CN1562876A - Piezoelectric ceramics of modified barium natrium bismuth titanate doped in use for miniwatt ultrasonic transducer and preparation method - Google Patents
Piezoelectric ceramics of modified barium natrium bismuth titanate doped in use for miniwatt ultrasonic transducer and preparation method Download PDFInfo
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- CN1562876A CN1562876A CN200410017307.9A CN200410017307A CN1562876A CN 1562876 A CN1562876 A CN 1562876A CN 200410017307 A CN200410017307 A CN 200410017307A CN 1562876 A CN1562876 A CN 1562876A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title 1
- 150000001552 barium Chemical class 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- KOJWXHDDSAMYEG-UHFFFAOYSA-N [Na].[Ba].[Bi] Chemical compound [Na].[Ba].[Bi] KOJWXHDDSAMYEG-UHFFFAOYSA-N 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- IVMNFHQJNDDYPO-UHFFFAOYSA-N [Ba].C(=O)=O Chemical compound [Ba].C(=O)=O IVMNFHQJNDDYPO-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 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 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 4
- 238000010304 firing Methods 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 abstract description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 229910017585 La2O3 Nd2O3 Inorganic materials 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910052573 porcelain Inorganic materials 0.000 abstract 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 abstract 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 abstract 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 8
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 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
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
Composed general formula of this kind of materials is (1-X)Bi0.5Na0.5 TiO3-xBaTiO3 (x=0.005-0.2). One or two kind of modified insition can be mixed in the material for suitable for application in ultrasonic transverter. The insitions includes Yb2O3, Y2O3, La2O3 Nd2O3, Sm2O3, Cr2O3, MnO2 and CeO2, mixed weight percentage ratio is 0.01-1.5. Traditional ceramics firing technology is utilized to do ball-milling to precomposed porcelain powder until that particle size is in range of 300-700nm, then to do firing 2-4 hours in temp. 1100-1200 deg.C. Said kind of material has characteristics of high Kt and Nt value, lower Kp value and dielectric constant sigma 33%, smaller mechanical quality factor Qmt and volume density.
Description
Technical field
The present invention relates to small power ultrasonic transducer doping vario-property barium sodium bismuth titanate piezoelectric ceramics and preparation method thereof is belonged to the piezoelectric ceramics field.
Background technology
Along with the development and the development of technology of modern science and technology, piezoelectric ceramics be widely applied to national defense construction, scientific research, industrial production and and the closely-related many fields of people's lives in, become a many-side people of information age.Traditional piezoelectric ceramics overwhelming majority is leaded pottery, wherein plumbous oxide content (or tri-lead tetroxide) accounts for about 70% of raw material gross weight, this type of material all is accompanied by serious lead volatilization in preparation and use, bring very big harm for the environment and the mankind.
In recent years, along with the enhancing of environmental consciousness and the demand of human social, novel environmental close friend's piezoelectric ceramics has become one of focus material of countries in the world scientist concern.The leadless piezoelectric ceramics system of the report of various countries' research at present mainly contains: BaTiO
3Based leadless piezoelectric ceramics, Bi
0.5Na
0.5TiO
3(BNT) based leadless piezoelectric ceramics, niobate base lead-free piezoelectric ceramic, tungsten bronze structure leadless piezoelectric ceramics and bismuth laminated leadless piezoelectric ceramic etc., the system that application prospect is wherein arranged most is exactly the BNT based leadless piezoelectric ceramics.
Sakata one youth had reported BaTiO in 1963
3-Bi
0.5Na
0.5TiO
3Be the piezoelectric ceramics performance in rich barium district, big former people such as grade had studied Bi again in 1967
0.5Na
0.5TiO
3-PbTiO
3The ferroelectric piezoelectric property of series piezoelectric ceramic, but material with practical value all do not obtained.Robot systems such as Wang Tianbao had been studied (1-x) Bi in 1985
0.5Na
0.5TiO
3-xBaTiO
3The piezoelectricity ferro performance of the piezoelectric ceramics of binary system, obtained certain progress, but this stupalith is owing to preparation technology and the preparation back sample reasons such as sign that can't polarize, and makes such piezoceramic material fail being applied in actual production so far.
