CN103539450B - KNN-LT-BF leadless piezoelectric ceramic and preparation method thereof - Google Patents
KNN-LT-BF leadless piezoelectric ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 239000000084 colloidal system Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 19
- 238000012546 transfer Methods 0.000 claims description 12
- 239000005416 organic matter Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 235000010413 sodium alginate Nutrition 0.000 claims description 8
- 229940005550 sodium alginate Drugs 0.000 claims description 8
- 239000000661 sodium alginate Substances 0.000 claims description 8
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- -1 alkali metal cation Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000010287 polarization Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910002902 BiFeO3 Inorganic materials 0.000 abstract 1
- 229910003334 KNbO3 Inorganic materials 0.000 abstract 1
- 229910012463 LiTaO3 Inorganic materials 0.000 abstract 1
- 229910003378 NaNbO3 Inorganic materials 0.000 abstract 1
- 230000032683 aging Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000001272 pressureless sintering Methods 0.000 abstract 1
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 16
- 238000001027 hydrothermal synthesis Methods 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 3
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 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 description 2
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 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
- 239000000470 constituent Substances 0.000 description 1
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- 239000006104 solid solution Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a KNN-LT-BF leadless piezoelectric ceramic and a preparation method thereof. Chemical formula of the KNN-LT-BF leadless piezoelectric ceramic is (1-x)(0.46KNbO3-0.46NaNbO3-0.08LiTaO3)-xBiFeO3, wherein x=0.004 to 0.010. KNbO3, NaNbO3, LiTaO3 and BiFeO3 powder are taken as raw materials. The preparation method comprises following steps: an organic binder and water are added into the raw materials so as to obtain a colloid by stirring; the colloid is dried to obtain a mixed material; water is added into the mixed material, the mixture is subjected to ageing and dry pressing for moulding, and then ceramic green compact sheets are obtained; and the ceramic green compact sheets are subjected to binder removal processing, and then pressureless sintering so as to obtain the KNN-LT-BF leadless piezoelectric ceramic. According to the preparation method, technology is simple, efficiency is high, energy consumption and cost are low, and practicality is high. The KNN-LT-BF leadless piezoelectric ceramic is stable in properties, and excellent in performances, and is compact.
Description
Technical field
The invention belongs to perovskite structure leadless piezoelectric ceramics field, relate to a kind of KNN-LT-BF leadless piezoelectric ceramics and preparation method thereof.
Background technology
Since middle 1940s finds the piezoelectricity of barium titanate ceramic, particularly there is lead zirconate titanate Pb (Ti, the Zr) O of excellent piezoelectric property and high-curie temperature
3after pottery is successfully developed, architectural feature is ABO
3the research and development of the lead-based perovskite piezoelectric ceramic of type are very active, and piezoelectric ceramic and piezoelectric ceramic devices have been widely used in industry particularly information industry field.With lead zirconate titanate (Pb (Ti, Zr) O
3) for the lead base binary system of representative with lead zirconate titanate (Pb (Ti, Zr) O
3) for base, add third element as with lead magnesio-niobate (Pb (Mg
1/3nb
2/3) O
3), the plumbous Pb (Mn of antimony mangaic acid
1/3sb
2/3) O
3for the lead base ternary system piezoelectric ceramic of representative has excellent piezoelectricity ferro performance, high Curie temperature.The piezoelectric ceramic overwhelming majority applied in industrial production is this perovskite-like lead base piezoelectric ceramic.
But, in lead base piezoceramic material, PbO or Pb
3o
4content account for 70% of raw material gross mass.Lead contamination has become one of mankind's public hazards.Lead base piezoelectric ceramic, producing, using and cause serious harm to the mankind and biological environment in discarded last handling process, is unfavorable for the sustainable development of human society.In recent years, the pay attention to day by day that piezoelectric ceramic system that is lead-free, superior performance is subject to countries in the world particularly American-European, Japan, Korea S and China is developed.
