CN1298670C - Sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic and its preparation method - Google Patents
Sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic and its preparation method Download PDFInfo
- Publication number
- CN1298670C CN1298670C CNB2004100884259A CN200410088425A CN1298670C CN 1298670 C CN1298670 C CN 1298670C CN B2004100884259 A CNB2004100884259 A CN B2004100884259A CN 200410088425 A CN200410088425 A CN 200410088425A CN 1298670 C CN1298670 C CN 1298670C
- Authority
- CN
- China
- Prior art keywords
- phthalate
- bnt
- tio
- bzt
- leadless piezoelectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PATCGGIXNSOMLL-UHFFFAOYSA-J bismuth sodium barium(2+) phthalate zirconium(4+) Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Zr+4].[Ba+2].C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Bi+3].[Na+] PATCGGIXNSOMLL-UHFFFAOYSA-J 0.000 title claims description 10
- 239000011734 sodium Substances 0.000 claims abstract description 20
- 230000010287 polarization Effects 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 235000003283 Pachira macrocarpa Nutrition 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 235000014364 Trapa natans Nutrition 0.000 claims description 6
- 235000009165 saligot Nutrition 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 6
- 238000001238 wet grinding Methods 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- YIMPFANPVKETMG-UHFFFAOYSA-N barium zirconium Chemical compound [Zr].[Ba] YIMPFANPVKETMG-UHFFFAOYSA-N 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 230000018199 S phase Effects 0.000 claims description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 240000001085 Trapa natans Species 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 229910002115 bismuth titanate Inorganic materials 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000005530 etching Methods 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 241001083492 Trapa Species 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 238000001739 density measurement Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention discloses sodium bismuth titanate-barium zirconium titanate leadless piezoelectric ceramics and a preparing method thereof, which belongs to the technical field of the preparation of functional ceramics. The sodium bismuth titanate-barium zirconium titanate leadless piezoelectric ceramics are favorable to environmental protection. The provided sodium bismuth titanate leadless piezoelectric ceramics have the compositions of (Bi<0.5>Na<0.5>)TiO3-xBa(Ti<1-y>Zr<y>)O3, wherein x is the molar content of BZT in the ceramic system, y is the atomic number of Ti atoms replaced by Zr atoms in BaTiO3, x is from 0 to 0.12, and y is from 0 to 0.10. The BNT-BZT leadless piezoelectric ceramics prepared by a two-step sintering method have high density and uniform crystal particles, and simultaneously, leakage current in a polarization process is lowered; the polarization of the ceramics is easy. The piezoelectric ceramics do not contain lead, and have favorable piezoelectric properties and ferroelectric properties.
Description
Technical field
The invention belongs to the function ceramics preparing technical field, particularly help a kind of sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic of environment protection and preparation method thereof.
Background technology
Piezoelectric ceramics is the important informational function stupalith of a class, but the extensive now piezoelectric ceramics that uses mainly is the lead base piezoelectric ceramics.The lead base piezoelectric produce, use and discarded last handling process in bring serious harm all can for the mankind and ecotope.It is inevitable to use leadless piezoelectric ceramics to replace the lead base piezoelectric ceramics to become.
Bismuth-sodium titanate (Bi
0.5Na
0.5) TiO
3(BNT) (A ', A ") BO that to be nineteen sixty found by people such as Smolensky
3Type composite perofskite ferroelectrics belongs to trigonal system during room temperature, Curie temperature is 320 ℃.BNT has strong (the room temperature remnant polarization P of ferroelectricity
r=38 μ C/cm
2), piezo-electric modulus is big, and specific inductivity is little, and acoustical behavior waits good characteristic well, and sintering temperature is low, is considered to one of the most attractive lead-free piezoceramic material system.Yet, the coercive field height (E of BNT
c=73kV/cm),, thereby be difficult to polarization at the specific conductivity height of ferroelectric phase region.Na in addition
2The easy moisture absorption of O, the sintering range of pottery is narrow, causes the stable chemical performance of system relatively poor.
