CN115745605A - Method for preparing niobium zirconate potassium sodium bismuth iron by using pretreated niobium pentoxide - Google Patents
Method for preparing niobium zirconate potassium sodium bismuth iron by using pretreated niobium pentoxide Download PDFInfo
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- -1 potassium sodium bismuth iron Chemical compound 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 27
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 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 title claims abstract description 20
- 239000010955 niobium Substances 0.000 title claims description 35
- 229910052758 niobium Inorganic materials 0.000 title description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title description 3
- 239000000919 ceramic Substances 0.000 claims abstract description 95
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 17
- RDQSSKKUSGYZQB-UHFFFAOYSA-N bismuthanylidyneiron Chemical compound [Fe].[Bi] RDQSSKKUSGYZQB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- VEUKJXRCHYAIAW-UHFFFAOYSA-N [Nb].[K] Chemical compound [Nb].[K] VEUKJXRCHYAIAW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 230000001680 brushing effect Effects 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- AGMKJFDTUWUMFE-UHFFFAOYSA-N [Nb].[K].[Na] Chemical compound [Nb].[K].[Na] AGMKJFDTUWUMFE-UHFFFAOYSA-N 0.000 claims description 13
- 230000010287 polarization Effects 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 6
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 230000001131 transforming effect Effects 0.000 claims description 2
- 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 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- ZFGFKQDDQUAJQP-UHFFFAOYSA-N iron niobium Chemical compound [Fe].[Fe].[Nb] ZFGFKQDDQUAJQP-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241001290864 Schoenoplectus Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing niobium potassium sodium bismuth iron zirconate by using pretreated niobium pentoxide and a preparation method thereof, wherein the method comprises the following steps: (1) To cross-phase Nb 2 O 5 Heating to 700-1000 ℃ and preserving heat; (2) Weighing, mixing, ball milling, baking according to a general formula, heating to 800-950 ℃, and preserving heat; (3) Adding a binder, granulating, pressing, discharging the binder at 700-950 ℃, heating to 1150-1200 ℃, preserving heat, cooling to 1050-1100 ℃ and sintering; (4) Brushing silver paste, sintering at 700-800 ℃, and polarizing to obtain the niobium potassium zirconate sodium bismuth iron ceramic. The invention solves the problems of poor piezoelectric performance and poor strain temperature stability in the prior art. The invention uses pretreated Nb 2 O 5 As the raw materials, the process parameters are optimized, and the piezoelectric property and the strain temperature stability of the prepared niobium sodium zirconate bismuth iron ceramic are both obviously improved.
Description
Technical Field
The invention belongs to the technical field of lead-free piezoelectric ceramics, and particularly relates to potassium sodium bismuth iron niobium zirconate prepared by using pretreated niobium pentoxide and a preparation method thereof.
Background
Due to the asymmetry of the internal crystal lattice of the piezoelectric material, the piezoelectric material can be used as a medium for mutual conversion of mechanical energy and electric energy, is widely applied to various electronic devices and plays an important role. The piezoelectric ferroelectric ceramic has the advantages of simple preparation, low cost, high reliability and the like, and is applied to the fields of aerospace, war industry, information and the like. At present, pb (Zr) is the most widely used piezoelectric ceramic 1-x Ti x )O 3 Lead-based piezoelectric ceramic systems represented by (PZT). However, the content of Pb used in PZT-based ceramics is about 60-70% of the total amount of raw materials, and the toxicity and volatility of Pb cause serious damage to the ecological environment and human health in the processes of production, use and disposal after treatment. Therefore, the development of lead-free piezoelectric ceramics which are environmentally friendly has become one of the hot spots of the current piezoelectric material research.
Potassium sodium niobate (K, na) NbO 3 (KNN) is a perovskite-structured piezoelectric material, and the piezoelectric constant d of the pure KNN-based ceramic prepared by the conventional method 33 It is only about 80 pC/N. A novel phase boundary is constructed by adding a cubic or tetragonal inducer into KNN-based lead-free piezoelectric ceramic at room temperature, and the essence is that the phase change point of the KNN-based ceramic is moved to be close to the room temperature, so that high piezoelectric performance is obtained. The novel phase boundary constructed in the KNN-based ceramic is a polycrystalline phase boundary, and not only has component dependence, but also has temperature dependence. Thus, from room temperature to less than the Curie temperature T C The existence of another polymorphic phase transition in the temperature range of (a) is an essential cause of poor temperature stability of the KNN-based piezoelectric ceramic. The poor component sensitivity and temperature stability are the main reasons for preventing further production of KNN-based ceramics.