The leadless piezoelectric ceramics system of extensively research has four classes at present: bismuth laminated leadless piezoelectric ceramic, BaTiO
3based leadless piezoelectric ceramics, Bi
0.5na
0.5tiO
3based leadless piezoelectric ceramics and K
0.5na
0.5nbO
3alkali Metals Niobate Lead Free Piezoelectric Ceramics.Wherein dielectric constant is little, piezoelectric property is high, frequency constant is large, density is little, Curie temperature high because having for KNN series lead-free piezoelectric ceramic, becomes one of system of current most possible replacement lead base piezoelectric ceramic.But traditional handicraft obtains KNN piezoelectric ceramic following shortcoming: (1), more than 1140 DEG C, KNN there will be liquid phase, so the temperature stability of KNN is limited in less than 1140 DEG C.(2) due to can with oxide Na at about 900 DEG C Na and K
2o and K
2o is formed and starts volatilization, causes the atmosphere of pre-burning and sintering to be difficult to control; (3) KNN is very easy to when the environment of humidity deliquescence occurs, and stoichiometry is departed from, and causes producing dephasign, makes pottery be difficult to densified sintering product.Above-mentioned reason all limits the practical application of KNN system material.In order to optimize the structure of KNN based leadless piezoelectric ceramics, improve the piezoelectric property of KNN base pottery, scholars from interpolation sintering aid, A position and B position doped and substituted, add the aspects such as new constituent element large quantity research carried out to KNN based leadless piezoelectric ceramics; Meanwhile, in conjunction with processes such as hot pressing, plasma discharging, HIP sintering, to obtaining fine and close KNN pottery; But above-mentioned preparation method is too high to equipment requirement, production technology is harsh, production cost is higher, scantling is restricted, and the stability of obtained pottery can not be satisfactory, is therefore difficult to obtain industrial applications.
Summary of the invention
The object of the present invention is to provide a kind of KNN-LT-BF leadless piezoelectric ceramics and preparation method thereof, the method technique is simple, energy consumption is low, cost is low, the chemical formula of obtained KNN-LT-BF leadless piezoelectric ceramics is (1-x) (0.46KNbO
3-0.46NaNbO
3-0.08LiTaO
3)-xBiFeO
3(x=0.004 ~ 0.010).
For achieving the above object, the technical solution used in the present invention is:
A kind of KNN-LT-BF leadless piezoelectric ceramics, its chemical formula is:
(1-x) (0.46KNbO
3-0.46NaNbO
3-0.08LiTaO
3)-xBiFeO
3, wherein x=0.004 ~ 0.010.
It is perovskite structure, its piezoelectric constant d
33=52 ~ 107pC/N, electromechanical coupling factor K
p=17.1 ~ 23.9%, mechanical quality factor Q
m=23.681 ~ 52.11, Curie temperature T
c=401.1 ~ 468.4 DEG C.
A preparation method for KNN-LT-BF leadless piezoelectric ceramics, comprises the following steps:
Step 1: by (1-x) (0.46KNbO
3-0.46NaNbO
3-0.08LiTaO
3)-xBiFeO
3, the stoichiometric proportion of x=0.004 ~ 0.010, calculating K NbO
3powder, NaNbO
3powder, LiTaO
3powder and BiFeO
3the quality of powder also takes, and obtains raw material;
Step 2: reaction vessel put into by raw material step 1 taken, adds organic matter binding agent and water, and stirred at ambient temperature, to mixing and forming colloid, is then dried, and obtains batch mixing; The quality of the organic matter binding agent wherein added is 0.7% ~ 2.3% of material quality, and the quality of the water added is 50 ~ 100% of material quality;
Step 3: the water adding material quality 3 ~ 5% in the batch mixing of step 2 gained, is placed in no light conditions old, then granulation after mixing, more dry-pressing formed, obtains ceramic green blank;
Step 4: ceramic green blank, through plastic removal process, at ambient pressure in 1045 ~ 1080 DEG C of sintering 1 ~ 2h, obtains KNN-LT-BF leadless piezoelectric ceramics after cooling.
