20～26h with deionized water rinsing to neutrality, obtains KNbO
3, NaNbO
3two kinds of powders.
Second step: leadless piezo-electric ceramic K
0.65na
0.35nbO
3synthesizing of powder
(1) by KNbO
3, NaNbO
3two kinds of powders, through grinding technics, weigh KNbO for 0.65:0.35 in molar ratio accurately
3, NaNbO
3powder mixes in deionized water; Use magnetic stirrer 30～80min; Re-use the precursor liquid that microwave concussion 30～80min obtains mixing, the uniform precursor liquid of physical mixed is poured in hydrothermal reaction kettle and sealing; Put into and in thermostat container, at 180～220 ℃, be incubated 2～6h and carry out Hydrothermal Synthesis;
(2) question response completes and is cooled to room temperature, after the dry materials in taking-up hydrothermal reaction kettle, obtains powder, with deionized water rinsing, to neutrality, at 70～110 ℃ of insulation 20～26h, dries, and obtains leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder.
In the present invention, can, according to required material, adjust the KNbO getting
3, NaNbO
3powder mol ratio, is converted to grams by mol ratio, can accurate weighing; This experiment need to make K
0.65na
0.35nbO
3powder, so get KNbO
3, NaNbO
3mol ratio is 0.65:0.35.
Embodiment 1
The first step, KNbO
3, NaNbO
3synthesizing of powder
(1) get the potassium hydroxide solution that 20mL concentration is 3mol/L, get the sodium hydroxide solution that 20mL concentration is 3mol/L;
(2) in potassium hydroxide solution, sodium hydroxide solution, add separately 0.03mol Niobium Pentxoxide, make the mol ratio of potassium hydroxide and Niobium Pentxoxide, sodium hydroxide and Niobium Pentxoxide be 2:1; Use magnetic stirring apparatus, stir 30min, form uniform KNbO
3precursor liquid, NaNbO
3precursor liquid; By KNbO
3precursor liquid, NaNbO
3precursor liquid is poured into respectively in different hydrothermal reaction kettles, and controlling compactedness is 90%, puts into thermostat container and at 180 ℃, be incubated 10h and carry out Hydrothermal Synthesis after sealing;
(3) be cooled to room temperature, the material in taking-up hydrothermal reaction kettle, is dried at 70 ℃ of insulation 26h with deionized water rinsing to neutrality, obtains KNbO
3, NaNbO
3two kinds of powders.
Second step: leadless piezo-electric ceramic K
0.65na
0.35nbO
3synthesizing of powder
(1) by KNbO
3, NaNbO
3two kinds of powders, through grinding technics, weigh KNbO for 0.65:0.35 in molar ratio accurately
3, NaNbO
3powder mixes in deionized water; Use magnetic stirrer 50min; Re-use the precursor liquid that microwave concussion 50min obtains mixing, the uniform precursor liquid of physical mixed is poured in hydrothermal reaction kettle and sealing; Put into and in thermostat container, at 185 ℃, be incubated 4.5h and carry out Hydrothermal Synthesis;
(2) be cooled to room temperature, after the dry materials in taking-up hydrothermal reaction kettle, obtain powder, with deionized water rinsing, to neutrality, at 100 ℃ of insulation 23h, dry, obtain leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder.
Embodiment 2
The first step, KNbO
3, NaNbO
3synthesizing of powder
(1) get the potassium hydroxide solution that 20mL concentration is 4mol/L, get the sodium hydroxide solution that 20mL concentration is 4mol/L;
(2) in potassium hydroxide solution, sodium hydroxide solution, add separately 0.02mol Niobium Pentxoxide, make the mol ratio of potassium hydroxide and Niobium Pentxoxide, sodium hydroxide and Niobium Pentxoxide be 4:1; Use magnetic stirring apparatus, stir 40min, form uniform KNbO
3precursor liquid, NaNbO
3precursor liquid; By KNbO
3precursor liquid, NaNbO
3precursor liquid is poured into respectively in different hydrothermal reaction kettles, and controlling compactedness is 65%, puts into thermostat container and at 220 ℃, be incubated 8h and carry out Hydrothermal Synthesis after sealing;
(3) be cooled to room temperature, the material in taking-up hydrothermal reaction kettle, is dried at 80 ℃ of insulation 25h with deionized water rinsing to neutrality, obtains KNbO
3, NaNbO
3two kinds of powders.