At present the research and development of bismuth-sodium titanate base lead-free piezoelectric ceramic are mainly concentrated on the substituting modification to A, B position.The polynary system performance of piezoelectric ceramics has bigger variation with the variation of component, especially near accurate homotype phase boundary (MPB), dielectric, the ferroelectric and piezoelectric properties of pottery all have the raising of mutagenicity, are to improve the key of low tension performance so seek the accurate homotype phase boundary of polynary ceramic systems.The dielectric that obtains at present, the ferroelectric and all bismuth sodium titanate based preferably binary pottery of piezoelectric properties mainly contain following several: (1-a) (Bi
0.5Na
0.5) TiO
3-aBaTiO
3The abbreviation of [abbreviation: BNBT-100a] system, at room temperature MPB is present in a=0.06-0.07, all has bigger remnant polarization P in the very wide compositing range near MPB
r=20C/cm
2, Curie temperature T
c=288 ℃.(1-b) (Bi
0.5Na
0.5) TiO
3-bNaNbO
3[abbreviation: BNTN-100b] system, its accurate homotype phase boundary MPB is present in b=0.03, the piezoelectric stress constant d of BNTN
33=71pC/N.(1-c) (Bi
0.5Na
0.5) TiO
3-c1/2 (Bi
2O
3Sc
2O
3) [abbreviation: BNST-100c] system, BNSN-2 has maximum electromechanical coupling constant k
33=0.42 and maximum piezoelectric stress constant d
33=92pC/N, relative permittivity is with 1/2 (Bi
2O
3Sc
2O
3) content increase and increase Curie temperature T
c=358 ℃.(1-d) (Bi
0.5Na
0.5) TiO
3-d (Bi
0.5K
0.5) TiO
3[BNKT-100d] system, accurate homotype phase boundary MPB is present in d=0.16-0.20, maximum piezoelectric stress constant d
33=151pC/N, Curie temperature T
c=317 ℃.About BNT is that the report of piezoelectric property has T.Takenaka and K.Maruyama:Jpn.J.Appl.Phys. near the accurate homotype phase boundary of multielement piezoelectric pottery, 30 (1991) 2236, Y.Hosono and K.Harada, Jpn.J.Appl.Phys., 40 (2001) 5722, H.Nagata and T.Takenake:J.Appl.Phys., 36 (1997) 2115, H.Nagata and T.Takenake:J.Appl.Phys., 36 (1997) 6055, A.Sasaki and T.Chiba:J.Appl.Phys., 38 (1999) 5564, H.Nagataand M.Toshiba:J.Appl.Phys., 42 (2003) 7401, H.Ishii and H.Nagata:J.Appl.Phys., 40 (2001) 5660; D.-M.Lin, D.-Q.Xiao, J.-G.Zhu, P.-Y.Yu, H.-J.Yan, L.-Z.Li and W.Zhang:Cryst.Res., 39 (2004) 30 etc.Recently, at J.Appl.Phys., in 92 (2002) 1489 reports, Z.Yu, C.Ang, R.Guo, people such as A.S.Bhalla prepare Ba (Ti, Zr) O
3Pottery is found Ba (Ti
0.95Zr
0.05) O
3The pottery of component has maximum piezoelectric constant d
33=236pC/N, remnant polarization P
r=13-18 μ C/cm
2, coercive field E
c＜35kV/cm.But preparation and the performance about BNT-BZT binary system leadless piezoelectric ceramics yet there are no report at present.
Summary of the invention
The object of the present invention is to provide a kind of sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic and preparation method thereof, it is characterized in that: described sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic is by the zirconium barium titanate Ba (Ti with tetragonal phase structure
1-yZr
y) O
3Solid solution is in the bismuth-sodium titanate (Bi with water chestnut side's phase structure
0.5Na
0.5) TiO
3In, form (Bi with accurate homotype phase boundary
0.5Na
0.5) TiO
3-xBa (Ti
1-yZr
y) O
3, wherein x is the molar weight of BZT in the ceramic systems, and x is 0.03,0.06,0.09,0.12, and y is BaTiO
3In the Ti atom by Zr metathetical molar weight, y=0.058.
