CN116639974A - Rare earth modified KNN-LT leadless piezoelectric ceramic and preparation method thereof - Google Patents
Rare earth modified KNN-LT leadless piezoelectric ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 133
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 32
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 27
- 239000011734 sodium Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 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 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 239000010955 niobium Substances 0.000 claims abstract description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 239000011591 potassium Substances 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 8
- 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 claims description 8
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000010431 corundum Substances 0.000 claims description 7
- 238000000713 high-energy ball milling Methods 0.000 claims description 7
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- 229920002545 silicone oil Polymers 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 230000005684 electric field Effects 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910001954 samarium oxide Inorganic materials 0.000 description 6
- 229940075630 samarium oxide Drugs 0.000 description 6
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 238000005303 weighing Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 0.95 (K) 0.55 Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 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 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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Abstract
The invention relates to the technical field of piezoelectric electronic ceramic materials, in particular to a preparation method of a rare earth modified leadless piezoelectric ceramic material. The rare earth modified leadless piezoelectric ceramics are represented by the following chemical formula: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 ‑0.05LiTaO 3 ‑xmol.％Sm 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is 0.2 to 0.6. The preparation method comprises the following steps: firstly, preparing a potassium source, a sodium source, a niobium source, a lithium source, a tantalum source and a samarium source according to the chemical formula of the rare earth modified KNN-LT leadless piezoelectric ceramic, and putting other components except the samarium source in the prepared raw materials into ball milling equipmentAnd ball milling for at least 15 hours by taking an organic matter as a solvent to obtain presintered powder, ball milling with a samarium source again after presintering treatment, compacting and sintering, and finally silver coating and polarization to obtain the product. The invention obtains the product with better performance by utilizing the trace Sm to modify and combine the preparation process of the lead-free piezoelectric ceramic material for the first time.
Description
Technical Field
The invention relates to the technical field of piezoelectric electronic ceramic materials, in particular to rare earth modified KNN-LT lead-free piezoelectric ceramic and a preparation method thereof.
Technical Field
The traditional piezoelectric ceramic lead zirconate titanate (PZT) has been widely applied to the fields of transducers, filters, sensors and the like, but the latest environmental protection standards put forward the lead-free requirements of the piezoelectric ceramics due to the toxicity of lead.
The KNN-based lead-free piezoelectric ceramic has a higher Curie temperature and an ultrahigh piezoelectric coefficient, and is attracting extensive attention and research by researchers. However, the KNN ceramic prepared by the traditional process still has the problems of low density, over-high dependence of piezoelectric coefficient on temperature, poor repeatability and the like.
In patent 2013104826961, there is described a KNN-LT lead-free piezoelectric ceramic having a composition of (1-x) (K 0.5 ,Na 0.5 )NbO 3 -xLiTaO 3 . The technology realizes d of the product 33 The maximum value of the electromechanical coupling coefficient Kp can be 167pC/N and is 37.3 percent. And after LT is introduced in this technology, the Qm value of the product is rapidly decreased. And the patent does not relate to piezoelectric coefficients at high temperatures.
In patent CN 113563073A, a high-stability lead-free piezoelectric ceramic and a preparation method thereof are developed, and the components of the lead-free piezoelectric ceramic are as follows: (1-x-y) (0.50 KNbO 3 -0.50NaNbO 3 )-xMgTiO 3 -yBa(Zr 0.5 Ti 0.5 )O 3 +zSm 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x=0.03 to 0.07, y=0.04 to 0.08, and z=0.008 to 0.02. However, the technology has excessively complex components, and a large amount of Sm is required to be added to play a role in improving the electromechanical coupling coefficient of the piezoelectric ceramic.
Disclosure of Invention
Aiming at the problem that the electrical property of the existing KNN lead-free piezoelectric ceramic has strong temperature dependence, the invention provides a lead-free piezoelectric ceramic material containing trace Sm and having better electrical property and better temperature stability and a preparation method thereof.