Second step: leadless piezo-electric ceramic K
0.65na
0.35nbO
3synthesizing of powder
(1) by KNbO
3, NaNbO
3two kinds of powders, through grinding technics, weigh KNbO for 0.65:0.35 in molar ratio accurately
3, NaNbO
3powder mixes in deionized water; Use magnetic stirrer 60min; Re-use the precursor liquid that microwave concussion 60min obtains mixing, the uniform precursor liquid of physical mixed is poured in hydrothermal reaction kettle and sealing; Put into and in thermostat container, at 190 ℃, be incubated 6h and carry out Hydrothermal Synthesis;
(2) be cooled to room temperature, after the dry materials in taking-up hydrothermal reaction kettle, obtain powder, with deionized water rinsing, to neutrality, at 110 ℃ of insulation 22h, dry, obtain leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder.
Embodiment 3
The first step, KNbO
3, NaNbO
3synthesizing of powder
(1) get the potassium hydroxide solution that 20mL concentration is 6mol/L, get the sodium hydroxide solution that 20mL concentration is 6mol/L;
(2) in potassium hydroxide solution, sodium hydroxide solution, add separately 0.01mol Niobium Pentxoxide, make the mol ratio of potassium hydroxide and Niobium Pentxoxide, sodium hydroxide and Niobium Pentxoxide be 12:1; Use magnetic stirring apparatus, stir 50min, form uniform KNbO
3precursor liquid, NaNbO
3precursor liquid; By KNbO
3precursor liquid, NaNbO
3precursor liquid is poured into respectively in different hydrothermal reaction kettles, and controlling compactedness is 70%, puts into thermostat container and at 210 ℃, be incubated 6h and carry out Hydrothermal Synthesis after sealing;
(3) be cooled to room temperature, the material in taking-up hydrothermal reaction kettle, is dried at 90 ℃ of insulation 24h with deionized water rinsing to neutrality, obtains KNbO
3, NaNbO
3two kinds of powders.
Second step: leadless piezo-electric ceramic K
0.65na
0.35nbO
3synthesizing of powder
(1) by KNbO
3, NaNbO
3two kinds of powders, through grinding technics, weigh KNbO for 0.65:0.35 in molar ratio accurately
3, NaNbO
3powder mixes in deionized water; Use magnetic stirrer 70min; Re-use the precursor liquid that microwave concussion 30min obtains mixing, the uniform precursor liquid of physical mixed is poured in hydrothermal reaction kettle and sealing; Put into and in thermostat container, at 180 ℃, be incubated 5h and carry out Hydrothermal Synthesis;
(2) be cooled to room temperature, after the dry materials in taking-up hydrothermal reaction kettle, obtain powder, with deionized water rinsing, to neutrality, at 95 ℃ of insulation 20h, dry, obtain leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder.
Embodiment 4
The first step, KNbO
3, NaNbO
3synthesizing of powder
(1) get the potassium hydroxide solution that 20mL concentration is 10mol/L, get the sodium hydroxide solution that 20mL concentration is 10mol/L;
(2) in potassium hydroxide solution, sodium hydroxide solution, add separately 0.01mol Niobium Pentxoxide, make the mol ratio of potassium hydroxide and Niobium Pentxoxide, sodium hydroxide and Niobium Pentxoxide be 20:1; Use magnetic stirring apparatus, stir 60min, form uniform KNbO
3precursor liquid, NaNbO
3precursor liquid; By KNbO
3precursor liquid, NaNbO
3precursor liquid is poured into respectively in different hydrothermal reaction kettles, and controlling compactedness is 80%, puts into thermostat container and at 200 ℃, be incubated 7h and carry out Hydrothermal Synthesis after sealing;
(3) be cooled to room temperature, the material in taking-up hydrothermal reaction kettle, is dried at 100 ℃ of insulation 23h with deionized water rinsing to neutrality, obtains KNbO
3, NaNbO
3two kinds of powders.