Therefore, in order to solve the application problem of the lead-free piezoelectric ceramic, it is necessary to reduce the component sensitivity of the KNN-based ceramic while maintaining good temperature stability. At present, niobium potassium sodium zirconate bismuth iron ceramic is a mainstream system in the research of KNN-based piezoelectric ceramic, but the piezoelectric performance and the strain temperature stability of the niobium potassium sodium zirconate bismuth iron ceramic are poor.
Disclosure of Invention
The invention aims to provide a method for preparing niobium potassium sodium bismuth iron zirconate by using pretreated niobium pentoxide and a preparation method thereof, which solve the problems of poor piezoelectric property and strain temperature stability in the prior art. The invention uses pretreated Nb 2 O 5 As the raw materials, the piezoelectric property and the strain temperature stability of the prepared niobium potassium sodium bismuth iron zirconate ceramic are both obviously improved.
In order to achieve the above object, the present invention provides a method for preparing potassium sodium bismuth iron niobium zirconate by using pretreated niobium pentoxide, which comprises the following steps:
(1) Nb in orthogonal phase 2 O 5 Heating to 700-1000 deg.C, and keeping the temperature to obtain Nb 2 O 5 Transforming from orthorhombic phase to monoclinic phase to obtain pretreated Nb 2 O 5 ；Nb 2 O 5 The raw material is the most used raw material in the KNN-based ceramic, and the crystal structure of the raw material has a crucial influence on the performance of the KNN-based ceramic;
(2) Potassium carbonate, sodium carbonate, bismuth oxide, ferric oxide, zirconium oxide and the pretreated Nb in the step (1) 2 O 5 According to the general formula (K) 0.4275 Na 0.5475 Bi 0.025 Fe 0.008 )Nb 0.95 Zr 0.05 O 3 Weighing and mixing, ball milling, drying, heating to 800-950 ℃, and preserving heat to obtain pre-sintered powder of niobium potassium zirconate sodium bismuth iron ceramic;
in the synthesized KNN-based ceramic, the doped iron and zirconium can effectively regulate and control the phase boundary temperature of the KNN-based ceramic, help to construct multiphase coexistence at room temperature, and improve the piezoelectric property of the KNN-based ceramic at normal temperature. .
(3) Adding a binder into the pre-sintered powder of the potassium sodium bismuth iron niobium zirconate ceramic obtained in the step (2), mixing, granulating, pressing into a blank, removing the binder at 700-950 ℃ (removing the binder in the formed blank, keeping the temperature for 2-3 hours, and in order to completely remove the binder, enabling the blank to obtain a certain mechanical strength before the next sintering without causing adverse effect on the subsequent sintering process), then heating to 1150-1200 ℃ for sintering, and cooling to 1050-1100 ℃ for sintering to prepare the potassium sodium bismuth iron niobium zirconate ceramic wafer;
sintering is the most important stage in the preparation of ceramic samples, the main purpose of which is densification. In the initial stage of sintering, the material particles are continuously diffused and migrated to form a ceramic skeleton; in the middle stage of sintering, ceramic crystal grains begin to grow, large crystal grains swallow small crystal grains, and pores are filled; in the later sintering stage, the texture is finished by eliminating residual air holes. Because the KNN-based ceramic system has very high sensitivity to the sintering temperature, the sintering temperature range is very narrow, and the pores of the ceramic chip are enlarged due to the over-high or over-low sintering temperature, so that the mechanical and electrical properties of the ceramic system are reduced.
(4) Brushing silver paste on the surface of the niobium potassium sodium zirconate bismuth iron ceramic chip prepared in the step (3), sintering at 700-800 ℃, and polarizing to obtain the niobium potassium sodium zirconate bismuth iron ceramic (K) 0.4275 Na 0.5475 Bi 0.025 Fe 0.008 )Nb 0.95 Zr 0.05 O 3 。
Preferably, the heat preservation time of the step (1) is 2 to 4 hours, the heat preservation time is too short, and Nb is 2 O 5 Incomplete structural transformation; too long does not change significantly.