Summary of the invention
The present invention is directed to (1-x) Bi
0.5Na
0.5TiO
3-xBaTiO
3The piezoelectric property characteristics of series piezoelectric ceramic and the application requiring of small power ultrasonic transducer, by the preparation technology of optimization material, and autotelic doping Yb
2O
3, Y
2O
3, La
2O
3, Nd
2O
3, Sm
2O
3, Cr
2O
3, MnO
2And CeO
2Deng modified materials, make such material have bigger K
t/ K
pValue, lower DIELECTRIC CONSTANT
33 TWith the mechanical quality factor Q
m t, and cost is low, does not contain the composition that causes public hazards.Thereby at the effect in fields such as industrial non-destructive test(ing)(NDT), thickness measuring, range finding and medical supersonic diagnosis significantly better than traditional Pb-based lanthanumdoped zirconate titanates (PZT) material.In existing document, still find no the report that closes this respect at present.
The composition general formula of leadless piezoelectric ceramics provided by the invention is (1-x) Bi
0.5Na
0.5TiO
3-xBaTiO
3(wherein x=0.005~0.2) mixes Yb simultaneously
2O
3, Y
2O
3, La
2O
3, Nd
2O
3, Sm
2O
3, Cr
2O
3, MnO
2And CeO
2Wait one or both modified materialses, the weight ratio of mixing is 0.01wt%~1.5wt%.Be x=0.01~0.11 best the composition, and mixing weight ratio simultaneously is one or both modified materialses of 0.01wt%~1wt%.
The present invention realizes by being prepared as follows technology: select anhydrous sodium carbonate, Carbon Dioxide barium, bismuth oxide, titanium dioxide and Yb for use
2O
3, Y
2O
3, La
2O
3, Nd
2O
3, Sm
2O
3, Cr
2O
3, MnO
2And CeO
2Wait one or both modified materialses to make raw material, press the compositing formula weighing, be that with the dehydrated alcohol medium ball milling mixed 3 hours, the crucible of packing into behind 50 mesh sieves is crossed in discharging and oven dry, carries out synthetic in advance in 2~4 hours 750~950 ℃ of insulations.After will synthesizing back powder piece (grog) grinding and crossing 20 mesh sieves still will be that the levigate powder particle size that is milled to of medium ball is between 300nm~700nm with the dehydrated alcohol.The discharging drying, and add the binding agent (can be polyvinyl alcohol, glycerine etc.) of 8~25wt% and cross 50 mesh sieves, precompressed granulation, dry-pressing or rolling formation.Base substrate after the moulding is warming up to 400-600 ℃ with the speed of 1-5 ℃/min, is incubated and is warming up to 1100~1200 ℃ with 1-5 ℃/min after 0.5-3 hour, in atmosphere, opened wide sintering 2~4 hours.
To burn till sample two-sided by behind the electrode in silicone oil making alive polarize, press the piezoelectric property that ieee standard is measured sample.Table 1 has provided the prescription and the performance thereof of 8 different x values and additive.
Table 2 has been listed mainly ferroelectric, the piezoelectric parameter of representative formula.
As can be seen from Table 1, (1-x) Bi
0.5Na
0.5TiO
3-xBaTiO
3The performance characteristics of (wherein x=0.005~0.2) series lead-free piezoelectric ceramic material is: have high thickness electromechanical coupling coefficient Kt, quite low planar electromechanical coupling factor K
p, big K
t/ K
pValue, high thickness vibration frequency constant N
tWith high Curie temperature T
C, lower mechanical quality factor Q
m tAnd smaller volume density and DIELECTRIC CONSTANT
33 T,, can obviously improve piezoelectric constant d by above-mentioned system is carried out a spot of ion doping
33, make it be more suitable for the application of small power ultrasonic transducer.
As can be seen from Table 2, this piezoceramic material has bigger K
t/ K
pValue, higher frequency constant N
tWith piezoelectric constant g
33, lower DIELECTRIC CONSTANT
33 TWith the mechanical quality factor Q
m t, these characteristics have determined it to be more suitable in as small power transverter piezoelectric than traditional PZT pottery.Be assembled into the probe of same model respectively with it and PZT pottery, be installed on the CST-22 type ultrasonic reflectoscope, carry out the performance comparison test according to GB, the result shows that the ultrasound probe with above-mentioned leadless piezoelectric ceramics wafer fabrication has all surpassed used PZT ceramic wafers on main performance index such as resolving power, signal to noise ratio, surplus sensitivity, initial pulse broadening and pulse panel height, and it is high more to detect frequency, and superiority is obvious more.In addition, the DIELECTRIC CONSTANT of this stupalith
33 TLower with volume density, make the not only easy and circuit coupling of probe with it, and help the specific acoustic resistance coupling.