The preparation of described sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic is to adopt two-step sintering method; Concrete technical process is:
1) with Bi
2O
3, Na
2CO
3, TiO
2Be raw material, according to chemical formula (Bi
0.5Na
0.5) TiO
3Prepare burden, pre-burning in 600-1000 ℃ of air, obtaining chemical formula after grinding is sieved is (Bi
0.5Na
0.5) TiO
3Abbreviation BNT solid-solution powder;
2) with BaCO
3, ZrO
2, TiO
2Be raw material, according to chemical formula Ba (Ti
1-yZr
y) O
3After preparing burden, wherein, BaTiO
3In the Ti atom by Zr metathetical molar weight y=0.058.Pre-burning in 800-1200 ℃ of air, obtaining chemical formula after grinding is sieved is Ba (Ti
1-yZr
y) O
3Abbreviation BZT solid-solution powder;
3) BNT, the BZT powder with pre-burning is raw material powder, and BNT-xBZT prepares burden according to chemical formula, through wet-milling and oven dry and dry-pressing formed; Wherein x is the molar content of BZT in the ceramic systems, and x is 0.03,0.06,0.09,0.12;
4), obtain fine and close piezoelectric ceramic piece with molding blank sintering in 1100-1250 ℃ of air;
5) to be milled to 1.00 ± 0.02mm with sand paper thick for the ceramic plate of densified sintering product, and the two-sided roasting silver of silver slurry that brushes roastingly polarizes after going up silver electrode, polarization process carries out in the silicone oil medium, the polarization temperature is 60-120 ℃, and polarized electric field is 3-5kV/mm, and the polarization time is 10-60min.
The invention has the beneficial effects as follows: compared with prior art, the invention has the advantages that: (1) obtains a kind of BNT-BZT series lead-free piezoelectric ceramic with better piezoelectric property, and finds optimal components point to form; (2) two-step sintering method can obtain the high-compactness stupalith; (3) reduce the leakage current in the polarization process, be easy to polarization.
Description of drawings
Fig. 1 is the XRD spectral line of the BNT powder that insulation pre-burning in 3 hours obtains in 850 ℃ of air.
Fig. 2. be the XRD spectral line of the BZT powder that insulation pre-burning in 3 hours obtains in 1200 ℃ of air.
Fig. 3 is the XRD spectral line of the BNT-BZT ceramic plate that insulation pre-burning in 3 hours obtains in 1180 ℃ of air.
Fig. 4 is scanning electron microscope (SEM) photo on the BNT-BZT9 ceramic plate surface after thermal etching.
Fig. 5 is the ferroelectric hysteresis loop of the BNT-BZT piezoelectric ceramics that measures under the room temperature 100Hz.
Fig. 6 is piezoelectric constant d
33, room temperature dielectric constant ε
33 T/ ε
0(test frequency 1kHz) is with the relation curve of BZT content.
Fig. 7 is BNT-BZT6, BNT-BZT9, and the curve that the dielectric constant with temperature of BNT-BZT12 pottery changes (temperature that is situated between spectrum), test frequency is 1MHz:(a) BNT-BZT6, (b) BNT-BZT9, (c) BNT-BZT12.
Fig. 8 is BNT-BZT6, BNT-BZT9, and the temperature variant curve of dielectric loss tan δ of BNT-BZT12 pottery, test frequency is 1MHz:(a) BNT-BZT6, (b) BNT-BZT9, (c) BNT-BZT12.
Embodiment
Exemplifying following embodiment is specified the present invention.Embodiment: with Bi
2O
3, Na
2CO
3, TiO
2Be raw material, according to chemical formula (Bi
0.5Na
0.5) TiO
3Prepare burden; With BaCO
3, ZrO
2, TiO
2Be raw material, according to chemical formula Ba (Ti
0.942Zr
0.058) O
3Prepare burden.Use dehydrated alcohol to be the medium wet-milling respectively, oven dry in wet-milling 2-3 hour obtains dry powder.The BNT raw material powder is incubated pre-burning in 3 hours in 850 ℃ of air, grind the BNT raw material powder that obtains having the composite perofskite phase after sieve (200 order); The BZT raw material powder is incubated pre-burning in 3 hours in 1200 ℃ of air, grind the BZT raw material powder that the back (200 order) of sieving obtains having the uhligite phase.BNT, BZT powder with pre-burning are raw material powder, according to chemical formula (Bi
0.5Na
0.5) TiO
3-x Ba (Ti
0.942Zr
0.058) O
3Preparing burden in [BNT-BZT100x] (x=0.03,0.06,0.09,0.12), obtains dry powder through same wet-milling drying course.Dry-pressing formed, forming mould is internal diameter 10mm, and applying pressure is 2-5MPa, pressurize 1 minute, matrix band thickness 1-2mm.Matrix band is incubated 3 hours sintering in 1180 ℃ of air, obtain fine and close piezoelectric ceramic piece, measures the density of ceramic plate.It is thick that the ceramic plate of densified sintering product is milled to 1.00 ± 0.02mm with sand paper, the two-sided roasting silver of silver slurry that brushes.The roasting silver electrode that goes up polarizes afterwards.Polarization process carries out in the silicone oil medium, and the polarization temperature is 60 ℃, and polarized electric field is 4kV/mm, and the polarization time is 30min.