Preferably, the ball milling in the step (2) is carried out at a rotating speed of 200-350 r/min for 10-15 hours.
In the preparation process, the use of the planetary ball mill can greatly improve the grinding efficiency. If the grinding time is too short, insufficient grinding can be caused, and the raw materials are not uniformly mixed; if the grinding time is too long, the grinding efficiency is reduced, the fineness is increased slowly, and a large amount of impurities are introduced (zirconium balls are planetary ball-milling media, and ZrO is introduced after too long time 2 Powder). And the larger the rotation speed of the ball mill is, the higher the pulverizing efficiency is, but when the rotation speed is too high, zircon ball impurities are introduced.
Preferably, the incubation time in step (2) is 6h.
Preferably, the binder in the step (3) is 5-10 wt% of polyvinyl alcohol solution, the pressing pressure is 10-15 MPa, and the thickness of the blank is 0.8-1.2 mm.
More preferably, the blank is circular, having a diameter of 10 to 15mm and a thickness of 1.0mm.
The molding is a step of greatly influencing the performance in the piezoelectric ceramic preparation process, wherein the volume of a sintered blank can shrink, and the shrinkage is related to the size, the water content, the binder concentration and the molding pressure of the blank. The density and shrinkage rate of the blank body are directly influenced by the molding pressure, and if the molding pressure is low, the product volume density is low, and the blank body shrinkage is large; if the forming pressure is too large, the ceramic blank is easy to crack, delaminate and have difficult demoulding and the like.
Preferably, the sintering time at 1150-1200 ℃ in step (3) is 5-10min, and the sintering time at 1050-1100 ℃ is 2-4 hours. The sintering time is too short, the growth of ceramic grains is not fully carried out, and more pores are formed; the sintering time is too long, and elements such as K, na, bi and the like are volatilized more, so that the actual chemical ratio is deviated.
Preferably, the concentration of the silver paste in the step (4) is 5-15 wt%, and the sintering time is 10-15 min. The sintering is mainly used for removing organic matters in the silver paste, so that the ceramic wafer is coated with silver, and if the time is too short, the organic matters are not completely removed, and the coated silver is incomplete.
Preferably, the polarization in step (4) is carried out in a silicon oil bath at 20 to 50 ℃ and the voltage of polarization is 2 to 5kV/mm.
In the process of preparing the piezoelectric ceramics, a polarization process is a key process, and the polarization process is a process of domain structure movement and development in the piezoelectric ceramics. The piezoelectric performance of the polarized piezoelectric ceramic is related to the polarization degree, and the piezoelectric ceramic cannot have very high polarization degree due to the overhigh or overlow field intensity and the polarized oil bath temperature, so that the potential piezoelectric performance of the piezoelectric ceramic is not fully exerted.
Preferably, the polarization voltage (2-5 kV/mm) is maintained in step (4) for 5-30 min.
The invention relates to niobium potassium sodium bismuth iron zirconate prepared by the method for preparing niobium potassium sodium bismuth iron zirconate by using the pretreated niobium pentoxide.
The invention relates to a method for preparing niobium potassium sodium bismuth iron zirconate by using pretreated niobium pentoxide and a preparation method thereof, which solve the problems of poor piezoelectric property and strain temperature stability in the prior art and have the following advantages:
1. nb raw material for use in the invention 2 O 5 After pretreatment, the structure of the material is obviously changed and is changed from an orthorhombic phase to a monoclinic phase.
2. The invention optimizes Nb 2 O 5 The piezoelectric performance of the prepared niobium potassium zirconate sodium bismuth iron ceramic is improved from 207pC/N to 303pC/N, and the strain temperature stability is respectively improved from 70 percent to 81 percent (from room temperature to 140 ℃).
3. The niobium potassium sodium bismuth iron zirconate ceramic has good piezoelectric property and strain temperature stability, can be used as lead-free piezoelectric ceramic and applied to electronic devices such as buzzers, resonators, atomizers, transducers, energy collectors and the like.