The invention relates to rare earth modified KNN-LT lead-free piezoelectric ceramic, which adopts Sm 2 O 3 Modifying the KNN-LT lead-free piezoelectric ceramic, wherein 0.01 to 0.7 percent of Sm is mixed with each mole of KNN-LT lead-free piezoelectric ceramic 2 O 3 。
Preferably, the rare earth modified KNN-LT lead-free piezoelectric ceramic is represented by the following chemical formula:
0.95(K 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -xmol.％Sm 2 O 3 ；
further, where x mol.% means that x mol.% of Sm is incorporated in 1mol KNN lead-free piezoelectric ceramic 2 O 3 。
Further, x is 0.2 to 0.6, more preferably 0.2 to 0.4. The incorporation of samarium oxide with proper content in the invention can refine ceramic grains and obtain compact and uniform ceramic microstructure. On the other hand, the refinement of the crystal grains can lead to the refinement of electric domains in the ceramic, which is beneficial to enhancing the coordination of electric domain deflection. In addition, the occurrence of electric domain polarity micro-regions can improve the relaxation coefficient of the ceramic, enhance the dielectric stability of the KNN-LT ceramic at high temperature and widen the high-temperature application field of the lead-free KNN-LT piezoelectric ceramic.
The invention discloses a preparation method of rare earth modified KNN-LT leadless piezoelectric ceramics, which comprises the following steps:
s1: preparing a potassium source, a sodium source, a niobium source, a lithium source, a tantalum source and a samarium source (Sm source) according to the chemical formula of the rare earth modified KNN-LT leadless piezoelectric ceramic, putting other components except the Sm source in a ball milling device, taking organic matters as a solvent, performing high-energy ball milling and mixing at a rotating speed of 250-300 r/min, preferably 270-290 r/min for at least 15h, preferably 20-25 h, sieving the obtained fully mixed powder, putting the sieved powder into a corundum crucible, and covering the corundum crucible for presintering at 840-860 ℃ for 100-140 min, preferably 115-125 min to obtain presintered powder; the potassium source, the sodium source, the niobium source, the lithium source, the tantalum source and the samarium source are at least one of oxide, carbonate and bicarbonate;
s2: grinding and crushing the presintered powder, putting the presintered powder and a prepared samarium source (Sm source) into a ball milling tank again, performing secondary ball milling for at least 15 hours at a rotating speed of 240-280 r/min, preferably 260r/min, adding 3-8 wt.%, preferably 5wt.% of PVA organic adhesive for granulating after ball milling, and obtaining ceramic powder (namely standby ceramic powder) with good fluidity, regular shape and larger average particle size; and pressing and forming the standby ceramic powder to obtain a ceramic green body.
S3: the ceramic green compact is put into a muffle furnace for sintering, the sintering process is divided into two stages, the first stage is 0-550 ℃, and the heating rate is less than or equal to 4 ℃/min, preferably 1.5-2.5 ℃/min, so that organic matters such as PVA and the like introduced in the granulating process can fully escape; the second stage is to heat to 1100-1150 deg.c at a temperature raising rate of 4.5-10 deg.c/min, preferably 4.5-6 deg.c/min and maintain the temperature for at least 100min, preferably 115-135 min.
S4: polishing the upper and lower surfaces of the sintered ceramic sample, coating silver electrodes, drying, and then performing heat treatment at 550-650 ℃ and preferably 590-610 ℃ for 10-20 min; obtaining a silver-coated ceramic sample;
s5: the ceramic sample after silver is polarized in silicone oil under the condition of 60-100 ℃ silicone oil bath and the pressure is maintained for 10-30 min, preferably 25min by a high-voltage direct current electric field of 1-4 kV/mm, preferably 1.8-2 kV/mm.
The chemical formula of the rare earth modified KNN-LT leadless piezoelectric ceramic is as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -xmol.％Sm 2 O 3 。
Preferably, in the preparation method of the rare earth modified KNN-LT lead-free piezoelectric ceramic, in S1, the molar ratio is converted into the mass ratio, and then the required mass of each component under the given total mass is weighed. Putting raw materials of potassium carbonate, sodium carbonate, lithium carbonate, niobium oxide and tantalum oxide into a zirconia ball milling tank, taking absolute ethyl alcohol as a solvent, performing high-energy ball milling and mixing at the rotating speed of 270-290 r/min for 20h, sieving the fully mixed powder, putting into a corundum crucible, and capping for presintering at 840-860 ℃ for 115-125 min to obtain presintered powder.
Further, in the ball milling process in S1, the mass ratio of the various media in the ball milling tank is as follows: grinding ball: alcohol is equal to 1:1:1.2.
