CN102910902B - BNT-BT-BKT-based perovskite system multielement lead-free piezoelectric ceramic and production method thereof - Google Patents
BNT-BT-BKT-based perovskite system multielement lead-free piezoelectric ceramic and production method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000000843 powder Substances 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 230000010287 polarization Effects 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 229910010252 TiO3 Inorganic materials 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 16
- 239000010955 niobium Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RSVNDSXNDIVMNV-UHFFFAOYSA-N [Ta].[Sb].[Li] Chemical compound [Ta].[Sb].[Li] RSVNDSXNDIVMNV-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- -1 antimony peroxide Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 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 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 230000026683 transduction Effects 0.000 description 1
- 238000010361 transduction Methods 0.000 description 1
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Abstract
The invention discloses a BNT-BT-BKT-based perovskite system multielement lead-free piezoelectric ceramic and a production method thereof. The BNT-BT-BKT-based perovskite multielement lead-free piezoelectric ceramic comprises the following raw material components by mole percent: (1-x)[a(Bi0.5Na0.5)TiO3-bBaTiO3-c(Bi0.5K0.5)TiO3]-x[(Na0.52K0.44Li0.04)(Nb0.88Sb0.08Ta0.04)O3], wherein in the formula, x is 0.001-0.05, a is 0.8-0.9, and b+c is 1-a and is more than 0.5 and less than 0.9. According to the BNT-BT-BKT-based perovskite multielement lead-free piezoelectric ceramic, the principal crystalline phase is of a perovskite structure, the piezoelectric performance is better, the maximum piezoelectric constant is 328pC/N, the maximum electromechanical coupling coefficient kp is 0.32, and the effects of stable production process, repeatability and practicality are obtained.
Description
Technical field
The present invention relates to a kind of ceramic composition take composition as feature, particularly relate to a kind of bismuth sodium titanate-barium titanate-Bismuth carbonate potassium (BNT-BT-BKT) base and mix potassium-sodium niobate lithium tantalum antimony (KNNLST) and mix polynary uhligite system piezoelectric ceramics and preparation method thereof.
Background technology
Piezoelectric ceramics, as modern and important hi-tech functional materials, its application has spreaded all over military affairs, the every field, particularly ultrasonic transduction such as civilian, sensor, the fields such as nondestructive testing and mechanics of communication.In recent years, be accompanied by the understanding of the whole world to mankind itself's environment, take Pb-based lanthanumdoped zirconate titanates, as main, containing plumbous oxide in lead piezoelectric ceramics or tri-lead tetroxide, account for raw-materially more than 3/4ths, to environment, bring the risk that can not estimate.So, in the urgent need to finding leadless piezoelectric material material, replace traditional lead base piezoceramic material.
At present, the piezoelectric ceramics of research mainly contains the leadless piezoelectric ceramics of perovskite structure, bismuth laminated and tungsten bronze structure.In general, bismuth laminated leadless piezoelectric ceramic Curie temperature is higher, and anisotropy is large and piezoelectric activity is lower.Tungsten bronze structure system piezoelectric ceramics has the features such as spontaneous polarization strength is large, Curie temperature is high, specific inductivity is low, and its composition and structure has material impact to its ferroelectric properties.
Bismuth-sodium titanate leadless piezoelectric ceramics is found in nineteen sixty, it is one of stable complex perovskite structure few in number, it is strong that BNT pottery has ferroelectricity, piezoelectric property is good, little and the acoustical behavior of the specific inductivity excellent characteristic such as well, be considered to most probable and replace one of leadless piezoelectric ceramics system of lead base piezoelectric ceramics, just obtaining broad research.But the coercive field of pure BNT pottery is large, and specific conductivity is high in ferroelectric phase region, thereby be difficult to polarization, and the firing range of pure BNT is narrower, so make ceramic dense not good enough.BNT-BT-BKT system " Hajime Nagata; Masaki Yoshida et e1.Jpn J Appl Phys; 42 (2003) 7404. " piezoelectric constant is larger, Curie temperature is high, but the coercive field of this system and specific conductivity are still larger, the field intensity that fully polarization needs is up to 5～9kV/mm.
Potassium-sodium niobate system particularly document " Y.Saito; et al. " Lead-Free Piezoceramics "; nature; 432 (2004) 84-87. " adopts traditional solid-phase sintering method to prepare to have the relatively potassium-sodium niobate lithium tantalum antimony leadless piezoelectric ceramics of high tension performance, piezoelectric ceramics sintering temperature prepared by the method is lower than 1100 ℃, but contain the volatile elements such as a large amount of lithiums, potassium and sodium, the more difficult densification of sintering process and sintering character are unstable.