Drawings
FIG. 1 shows Nb after pretreatment at different temperatures in examples 1 to 4 of the present invention and comparative example 1 2 O 5 X-ray diffraction pattern of (a).
FIG. 2 shows Nb after pretreatment at different temperatures in examples 1 to 4 of the present invention and comparative example 1 2 O 5 Preparation of 1 # ～5 # The X-ray diffraction pattern of the niobium potassium sodium bismuth iron zirconate ceramic.
FIG. 3 shows Nb after pretreatment at different temperatures in examples 1 to 4 of the present invention and comparative example 1 2 O 5 Preparation of 1 # ～5 # D of niobium potassium sodium zirconate bismuth iron ceramic 33 Drawing.
FIG. 4 shows (Nb) prepared in example 2 of the present invention 2 O 5 At a pretreatment temperature of 800 ℃ C.) of 3 # SEM image of niobium zirconium potassium sodium bismuth iron ceramic.
FIG. 5 is 3 prepared according to example 2 of the present invention and comparative example 1 # 、1 # High temperature medium temperature curve chart of niobium potassium sodium bismuth iron zirconate ceramic.
FIG. 6 shows 3 prepared in example 2 of the present invention and comparative example 1 # 、1 # The low-temperature medium temperature curve chart of the niobium potassium sodium bismuth iron zirconate ceramic.
FIG. 7 shows comparative example 1 of the present inventionPreparation of 1 # Temperature-changing uniaxial strain curve diagram of niobium potassium sodium zirconate bismuth iron ceramic.
FIG. 8 is 3 prepared according to example 2 of the present invention # Temperature-changing uniaxial strain curve diagram of niobium potassium zirconate sodium bismuth iron ceramic.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A process for preparing potassium sodium bismuth iron niobium zirconate from pretreated niobium pentoxide, which comprises:
(1) Will be numbered as 2 # Of (2) quadrature phase Nb 2 O 5 Heating to 700 ℃ (number 2) # ) And keeping the temperature for 2 hours to respectively obtain the pretreated Nb 2 O 5 ；
(2) Potassium carbonate, sodium carbonate, bismuth oxide, ferric oxide, zirconium oxide and the pretreated Nb obtained in the step (1) 2 O 5 According to the general formula (K) 0.4275 Na 0.5475 Bi 0.025 Fe 0.008 )Nb T 0.95 Zr 0.05 O 3 (T =700 ℃, no. 2) # ) Weighing and mixing, placing the mixture into a nylon ball milling tank, using absolute ethyl alcohol as a dispersion medium, using a planetary ball mill with the rotating speed of 250r/min to perform ball milling for 10 hours (wherein zirconium balls are planetary ball milling balls), drying, then heating to 850 ℃ in a program temperature control box type furnace, and preserving heat for 6 hours to obtain niobium potassium zirconate sodium bismuth iron ceramic pre-sintering powder;
(3) Adding a polyvinyl alcohol solution with the concentration of 8wt% into the pre-sintered powder of potassium sodium bismuth iron niobium zirconate obtained in the step (2), fully mixing, pressing into a potassium sodium bismuth iron niobium zirconate ceramic wafer with the diameter of 10mm and the thickness of 0.8mm under the pressure of 10MPa, then removing glue and preserving heat for 2 hours at 850 ℃, then heating to 1160 ℃, sintering for 5 minutes, cooling to 1090 ℃, and sintering for 2 hours to obtain the potassium sodium bismuth iron niobium zirconate ceramic wafer;
(4) Brushing silver paste with the concentration of 5wt% on the sintered potassium sodium bismuth iron niobium zirconate ceramic wafer in the step (3), sintering at the temperature of 750 ℃ for 10 minutes to prepare a sample, putting the sample into a silicon oil bath at the temperature of 20 ℃ for polarization, wherein the polarization voltage is 3kV/mm, and keeping the polarization voltage for 15 minutes to prepare 2 # Niobium potassium sodium bismuth iron zirconate ceramics.