Further, the particle size of the grinding balls is selected to be 0.1-1.0cm, wherein the particle size of the small grinding balls is 0.5+/-0.05 cm, the particle size of the medium grinding balls is 0.8+/-0.05 cm, and the particle size of the large grinding balls is 1.1+/-0.05 cm. Still further, the mass ratio of the large, medium and small grinding balls is 1:1.5:1.
in S2, the doping element Sm is added to the ball milling apparatus in the form of oxide particles. Preferably Sm 2 O 3 The particles were added to the ball milling apparatus in the form of granules. Sm (Sm) 2 O 3 The particle size of the particles is 70 to 90 microns, preferably 75 to 80 microns.
In S2, the second ball milling is carried out for 18-25 h.
Further, in the process of granulating S2, water bath heating at 75-85 ℃ is used, continuous stirring is needed, and sedimentation caused by uneven mixing of PVA and powder is prevented.
Further, the ceramic powder (i.e., spare ceramic powder) obtained in S2 has a relatively good fluidity, a regular shape, and a relatively large average particle diameter, and has an average particle diameter of 200 to 250 μm.
Further, during the green pressing of S2, care should be taken to avoid powder build up to one side during the filling, otherwise the powder will be relatively displaced under pressure to cause delamination or cracking.
S2, adding ceramic powder into the mixtureSlowly loading the ceramic green body onto the die at a pressure of 100MPa and maintaining the pressure for 20s to obtain the ceramic green body.
Further, in the sintering process of S3, the powder obtained after the secondary ball milling is adopted in a corundum crucible for burial sintering. In order to further improve the effect, a double-layer crucible can be used for protecting the sintered and pressed ceramic plate.
Furthermore, in the sintering process of S3, the temperature rising rate of the first stage is 2 ℃/min, and the temperature is kept for 2 hours, so that the adhesive is ensured to slowly and fully overflow, and the generation of holes in the ceramic is reduced. The temperature rising rate in the second stage is 5 ℃/min, the temperature is kept for 2h, the ceramic grains are ensured to fully grow up, and finally the ceramic grains are cooled by air along with the furnace.
And S4, polishing the upper and lower surfaces of the sintered ceramic sample, coating a silver electrode by adopting a soft brush coating mode, drying in an oven at 80 ℃ for 1h, and performing heat treatment at 600 ℃ for 10-20 min.
Still further, in the silver coating process of S5, the silver electrode is completely coated on one side of the sample, and the silver electrode with a diameter of 6mm is coated on the other side, so that an accurate effective area can be ensured.
Compared with the prior art, the invention has the following benefits:
the invention provides a rare earth element doped KNN-LT leadless piezoelectric ceramic formula with higher temperature stability, which comprises 5wt.% LiTaO 3 The KNN ceramic is doped and modified, and an orthogonal-tetragonal phase boundary with the same shape is built in the KNN ceramic, so that the piezoelectric performance of the KNN ceramic is greatly improved. Then adding trace rare earth element samarium oxide to carry out doping modification on KNN-LT ceramic, namely 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -xmol.％Sm 2 O 3 The internal square degree of the ceramic is improved, and the stability and stability of the KNN ceramic are further widened.
The KNN-LT lead-free piezoelectric ceramic formula provided by the invention has excellent piezoelectric performance in all aspects and the piezoelectric constant d 33 The mechanical quality factor qm=101 to 107, and the curie temperature tc=373 to 392 ℃.
Further, when x=0.4, that is, the piezoelectric ceramic formulation is 0.95 (K 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -0.4mol.％Sm 2 O 3 At the moment, the ceramic is not only in a tetragonal phase-orthorhombic phase coexisting polymorphic phase boundary structure, but also has excellent piezoelectric coefficient, and meanwhile, the ceramic has a two-phase coexisting temperature zone inside the formula ceramicThe piezoelectric coefficient can be kept stable at about room temperature to 125 ℃ and has a strong practical application value. The relaxation coefficient of the product is up to 1.675 at this time.
Further, when x=0.6, that is, the piezoelectric ceramic formulation is 0.95 (K 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -0.6mol.％Sm 2 O 3 At the moment, the internal structure of the ceramic is a single tetragonal phase structure, the internal phase structure can not change with the temperature within the Curie temperature, the piezoelectric coefficient of the formula ceramic can be kept stable at about room temperature to 350 ℃, and the application scene of the formula lead-free piezoelectric ceramic is greatly widened.