With the KNbO of water heat transfer
3, NaNbO
3, LiTaO
3and BiFeO
3powder is raw material.
Organic binder bond in described step 2 is the Sodium Polyacrylate of the sodium alginate of material quality 0.1% ~ 0.3%, the sodium humate of material quality 0.5% ~ 1.5% and material quality 0.1% ~ 0.5%.
Mixing time in described step 2 is 1 ~ 2h, and bake out temperature is 60 ~ 80 DEG C.
The old time in described step 3 is 12 ~ 48h, and dry-pressing formed pressure is 20 ~ 30MPa.
The temperature of the plastic removal process in described step 4 is 600 ~ 700 DEG C.
In the sintering process of described step 4 around ceramic green blank with same constitutive material as buried powder to reduce the volatilization of alkali metal cation in sintering process.
Described KNN-LT-BF leadless piezoelectric ceramics also needs to carry out polarization operations, and concrete steps are: by KNN-LT-BF leadless piezoelectric ceramics by upper silver electrode, and in the silicone oil of 100 ~ 120 DEG C, polarize 30 ~ 60mins under 3 ~ 3.5kV/mm voltage.
Relative to prior art, beneficial effect of the present invention is:
The preparation method of KNN-LT-BF leadless piezoelectric ceramics provided by the invention, with KNbO
3, NaNbO
3, LiTaO
3and BiFeO
3powder is raw material, theoretical according to diffuse double layer, utilize diffuse double layer principle batch mixing method, add organic matter binding agent and water to stir into stable colloid and make it mix, recycling dry pressing obtains ceramic green blank, again in atmospheric conditions by obtained for ceramic green blank sintering KNN-LT-BF leadless piezoelectric ceramics, i.e. (1-x) (0.46KNbO
3-0.46NaNbO
3-0.08LiTaO
3)-xBiFeO
3(x=0.004 ~ 0.010) leadless piezoelectric ceramics.Be that a kind of technique is simple, high efficiency, low energy consumption, with low cost and have very much a leadless piezoelectric ceramics preparation method of practicality.And obtained (1-x) (0.46KNbO
3-0.46NaNbO
3-0.08LiTaO
3)-xBiFeO
3(x=0.004 ~ 0.010) leadless piezoelectric ceramics stable in properties, densification, functional.
Further, KNN-LT-BF leadless piezoelectric ceramics provided by the invention is perovskite structure, is Tetragonal, has good piezoelectricity, ferroelectric properties, its piezoelectric constant d
33=52 ~ 107pC/N, electromechanical coupling factor K
p=17.1 ~ 23.9%, mechanical quality factor Q
m=23.681 ~ 52.11, Curie temperature T
c=401.1 ~ 468.4 DEG C.
Further, the present invention in sintering process around ceramic green blank with same constitutive material as buried powder to reduce the volatilization of alkali metal cation in sintering process.
Accompanying drawing explanation
Fig. 1 is the NaNbO of Hydrothermal Synthesis of the present invention
3powder, KNbO
3powder, BiFeO
3powder and LiTaO
3the XRD figure of powder, wherein a is NaNbO
3xRD figure, b is KNbO
3xRD figure, c is BiFeO
3xRD figure, d is LiTaO
3xRD figure;
Fig. 2 is the XRD collection of illustrative plates of KNN-LT-BF leadless piezoelectric ceramics prepared by the present invention, and wherein a ~ d is respectively the XRD collection of illustrative plates of KNN-LT-BF leadless piezoelectric ceramics prepared by embodiment 1 ~ 4;
Fig. 3 is KNN-LT-BF leadless piezoelectric ceramics piezoelectric property figure prepared by the embodiment of the present invention 1 ~ 4.