Determine the ceramic powder sample after the pre-burning and the crystalline structure of the ceramic plate sample behind the sintering with x-ray diffraction analysis (XRD).The microscopic appearance of stupalith uses scanning electronic microscope (SEM) analysis behind the sintering, the SEM sample need pass through thermal etching, after the thermal etching process is the polishing of ceramic plate process, use the diamond polishing agent polishing of granularity, then in 1080 ℃ of insulations thermal etching in 30 minutes as 1m.The ceramics sample of thermal etching can be seen ceramic crystalline grain of uniform size down in scanning electronic microscope (SEM).The silver-plated polarization of ceramics sample and place for some time after, measure ferroelectric, the piezoelectricity and the dielectric properties of ceramics sample.The ferroelectric hysteresis loop of measure sample is the P-E curve under room temperature 100Hz frequency, with the ferroelectric properties of research stupalith.Use type quasistatic d
33Survey meter is at room temperature measured the piezoelectric constant d of ceramic plate
33DIELECTRIC CONSTANT
33 T/ ε
0Measuring condition be room temperature 1kHz.Piezoelectric has Curie temperature T
c, more than Curie temperature, be paraelectric phase, when being lower than Curie temperature, temperature just has ferroelectricity.Near Curie point, the dielectric properties generation obvious variation of material comprises DIELECTRIC CONSTANT
sWith dielectric loss tan δ, so the DIELECTRIC CONSTANT of measure sample
sWith dielectric loss tan δ with the variation of temperature curve, can obtain the Curie temperature T of stupalith
c
1.XRD experiment and density measurement interpretation of result: on Fig. 1 and Fig. 2 as can be seen, insulation pre-burning in 3 hours can access the bismuth-sodium titanate BNT with water chestnut side's symmetrical property perovskite structure in 850 ℃ of air, is incubated the zirconium barium titanate BZT that pre-burning in 3 hours can obtain to have cubic symmetrical property perovskite structure simultaneously in 1200 ℃ of air.Water chestnut side is that with the difference of cubic perovskite structure mutually (200) peak of water chestnut side phase perovskite structure XRD is unimodal mutually, and (200) peak of cubic phase perovskite structure XRD is split into (200) and (002) two peak.Fig. 3 is the XRD spectral line of ceramic plate behind the ceramic systems BNT-BZT100x sintering, and as can be seen from the figure (200) peak of BNT-BZT0 is unimodal, and (200) peak of BNT-BZT12 significantly is split into (200) and (002) two peak.Along with the increase of BZT content, the division at (200) peak is more and more obvious, shows that the content of cubic phase is more and more.The BNT-BZT ceramic systems has the accurate homotype phase boundary of water chestnut side's phase-cubic phase, and its position is positioned near the BNT-BZT9.It can also be seen that simultaneously along with the increase of Zr content, the peak position of XRD spectral line moves towards low-angle direction, this explanation Zr enters lattice, because the Zr atomic radius is big than the Ti atom, thereby has finally influenced lattice parameter.The density measurement result is as shown in table 1, and ceramic plates all behind the sintering have 5.69-5.82g/cm
3High-compactness, be equivalent to 97% of theoretical density.