Furthermore, the corundum crucible is filled with KNN raw material powder and sintered and pressed ceramic sheets are protected by the double-layer crucible, so that the ceramic has higher ceramic density and excellent piezoelectric and ferroelectric properties.
Drawings
Fig. 1 is an XRD scan data pattern and a partially enlarged view of examples and comparative examples in the present invention.
Fig. 2 is an SEM scan and a partial magnified view of an example and a comparison of the present invention.
FIG. 3 is a graph showing the piezoelectric coefficient and the electromechanical coupling coefficient of the examples and comparative examples according to the present invention, and the temperature aging resistance.
In fig. 1, x=0 is the XRD pattern of the product obtained in comparative example 4, x=0.2 is the XRD pattern of the product obtained in comparative example 1, x=0.4 is the XRD pattern of the product obtained in example 1, x=0.6 is the XRD pattern of the product obtained in example 2, x=0.8 is the XRD pattern of the product obtained in comparative example 2, and x=1.0 is the XRD pattern of the product obtained in comparative example 3. Sm can be seen in FIG. 1 3+ Ions have entered the KNN-LT lattice without adversely affecting the bulk phase structure, and according to the degree of peak separation of the (001)/(100) and (002)/(200) diffraction peaks around 32 ° and 46 °, example 1 is a polymorphous phase boundary structure in which tetragonal-orthorhombic phases coexist, example 2 is a single tetragonal phase structure, and comparative example 3 is a pseudocubic phase structure.
As shown in FIG. 2, with the addition of Sm, the grains of KNN-LT ceramic are significantly refined, and the temperature at which the ceramic reaches final densification is gradually increased. The ceramic of example 1 had fine and uniform grains with the highest density.
As shown in fig. 3, example 1 has the most dense and uniform microstructure, and has a multicrystalline phase boundary structure in which two phases coexist, so that it has the highest piezoelectric coefficient and electromechanical coupling coefficient. However, the polymorphic phase boundary is directly related to temperature, so that the piezoelectric performance is degraded at around 125 ℃. In addition, the addition of Sm can improve the tetragonality of the internal structure of the ceramic, the internal structure of the ceramic in the embodiment 2 is a single tetragonal phase, is far away from the polymorphic phase boundary, and has slightly poorer piezoelectric coefficient than that in the embodiment 1, but the piezoelectric coefficient of the ceramic can still be kept stable at about 350 ℃, so that the application value of the leadless piezoelectric ceramic in actual production is greatly improved.
Detailed Description
In the embodiment of the invention, the temperature change rate is d 33 The amount of change at different temperatures; the calculation method comprises the following steps:
Tvd 33 ＝|Δd 33 /d 33 (25℃)|
wherein Δd 33 Calculated from the following formula:
Δd 33 ＝d 33max -d 33min
wherein Tvd 33 Is the rate of change of temperature; d, d 33 (25 ℃) means d of the product at 25 DEG C 33 。
Example 1
A formula of lead-free KNN-LT piezoelectric ceramic has a chemical formula as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -0.4mol.％Sm 2 O 3 。
The preparation method of the ceramic comprises the following steps:
and (3) batching: firstly converting the molar ratio into mass ratio according to chemical structural formula, and then weighing the required mass of each component such as sodium carbonate, potassium carbonate, lithium carbonate, niobium oxide, tantalum oxide, samarium oxide and the like.
Mixing: putting raw materials of potassium carbonate, sodium carbonate, lithium carbonate, niobium oxide and tantalum oxide into a zirconia ball milling tank, and taking absolute ethyl alcohol as a solvent to prepare ZrO 2 Grinding ball (the particle size of the grinding ball is selected to be 0.1-1.0cm, which is the same as that of the grinding ball)The grain diameter of the medium and small grinding balls is 0.5+/-0.05 cm, the grain diameter of the medium grinding ball is 0.8+/-0.05 cm, and the grain diameter of the large grinding ball is 1.1+/-0.05 cm. The mass ratio of the large grinding ball to the medium grinding ball to the small grinding ball is 1:1.5: 1). The mass ratio of various mediums in the ball milling tank is selected as follows: grinding ball: alcohol is equal to 1:1:1.2. And (3) ball milling the raw materials for 20 hours by using high-energy ball milling at 260 r/min.
Presintering: stirring and drying the slurry at the temperature of 70 ℃ in a water bath kettle, and presintering the raw materials in a muffle furnace at the temperature of 750 ℃.