Fig. 4 is the dielectric thermogram of KNN-LT-BF leadless piezoelectric ceramics prepared by the present invention, and wherein a ~ d is respectively the dielectric thermogram of KNN-LT-BF leadless piezoelectric ceramics prepared by embodiment 1 ~ 4.
Fig. 5 is the SEM figure of KNN-LT-BF leadless piezoelectric ceramics prepared by the present invention, and its a, b, c are respectively embodiment 1, the SEM figure of the KNN-LT-BF leadless piezoelectric ceramics of 3,4 preparations.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
With the KNbO of water heat transfer in following examples
3, NaNbO
3, LiTaO
3and BiFeO
3powder is that KNN-LT-BF leadless piezoelectric ceramics prepared by raw material, and wherein the concrete preparation method of each raw material is:
KNbO
3the Hydrothermal Synthesis of powder:
Weigh 13mol/L KOH, 0.5mol/L Nb
2o
5be dissolved in ionized water, magnetic agitation 1h, move in teflon-lined reactor, adding water to compactedness is hydro-thermal reaction 24h under 70%, 230 DEG C of constant temperature, naturally cools to room temperature, and with distilled water cleaning to neutral, at 80 DEG C, drying obtains KNbO
3powder.
NaNbO
3the Hydrothermal Synthesis of powder:
Weigh 6mol/L NaOH, 0.5mol/L Nb
2o
5be dissolved in ionized water, magnetic agitation 1h, move in teflon-lined reactor, adding water to compactedness is hydro-thermal reaction 24h under 70%, 230 DEG C of constant temperature, naturally cools to room temperature, and with distilled water cleaning to neutral, at 80 DEG C, drying obtains NaNbO
3powder.
LiTaO
3the Hydrothermal Synthesis of powder:
Weigh the Li of 0.2mol/L
2cO
3, 0.1mol/L Ta
2o
5, 0.40 ~ 0.61mol/L LiOHH
2o is dissolved in ionized water, magnetic agitation 1h, and move in teflon-lined reactor, adding water to compactedness is hydro-thermal reaction 36h under 70%, 240 DEG C of constant temperature, naturally cools to room temperature, and with distilled water cleaning to neutral, at 80 DEG C, drying obtains LiTaO
3powder.
BiFeO
3the Hydrothermal Synthesis of powder:
Weigh 0.03mol/L FeCl
36H
2o, 0.03mol/L Bi (NO
3)
35H
2o is dissolved in ethylene glycol solution, and magnetic agitation is to all dissolving.Mixed solution is instilled in 0.3mol/L ammonia spirit, to precipitating completely, sediment is moved in teflon-lined reactor and add 0.15mol/L KOH, adding water to compactedness is 70%, hydro-thermal reaction 20h under 220 DEG C of constant temperature, naturally cool to room temperature, with distilled water cleaning to neutral, at 80 DEG C, drying obtains BiFeO
3powder.
Fig. 1 is the NaNbO of Hydrothermal Synthesis of the present invention
3, KNbO
3, BiFeO
3and LiTaO
3the XRD figure of powder.Wherein a is NaNbO
3the XRD figure of powder, NaNbO
3all diffraction maximums are consistent with PDF card (JCPDS NO.73-0803), and it is orthorhombic phase, and it is space group Pbcm; B is KNbO
3the XRD figure of powder, KNbO
3the all diffraction maximums of powder are consistent with PDF card (JCPDS NO.71-0946), are orthorhombic phase structure, and it is space group Amm2; C is BiFeO
3the XRD figure of powder, BiFeO
3the all diffraction maximums of powder are consistent with PDF card (JCPDS NO.86-1518), and be the rhombohedral structure extended along [111], its space group is R3c; D is LiTaO
3the XRD figure of powder, LiTaO
3the all diffraction maximums of powder are consistent with PDF card (JCPDS NO.71-0951), and be the rhombohedral structure extended along [111], its space group is R-3c.