Above-mentioned two kinds due to intrinsic separately shortcoming, apart from practical application, also have a certain distance, existing electrical property and the preparation technology's report that yet there are no in the literature the doping KNNLST piezoelectric ceramics take BNT-BT-BKT as matrix.
Summary of the invention
The object of the invention is to, overcome the shortcoming and defect of prior art, provide a kind of and there is good piezo-electric modulus, BNT-BT-BKT based perovskite system multicomponent system high tension performance piezoelectric ceramics that sintering character is stable is prepared and preparation method thereof.
The present invention is achieved by following technical solution.
A kind of BNT-BT-BKT based perovskite system multi-component leadless piezoelectric ceramics, its feed composition and molar percentage thereof are (1-x) [a (Bi
0.5na
0.5) TiO
3-bBaTiO
3-c (Bi
0.5k
0.5) TiO
3]-x[(Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3], x=0.001～0.05 in formula, a=0.8～0.9, b+c=1-a, 0.1<b+c<0.2;
The preparation method of above-mentioned BNT-BT-BKT based perovskite system multi-component leadless piezoelectric ceramics, step is:
(1) use K
2cO
3, Na
2cO
3, TiO
2, Bi
2o
3with BaCO3 be initial feed, by a (Bi
0.5na
0.5) TiO
3-bBaTiO
3-c (Bi
0.5k
0.5) TiO
3be abbreviated as BNT-BT-BKT and prepare burden, a=0.8～0.9 in formula, b+c=1-a; Through ball milling mixing, pre-burning, obtain BNT-BT-BKT ceramic powder, wherein calcined temperature is 850 ℃;
(2) use Li
2cO
3, K
2cO
3, Na
2cO
3, Nb
2o
5, Ta
2o
5and Sb
2o
3for initial feed, by (Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3be abbreviated as KNNLST and prepare burden, through ball milling mixing, pre-burning, obtain KNNLST ceramic powder, wherein calcined temperature is 850 ℃;
(3) by (1-x) (BNT-BT-BKT)-x(KNNLST), x=0.001～0.05 in formula, BNT-BT-BKT and KNNLST ceramic powder prepared by step (1) and step (2) are mixed in proportion, through ball milling, mix, dry, obtain multicomponent system ceramic powder;
(4) the multicomponent system ceramic powder obtaining in step (3) drips polyvinyl alcohol dicarbaldehyde spirituous solution and grinds in mortar as binding agent, and wherein the mass percent of polyvinyl alcohol dicarbaldehyde is 1～10%;
(5) pour the BNT-BT-BKT-KNNLST mangcorn of step (4) into grinding tool, press mold is shaped to base substrate;
(6) base substrate of step (5) is placed in to retort furnace and carries out binder removal, with the temperature rise rate of 5 ℃/min, be warming up to 600 ℃, insulation 10min, furnace cooling;
(7) base substrate after step (6) binder removal is placed in to retort furnace, with the temperature rise rate of 5 ℃/min, be warming up to 1040～1140 ℃ of sintering, insulation 1～2h, furnace cooling, obtains BNT-BT-BKT-KNNLST uhligite system multi-component leadless piezoelectric ceramics goods;
(8) the uhligite system multi-component leadless piezoelectric ceramics goods of step (7) are applied to low-temperature silver slurry, in 700 ℃ of insulation 10min, make electrode;
(9) electrode slice of being prepared by step (8) is put into silicone oil and is polarized.
The Ball-milling Time of described step (1) and (2) is 6h.
The pressure of described step (5) press mold moulding is 65～130MPa.
The preferred sintering temperature of described step (7) is 1300～1400 ℃.
The polarization time of described step (9) is 10～30min, and polarized electric field is 2～4KV/mm.
The invention has the beneficial effects as follows, adopting bismuth sodium titanate-barium titanate-bismuth potassium titanate is the uhligite system leadless piezoelectric ceramics of matrix doping potassium-sodium niobate lithium tantalum antimony preparation containing nine kinds of elements, only comprise perovskite structure, without dephasign, occur, piezoelectric constant d33 is 167～238pC/N.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of example 1 of the present invention;
Fig. 2 is the scanning electron microscope picture of example 2 of the present invention.