Secondary ball milling: and (3) grinding and crushing the presintered raw material blocks, weighing the raw material blocks and the doping element Sm according to the stoichiometric ratio, and putting the raw material blocks into a ball milling tank again for secondary ball milling at the rotating speed of 260 r/min. The ball milling parameters are the same as the first ball milling.
Mixing: PVA was stirred with deionized water in a 80℃water bath to prepare a 5wt.% PVA solution. Adding the powder into the dried secondary ball grinding material, stirring uniformly, continuously stirring in the granulating process, drying the water in a water bath kettle at 80 ℃, and sieving the dried powder with a 60-mesh sieve.
Pressing: at the position ofThe mold of (2) was filled with ceramic powder of about 1mm thickness, and the mold was slowly loaded with a pressure of 100MPa and maintained for 20s.
Sintering: slowly heating at a heating rate of 2 ℃/min, preserving heat at 550 ℃ for two hours, heating to 1100 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and then cooling with a furnace.
Silver is coated with: and polishing the upper and lower surfaces of the sintered ceramic, coating a silver electrode by adopting a soft brush coating mode, drying in an oven at 80 ℃ for 1h, and then carrying out heat treatment at 600 ℃ for 10-20 min.
Polarization: and maintaining the pressure for 25min by a high-voltage direct current electric field of 2kV/mm under the condition of 60 ℃ silicone oil bath. After polarization was completed, electrical property detection was performed after standing overnight.
The prepared ceramic has no volatilization of lead elements in the use process, meets the environment-friendly requirement of electronic equipment, and has higher piezoelectric coefficient d 33 =237 pC/N, othersElectrical properties, kp=43.72, qm=106.54, tc=392 ℃. And the ceramic can keep better heat aging resistance at about 125 ℃, and the temperature change rate is only 3%.
Example 2
A formula of lead-free KNN-LT piezoelectric ceramic has a chemical formula as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -0.6mol.％Sm 2 O 3 。
The preparation method of the ceramic comprises the following steps:
and (3) batching: firstly converting the molar ratio into mass ratio according to chemical structural formula, and then weighing the required mass of each component such as sodium carbonate, potassium carbonate, lithium carbonate, niobium oxide, tantalum oxide, samarium oxide and the like.
Mixing: putting raw materials of potassium carbonate, sodium carbonate, lithium carbonate, niobium oxide and tantalum oxide into a zirconia ball milling tank, and taking absolute ethyl alcohol as a solvent to prepare ZrO 2 Grinding balls (the particle size of the grinding balls is selected to be 0.1-1.0cm, wherein the particle size of the small grinding balls is 0.5+/-0.05 cm, the particle size of the medium grinding balls is 0.8+/-0.05 cm, the particle size of the large grinding balls is 1.1+/-0.05 cm, and the mass ratio of the large grinding balls to the medium grinding balls to the small grinding balls is 1:1.5:1). The mass ratio of various mediums in the ball milling tank is selected as follows: grinding ball: alcohol is equal to 1:1:1.2. And (3) ball milling the raw materials for 20 hours by using high-energy ball milling at 260 r/min.
Presintering: stirring and drying the slurry at the temperature of 70 ℃ in a water bath kettle, and presintering the raw materials in a muffle furnace at the temperature of 750 ℃.
Secondary ball milling: grinding and crushing the presintered raw material block, and mixing with doped element Sm 2 O 3 Weighing according to the stoichiometric ratio, and then putting the mixture into a ball milling tank again to perform secondary ball milling at the rotating speed of 260 r/min. The ball milling parameters are the same as the first ball milling.
Mixing: PVA was stirred with deionized water in a 80℃water bath to prepare a 5wt.% PVA solution. Adding the powder into the dried secondary ball grinding material, stirring uniformly, continuously stirring in the granulating process, drying the water in a water bath kettle at 80 ℃, and sieving the dried powder with a 60-mesh sieve.
Pressing: at the position ofThe mold of (2) was filled with ceramic powder of about 1mm thickness, and the mold was slowly loaded with a pressure of 100MPa and maintained for 20s.
Sintering: slowly heating at a heating rate of 2 ℃/min, preserving heat at 550 ℃ for two hours, heating to 1120 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and then cooling with a furnace.