Piezoelectric constant, room temperature dielectric constant, dielectric loss, Curie temperature and the density of table 1.BNT-BZT100x pottery
| d 33 (pC/N) | T c (℃) | ρ (g/cm 3) | ε 33 T/ε 0 | tanδ (％) | |
| BNT-BZT3 BNT-BZT6 BNT-BZT9 BNT-BZT12 | 79 107 147 112 | N/A 235 240 250 | 5.76 5.72 5.82 5.69 | 345.6 844.6 881.4 788.7 | 1.765 2.185 2.636 2.980 |
2.SEM experimental analysis: Fig. 4 is the typical pattern (BNT-BZT9) of ceramic crystalline grain after the thermal etching, and crystal grain is tightly packed, does not have tangible gross blow hole, and the void content of sample is low, and this result with the front density measurement conforms to.The ceramic crystalline grain size distribution is in the scope of 1-5um simultaneously.
3. ferroelectric properties test and analyzing: Fig. 5 has provided BNT-BZT3, the ferroelectric hysteresis loop of 6,9,12 samples, the ferroelectric hysteresis loop of BNT-BZT3 is almost linearity, analyze reason and may be since the coercive field of BNT-BZT3 greater than the excitation electrical field of using in the experimentation.BNT-BZT9 has saturated ferroelectric hysteresis loop, remnant polarization P under the same measuring condition
rSample than other moiety is big.Find out that in conjunction with the XRD spectral line BNT-BZT9 is positioned near the zone of the cubic phase of accurate homotype phase boundary.
4. test of piezoelectric property and dielectric properties and interpretation of result: as can be seen from Figure 6 piezoelectric constant d
33With room temperature dielectric constant ε
33 T/ ε
0Variation with BZT content has identical trend.When the content of BZT is lower than 9mol%, piezoelectric constant d
33With room temperature dielectric constant ε
33 T/ ε
0Increase with BZT content increases, but along with the further rising of BZT content, piezoelectric constant d
33And DIELECTRIC CONSTANT
33 T/ ε
0Value descends.BNT-BZT9 has maximum piezoelectric constant d
33=147pC/N and room temperature dielectric constant ε
33 T/ ε
0=881.4, this analytical results with accurate homotype phase boundary in front and ferroelectric properties conforms to.
5. provided BNT-BZT6 among the test of Curie temperature and interpretation of result: Fig. 7 and Fig. 8, the DIELECTRIC CONSTANT of 9,12 samples
sWith dielectric loss tan δ with the variation of temperature curve, as can be seen from the figure, along with the increase of BZT content, Curie temperature moves towards the high-temperature zone, the Curie temperature of BNT-BZT9 is positioned at T
cNear=240 ℃.
Claims (2)
1. sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic, it is characterized in that: described sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic is by the zirconium barium titanate Ba (Ti with tetragonal phase structure
1-yZr
y) O
3Solid solution is in the bismuth-sodium titanate (Bi with water chestnut side's phase structure
0.5Na
0.5) TiO
3In, form (Bi with accurate homotype phase boundary
0.5Na
0.5) TiO
3-xBa (Ti
1-yZr
y) O
3, wherein x is the molar weight of BZT in the ceramic systems, and x is 0.03,0.06,0.09,0.12, and y is BaTiO
3In the Ti atom by Zr metathetical molar weight y=0.058.
2. preparation method of sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic according to claim 1, it is characterized in that: the preparation of described sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic is to adopt two-step sintering method; Concrete technical process is:
1) with Bi
2O
3, Na
2CO
3, TiO
2Be raw material, according to chemical formula (Bi
0.5Na
0.5) TiO
3Prepare burden, pre-burning in 600-1000 ℃ of air, obtaining chemical formula after grinding is sieved is (Bi
0.5Na
0.5) TiO
3Abbreviation BNT solid-solution powder;
2) with BaCO
3, ZrO
2, TiO
2Be raw material, according to chemical formula Ba (Ti
1-yZr
y) O
3After preparing burden, wherein, BaTiO
3In the Ti atom by Zr metathetical molar weight y=0.058, pre-burning in 800-1200 ℃ of air, grinding and obtaining chemical formula after sieving is Ba (Ti
1-yZr
y) O
3Abbreviation BZT solid-solution powder;