Embodiment
Barium carbonate (BaCO used in the present invention
3), bismuth oxide (Bi
2o
3), titanium dioxide (TiO
2), Quilonum Retard (Li
2cO
3), sodium carbonate (Na
2cO
3), salt of wormwood (K
2cO
3), Niobium Pentxoxide (Nb
2o
5), antimony peroxide (Sb
2o
5), tantalum pentoxide (Ta
2o
5) etc. raw material be commercially available chemically pure reagent.Specific embodiment is as follows.
Embodiment 1
The present embodiment matrix component be 0.88 (Bi
0.5na
0.5) TiO
3-0.0305BaTiO
3-0.0895 (Bi
0.5k
0.5) TiO
3, another component is (Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3.
The first step, with analytical pure level mass percent be B
2iO
3, TiO
2, Na
2cO
3, K
2cO
3, and BaCO
3by 0.88 (Bi
0.5na
0.5) TiO
3-0.0305BaTiO
3-0.0895 (Bi
0.5k
0.5) TiO
3stoichiometric ratio is prepared burden.By the raw material preparing ball milling 6h in dehydrated alcohol, be incubated 2h at 100 ℃, dry after powder, 850 ℃ of pre-burnings, insulation 2h, obtains BNT-BT-BKT powder.Use Li
2cO
3, K
2cO
3, Na
2cO
3, Nb
2o
5, Ta
2o
5and Sb
2o
3by (Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3stoichiometric ratio is prepared burden, and by the raw material preparing ball milling 6h in anhydrous ethanol medium, is incubated 2h at 100 ℃, and after oven dry, in 850 ℃ of pre-burnings, insulation 2h, obtains KNNLST powder.
Second step, preparation (1-x) (BNT-BT-BKT)-xKNNLST powder.The BNT-BT-BKT obtaining with the first step and KNNLST weigh in x=0.02 ratio, and ball milling 6h in anhydrous ethanol medium is incubated 2h at 100 ℃, dry powder, obtain 0.98 (BNT-BT-BKT)-0.02KNNLST powder.
The 3rd step: moulding.The powder weighing that second step is obtained is poured in mortar, by powder: PVB spirituous solution=1g:2g drips 6%PVB spirituous solution, granulation, compression moulding under the pressure of 100MPa.
The 4th step: sintering.By the ceramic green of the 3rd step dry 10min at 600 ℃, binder removal; In 1140 ℃ of sintering, insulation 2h, furnace cooling, obtains BNT-BT-BKT-KNNLST leadless piezoelectric ceramics.
The 5th step: detect.The leadless piezoelectric ceramics surface-coated low-temperature silver slurry making in the 4th step, 700 ℃ of insulation 10min make electrode, then by the 10min that polarizes in leadless piezoelectric ceramics electrode slice immersion room temperature silicone oil, polarized electric field is 2kV.
The performance test results of embodiment 1 is as follows:
d33(pC/N) Kp εr Kt
238 0.312 1725 0.479
Fig. 1 is the X ray diffracting spectrum of embodiment 1 uhligite multicomponent system piezoelectric ceramics.Show that this ceramic plate is perovskite structure.
Embodiment 2
The present embodiment matrix component be 0.8325 (Bi
0.5na
0.5) TiO
3-0.0426BaTiO
3-0.1249 (Bi
0.5k
0.5) TiO
3, another component is (Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3.
The first step, with analytical pure level mass percent be B
2iO
3, TiO
2, Na
2cO
3, K
2cO
3, and BaCO
3by 0.8325 (Bi
0.5na
0.5) TiO
3-0.0426BaTiO
3-0.1249 (Bi
0.5k
0.5) TiO
3stoichiometric ratio is prepared burden.By the raw material preparing ball milling 6h in dehydrated alcohol, be incubated 2h at 100 ℃, dry after powder, 850 ℃ of pre-burnings, insulation 2h, obtains BNT-BT-BKT powder.Use Li
2cO
3, K
2cO
3, Na
2cO
3, Nb
2o
5, Ta
2o
5and Sb
2o
3by (Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3stoichiometric ratio is prepared burden, and by the raw material preparing ball milling 6h in anhydrous ethanol medium, is incubated 2h at 100 ℃, dries after powder, at 850 ℃ of pre-burning 2h, obtains KNNLST powder.
Second step, preparation (1-x) (BNT-BT-BKT)-xKNNLST powder.The BNT-BT-BKT obtaining with the first step and KNNLST weigh in x=0.005 ratio, and ball milling 6h in anhydrous ethanol medium is incubated 2h at 100 ℃, dry powder, obtain 0.98 (BNT-BT-BKT)-0.02KNNLST powder.