Second step: leadless piezo-electric ceramic K
0.65na
0.35nbO
3synthesizing of powder
(1) by KNbO
3, NaNbO
3two kinds of powders, through grinding technics, weigh KNbO for 0.65:0.35 in molar ratio accurately
3, NaNbO
3powder mixes in deionized water; Use magnetic stirrer 80min; Re-use the precursor liquid that microwave concussion 40min obtains mixing, the uniform precursor liquid of physical mixed is poured in hydrothermal reaction kettle and sealing; Put into and in thermostat container, at 220 ℃, be incubated 3h and carry out Hydrothermal Synthesis;
(2) be cooled to room temperature, after the dry materials in taking-up hydrothermal reaction kettle, obtain powder, with deionized water rinsing, to neutrality, at 70 ℃ of insulation 26h, dry, obtain leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder.
Embodiment 5
The first step, KNbO
3, NaNbO
3synthesizing of powder
(1) get the potassium hydroxide solution that 20mL concentration is 12mol/L, get the sodium hydroxide solution that 20mL concentration is 12mol/L;
(2) in potassium hydroxide solution, sodium hydroxide solution, add separately 0.01mol Niobium Pentxoxide, make the mol ratio of potassium hydroxide and Niobium Pentxoxide, sodium hydroxide and Niobium Pentxoxide be 24:1; Use magnetic stirring apparatus, stir 70min, form uniform KNbO
3precursor liquid, NaNbO
3precursor liquid; By KNbO
3precursor liquid, NaNbO
3precursor liquid is poured into respectively in different hydrothermal reaction kettles, and controlling compactedness is 85%, puts into thermostat container and at 190 ℃, be incubated 9h and carry out Hydrothermal Synthesis after sealing;
(3) be cooled to room temperature, the material in taking-up hydrothermal reaction kettle, is dried at 110 ℃ of insulation 22h with deionized water rinsing to neutrality, obtains KNbO
3, NaNbO
3two kinds of powders.
Second step: leadless piezo-electric ceramic K
0.65na
0.35nbO
3synthesizing of powder
(1) by KNbO
3, NaNbO
3two kinds of powders, through grinding technics, weigh KNbO for 0.65:0.35 in molar ratio accurately
3, NaNbO
3powder mixes in deionized water; Use magnetic stirrer 30min; Re-use the precursor liquid that microwave concussion 70min obtains mixing, the uniform precursor liquid of physical mixed is poured in hydrothermal reaction kettle and sealing; Put into and in thermostat container, at 210 ℃, be incubated 2h and carry out Hydrothermal Synthesis;
(2) be cooled to room temperature, after the dry materials in taking-up hydrothermal reaction kettle, obtain powder, with deionized water rinsing, to neutrality, at 80 ℃ of insulation 25h, dry, obtain leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder.
Embodiment 6
The first step, KNbO
3, NaNbO
3synthesizing of powder
(1) get the potassium hydroxide solution that 20mL concentration is 8mol/L, get the sodium hydroxide solution that 20mL concentration is 6mol/L;
(2) in potassium hydroxide solution, sodium hydroxide solution, add separately 0.02mol Niobium Pentxoxide, make the mol ratio of potassium hydroxide and Niobium Pentxoxide, sodium hydroxide and Niobium Pentxoxide be 6:1; Use magnetic stirring apparatus, stir 60min, form uniform KNbO
3precursor liquid, NaNbO
3precursor liquid; By KNbO
3precursor liquid, NaNbO
3precursor liquid is poured into respectively in different hydrothermal reaction kettles, and controlling compactedness is 75%, puts into thermostat container and at 195 ℃, be incubated 9h and carry out Hydrothermal Synthesis after sealing;
(3) be cooled to room temperature, the material in taking-up hydrothermal reaction kettle, is dried at 95 ℃ of insulation 20h with deionized water rinsing to neutrality, obtains KNbO
3, NaNbO
3two kinds of powders.