Silver is coated with: and polishing the upper and lower surfaces of the sintered ceramic, coating a silver electrode by adopting a soft brush coating mode, drying in an oven at 80 ℃ for 1h, and then carrying out heat treatment at 600 ℃ for 10-20 min.
Polarization: and maintaining the pressure for 25min by a high-voltage direct current electric field of 2kV/mm under the condition of 60 ℃ silicone oil bath. After polarization was completed, electrical property detection was performed after standing overnight.
The prepared ceramic has no volatilization of lead elements in the use process, meets the environment-friendly requirement of electronic equipment, and has higher piezoelectric coefficient d 33 154pC/N, other electrical properties, kp=30.15, qm=101.23, tc=379 ℃. The ceramic has a tetragonal phase structure inside, and compared with the ceramic in the embodiment 1, the ceramic has slightly poorer piezoelectric performance, but can be kept stable all the time at about room temperature to 350 ℃, has a change rate of only 16 percent and has higher ageing resistance.
Comparative example 1
A formula of lead-free KNN-LT piezoelectric ceramic has a chemical formula as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -0.2mol.％Sm 2 O 3 . The preparation procedure and parameters of the above ceramics were the same as in example 1.
Comparative example 2
A formula of lead-free KNN-LT piezoelectric ceramic has a chemical formula as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -0.8mol.％Sm 2 O 3 . The preparation procedure and parameters of the above ceramic were substantially the same as in example 1, except that the sintering temperature was 1120 ℃.
Comparative example 3
Formula of lead-free KNN-LT piezoelectric ceramic and its chemicalThe structural formula is as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -1.0mol.％Sm 2 O 3 . The preparation procedure and parameters of the above ceramic were substantially the same as in example 1, except that the sintering temperature was 1150 ℃.
Comparative example 4
A formula of lead-free KNN-LT piezoelectric ceramic has a chemical formula as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 。
The preparation process and parameters of the ceramic are basically the same as those of example 1, except that the formulation does not contain Sm 2 O 3 。
Comparative example 5
A formula of lead-free KNN-LT piezoelectric ceramic has a chemical formula as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -0.4mol.％Sm 2 O 3 . The preparation process of the above ceramic was substantially identical in example 1, except that the sintering temperature was 1200 ℃.
Comparative example 6
A formula of lead-free KNN-LT piezoelectric ceramic has a chemical formula as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -0.4mol.％Sm 2 O 3 . The preparation process and parameters of the ceramic are basically the same as those of the embodiment 1, except that the ball milling time is only 10 hours.
Comparative example 7
A formula of lead-free KNN-LT piezoelectric ceramic has a chemical formula as follows: 0.95 (K) 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -0.4mol.％Sm 2 O 3 。
The preparation method of the ceramic comprises the following steps:
and (3) batching: firstly converting the molar ratio into mass ratio according to chemical structural formula, and then weighing the required mass of each component such as sodium carbonate, potassium carbonate, lithium carbonate, niobium oxide, tantalum oxide, samarium oxide and the like.
Mixing: the raw materials of potassium carbonate, sodium carbonate, lithium carbonate, niobium oxide, tantalum oxide and samarium oxide are put into a zirconia ball milling tank,ZrO using absolute ethyl alcohol as solvent 2 Grinding balls (the particle size of the grinding balls is 0.8+/-0.05 cm). The mass ratio of various mediums in the ball milling tank is selected as follows: grinding ball: alcohol is equal to 1:1:1.2. And (3) ball milling the raw materials for 20 hours by using high-energy ball milling at 260 r/min.
Presintering: stirring and drying the slurry in a water bath at the temperature of 70 ℃, and presintering the raw materials in a muffle furnace at the temperature of 750 ℃ for 5 hours; crushing and then sieving with a 60-mesh sieve;
the mixing, pressing, sintering, silver coating, polarizing conditions parameters were the same as in example 1.
The prepared ceramic has no volatilization of lead element in the use process, and the piezoelectric coefficient d of the ceramic 33 189pC/N, other electrical properties, kp=38.72, qm=98.94, tc=381 ℃.
As can be seen from the comparison of the experimental groups (i.e. examples 1 and 2) and the control group, the ceramic density of the experimental groups is above 95%, the piezoelectric coefficients are greater than 150pC/N, and the ceramic has good stability and mechanical properties. Can meet the application requirements of piezoelectric ceramics in electronic equipment.