The 3rd step: moulding.The powder weighing that second step is obtained is poured in mortar, by powder: PVB spirituous solution=1g:2g drips 6%PVB spirituous solution, granulation, compression moulding under the pressure of 100MPa.
The 4th step: sintering.By the ceramic green of the 3rd step dry 10min at 600 ℃, binder removal.In 1100 ℃ of sintering, insulation 2h, furnace cooling, obtains BNT-BT-BKT-KNNLST leadless piezoelectric ceramics.
The 5th step: detect.The leadless piezoelectric ceramics surface-coated low-temperature silver slurry making in the 4th step, 700 ℃ of insulation 10min make electrode.By the 10min that polarizes in leadless piezoelectric ceramics electrode immersion room temperature silicone oil, polarized electric field is 2.4kV again.
The performance test results of embodiment 2 is as follows:
d33(pC/N) Kp εr Kt
190 0.274 1546 0.415
Fig. 2 is the scanning electron microscope picture of embodiment 2 piezoelectric ceramics, and from picture, this ceramic plate has finer and close structure.
Embodiment 3
The present embodiment matrix component be 0.80 (Bi
0.5na
0.5) TiO
3-0.0509BaTiO
3-0.1491 (Bi
0.5k
0.5) TiO
3, another component is (Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3.
By stoichiometric ratio, carry out BNT-BT-BKT and KNNLST batching, ball milling 6h respectively, dries, and 850 ℃ of pre-burning 2h, obtain BNT-BT-BKT and KNNLST powder.The BNT-BT-BKT obtaining and KNNLST are weighed in x=0.05 ratio, and ball milling 6h, dries, and obtains 0.95 (BNT-BT-BKT)-0.05KNNLST powder.The powder weighing obtaining is poured in mortar, dripped PVB spirituous solution, granulation, compression moulding under the pressure of 100MPa.By dry 10min at 600 ℃ of ceramic greens, binder removal.In 1040 ℃ of heat preservation sinterings, 2h, furnace cooling, obtains BNT-BT-BKT-KNNLST pottery.At ceramic surface, apply silver slurry, 700 ℃ of insulation 10min.The ceramic plate polarization 10min making, polarized electric field is 2.4kV.
Other processing parameter of the present embodiment is same as embodiment 1.
The performance test results of embodiment 3 is as follows:
d33(pC/N) Kp εr Kt
157 0.252 1324 0.376
Embodiment 4
The present embodiment matrix component be 0.8625 (Bi
0.5na
0.5) TiO
3-0.0350BaTiO
3-0.1025 (Bi
0.5k
0.5) TiO
3, another component is (Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3.
By stoichiometric ratio, carry out BNT-BT-BKT and KNNLST batching, ball milling 6h respectively, dries, and 850 ℃ of pre-burning 2h, obtain BNT-BT-BKT and KNNLST powder.BNT-BT-BKT and KNNLST powder are pressed to x=0.015 weighing, and ball milling 6h, dries, and obtains 0.985 (BNT-BT-BKT)-0.015KNNLST powder.Powder is poured in mortar, dripped PVB spirituous solution, granulation, the compression moulding of 100MPa pressure.By 600 ℃ of dry 10min of green compact, binder removal.In 1140 ℃ of sintering, insulation 2h, furnace cooling, obtains BNT-BT-BKT-KNNLST pottery.At ceramic surface, apply silver slurry, 700 ℃ of insulation 10min.The ceramic plate polarization 9min making, polarized electric field is 2.2kV/mm.
Other processing parameter of the present embodiment is same as embodiment 1.