Second step: leadless piezo-electric ceramic K
0.65na
0.35nbO
3synthesizing of powder
(1) by KNbO
3, NaNbO
3two kinds of powders, through grinding technics, weigh KNbO for 0.65:0.35 in molar ratio accurately
3, NaNbO
3powder mixes in deionized water; Use magnetic stirrer 40min; Re-use the precursor liquid that microwave concussion 80min obtains mixing, the uniform precursor liquid of physical mixed is poured in hydrothermal reaction kettle and sealing; Put into and in thermostat container, at 200 ℃, be incubated 4h and carry out Hydrothermal Synthesis;
(2) be cooled to room temperature, after the dry materials in taking-up hydrothermal reaction kettle, obtain powder, with deionized water rinsing, to neutrality, at 90 ℃ of insulation 24h, dry, obtain leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder.
Refer to shown in Fig. 1, by prepared K
0.65na
0.5nbO
3rigaku D/max2000PCX-x ray diffractometer x analytic sample for powder, finds that product is the K that JCPDS is numbered 77-0038
0.65na
0.35nbO
3.
Refer to shown in Fig. 2 the cube K being prepared by the inventive method
0.65na
0.35nbO
3powder, particle surface rule, particle is grown complete, and component is even.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of any equivalence that the logical technician in this area takes technical solution of the present invention by reading specification sheets of the present invention, is claim of the present invention and contains.
Claims (10)
1. an one-step hydrothermal synthesizes leadless piezo-electric ceramic K
0.65na
0.35nbO
3the method of powder, is characterized in that: comprise the following steps:
The first step: add Niobium Pentxoxide respectively in potassium hydroxide solution and sodium hydroxide solution, wherein the mol ratio of potassium hydroxide and Niobium Pentxoxide, sodium hydroxide and Niobium Pentxoxide is (2～24): 1, stir and form uniform KNbO
3precursor liquid and NaNbO
3precursor liquid, by KNbO
3precursor liquid and NaNbO
3precursor liquid seals respectively and carries out Hydrothermal Synthesis, after having reacted, obtains powder, finally powder is washed respectively, dries and obtain KNbO
3powder and NaNbO
3powder;
Second step: through grinding technics, get KNbO by the required stoichiometric ratio of preparing powder
3, NaNbO
3powder mixes and seals and carries out Hydrothermal Synthesis in water, after having reacted, obtains mixing solutions, is dried and both obtains leadless piezo-electric ceramic K
0.65na
0.35nbO
3powder.
2. two one-step hydrothermals according to claim 1 synthesize leadless piezo-electric ceramic K
0.65na
0.35nbO
3the method of powder, is characterized in that: the concentration of described potassium hydroxide solution and sodium hydroxide solution is 3～12mol/L.
3. two one-step hydrothermals according to claim 1 synthesize leadless piezo-electric ceramic K
0.65na
0.35nbO
3the method of powder, is characterized in that: in the described the first step, stirring is to use magnetic stirring apparatus to stir 30～70min.
4. according to the synthetic leadless piezo-electric ceramic K of two one-step hydrothermals described in claim 1-3 any one
0.65na
0.35nbO
3the method of powder, is characterized in that: the hydrothermal synthesis reaction in the described the first step is by KNbO
3precursor liquid and NaNbO
3precursor liquid is sealed in respectively in hydrothermal reaction kettle, at the temperature of 180～220 ℃, is incubated 6～10h, has reacted cool to room temperature.
5. two one-step hydrothermals according to claim 4 synthesize leadless piezo-electric ceramic K
0.65na
0.35nbO
3the method of powder, is characterized in that: the compactedness of described hydrothermal reaction kettle is 65～90%.