Example 2
A process for preparing potassium sodium bismuth iron niobium zirconate from pretreated niobium pentoxide in substantially the same manner as in example 1, except that:
in step (1), nb in an orthogonal phase is added 2 O 5 At 800 ℃ (number 3) # ) Carrying out treatment, wherein the heat preservation time is 2 hours;
in the step (2), potassium carbonate, sodium carbonate, bismuth oxide, ferric oxide, zirconium oxide and the pretreated Nb obtained in the step (1) 2 O 5 According to the general formula (K) 0.4275 Na 0.5475 Bi 0.025 Fe 0.008 )Nb T 0.95 Zr 0.05 O 3 (T =800 ℃ C., no. 3 # ) And weighing and mixing.
Example 3
A process for preparing potassium sodium bismuth iron niobium zirconate from pretreated niobium pentoxide which is substantially the same as in example 1 except that:
(1) In step (1), nb in an orthogonal phase is added 2 O 5 At 900 ℃ (number 4) # ) Carrying out treatment;
(2) In the step (2), potassium carbonate, sodium carbonate, bismuth oxide, iron oxide, zirconium oxide and the pretreated Nb obtained in the step (1) 2 O 5 According to the general formula (K) 0.4275 Na 0.5475 Bi 0.025 Fe 0.008 )Nb T 0.95 Zr 0.05 O 3 (T =900 ℃, no. 4) # ) And weighing and mixing.
Example 4
A process for preparing potassium sodium bismuth iron niobium zirconate from pretreated niobium pentoxide which is substantially the same as in example 1 except that:
(1) In step (1), nb in an orthorhombic phase is added 2 O 5 At 1000 deg.C (number 5) # ) Carrying out treatment;
(2) In the step (2), potassium carbonate, sodium carbonate, bismuth oxide, iron oxide, zirconium oxide and the pretreated Nb obtained in the step (1) 2 O 5 According to the general formula (K) 0.4275 Na 0.5475 Bi 0.025 Fe 0.008 )Nb T 0.95 Zr 0.05 O 3 (T =1000 ℃, no. 5) # ) And weighing and mixing.
Comparative example 1
A process for preparing potassium sodium bismuth iron niobium zirconate from niobium pentoxide which is essentially the same as in example 1 except that:
without step (1);
in step (2), the non-pretreated Nb is 2 O 5 The raw materials are represented by the general formula (K) 0.4275 Na 0.5475 Bi 0.025 Fe 0.008 )Nb 0.95 Zr 0.05 O 3 (No. 1) # ) Weighing and batching;
followed by the same operation as in example 1 to give 1 # Niobium potassium sodium bismuth iron zirconate ceramics.
Experimental example 1 analysis of Nb after pretreatment at various temperatures 2 O 5 Structural change of
Nb after pretreatment at different temperatures in examples 1 to 4 of the present invention 2 O 5 Comparative example 1 non-pretreated Nb 2 O 5 The structure of (2) was subjected to X-ray diffraction analysis.
As shown in FIG. 1, the Nb obtained by pretreating the Nb films of examples 1 to 4 of the present invention at different temperatures from comparative example 1 2 O 5 X-ray diffraction pattern of (a). As can be seen from FIG. 1, nb is increased with the pretreatment temperature 2 O 5 The structure of (A) is changed from an orthorhombic phase to a monoclinic phase, and after 1000 ℃, nb 2 O 5 Completely changed into a monoclinic phase.
Experimental example 2 analysis of Nb pretreated with different temperatures 2 O 5 Preparation of 1 # ～5 # Structural change of niobium potassium zirconate sodium bismuth iron ceramic
Pretreated Nb of example 1 of the invention 2 O 5 Preparation of 2 # ～5 # Niobium potassium sodium bismuth iron zirconate ceramic comparative example 1 non-pretreated Nb 2 O 5 Preparation of 1 # The structure of the niobium potassium zirconate sodium bismuth iron ceramic is analyzed by X-ray diffraction.
As shown in FIG. 2, nb after pretreatment at different temperatures in examples 1 to 4 of the present invention and comparative example 1 2 O 5 Preparation of 1 # ～5 # The X-ray diffraction pattern of the niobium potassium sodium bismuth iron zirconate ceramic. From FIG. 2, 1 # XRD and 2 of # 、3 # 、4 # 、5 # The XRD of (2) differs between the (002) and (200) peaks, showing that 1 # The ceramics coexist in a trigonal-orthorhombic-tetragonal system; 2 # ～5 # The ceramic is in a three-square multi-phase coexistence at room temperature, wherein the content of the square phase is reduced firstly and then increased, and 3 # The tetragonal phase content of the ceramic is the lowest.