Embodiment 1:
Step 1: with the KNbO of water heat transfer
3powder, NaNbO
3powder, LiTaO
3powder and BiFeO
3powder is raw material, by 0.45816KNbO
3-0.45816NaNbO
3-0.07968LiTaO
3-0.004BiFeO
3(x=0.004) stoichiometric proportion, calculates required each powder quality and takes, obtaining raw material.
Step 2: beaker put into by raw material step 1 taken; add the distilled water that organic matter binding agent (being made up of the Sodium Polyacrylate of the sodium alginate of material quality 0.15%, the sodium humate of material quality 1.25% and material quality 0.1%) and quality are 100% of material quality; adopt diffuse double layer principle batch mixing method; room temperature lower magnetic force stirs 1h to mixing and forming colloid; then the baking oven putting into 80 DEG C is dried, and obtains batch mixing;
Step 3: the distilled water adding material quality 3% in the batch mixing of step 2 gained, old 24h in no light conditions is placed on after mixing, then the particle of good fluidity is obtained through granulation, more dry-pressing formed under 25MPa pressure, obtain the ceramic green blank that diameter is about 10mm;
Step 4: ceramic green blank, through plastic removal (binder removal) process of 700 DEG C, at ambient pressure in 1060 DEG C of sintering 2h, obtains KNN-LT-BF leadless piezoelectric ceramics after cooling.
KNN-LT-BF leadless piezoelectric ceramics is by upper silver electrode, and in the silicone oil of 120 DEG C, polarize 40mins under 3kV/mm voltage, after having polarized, places diel test ceramic performance.
Obtained ceramic performance: d
33=107pC/N, K
p=23.8%, Q
m=26.139, T
c=468.4 DEG C.
Embodiment 2:
Step 1: with the KNbO of water heat transfer
3powder, NaNbO
3powder, LiTaO
3powder and BiFeO
3powder is raw material, by 0.45724KNbO
3-0.45724NaNbO
3-0.07952LiTaO
3-0.006BiFeO
3(x=0.006) stoichiometric proportion, calculates required each powder quality and takes, obtaining raw material.
Step 2: beaker put into by raw material step 1 taken; add the distilled water that organic matter binding agent (being made up of the Sodium Polyacrylate of the sodium alginate of material quality 0.18%, the sodium humate of material quality 1.2% and material quality 0.12%) and quality are 100% of material quality; adopt diffuse double layer principle batch mixing method; room temperature lower magnetic force stirs 1h to mixing rear and forming colloid; the baking oven so putting into 80 DEG C is dried, and obtains batch mixing;
Step 3: the distilled water adding material quality 3% in the batch mixing of step 2 gained, old 24h in no light conditions is placed on after mixing, then the particle of good fluidity is obtained through granulation, more dry-pressing formed under 25MPa pressure, obtain the ceramic green blank that diameter is about 10mm;
Step 4: ceramic green blank, through the plastic removal process of 700 DEG C, at ambient pressure in 1060 DEG C of sintering 2h, obtains KNN-LT-BF leadless piezoelectric ceramics after cooling.
KNN-LT-BF leadless piezoelectric ceramics is by upper silver electrode, and in the silicone oil of 120 DEG C, polarize 40mins under 3kV/mm voltage, after having polarized, places diel test ceramic performance.
Obtained ceramic performance: d
33=83pC/N, K
p=23.7%, Q
m=23.945, T
c=452.3 DEG C.
Embodiment 3:
Step 1: with the KNbO of water heat transfer
3powder, NaNbO
3powder, LiTaO
3powder and BiFeO
3powder is raw material, by 0.45632KNbO
3-0.45632NaNbO
3-0.07936LiTaO
3-0.008BiFeO
3(x=0.008) stoichiometric proportion, calculates required each powder quality and takes, obtaining raw material.