6. two one-step hydrothermals according to claim 1 synthesize leadless piezo-electric ceramic K
0.65na
0.35nbO
3the method of powder, is characterized in that: the KNbO in described second step
3, NaNbO
3powder mixes and refers in water, uses magnetic stirrer 30～80min, re-uses microwave concussion 30～80min.
7. according to the synthetic leadless piezo-electric ceramic K of two one-step hydrothermals described in claim 1 or 6
0.65na
0.35nbO
3the method of powder, is characterized in that: described second step hydrothermal synthesis reaction is by KNbO
3, NaNbO
3powder is sealed in hydrothermal reaction kettle after mixing in water, at the temperature of 180～220 ℃, is incubated 2～6h, has reacted cool to room temperature.
8. two one-step hydrothermals according to claim 7 synthesize leadless piezo-electric ceramic K
0.65na
0.35nbO
3the method of powder, is characterized in that: the leadless piezo-electric ceramic K that described second step obtains
0.65na
0.35nbO
3powder is through washing and oven dry.
9. two one-step hydrothermals according to claim 8 synthesize leadless piezo-electric ceramic K
0.65na
0.35nbO
3the method of powder, is characterized in that: described washing, for using deionized water rinsing to neutral, is dried as being incubated 20～26h at 70～110 ℃.
10. two one-step hydrothermals according to claim 9 synthesize leadless piezo-electric ceramic K
0.65na
0.35nbO
3the method of powder, is characterized in that: in described hydrothermal synthesis reaction, hydrothermal reaction kettle is placed in to thermostat container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410333443.2A CN104098334B (en) | 2014-07-14 | 2014-07-14 | A kind of two one-step hydrothermal synthesis leadless piezo-electric ceramic Ks0.65na0.35nbO3the method of powder body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410333443.2A CN104098334B (en) | 2014-07-14 | 2014-07-14 | A kind of two one-step hydrothermal synthesis leadless piezo-electric ceramic Ks0.65na0.35nbO3the method of powder body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104098334A true CN104098334A (en) | 2014-10-15 |
| CN104098334B CN104098334B (en) | 2016-08-24 |
Family
ID=51666922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410333443.2A Expired - Fee Related CN104098334B (en) | 2014-07-14 | 2014-07-14 | A kind of two one-step hydrothermal synthesis leadless piezo-electric ceramic Ks0.65na0.35nbO3the method of powder body |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104098334B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110217821A (en) * | 2019-07-02 | 2019-09-10 | 华南理工大学 | A kind of method that solid phase-hydro-thermal method prepares cubic potassium-sodium niobate nano particle |
| CN115924970A (en) * | 2022-09-19 | 2023-04-07 | 济南大学 | Potassium niobate nanowire and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475376A (en) * | 2008-12-08 | 2009-07-08 | 北京科技大学 | Method for microwave-hydrothermal synthesis of potassium-sodium niobate leadless piezoelectric ceramic |
| CN101613201A (en) * | 2009-06-25 | 2009-12-30 | 南京航空航天大学 | The method of synthesizing potassium-sodium niobate leadless piezoelectric ceramic powder by two hydro-thermal steps |
| CN101891473A (en) * | 2010-07-12 | 2010-11-24 | 北京理工大学 | Method for preparing potassium-sodium niobate lead-free piezoelectric ceramics |
-
2014
- 2014-07-14 CN CN201410333443.2A patent/CN104098334B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475376A (en) * | 2008-12-08 | 2009-07-08 | 北京科技大学 | Method for microwave-hydrothermal synthesis of potassium-sodium niobate leadless piezoelectric ceramic |
| CN101613201A (en) * | 2009-06-25 | 2009-12-30 | 南京航空航天大学 | The method of synthesizing potassium-sodium niobate leadless piezoelectric ceramic powder by two hydro-thermal steps |