Experimental example 3 testing of Nb after pretreatment by various temperatures 2 O 5 Preparation of 1 # ～5 # Piezoelectric constant d of niobium potassium sodium bismuth iron zirconate ceramic 33
Testing of pretreated Nb's of examples 1-4 of the invention 2 O 5 Preparation of 2 # ～5 # Potassium sodium bismuth iron niobium zirconate ceramic, comparative example 1, non-pretreated Nb 2 O 5 Preparation of 1 # The piezoelectric constant of the niobium potassium zirconate sodium bismuth iron ceramic is tested by the following specific test process: preparation of 1 after polarization at room temperature # ～5 # The niobium potassium sodium bismuth iron zirconate ceramics are all kept still for 24 hours and are in a quasi-static state d 33 The tester (ZJ-3A, national academy of sciences Acoustic research institute) tests the specific piezoelectric performance value.
As shown in FIG. 3, nb after pretreatment at different temperatures in examples 1 to 4 of the present invention and comparative example 1 2 O 5 Preparation of 1 # ～5 # D of niobium potassium sodium zirconate bismuth iron ceramic 33 Figure (a). FIG. 3 shows 3 # Piezoelectric constant d of 33 Compare with 1 # The increase is obvious, namely the increase is from 207pC/N to 303pC/N.
Experimental example 4 Observation channelNb after 800 ℃ pretreatment 2 O 5 Preparation of 3 # Microstructure of niobium potassium sodium zirconate bismuth iron ceramic
For 3 prepared in examples 1 to 4 of the present invention # The niobium sodium potassium zirconate bismuth iron ceramic is analyzed by an electron microscope.
(Nb) of inventive example 2, as shown in FIG. 4 2 O 5 At a pretreatment temperature of 800 ℃ C.) of 3 # SEM image of niobium zirconium potassium sodium bismuth iron ceramic. As can be seen from FIG. 4, the ceramic has fewer pores on the surface, compact crystal grains and good compactness.
Experimental example 5 test 1 # 、3 # Performance of niobium potassium sodium zirconate bismuth iron ceramic
1. Dielectric constant of
Testing of 3 prepared in examples 1 to 4 of the present invention # Niobium potassium sodium bismuth iron zirconate ceramic, 1 prepared in comparative example 1 # The specific test process of the dielectric constant of the niobium potassium zirconate sodium bismuth iron ceramic is as follows: after the ceramic sheet was finished with silver, the dielectric constant was measured using an LCR analyzer (HP 4980, agilent, U.S.A.).
As shown in FIG. 5, 3 prepared in inventive example 2 and comparative example 1 # 、1 # High temperature medium temperature curve chart of niobium potassium sodium bismuth iron zirconate ceramic. FIG. 5 shows clearly the view 1 # The high temperature medium temperature peak is at a temperature of more than 3 # Therefore 1 is # Curie temperature T of C A value higher than 3 # 。
As shown in FIG. 6, 3 prepared in inventive example 2 and comparative example 1 # 、1 # The low-temperature medium temperature curve chart of the niobium potassium zirconate sodium bismuth iron ceramic. FIG. 6 shows 1 # There are two mesophilic peaks (mesophilic peaks corresponding to the trigonal-orthogonal phase transition and the orthorhombic-tetragonal phase transition temperature), and 3 # Only one mesophase peak (corresponding to the trigonal-tetragonal phase transition temperature) exists, which indicates 1 # Coexistence of trigonal-orthogonal-tetragonal phase at room temperature, 3 # Is composed of a trigonal-tetragonal phase.
2. Strain curve
Testing of 3 prepared in examples 1 to 4 of the present invention # Niobium potassium sodium bismuth iron zirconate ceramic, 1 prepared in comparative example 1 # Niobium zirconiumThe strain curve of the potassium sodium bismuth iron ceramic comprises the following specific test processes: the silver-coated ceramic sheet was measured for uniaxial strain curve with a ferroelectric analyzer (aixact TFAnalyzer 2000, germany) at 20 ℃ intervals from room temperature to 150 ℃.