3) BNT, the BZT powder with pre-burning is raw material powder, and BNT-xBZT prepares burden according to chemical formula, through wet-milling and oven dry and dry-pressing formed; Wherein molar weight x is 0.03,0.06,0.09,0.12;
4), obtain fine and close piezoelectric ceramic piece with molding blank sintering in 1100-1250 ℃ of air;
5) to be milled to 1.00 ± 0.02mm with sand paper thick for the ceramic plate of densified sintering product, and the two-sided roasting silver of silver slurry that brushes roastingly polarizes after going up silver electrode, polarization process carries out in the silicone oil medium, the polarization temperature is 60-120 ℃, and polarized electric field is 3-5kV/mm, and the polarization time is 10-60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100884259A CN1298670C (en) | 2004-11-02 | 2004-11-02 | Sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100884259A CN1298670C (en) | 2004-11-02 | 2004-11-02 | Sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1623954A CN1623954A (en) | 2005-06-08 |
| CN1298670C true CN1298670C (en) | 2007-02-07 |
Family
ID=34766081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100884259A Expired - Fee Related CN1298670C (en) | 2004-11-02 | 2004-11-02 | Sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1298670C (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298672C (en) * | 2005-07-19 | 2007-02-07 | 清华大学 | Bismuth-sodium titanate-bismuth potassium titanate barium zirconate titanate lead free piezoelectric ceramics |
| CN100357222C (en) * | 2006-01-19 | 2007-12-26 | 湖北大学 | No-prebaking sodium bismuth titanate-barium titanate lead-less piezoelectric ceramic doping material and its prepn |
| WO2011158492A1 (en) * | 2010-06-16 | 2011-12-22 | パナソニック株式会社 | Piezoelectric film, inkjet head, method for forming image using inkjet head, angular velocity sensor, method for determining angular velocity using angular velocity sensor, piezoelectric power generating element, and power generation method using piezoelectric power generating element |
| CN102199035B (en) * | 2011-03-22 | 2013-06-26 | 清华大学 | X9r ceramic capacitor dielectric material and preparation method thereof |
| JP5754660B2 (en) * | 2013-06-28 | 2015-07-29 | セイコーエプソン株式会社 | Piezoelectric material, piezoelectric element, liquid ejecting head, liquid ejecting apparatus, ultrasonic sensor, piezoelectric motor, and power generation apparatus |
| CN103979961B (en) * | 2014-05-19 | 2016-08-24 | 西安航空学院 | Zr doping is to the energy storage effect of antiferroelectric ceramics and preparation method |
| CN104310995B (en) * | 2014-09-24 | 2016-04-13 | 陕西理工学院 | A kind of BZT thick film with EC effect and preparation method thereof |
| CN104788093B (en) * | 2015-03-09 | 2016-07-20 | 南京大学 | A kind of preparation method of 0.94Bi0.5Na0.5TiO3-0.06BaTiO3 leadless piezoelectric ceramics |
| CN106045501A (en) * | 2016-06-01 | 2016-10-26 | 北京中科奥倍超声波技术研究院 | Lead-free piezoelectric ceramic and preparation method thereof |
| CN107324804B (en) * | 2017-07-12 | 2020-07-24 | 歌尔股份有限公司 | Leadless piezoelectric ceramic and preparation method thereof |
| CN112500160A (en) * | 2019-09-16 | 2021-03-16 | 桐乡清锋科技有限公司 | Potassium-sodium niobate-based lead-free piezoelectric ceramic for piezoelectric atomization sheet and manufacturing process |
| CN110937893B (en) * | 2019-11-22 | 2020-11-24 | 华中科技大学 | Method for improving energy density of pyroelectric composite ceramic material |
| CN110981467B (en) * | 2019-12-09 | 2020-12-29 | 华中科技大学 | Lead-free pyroelectric composite ceramic material and preparation method thereof |
| CN111875389B (en) * | 2020-08-13 | 2022-10-28 | 西安科技大学 | Method for regulating and controlling performance of lead-free piezoelectric ceramic |
| CN112661508B (en) * | 2021-01-20 | 2022-12-13 | 西北大学 | Low-sintering high-energy-storage barium strontium zirconate titanate-based ceramic material and preparation method thereof |
| CN112919907B (en) * | 2021-02-09 | 2022-09-20 | 杭州电子科技大学 | Lead-free ferroelectric ceramic material with enhanced energy storage efficiency and high energy storage capacity and preparation method thereof |