In conclusion, the ceramic prepared by the invention has an electromechanical coupling coefficient of more than 30% and a quality factor of more than 90, and meanwhile, the condition that toxic lead element volatilizes in the use process can not occur. In addition, the formula of the embodiment 1 provided by the invention has the highest piezoelectric coefficient and electromechanical coupling coefficient, but can only keep stable at about room temperature to 125 ℃. The ceramic piezoelectric coefficient of the formula of the embodiment 2 is slightly worse than that of the embodiment 1, but has ultrahigh ageing resistance, and can keep excellent piezoelectric performance at about room temperature to 350 ℃, so that the application temperature of the lead-free piezoelectric ceramic is greatly improved, and the application scene of the lead-free piezoelectric ceramic is expanded.
Performance tables of the products obtained in examples and comparative examples 1 to 6
Claims (10)
1. A rare earth modified KNN-LT leadless piezoelectric ceramic is characterized in that: the rare earth modified KNN-LT leadless piezoelectric ceramics is represented by the following chemical formula:
0.95(K 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -xmol.％Sm 2 O 3 ；
wherein x is 0.2 to 0.6.
2. The rare earth modified KNN-LT leadless piezoelectric ceramic according to claim 1, wherein: x is 0.2 to 0.4.
3. A method for producing the rare earth-modified KNN-LT leadless piezoelectric ceramics according to any one of claims 1 to 2, characterized by comprising the steps of:
s1: preparing a potassium source, a sodium source, a niobium source, a lithium source, a tantalum source and a samarium source according to the chemical formula of the rare earth modified KNN-LT leadless piezoelectric ceramic, putting other components except the samarium source in the prepared raw materials into ball milling equipment, performing high-energy ball milling and mixing ball milling for at least 15 hours, preferably 20-25 hours at the rotating speed of 250-300 r/min, preferably 270-290 r/min by taking organic matters as solvents, sieving the obtained fully mixed powder, putting the sieved powder into a corundum crucible, and presintering for 100-140 minutes, preferably 115-125 minutes at the temperature of 840-860 ℃ by covering to obtain presintered powder; the potassium source, the sodium source, the niobium source, the lithium source, the tantalum source and the samarium source are at least one of oxide, carbonate and bicarbonate; the rare earth modified KNN-LT leadless piezoelectric ceramics is represented by the following chemical formula:
0.95(K 0.55 ,Na 0.45 )NbO 3 -0.05LiTaO 3 -xmol.％Sm 2 O 3 ；
wherein x is 0.2-0.6;
s2: grinding and crushing the presintered powder, putting the presintered powder and the prepared samarium source into a ball milling tank again, performing secondary ball milling for at least 15 hours at a rotating speed of 240-280 r/min, preferably 260r/min, adding 3-8 wt.%, preferably 5wt.% of PVA organic adhesive after ball milling, and granulating to obtain standby ceramic powder; pressing and forming the standby ceramic powder to obtain a ceramic green body;
s3: the ceramic green compact is put into a muffle furnace for sintering, the sintering process is divided into two stages, the first stage is 0-550 ℃, and the heating rate is less than or equal to 4 ℃/min, preferably 1.5-2.5 ℃/min, so that organic matters such as PVA and the like introduced in the granulating process can fully escape; the second stage is to heat to 1100-1150 deg.c at a temperature raising rate of 4.5-10 deg.c/min, preferably 4.5-6 deg.c/min and maintain the temperature for at least 100min, preferably 115-135 min.
S4: after polishing the upper and lower surfaces of the sintered ceramic sample, silver electrodes are coated, dried, and then heat-treated at 550-650 c, preferably 590-610 c, for 10-20 min.
S5: the ceramic sample after silver is polarized in silicone oil under the condition of 60-100 ℃ silicone oil bath and the pressure is maintained for 10-30 min, preferably 25min by a high-voltage direct current electric field of 1-4 kV/mm, preferably 1.8-2 kV/mm.
4. The method for preparing the rare earth modified KNN-LT lead-free piezoelectric ceramic according to claim 3, wherein the method comprises the following steps:
in S1, the molar ratio is converted into a mass ratio, and then the required mass of each component under the given total mass is weighed. Putting raw materials of potassium carbonate, sodium carbonate, lithium carbonate, niobium oxide and tantalum oxide into a zirconia ball milling tank, taking absolute ethyl alcohol as a solvent, performing high-energy ball milling and mixing at the rotating speed of 270-290 r/min for 20h, sieving the fully mixed powder, putting into a corundum crucible, and capping for presintering at 840-860 ℃ for 115-125 min to obtain presintered powder.