| CN101891473A (en) * | 2010-07-12 | 2010-11-24 | 北京理工大学 | Method for preparing potassium-sodium niobate lead-free piezoelectric ceramics |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110217821A (en) * | 2019-07-02 | 2019-09-10 | 华南理工大学 | A kind of method that solid phase-hydro-thermal method prepares cubic potassium-sodium niobate nano particle |
| CN110217821B (en) * | 2019-07-02 | 2021-08-10 | 华南理工大学 | Method for preparing cubic potassium-sodium niobate nanoparticles by solid-phase hydrothermal method |
| CN115924970A (en) * | 2022-09-19 | 2023-04-07 | 济南大学 | Potassium niobate nanowire and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104098334B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Poterala et al. | Mechanistic interpretation of the aurivillius to perovskite topochemical microcrystal conversion process | |
| CN101186338B (en) | Hydro-thermal synthesis method for tantalum adulterated potassium sodium niobate leadless piezoelectric ceramic powder | |
| CN104119077B (en) | A kind of hydrothermal method one-step synthesis leadless piezoelectric K 0.1na 0.9nbO 3the method of powder | |
| CN103553605B (en) | KNN-BF leadless piezoelectric ceramic and preparation method thereof | |
| CN101525239B (en) | Microwave hydrothermal method for synthesizing Bi0.5Na0.5TiO3Method for producing spherical particles | |
| CN104628379B (en) | Height-oriented leadless piezoelectric structured ceramic material and its preparation method and application | |
| CN107098699A (en) | The leadless piezoelectric structured ceramics and preparation method of width sintering warm area and wide composition regulation | |
| CN103541014A (en) | Lead-free high-voltage active crystal material and preparation method thereof | |
| CN105417580B (en) | A kind of method that hydro-thermal method controls potassium tantalate-niobate nano-powder size uniformity | |
| CN101475376A (en) | Method for microwave-hydrothermal synthesis of potassium-sodium niobate leadless piezoelectric ceramic | |
| CN102205988B (en) | Method for preparing lithium-doped potassium sodium niobate-based lead-less piezoelectric ceramic powder by microwave water heating way | |
| CN104098334B (en) | A kind of two one-step hydrothermal synthesis leadless piezo-electric ceramic Ks0.65na0.35nbO3the method of powder body | |
| Lusiola et al. | Molten hydroxide synthesis as an alternative to molten salt synthesis for producing K 0.5 Na 0.5 NbO 3 lead free ceramics | |
| Li et al. | Hydrothermal synthesis and characterization of (1− x) K0. 5Na0. 5NbO3–xBi0. 5Na0. 5TiO3 lead-free ceramics | |
| CN104152999A (en) | Potassium-sodium niobate-based leadless piezoelectric monocrystalline and growth method therefor | |
| CN101550014A (en) | Preparation method of lead based relaxor ferroelectric ceramic powder material with pure perovskite structure | |
| CN112608150A (en) | Potassium-sodium niobate-based leadless piezoelectric ceramic powder and slurry and preparation process thereof | |
| CN105016723A (en) | Method for preparation of pure phase Na1/2Bi1/2TiO3 ceramic powder | |
| CN100410427C (en) | Method for preparing material of ZrW1.7Mo0.308 single crystal in minus heat expansion | |
| Liu et al. | Phase transition and piezoelectric properties of (1− x) K 0.5 Na 0.5 NbO 3–x LiSbO 3 ceramics by hydrothermal powders | |
| CN111792934B (en) | Synthesis method and application of potassium-sodium niobate powder | |
| CN104131333A (en) | Method for preparing K0.5Na0.5NbO3 single crystal | |
| CN101333005A (en) | Method for low-temperature preparing K0.5Na0.5NbO3 super fines | |
| CN104119078B (en) | A kind of KNN system low-loss leadless piezoelectric ceramics preparation method | |
| CN102557636B (en) | Sol-gel synthesis method for bismuth layer high-temperature piezoelectric ceramic sodium bismuth niobate nanopowder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 |