Pottery of the present invention is produced as a trial on existing production line, production is the result show: sintering temperature is lower about 100~200 ℃ than PZT, and raw materials cost is low, component volatilization is little, therefore can in air, open wide sintering, and do not need sealing or bury powder sintering, thereby technological process is simpler, and cost is lower and consistence sample performance is better.
Embodiment
Further specify substantive distinguishing features of the present invention and marked improvement below in conjunction with embodiment.Be noted that the present invention is not limited to following embodiment.
Embodiments of the invention are that x is prescription-0.98Bi of 0.02
0.5Na
0.5TiO
3-0.02BaTiO
3, mix 0.5wt%CeO simultaneously
2Preparation process as previously mentioned.Pre-synthesis condition is 900 ℃ of insulations 3 hours, grog is levigate to the 500nm, in 1140 ℃~1180 ℃ atmosphere, opened wide sintering 3 hours then, the base sample is made the disk of ф 20 * 1mm, two-sided by silver, making alive polarizes in silicone oil, measures its piezoelectric property by ieee standard, and detailed results sees Table 3.
Table 1 (1-x) Bi
0.5Na
0.5TiO
3-xBaTiO
3Series piezoelectric ceramic prescription and salient features thereof
Prescription is formed | ????K t | ????K p | ????ε 33 T/ε 0 | ????d 33??×10 -12C/N | ????T C????℃ | ????N t????Hz·m |
?0.98Bi 0.5Na 0.5TiO 3-0.02BaTiO 3 | ????0.46 | ????0.18 | ????373 | ????86 | ????274 | ????2525 |
?0.96Bi 0.5Na 0.5TiO 3-0.04BaTiO 3 | ????0.44 | ????0.2 | ????407 | ????94 | ????243 | ????2485 |
?0.94Bi 0.5Na 0.5TiO 3-0.06BaTiO 3 | ????0.42 | ????0.27 | ????583 | ????117 | ????237 | ????2457 |
?0.92Bi 0.5Na 0.5TiO 3-0.08BaTiO 3 | ????0.44 | ????0.16 | ????526 | ????104 | ????236 | ????2443 |
?0.90Bi 0.5Na 0.5TiO 3-0.10BaTiO 3 | ????0.43 | ????0.14 | ????482 | ????96 | ????234 | ????2460 |
?0.98Bi 0.5Na 0.5TiO 3-0.02BaTiO 3?+1wt%Yb 2O 3 | ????0.46 | ????0.2 | ????352 | ????152 | ????272 | ????2515 |
?0.98Bi 0.5Na 0.5TiO 3-0.02BaTiO 3?+0.5wt%Y 2O 3+0.5wt%CeO 2 | ????0.46 | ????0.2 | ????366 | ????168 | ????272 | ????2520 |
?0.98Bi 0.5Na 0.5TiO 3-0.02BaTiO 3?+1wt%La 2O 3 | ????0.46 | ????0.2 | ????361 | ????143 | ????272 | ????2522 |
Ferroelectric, the piezoelectric property of table 2 representative formula
Electromechanical coupling factor | ????K p | ????0.16 |
????K t | ????0.46 | |
Piezoelectric constant | ????d 33×10 -12C/N | ????87 |
????g 33×10 -3V·m/N | ????25.2 | |
Frequency constant | ????N r?Hz·m | ????3054 |
????N t?Hz·m | ????2535 | |
Specific inductivity | ????ε 33 T/ε 0 | ????389 |
The mechanical quality factor | ????Q m r | ????222 |
????Q m t | ????25 | |
Dielectric loss | ????tgδ?% | ????1.9 |
Curie temperature | ????T C??℃ | ????276 |
Remnant polarization | ????P r??μC/cm 2 | ????35 |
Coercive field is strong | ????E C??V/mm | ????4600 |
Volume density | ????ρ v?g/cm 3 | ????5.78 |
Elastic compliance constant | ????S 11 E?×10 -12m 2?/N | ????8.3 |
The piezoelectric property of table 3 embodiment pottery
Embodiment | Firing temperature | ?K p | ?K t | ε 33 T/ε 0 | Q m t | tgδ% | ?d 33?×10 -12C/N | ρ v?g/cm 3 |
Embodiment 1 | ?1180℃ | ?0.20 | ?0.41 | ?389 | ?38 | ?1.7 | ?85 | ?5.74 |
Embodiment 2 | ?1160℃ | ?0.18 | ?0.46 | ?373 | ?26 | ?1.6 | ?86 | ?5.78 |
