CN100537475C - Lead-free piezoelectric knitting ceramic of titanic acid bismuth sodium-titanic acid bismuth potassium and its production - Google Patents
Lead-free piezoelectric knitting ceramic of titanic acid bismuth sodium-titanic acid bismuth potassium and its production Download PDFInfo
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- CN100537475C CN100537475C CNB2006100418304A CN200610041830A CN100537475C CN 100537475 C CN100537475 C CN 100537475C CN B2006100418304 A CNB2006100418304 A CN B2006100418304A CN 200610041830 A CN200610041830 A CN 200610041830A CN 100537475 C CN100537475 C CN 100537475C
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- 239000000919 ceramic Substances 0.000 title claims abstract description 23
- 229910052797 bismuth Inorganic materials 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title description 2
- YPQJHZKJHIBJAP-UHFFFAOYSA-N [K].[Bi] Chemical compound [K].[Bi] YPQJHZKJHIBJAP-UHFFFAOYSA-N 0.000 title 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title 1
- 238000009940 knitting Methods 0.000 title 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229910002115 bismuth titanate Inorganic materials 0.000 claims abstract description 29
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 24
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 24
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 claims abstract description 23
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000005520 cutting process Methods 0.000 claims abstract description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 22
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 21
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 230000003068 static effect Effects 0.000 claims description 15
- 235000015320 potassium carbonate Nutrition 0.000 claims description 14
- 235000017550 sodium carbonate Nutrition 0.000 claims description 14
- 238000007766 curtain coating Methods 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 8
- 235000010215 titanium dioxide Nutrition 0.000 claims description 8
- 235000015895 biscuits Nutrition 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000462 isostatic pressing Methods 0.000 abstract description 5
- 238000010030 laminating Methods 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 239000001103 potassium chloride Substances 0.000 abstract 1
- 235000011164 potassium chloride Nutrition 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 238000010345 tape casting Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 7
- 238000001311 chemical methods and process Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020684 PbZr Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 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
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 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
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
A lead-free piezoelectric sodium bismuth titanate-potassium bismuth titanate texture ceramics is prepared from the microcrystalline template (bismuth titanate) prepared from TiO2, bismuth oxide, sodium chloride and potassium chloride, the raw powder of sodium carbonate, potassium carbonate, TiO2 and bismuth oxide, organic solvent, and adhesive through mixing, ball grinding, doctor blading, laminating, isostatic pressing in hot water, cutting pre-calcining, and coating Ag.
Description
(1) technical field
The present invention relates to the leadless piezoelectric ceramics field of material subject, is leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate and preparation method thereof.
(2) background technology
Piezoelectric is the hi tech and new material that a class is important, international competition is very fierce, is widely used at high-technology fields such as information, laser, navigation and biologies.
At present, most widely used piezoelectric is the Pb-based lanthanumdoped zirconate titanates (PbZr of perovskite typed
xTi
1-xO
3, be abbreviated as PZT) and piezoelectric ceramics, it uses the every aspect related to human society life, but these materials are all lead-containing materials, thereby no matter how high their performance have, its development all can be subjected to the restriction of environmental issue.In leaded piezoelectric, plumbous oxide (or tri-lead tetroxide) content approximately will account for about 70% of raw material total mass.Plumbous oxide toxicity is very strong, and (about 880 ℃) volatilization fast more than fusing point so lead-containing materials all pollutes the environment in preparation, use and waste treatment process, brings very big harm for biology and human health.Along with the enhancing of people's environmental consciousness, the decision of European various countries will progressively stop the import of lead-containing materials in recent years.European Union is at hazardous substance illegal instruction (Restrict of HazardousSubstance, be called for short RoHS) in, clearly limiting chemical substances such as cadmium, lead, sexavalent chrome and the halogen-containing flame retardant of PBB/PBDE is used on the motor electronics, determined unleaded policy, and require each member states before 13 days Augusts in 2004, to make laws, to come into effect in July, 2006 subsequently, realize unleaded.Developed country such as the U.S., Japan also pays close attention to the damaging influence that environment brings with regard to such material, and for example Japan has announced to realize the unleaded of piezoelectric ceramics in the period of 2010～2015, and with the protection environment, the U.S. has also made corresponding measure.