| CN114315350B (en) * | 2022-01-24 | 2023-05-23 | 武汉理工大学 | Bismuth sodium titanate-barium zirconate titanate leadless wide-temperature energy storage ceramic and preparation method thereof |
| CN116606138A (en) * | 2022-02-08 | 2023-08-18 | 成都理想境界科技有限公司 | Piezoelectric ceramic and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381425A (en) * | 2001-04-18 | 2002-11-27 | 日本特殊陶业株式会社 | Piezoelectric ceramic material |
| CN1456531A (en) * | 2003-06-05 | 2003-11-19 | 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 |
-
2004
- 2004-11-02 CN CNB2004100884259A patent/CN1298670C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381425A (en) * | 2001-04-18 | 2002-11-27 | 日本特殊陶业株式会社 | Piezoelectric ceramic material |
| CN1456531A (en) * | 2003-06-05 | 2003-11-19 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1623954A (en) | 2005-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1298670C (en) | Sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic and its preparation method | |
| Wang et al. | (Bi1/2Na1/2) TiO3–Ba (Cu1/2W1/2) O3 Lead‐Free Piezoelectric Ceramics | |
| Wu et al. | Lead-free piezoelectric ceramics with composition of (0.97− x) Na 1/2 Bi 1/2 TiO 3-0.03 NaNbO 3-x BaTiO 3 | |
| JP2007031219A (en) | Bismuth sodium titanate-barium zirconium titanate base lead-free piezoelectric ceramic and its producing method | |
| CN108238795B (en) | Novel ternary ferroelectric ceramic system with high Curie temperature and preparation method and application thereof | |
| Lee et al. | Poling of Coprecipitated Lead Titanate‐Epoxy 0–3 Piezoelectric Composites | |
| Jiayu et al. | Effects of rare earth oxides on dielectric properties of Y2Ti2O7 series ceramics | |
| Chang et al. | Phase coexistence and high electrical properties in (KxNa0. 96− xLi0. 04)(Nb0. 85Ta0. 15) O3 piezoelectric ceramics | |
| Oh et al. | Optical study of domains in Ba (Ti, Sn) O3 ceramics | |
| Pardo et al. | Enhanced properties for ultrasonic transduction, phase transitions and thermal depoling in 0.96 (Bi0. 5Na0. 5) TiO3-0.04 BaTiO3 submicrometre-structured ceramics | |
| Marshall et al. | Bismuth zinc niobate: BZN-BT, a new lead-free BaTiO3-based ferroelectric relaxor? | |
| Shu et al. | Effects of BNT precursor prepared by molten salt method on BCZT-based lead-free piezoelectric ceramics | |
| Thapa et al. | Structural and dielectric properties of Ba-doped BNT ceramics | |
| CN115894020B (en) | PMNZT-based piezoelectric ceramic with high piezoelectric coefficient and preparation method and application thereof | |
| Zhang et al. | Study of the structure and dielectric relaxation behavior of Pb (Mg1/3Nb2/3) O3–PbTiO3 ferroelectric ceramics | |
| Wang et al. | Structure, electrical properties and temperature stability of PIN–PZN–PT piezoelectric ceramics with morphotropic phase boundary compositions | |
| Dutta et al. | Impedance spectroscopy studies on Ga‐ion‐modified PLZT ceramics | |
| Zheng et al. | The structure and properties of Bi-layered piezoelectric ceramics Bi4 (Ca, Sr) Ti4O15 | |
| Wang et al. | Enhanced ferroelectric and piezoelectric properties in SnO2 modified Ba0. 85Ca0. 15Zr0. 1Ti0. 9O3 lead-free ceramics | |
| Yokosuka | Dielectric and piezoelectric properties of Mn-modified Bi4CaTi4O15 based ceramics | |
| Zheng et al. | Study on ferroelectric and dielectric properties of La-doped CaBi4Ti4O15-based ceramics | |
| Wu et al. | Piezoelectric properties of (Pb, Sr)(Zr, Ti, Mn, Zn, Nb) O 3 piezoelectric ceramic | |
| Han et al. | A dielectric and ferroelectric solid solution of (1− x) BaSnO 3–x PbTiO 3 with morphotropic phase boundary | |
| Troilo et al. | Modified lead calcium titanate ceramics with a relatively large dielectric constant for hydrophone applications | |
| KR101454341B1 (en) | Piezoelectric ceramic composite and method of fabricating the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070207 Termination date: 20141102 |
|
| EXPY | Termination of patent right or utility model |