Embodiment 3 | ?1140℃ | ?0.16 | ?0.37 | ?351 | ?20 | ?1.9 | ?75 | ?5.72 |
Claims (6)
1, small power ultrasonic transducer doping vario-property barium sodium bismuth titanate piezoelectric ceramics, it is characterized in that forming general formula is (1-x) Bi
0.5Na
0.5TiO
3-xBaTiO
3, x=0.005~0.2 is mixed Yb simultaneously
2O
3, Y
2O
3, La
2O
3, Nd
2O
3, Sm
2O
3, Cr
2O
3, MnO
2And CeO
2Wait one or both modified materialses, the weight ratio of mixing is 0.01wt%~1.5wt%.
2, by the described small power ultrasonic transducer of claim 1 doping vario-property barium sodium bismuth titanate piezoelectric ceramics, it is characterized in that be x=0.01~0.11 best the composition, mixing weight ratio simultaneously is 0.01wt%~1wt%.
3, by claim 1 or 2 described small power ultrasonic transducers preparation method with doping vario-property barium sodium bismuth titanate piezoelectric ceramics, comprise batch mixes, pre-synthetic, fine grinding, moulding, plastic removal sintering, it is characterized in that:
(1) selects anhydrous sodium carbonate, Carbon Dioxide barium, bismuth oxide, titanium dioxide and Yb for use
2O
3, Y
2O
3, La
2O
3, Nd
2O
3, Sm
2O
3, Cr
2O
3, MnO
2And CeO
2Wait one or both modified materialses to make raw material, press compositing formula and doping weighing;
(2) the plastic removal sintering schedule is that the speed of 1-5 ℃/min is warming up to 400-600 ℃, is incubated and is warming up to 1100~1200 ℃ with 1-5 ℃/min after 0.5-3 hour, opens wide sintering 2~4 hours in atmosphere.
4,, it is characterized in that diameter of particle after the fine grinding process is between 300nm~700nm by the preparation method of the described small power ultrasonic transducer of claim 3 with doping vario-property barium sodium bismuth titanate piezoelectric ceramics.
5, use the preparation method of doping vario-property barium sodium bismuth titanate piezoelectric ceramics by claim 3 or 4 described small power ultrasonic transducers, it is characterized in that synthetic in advance system is 750~950 ℃ of insulations 2~4 hours.
6, use the preparation method of doping vario-property barium sodium bismuth titanate piezoelectric ceramics by claim 3 or 4 described small power ultrasonic transducers, it is characterized in that moulding process is dry-pressing or rolling formation.
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Family Cites Families (3)
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EP1231192A1 (en) * | 2001-02-08 | 2002-08-14 | Ngk Spark Plug Co., Ltd | Lead-free piezoelectric ceramic materials |
CN1204085C (en) * | 2003-06-05 | 2005-06-01 | 中国科学院上海硅酸盐研究所 | Ion dosed sodium barium titanate-barium titanate piezo ceramics and preparation thereof |
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CN106866135B (en) * | 2017-03-13 | 2019-12-06 | 中国地质大学(北京) | Preparation method of lead-free high-Curie temperature BaTiO 3-based positive temperature coefficient thermal sensitive ceramic |
CN107188554A (en) * | 2017-06-22 | 2017-09-22 | 广西大学 | A kind of preparation method of ceramic target |
CN107721412A (en) * | 2017-11-13 | 2018-02-23 | 陕西科技大学 | A kind of NBT based semiconductor ceramics and preparation method thereof |
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