As seen, the research and development leadless piezoelectric ceramics is urgent, as to have a great society and economic worth problem.Can particularly after the China joined WTO, successfully develop and have leadless piezoelectric ceramics system original creativity, that have independent intellectual property right, excellent property, concerning China's piezoelectric ceramics industry, be stern challenge, is again the opportunity of rapid development.
(3) summary of the invention
For solving the problem that existing piezoelectric ceramics pollutes to environment because of meeting in the leaded treating processes after using and discarding, the present invention proposes leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate and preparation method thereof, to substitute traditional leady piezoelectric ceramic.
The present invention mixes with original powder, organic solvent and binding agent with crystallite template bismuth titanates to generate the final leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate.The crystallite template of textured ceramic is to be flaky bismuth titanate powder with titanium dioxide, bismuth oxide, sodium-chlor and Repone K with generating pattern, its proportioning is: 2 parts of bismuth oxides, 3 parts of titanium dioxide, add sodium-chlor and the Repone K of 5～15 weight %, and sodium-chlor and Repone K mol ratio are 1:1, serve as the crystallite template that generates textured ceramic with this powder; Original powder comprises yellow soda ash, salt of wormwood, titanium dioxide and bismuth oxide, and its proportioning raw materials is: yellow soda ash 10 weight %, salt of wormwood 2.5 weight %, titanium dioxide 22～34 weight %, bismuth oxide 0～45 weight %; Crystallite template bismuth titanates 10～40 weight %; Binding agent is 30%～45% of a powder gross weight, and organic solvent is 50～60% of a powder gross weight.
The present invention has adopted chemical process to obtain the crystallite template bismuth titanates of preparation textured ceramic, resulting bismuth titanates is a sheet, this crystallite template is mixed with original powder, organic solvent and binding agent, acquisition has the slurry of certain viscosity, slurry is prepared the diaphragm that thickness is 20～25 μ m through casting technique, diaphragm obtains the biscuit print by laminating with static pressure such as hot water and cutting technique, and sintering behind binder removal finally makes the leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate.Detailed process is:
The first step: preparation crystallite template bismuth titanates
(1) with analytically pure bismuth oxide with after the titanium dioxide proportioning is mixed, add sodium-chlor and Repone K;
(2) said mixture adds dehydrated alcohol, ball milling oven dry after 24 hours, grinding, pre-burning.Wherein calcined temperature is 1000 ℃, and the time is 2 hours;
(3) powder after the pre-burning is cleaned after ultrasonic dispersing, empirical tests does not have Cl
-The back oven dry.
Second step: the leadless piezoelectric structured pottery of preparation bismuth-sodium titanate-bismuth potassium titanate
(1) yellow soda ash, salt of wormwood, titanium dioxide, bismuth oxide are mixed by weight ratio, ball milling added the bismuth titanates crystallite template of 10～40 weight % after 48 hours, continued ball milling discharging after 1～3 hour;
(5) carry out curtain coating behind the slurries filtration.The casting technique parameter is: blade thickness 30～50 μ m, and three sections oven dry warm areas are respectively: 50～65 ℃, 70～80 ℃ and 60～75 ℃, diaphragm cuts into through cutting membrane knife needs size;
(6) diaphragm of well cutting is placed 24 hours after, laminate, the press parameter is 40～50 ℃ of upper holder temperature, the bottom platen temperature is 40～50 ℃, pressure is 1000～1500PSI;
(7) diaphragm after laminating is waited static pressure, peak pressure is 6000～8000PSI, and the time is 3000～4000 seconds, and water temperature is 60～70 ℃;
(8) etc. the diaphragm behind the static pressure cuts into the biscuit print of desired size through cutting machine, carries out sintering after the binder removal operation, and dump temperature is 560 ℃, and sintering temperature is 1100～1170 ℃;
(9) print behind the sintering through the polishing, the polishing, by silver electrode after silver ink firing, can carry out the test of electrical property behind the silver ink firing.
The invention has the advantages that and to utilize the existing electronic element production unit of factory, need not purchase new equipment in addition and just can finish the preparation of leadless piezoelectric structured pottery, the objectionable impurities that does not have simultaneously plumbous oxide etc. that environment is polluted in the whole process participates in, reached environmental protection requirement fully, its electrical property of the leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate of preparing has simultaneously reached the requirement of piezoelectric ceramics practicability.