Step 2: beaker put into by raw material step 1 taken; add the distilled water that organic matter binding agent (being made up of the Sodium Polyacrylate of the sodium alginate of material quality 0.2%, the sodium humate of material quality 1.15% and material quality 0.15%) and quality are 100% of material quality; adopt diffuse double layer principle batch mixing method; room temperature lower magnetic force stirs 1h to mixing and forming colloid; then the baking oven putting into 80 DEG C is dried, and obtains batch mixing;
Step 3: the distilled water adding material quality 3% in the batch mixing of step 2 gained, old 24h in no light conditions is placed on after mixing, then the particle of good fluidity is obtained through granulation, more dry-pressing formed under 25MPa pressure, obtain the ceramic green blank that diameter is about 10mm;
Step 4: ceramic green blank, through the plastic removal process of 700 DEG C, at ambient pressure in 1060 DEG C of sintering 2h, obtains KNN-LT-BF leadless piezoelectric ceramics after cooling.
KNN-LT-BF leadless piezoelectric ceramics is by upper silver electrode, and in the silicone oil of 120 DEG C, polarize 40mins under 3kV/mm voltage, after having polarized, places diel test ceramic performance.
Obtained ceramic performance: d
33=58pC/N, K
p=23.9%, Q
m=23.681, T
c=417.7 DEG C.
Embodiment 4:
Step 1: with the KNbO of water heat transfer
3powder, NaNbO
3powder, LiTaO
3powder and BiFeO
3powder is raw material, by 0.4554KNbO
3-0.4554NaNbO
3-0.0792LiTaO
3-0.010BiFeO
3(x=0.010) stoichiometric proportion, calculates required each powder quality and takes, obtaining raw material.
Step 2: beaker put into by raw material step 1 taken, add the distilled water that organic matter binding agent (being made up of the Sodium Polyacrylate of the sodium alginate of material quality 0.25%, the sodium humate of material quality 1% and material quality 0.25%) and quality are 100% of material quality, adopt diffuse double layer principle batch mixing method, room temperature lower magnetic force stirs 1h to mixing and forming colloid, then the baking oven putting into 80 DEG C is dried, and obtains batch mixing;
Step 3: the distilled water adding material quality 3% in the batch mixing of step 2 gained, old 24h in no light conditions is placed on after mixing, then the particle of good fluidity is obtained through granulation, more dry-pressing formed under 25MPa pressure, obtain the green sheet that diameter is about 10mm pottery;
Step 4: ceramic green blank, through the plastic removal process of 700 DEG C, at ambient pressure in 1060 DEG C of sintering 2h, obtains KNN-LT-BF leadless piezoelectric ceramics after cooling.
KNN-LT-BF leadless piezoelectric ceramics is by upper silver electrode, and in the silicone oil of 120 DEG C, polarize 40mins under 3kV/mm voltage, after having polarized, places diel test ceramic performance.
Obtained ceramic performance: d
33=52pC/N, K
p=17.1%, Q
m=52.11, T
c=401.1 DEG C.
Fig. 2 is the XRD collection of illustrative plates of KNN-LT-BF leadless piezoelectric ceramics prepared by the present invention, and wherein a ~ d is respectively the XRD collection of illustrative plates of KNN-LT-BF leadless piezoelectric ceramics prepared by embodiment 1 ~ 4.Can find that from figure all KNN-LT-BF leadless piezoelectric ceramics samples are at room temperature perovskite structure, not find obvious second-phase, illustrate that KNN-LT-BF leadless piezoelectric ceramics sample defines solid solution.According to 46 ° of swarming height relations, it can also be seen that as x=0.004 from figure, KNN-LT-BF leadless piezoelectric ceramics (040) crystallographic plane diffraction peak is higher than (400) crystallographic plane diffraction peak, and now KNN-LT-BF leadless piezoelectric ceramics structure is Tetragonal; Along with BiFeO
3doping increases, and KNN-LT-BF leadless piezoelectric ceramics sample tetragonality weakens.