The performance test results of embodiment 4 is as follows:
d33(pC/N) Kp εr Kt
212 0.297 1628 0.408
Claims (5)
1. a BNT-BT-BKT based perovskite system multi-component leadless piezoelectric ceramics, its feed composition and molar percentage thereof are (1-x) [a (Bi
0.5na
0.5) TiO
3-bBaTiO
3-c (Bi
0.5k
0.5) TiO
3]-x[(Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3], x=0.001～0.05 in formula, a=0.8～0.9, b+c=1-a, 0.1<b+c<0.2;
The preparation method of above-mentioned BNT-BT-BKT based perovskite system multi-component leadless piezoelectric ceramics, step is:
(1) use K
2cO
3, Na
2cO
3, TiO
2, Bi
2o
3with BaCO3 be initial feed, by a (Bi
0.5na
0.5) TiO
3-bBaTiO
3-c (Bi
0.5k
0.5) TiO
3be abbreviated as BNT-BT-BKT and prepare burden, a=0.8～0.9 in formula, b+c=1-a; Through ball milling mixing, pre-burning, obtain BNT-BT-BKT ceramic powder, wherein calcined temperature is 850 ℃;
(2) use Li
2cO
3, K
2cO
3, Na
2cO
3, Nb
2o
5, Ta
2o
5and Sb
2o
3for initial feed, by (Na
0.52k
0.44li
0.04) (Nb
0.88sb
0.08ta
0.04) O
3be abbreviated as KNNLST and prepare burden, through ball milling mixing, pre-burning, obtain KNNLST ceramic powder, wherein calcined temperature is 850 ℃;
(3) by (1-x) (BNT-BT-BKT)-x(KNNLST), x=0.001～0.05 in formula, BNT-BT-BKT and KNNLST ceramic powder prepared by step (1) and step (2) are mixed in proportion, through ball milling, mix, dry, obtain multicomponent system ceramic powder;
(4) the multicomponent system ceramic powder obtaining in step (3) drips polyvinyl alcohol dicarbaldehyde spirituous solution and grinds in mortar as binding agent, and wherein the mass percent of polyvinyl alcohol dicarbaldehyde is 1～10%;
(5) pour the BNT-BT-BKT-KNNLST mangcorn of step (4) into grinding tool, press mold is shaped to base substrate;
(6) base substrate of step (5) is placed in to retort furnace and carries out binder removal, with the temperature rise rate of 5 ℃/min, be warming up to 600 ℃, insulation 10min, furnace cooling;
(7) base substrate after step (6) binder removal is placed in to retort furnace, with the temperature rise rate of 5 ℃/min, be warming up to 1040～1140 ℃, insulation 1～2h sintering, furnace cooling, obtains BNT-BT-BKT-KNNLST uhligite system multi-component leadless piezoelectric ceramics goods;
(8) the uhligite system multi-component leadless piezoelectric ceramics goods of step (7) are applied to low-temperature silver slurry, in 700 ℃ of insulation 10min, make electrode;
(9) electrode slice of being prepared by step (8) is put into silicone oil and is polarized.
2. according to a kind of BNT-BT-BKT based perovskite system multi-component leadless piezoelectric ceramics of claim 1, it is characterized in that, the Ball-milling Time of described step (1) and (2) is 6h.
3. according to a kind of BNT-BT-BKT based perovskite system multi-component leadless piezoelectric ceramics of claim 1, it is characterized in that, the pressure of described step (5) press mold moulding is 65～130MPa.
4. according to a kind of BNT-BT-BKT based perovskite system multi-component leadless piezoelectric ceramics of claim 1, it is characterized in that, the preferred sintering temperature of described step (7) is 1080 ℃.
5. according to a kind of BNT-BT-BKT based perovskite system multi-component leadless piezoelectric ceramics of claim 1, it is characterized in that, the polarization time of described step (9) is 10～30min, and polarized electric field is 2～4KV/mm.
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| KR101590703B1 (en) * | 2014-05-12 | 2016-02-01 | 울산대학교 산학협력단 | Lead-free piezoelectric ceramic composition and Preparation method thereof |
| CN105130419B (en) * | 2015-08-26 | 2018-06-26 | 同济大学 | A kind of high electric field induced strain lead-free piezoceramic material and preparation method and application |
| CN105837205A (en) * | 2016-03-24 | 2016-08-10 | 天津大学 | Sodium bismuth titanate-system lead-free piezoelectric ceramic and preparation method thereof |
| CN106007706A (en) * | 2016-05-12 | 2016-10-12 | 天津大学 | High-performance sodium bismuth titanate-based leadless piezoelectric ceramic and preparation method thereof |
| CN106045499A (en) * | 2016-05-27 | 2016-10-26 | 西北工业大学 | Preparation method of zirconium-doped and lanthanum-doped sodium titanate-barium titanate ceramics |
| CN107935586B (en) * | 2017-11-13 | 2020-04-21 | 陕西科技大学 | Potassium niobate modified BT-KBT-based energy storage ceramic and preparation method thereof |
| CN110128169B (en) * | 2019-05-10 | 2021-05-18 | 济南大学 | SiO doped with calcium ions2Method for modifying piezoelectric ceramic surface by membrane and application thereof |
| GB2584131B (en) * | 2019-05-22 | 2022-06-01 | Xaar Technology Ltd | Method of preparing a solid solution ceramic material having increased electromechanical strain, and ceramic materials obtainable therefrom |
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