(4) description of drawings
1. accompanying drawing 1 is the XRD spectrum of differing temps agglomerating NBT-KBT textured ceramic;
2. accompanying drawing 2 is synoptic diagram of textured ceramic;
3. accompanying drawing 3 is textured ceramic salient featuress along vertical curtain coating direction.
(5) embodiment
Embodiment one:
Present embodiment is to mix with original powder, organic solvent and binding agent with crystallite template bismuth titanates, wherein:
The crystallite template of textured ceramic is that wherein sodium-chlor and Repone K mol ratio are 1:1 with sodium-chlor and the Repone K of 3 parts of titanium dioxide, 2 parts of bismuth oxides, 15 weight %.Original powder comprises yellow soda ash 10 weight %, salt of wormwood 2.5 weight %, titanium dioxide 22 weight % and bismuth oxide 24.5 weight %.Binding agent is 30% of a powder gross weight, and organic solvent is 50% of a powder gross weight.
Present embodiment adopts chemical process to prepare the leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate.Concrete preparation process is:
The first step: preparation crystallite template bismuth titanates
(1) with analytically pure bismuth oxide with after titanium dioxide mixes, add sodium-chlor and Repone K;
(2) said mixture adds dehydrated alcohol, and ball milling 24 hours is dried, grinding, pre-burning then.Wherein calcined temperature is 1000 ℃, and the time is 2 hours; Powder after the pre-burning is cleaned after ultrasonic dispersing in water-bath, and empirical tests does not have Cl
-The back oven dry;
Second step: the leadless piezoelectric structured pottery of preparation bismuth-sodium titanate-bismuth potassium titanate
(1) yellow soda ash, salt of wormwood, titanium dioxide, bismuth oxide are mixed by weight ratio, ball milling added the bismuth titanates crystallite template of 40 weight % after 48 hours, continued ball milling discharging after 1 hour;
(2) carry out curtain coating behind the slurry filter screen, the casting technique parameter is: blade thickness 30 μ m, three sections oven dry warm areas are respectively: 50 ℃, 70 ℃ and 60 ℃.Diaphragm cuts into desired size through cutting membrane knife;
(3) diaphragm of well cutting is placed 24 hours after, laminate, the press parameter is 40 ℃ of upper holder temperature, the bottom platen temperature is 40 ℃, pressure is 800PSI;
(4) diaphragm that will laminate waits static pressure by the hot water isostatic pressing machine, and peak pressure is 5000PSI, and the time is 2500 seconds, and water temperature is 60 ℃;
(5) etc. the diaphragm behind the static pressure cuts into the biscuit print of desired size through cutting machine, carries out sintering after the binder removal operation, and dump temperature is 560 ℃, and sintering temperature is 1100 ℃;
(6) print behind the sintering through the polishing, the polishing, by silver electrode after silver ink firing, sintering temperature is 560 ℃, can carry out the test of electrical property behind the silver ink firing.Test is carried out on perpendicular to the curtain coating direction.
Embodiment two:
Present embodiment is to mix with original powder, organic solvent and binding agent with crystallite template bismuth titanates, wherein:
The crystallite template of textured ceramic is that wherein sodium-chlor and Repone K mol ratio are 1:1 with sodium-chlor and the Repone K of 3 parts of titanium dioxide, 2 parts of bismuth oxides, 15 weight %.Original powder comprises yellow soda ash 10 weight %, salt of wormwood 2.5 weight %, titanium dioxide 28.5 weight % and bismuth oxide 24 weight %.Binding agent is 40% of a powder gross weight.Organic solvent is 55% of a powder gross weight.