Fig. 3 is the piezoelectricity performance map of KNN-LT-BF leadless piezoelectric ceramics prepared by the embodiment of the present invention 1 ~ 4, and wherein abscissa BF represents BiFeO in KNN-LT-BF leadless piezoelectric ceramics sample
3stoichiometric number, i.e. the numerical value of x.As can be seen from the figure, along with BiFeO
3the increase of doping, the piezoelectric constant d of KNN-LT-BF leadless piezoelectric ceramics sample
33show as and reduce gradually, the electromechanical coupling factor of KNN-LT-BF leadless piezoelectric ceramics sample then shows as first to remain unchanged and reduces afterwards.As x=0.004, KNN-LT-BF leadless piezoelectric ceramics sample obtains best piezoelectric property, d
33and K
preach 107pC/N and 23.8% respectively.
Fig. 4 is the dielectric thermogram of KNN-LT-BF leadless piezoelectric ceramics prepared by the present invention, and wherein a ~ d is respectively the dielectric thermogram of KNN-LT-BF leadless piezoelectric ceramics prepared by embodiment 1 ~ 4, and wherein ordinate represents relative dielectric constant.As can be seen from the figure, all there is an obvious dielectric peak in all KNN-LT-BF leadless piezoelectric ceramics samples in high-temperature region, be four directions-cubic phase transition (T
c); Work as BF(BiFeO
3) doping x=0.004 time, the Curie temperature T of KNN-LT-BF leadless piezoelectric ceramics sample
c=468.4 DEG C, as BF doping x=0.010, the Curie temperature T of KNN-LT-BF leadless piezoelectric ceramics sample
c=401.1 DEG C, namely along with the increase of BF doping x, sample Curie temperature T
cthere is reduction trend;
Fig. 5 is the SEM figure of KNN-LT-BF leadless piezoelectric ceramics prepared by the present invention, and its a, b, c are respectively embodiment 1, the SEM figure of the KNN-LT-BF leadless piezoelectric ceramics of 3,4 preparations.As can be seen from the figure, as BF doping x=0.004, KNN-LT-BF leadless piezoelectric ceramics sample interior grain development comparatively evenly and there is a small amount of pore; When increasing along with BF doping, KNN-LT-BF leadless piezoelectric ceramics sample interior pore reduces gradually, thus KNN-LT-BF leadless piezoelectric ceramics sample density is improved gradually, but there is obvious individual crystalline grains abnormal growth phenomenon in KNN-LT-BF leadless piezoelectric ceramics sample interior, as Fig. 5 c.
Embodiment 5:
Step 1: with the KNbO of water heat transfer
3powder, NaNbO
3powder, LiTaO
3powder, BiFeO
3powder is raw material, by 0.45678KNbO
3-0.45678NaNbO
3-0.07944LiTaO
3-0.007BiFeO
3(x=0.007) stoichiometric proportion, calculates required each powder quality and takes, obtaining raw material.
Step 2: beaker put into by raw material step 1 taken; add the distilled water that organic matter binding agent (being made up of the Sodium Polyacrylate of the sodium alginate of material quality 0.1%, the sodium humate of material quality 0.5% and material quality 0.1%) and quality are 50% of material quality; adopt diffuse double layer principle batch mixing method; room temperature lower magnetic force stirs 1.5h to mixing and forming colloid; then the baking oven putting into 60 DEG C is dried, and obtains batch mixing;
Step 3: the distilled water adding material quality 4% in the batch mixing of step 2 gained, old 12h in no light conditions is placed on after mixing, then the particle of good fluidity is obtained through granulation, more dry-pressing formed under 20MPa pressure, obtain the ceramic green blank that diameter is about 10mm;
Step 4: ceramic green blank, through the plastic removal process of 650 DEG C, at ambient pressure in 1045 DEG C of sintering 1.5h, obtains KNN-LT-BF leadless piezoelectric ceramics after cooling.