As shown in FIG. 7, comparative example 1 of the present invention # The temperature-changing uniaxial strain curve of the niobium potassium sodium bismuth iron zirconate ceramic can be seen from figure 7, the strain capacity of the niobium potassium sodium bismuth iron zirconate ceramic is firstly reduced along with the temperature rise, the maximum value is reached at 90 ℃, and the strain fluctuation range of the whole process along with the temperature reaches 30%.
As shown in FIG. 8, 3 prepared in example 2 of the present invention # The temperature-changing uniaxial strain curve diagram of the niobium potassium sodium bismuth iron zirconate ceramic is shown in figure 8, the strain capacity of the niobium sodium bismuth iron zirconate ceramic is increased and then reduced along with the temperature, and the strain fluctuation range of the whole process reaches 19 percent along with the temperature.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. A method for preparing potassium, sodium, bismuth and iron niobium zirconate by using pretreated niobium pentoxide is characterized by comprising the following steps of:
(1) Nb in orthogonal phase 2 O 5 Heating to 700-1000 deg.C, and keeping the temperature to obtain Nb 2 O 5 Transforming from orthorhombic phase to monoclinic phase to obtain pretreated Nb 2 O 5 ；
(2) Potassium carbonate, sodium carbonate, bismuth oxide, ferric oxide, zirconium oxide and the pretreated Nb in the step (1) 2 O 5 According to the general formula (K) 0.4275 Na 0.5475 Bi 0.025 Fe 0.008 )Nb 0.95 Zr 0.05 O 3 Weighing, mixing, ball-milling, drying, heating to 800-950 ℃, and preserving heat to obtain pre-sintered powder of niobium potassium zirconate sodium bismuth iron ceramic;
(3) Adding a binder into the pre-sintered powder of the potassium sodium bismuth iron niobium zirconate ceramic obtained in the step (2), granulating, pressing into a green body, removing the binder at 700-950 ℃, heating to 1150-1200 ℃, sintering, cooling to 1050-1100 ℃, and sintering to obtain the potassium sodium bismuth iron niobium zirconate ceramic wafer;
(4) Brushing silver paste on the surface of the niobium potassium sodium zirconate bismuth iron ceramic chip prepared in the step (3), sintering at 700-800 ℃, and polarizing to obtain the niobium potassium sodium zirconate bismuth iron ceramic (K) 0.4275 Na 0.5475 Bi 0.025 Fe 0.008 )Nb 0.95 Zr 0.05 O 3 。
2. The process for preparing potassium sodium bismuth iron niobium zirconate from pretreated niobium pentoxide as claimed in claim 1, wherein the holding time in step (1) is 2-4 h.
3. The process of claim 1 wherein the ball milling in step (2) is carried out at a speed of 200 to 350r/min for 10 to 15 hours.
4. The process for preparing potassium sodium bismuth iron niobium zirconate from pretreated niobium pentoxide as claimed in claim 1, wherein the holding time in step (2) is 6h.
5. The process of claim 1 wherein the binder in step (3) is a polyvinyl alcohol solution of 5-10 wt%, the pressing pressure is 10-15 MPa, and the thickness of the green body is 0.8-1.2 mm.
6. The process for preparing potassium sodium bismuth iron niobium zirconate by using the pretreated niobium pentoxide as claimed in claim 1, wherein the sintering time at 1150-1200 ℃ in the step (3) is 5-10 min, and the sintering time at 1050-1100 ℃ is 2-4 h.
7. The method for preparing niobium sodium potassium zirconate bismuth iron with niobium pentoxide as claimed in claim 1, wherein the concentration of silver paste in step (4) is 5-15 wt%, and the sintering time is 10-15 min.
8. The process of claim 1 wherein the polarization in step (4) is carried out in a silicon oil bath at 20-50 ℃ and the polarization voltage is 2-5 kV/mm.
9. The process for preparing potassium sodium bismuth iron niobium zirconate from niobium pentoxide as claimed in claim 1, wherein the poling voltage is maintained in step (4) for 5-30 min.
10. A potassium sodium bismuth iron niobium zirconate produced by the process for producing potassium sodium bismuth iron niobium zirconate from a pretreated niobium pentoxide as claimed in any one of claims 1 to 9.
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