Present embodiment adopts chemical process to prepare the leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate.Concrete preparation process is:
The first step: preparation crystallite template bismuth titanates
(1) with analytically pure bismuth oxide with after titanium dioxide mixes, add sodium-chlor and Repone K;
(2) said mixture adds dehydrated alcohol, and ball milling 24 hours is dried, grinding, pre-burning then.Wherein calcined temperature is 1000 ℃, and the time is 2 hours; Powder after the pre-burning is cleaned after ultrasonic dispersing in water-bath, and empirical tests does not have Cl
-The back oven dry;
Second step: the leadless piezoelectric structured pottery of preparation bismuth-sodium titanate-bismuth potassium titanate
(1) yellow soda ash, salt of wormwood, titanium dioxide, bismuth oxide are mixed by weight ratio, ball milling added the bismuth titanates crystallite template of 35 weight % after 48 hours, continued ball milling discharging after 2 hours;
(2) carry out curtain coating behind the slurry filter screen, the casting technique parameter is: blade thickness 40 μ m, three sections oven dry warm areas are respectively: 60 ℃, 75 ℃ and 65 ℃.Diaphragm cuts into desired size through cutting membrane knife;
(3) diaphragm of well cutting is placed 24 hours after, laminate, the press parameter is 45 ℃ of upper holder temperature, the bottom platen temperature is 45 ℃, pressure is 1000PSI;
(4) diaphragm that will laminate waits static pressure by the hot water isostatic pressing machine, and peak pressure is 6000PSI, and the time is 3000 seconds, and water temperature is 65 ℃;
(5) etc. the diaphragm behind the static pressure cuts into the biscuit print of desired size through cutting machine, carries out sintering after the binder removal operation, and dump temperature is 560 ℃, and sintering temperature is 1130 ℃;
(6) print behind the sintering through the polishing, the polishing, by silver electrode after silver ink firing, sintering temperature is 560 ℃, can carry out the test of electrical property behind the silver ink firing.Test is carried out on perpendicular to the curtain coating direction.
Embodiment three:
Present embodiment is to mix with original powder, organic solvent and binding agent with crystallite template bismuth titanates, wherein:
The crystallite template of textured ceramic is that wherein sodium-chlor and Repone K mol ratio are 1:1 with sodium-chlor and the Repone K of 3 parts of titanium dioxide, 2 parts of bismuth oxides, 15 weight %.Original powder comprises yellow soda ash 10 weight %, salt of wormwood 2.5 weight %, titanium dioxide 28.5 weight % and bismuth oxide 29 weight %.Binding agent is 45% of a powder gross weight.Organic solvent is 60% of a powder gross weight.
Present embodiment adopts chemical process to prepare the leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate.Concrete steps are:
The first step: preparation crystallite template bismuth titanates
(1) with analytically pure bismuth oxide with after titanium dioxide mixes, add sodium-chlor and Repone K;
(2) said mixture adds dehydrated alcohol, and ball milling 24 hours is dried, grinding, pre-burning then.Wherein calcined temperature is 1000 ℃, and the time is 2 hours; Powder after the pre-burning is cleaned after ultrasonic dispersing in water-bath, and empirical tests does not have Cl
-The back oven dry;
Second step: the leadless piezoelectric structured pottery of preparation bismuth-sodium titanate-bismuth potassium titanate
(1) yellow soda ash, salt of wormwood, titanium dioxide, bismuth oxide are mixed by weight ratio, ball milling added the bismuth titanates crystallite template of 30 weight % after 48 hours, continued ball milling discharging after 2 hours;
(2) carry out curtain coating behind the slurry filter screen, the casting technique parameter is: blade thickness 50 μ m, three sections oven dry warm areas are respectively: 65 ℃, 80 ℃ and 75 ℃.Diaphragm cuts into desired size through cutting membrane knife;
(3) diaphragm of well cutting is placed 24 hours after, laminate, the press parameter is 45 ℃ of upper holder temperature, the bottom platen temperature is 45 ℃, pressure is 1000PSI;
(4) diaphragm that will laminate waits static pressure by the hot water isostatic pressing machine, and peak pressure is 6000PSI, and the time is 3000 seconds, and water temperature is 70 ℃;
(5) etc. the diaphragm behind the static pressure cuts into the biscuit print of desired size through cutting machine, carries out sintering after the binder removal operation, and dump temperature is 560 ℃, and sintering temperature is 1150 ℃;
(6) print behind the sintering through the polishing, the polishing, by silver electrode after silver ink firing, sintering temperature is 560 ℃, can carry out the test of electrical property behind the silver ink firing.Test is carried out on perpendicular to the curtain coating direction.