5. The method for preparing the rare earth modified KNN-LT lead-free piezoelectric ceramic according to claim 3, wherein the method comprises the following steps:
in the ball milling process in S1, the mass ratio of various mediums in a ball milling tank is as follows: grinding ball: alcohol is equal to 1:1:1.2.
6. The method for preparing the rare earth modified KNN-LT lead-free piezoelectric ceramic according to claim 3, wherein the method comprises the following steps:
in S2, the element Sm is doped with oxide particlesIs added to the ball milling equipment in the form of (a) and (b); preferably Sm 2 O 3 The particles were added to the ball milling apparatus in the form of granules. Sm (Sm) 2 O 3 The particle size of the particles is 70-90 microns, preferably 75-80 microns;
in S2, the second ball milling is carried out for 18-25 h.
7. The method for preparing the rare earth modified KNN-LT lead-free piezoelectric ceramic according to claim 3, wherein the method comprises the following steps: and S2, the average grain diameter of the standby ceramic powder obtained by the step S2 is 200-250 micrometers.
8. The method for preparing the rare earth modified KNN-LT lead-free piezoelectric ceramic according to claim 3, wherein the method comprises the following steps: and S3, in the sintering process, burying and sintering the powder obtained after the secondary ball milling in a crucible.
9. The method for preparing the rare earth modified KNN-LT lead-free piezoelectric ceramic according to claim 3, wherein the method comprises the following steps: in the sintering process of S3, the temperature rising rate of the first stage is 2 ℃/min, the temperature is kept for 2 hours, the slow and sufficient overflow of the adhesive is ensured, and the generation of holes in the ceramic is reduced; the temperature rising rate in the second stage is 5 ℃/min, the temperature is kept for 2h, the ceramic grains are ensured to fully grow up, and finally the ceramic grains are cooled by air along with the furnace.
10. The method for preparing the rare earth modified KNN-LT lead-free piezoelectric ceramic according to claim 3, wherein the method comprises the following steps: and S4, polishing the upper and lower surfaces of the sintered ceramic sample, coating a silver electrode by adopting a soft brush coating mode, drying in an oven at 80 ℃ for 1h, and performing heat treatment at 600 ℃ for 10-20 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541447A (en) * | 2001-08-14 | 2004-10-27 | 皇家飞利浦电子股份有限公司 | Filter system with bulk wave resonator |
| KR100790407B1 (en) * | 2006-10-12 | 2008-01-02 | 한국전기연구원 | Composition of lead-free piezoelectric ceramics and method for manufacturing the same |
| KR20110015713A (en) * | 2009-08-10 | 2011-02-17 | 한국과학기술연구원 | Lead-free piezoelectric ceramics and method for the preparation thereof |
| CN103601492A (en) * | 2013-10-15 | 2014-02-26 | 陕西科技大学 | KNN-LT leadless piezoelectric ceramics and preparation method thereof |
-
2023
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541447A (en) * | 2001-08-14 | 2004-10-27 | 皇家飞利浦电子股份有限公司 | Filter system with bulk wave resonator |
| KR100790407B1 (en) * | 2006-10-12 | 2008-01-02 | 한국전기연구원 | Composition of lead-free piezoelectric ceramics and method for manufacturing the same |
| KR20110015713A (en) * | 2009-08-10 | 2011-02-17 | 한국과학기술연구원 | Lead-free piezoelectric ceramics and method for the preparation thereof |
| CN103601492A (en) * | 2013-10-15 | 2014-02-26 | 陕西科技大学 | KNN-LT leadless piezoelectric ceramics and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIGONG HAO: "Bright reddish-orange emission and good piezoelectric properties of Sm2O3-modified (K0.5Na0.5)NbO3-based lead-free piezoelectric ceramics", 《J. APPL. PHYS.》, vol. 117, 31 December 2015 (2015-12-31), pages 194104 - 194113 * |
| 李震宇: "K0.5Na0.5NbO3-LiTaO3无铅压电陶瓷掺杂改性研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, 15 January 2019 (2019-01-15), pages 20 - 24 * |
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