Embodiment four:
Present embodiment is to mix with original powder, organic solvent and binding agent with crystallite template bismuth titanates, wherein:
The crystallite template of textured ceramic is that wherein sodium-chlor and Repone K mol ratio are 1:1 with sodium-chlor and the Repone K of 3 parts of titanium dioxide, 2 parts of bismuth oxides, 15 weight %.Original powder comprises yellow soda ash 10 weight %, salt of wormwood 2.5 weight %, titanium dioxide 34 weight % and bismuth oxide 43.5 weight %.Binding agent is 45% of a powder gross weight.Organic solvent is 60% of a powder gross weight.
Present embodiment adopts chemical process to prepare the leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate.Concrete steps are:
The first step: preparation crystallite template bismuth titanates
(1) with analytically pure bismuth oxide with after titanium dioxide mixes, add sodium-chlor and Repone K;
(2) said mixture adds dehydrated alcohol, and ball milling 24 hours is dried, grinding, pre-burning then.Wherein calcined temperature is 1000 ℃, and the time is 2 hours; Powder after the pre-burning is cleaned after ultrasonic dispersing in water-bath, and empirical tests does not have Cl
-The back oven dry;
Second step: the leadless piezoelectric structured pottery of preparation bismuth-sodium titanate-bismuth potassium titanate
(1) yellow soda ash, salt of wormwood, titanium dioxide, bismuth oxide are mixed by weight ratio, ball milling added the bismuth titanates crystallite template of 10 weight % after 48 hours, continued ball milling discharging after 3 hours;
(2) carry out curtain coating behind the slurry filter screen, the casting technique parameter is: blade thickness 50 μ m, three sections oven dry warm areas are respectively: 65 ℃, 80 ℃ and 75 ℃.Diaphragm cuts into desired size through cutting membrane knife;
(3) diaphragm of well cutting is placed 24 hours after, laminate, the press parameter is 50 ℃ of upper holder temperature, the bottom platen temperature is 50 ℃, pressure is 1200PSI;
(4) diaphragm that will laminate waits static pressure by the hot water isostatic pressing machine, and peak pressure is 7000PSI, and the time is 3500 seconds, and water temperature is 70 ℃;
(5) etc. the diaphragm behind the static pressure cuts into the biscuit print of desired size through cutting machine, carries out sintering after the binder removal operation, and dump temperature is 560 ℃, and sintering temperature is 1170 ℃;
(6) print behind the sintering through the polishing, the polishing, by silver electrode after silver ink firing, sintering temperature is 560 ℃, can carry out the test of electrical property behind the silver ink firing.Test is carried out on perpendicular to the curtain coating direction.
Use HP-4294A type electric impedance analyzer to test dielectric properties and resonance-anti-resonance frequency at ambient temperature, test frequency is 1 megahertz, calculates DIELECTRIC CONSTANT respectively
r, electromechanical coupling factor k
3With mechanical quality factor Q
mAdopt Chinese Academy of Sciences's acoustics JZ-4 type d
33The piezoelectric constant d of quasi static test instrument specimen
33By analysis to its XRD, calculate the texture degree f of the leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate, the calculation formula of texture degree is as follows:
f＝(p-p
0)/(1-p
0)
In the formula, p=(I (
100)+I (
200))/∑ I
(hkl), I be the relative intensity at corresponding XRD peak, p
0P value for the free orientation ceramic of crystal grain.The f span is 0＜f＜1, and the texture degree of the big more pottery of f is high more, and promptly the preferable grain orientation degree is big more.
Claims (3)
1. leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate is characterized in that: mix generating the final leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate with original powder, organic solvent and binding agent with crystallite template bismuth titanates, wherein:
A. the crystallite template of textured ceramic is with generating bismuth titanate powder with titanium dioxide, bismuth oxide, sodium-chlor and Repone K, its proportioning is: 2 parts of bismuth oxides, 3 parts of titanium dioxide add sodium-chlor and the Repone K of 15 weight %, and wherein sodium-chlor and Repone K mol ratio are 1:1;
B. original powder comprises yellow soda ash, salt of wormwood, titanium dioxide and bismuth oxide, and its proportioning raw materials is: yellow soda ash 10 weight %, salt of wormwood 2.5 weight %, titanium dioxide 22～34 weight %, bismuth oxide 20～45 weight %; Crystallite template bismuth titanates 10～40 weight %; Binding agent is 30%～45% of a powder gross weight, and organic solvent is 50～60% of a powder gross weight.
2. one kind prepares the method for the leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate according to claim 1, after proportioning raw materials, through ball milling slurrying, curtain coating, laminate, static pressure, cutting, pre-burning such as hot water and be coated with silver-colored operation, it is characterized in that: at first prepare crystallite template bismuth titanates, crystallite template bismuth titanates is mixed generating the final leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate with original powder, organic solvent and binding agent, its detailed process is again:
A. with analytically pure bismuth oxide with after the titanium dioxide proportioning is mixed, add sodium-chlor and Repone K;
B. add dehydrated alcohol in the said mixture, with oven dry behind the ball milling, grinding, pre-burning;
C. the powder after the pre-burning is also cleaned after ultrasonic dispersing, empirical tests does not have Cl
-The back oven dry;
D. yellow soda ash, salt of wormwood, titanium dioxide, bismuth oxide are mixed by weight ratio the back ball milling, add bismuth titanates crystallite template, discharging behind the continuation ball milling;
E. carry out curtain coating behind the slurries filtration;
F. diaphragm is laminated;
G. diaphragm is waited static pressure;
H. diaphragm is cut into the biscuit print, after the binder removal operation, carry out sintering;
I. the print behind the sintering through the polishing, the polishing, by silver electrode after silver ink firing.
3. as preparing the method for the leadless piezoelectric structured pottery of bismuth-sodium titanate-bismuth potassium titanate as described in the claim 2, be characterised in that:
When a. preparing crystallite template bismuth titanates: the ball milling time is 24 hours; Calcined temperature is 1000 ℃, and the time is 2 hours;
B. prepare bismuth-sodium titanate-bismuth potassium titanate leadless piezoelectric structured when pottery: the ball milling time of original powder is 48 hours; Ball milling is 1～3 hour after the adding bismuth titanates crystallite template; The casting technique parameter is: blade thickness 30～50 μ m, and three sections oven dry warm areas are respectively: 50～65 ℃, 70～80 ℃ and 60～75 ℃; The press parameter is 40～50 ℃ of upper holder temperature, and the bottom platen temperature is 40～50 ℃, and pressure is 800～1200PSI; Peak pressure Deng static pressure is 5000～7000PSI, and the time is 2500～3500 seconds, and water temperature is 60～70 ℃; Sintering temperature is 1100～1170 ℃.
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| CN101486570B (en) * | 2009-02-25 | 2012-08-22 | 同济大学 | Leadless piezoelectric structured thick film and preparation thereof |
| WO2010147675A1 (en) * | 2009-06-19 | 2010-12-23 | Sonavation, Inc. | Method for manufacturing a piezoelectric ceramic body |
| CN103058633A (en) * | 2011-10-18 | 2013-04-24 | 中国科学院福建物质结构研究所 | Method of YAG composite transparent laser ceramic |
| CN103360060B (en) * | 2013-07-19 | 2014-11-19 | 景德镇陶瓷学院 | Sodium bismuth titanate based textured piezoelectric ceramic water-based tape casting slurry and preparation method of ceramic membrane thereof |
| CN104628379B (en) * | 2013-11-06 | 2017-11-07 | 同济大学 | Height-oriented leadless piezoelectric structured ceramic material and its preparation method and application |
| CN105645952B (en) * | 2015-12-30 | 2017-03-15 | 北京七星飞行电子有限公司 | A kind of little loss super-pressure ceramic capacitor dielectric material |
| CN115196961B (en) * | 2022-07-12 | 2023-06-09 | 中山大学 | Bismuth sodium titanate-based leadless piezoelectric textured ceramic with high texture degree and high electro-induced strain performance and preparation method thereof |
| CN116065075A (en) * | 2023-01-28 | 2023-05-05 | 哈尔滨工业大学 | Metal-relaxation ferroelectric ceramic with micro-nano composite structure and preparation method thereof |
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