KNN-LT-BF leadless piezoelectric ceramics is by upper silver electrode, and in the silicone oil of 100 DEG C, polarize 60mins under 3.5kV/mm voltage.
Embodiment 6:
Step 1: with the KNbO of water heat transfer
3powder, NaNbO
3powder, LiTaO
3powder, BiFeO
3powder is raw material, by 0.4577KNbO
3-0.4577NaNbO
3-0.0796LiTaO
3-0.005BiFeO
3(x=0.005) stoichiometric proportion, calculates required each powder quality and takes, obtaining raw material.
Step 2: beaker put into by raw material step 1 taken; add the distilled water that organic matter binding agent (being made up of the Sodium Polyacrylate of the sodium alginate of material quality 0.3%, the sodium humate of material quality 1.5% and material quality 0.5%) and quality are 75% of material quality; adopt diffuse double layer principle batch mixing method; room temperature lower magnetic force stirs 2h to mixing and forming colloid; then the baking oven putting into 70 DEG C is dried, and obtains batch mixing;
Step 3: the distilled water adding material quality 5% in the batch mixing of step 2 gained, old 48h in no light conditions is placed on after mixing, then the particle of good fluidity is obtained through granulation, more dry-pressing formed under 30MPa pressure, obtain the green sheet that diameter is about 10mm pottery;
Step 4: ceramic green blank, through the plastic removal process of 600 DEG C, at ambient pressure in 1080 DEG C of sintering 1h, obtains KNN-LT-BF leadless piezoelectric ceramics after cooling.
KNN-LT-BF leadless piezoelectric ceramics is by upper silver electrode, and in the silicone oil of 110 DEG C, polarize 30mins under 3.2kV/mm voltage.
The foregoing is only one embodiment of the present invention, it not whole or unique execution mode, the conversion of those of ordinary skill in the art by reading specification of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Claims (6)
1. a preparation method for KNN-LT-BF leadless piezoelectric ceramics, is characterized in that: comprise the following steps:
Step 1: by (1-x) (0.46KNbO
3-0.46NaNbO
3-0.08LiTaO
3)-xBiFeO
3, the stoichiometric proportion of x=0.004 ~ 0.010, calculates the KNbO of water heat transfer
3the NaNbO of powder, water heat transfer
3the LiTaO of powder, water heat transfer
3the BiFeO of powder and water heat transfer
3the quality of powder also takes, and obtains raw material;
Step 2: reaction vessel put into by raw material step 1 taken, adds organic matter binding agent and water, and stirred at ambient temperature, to mixing and forming colloid, is then dried, and obtains batch mixing; The organic binder bond wherein added is the Sodium Polyacrylate of the sodium alginate of material quality 0.1% ~ 0.3%, the sodium humate of material quality 0.5% ~ 1.5% and material quality 0.1% ~ 0.5%, and the quality of the water added is 50 ~ 100% of material quality;
Step 3: the water adding material quality 3 ~ 5% in the batch mixing of step 2 gained, is placed in no light conditions old, then granulation after mixing, more dry-pressing formed, obtains ceramic green blank;
Step 4: ceramic green blank is through plastic removal process, at ambient pressure in 1045 ~ 1080 DEG C of sintering 1 ~ 2h, in sintering process around ceramic green blank by same component raw material as buried powder to reduce the volatilization of alkali metal cation in sintering process, sinter rear cooling, obtain KNN-LT-BF leadless piezoelectric ceramics.
2. the preparation method of KNN-LT-BF leadless piezoelectric ceramics according to claim 1, is characterized in that: the mixing time in described step 2 is 1 ~ 2h, and bake out temperature is 60 ~ 80 DEG C.
3. the preparation method of KNN-LT-BF leadless piezoelectric ceramics according to claim 1, is characterized in that: the old time in described step 3 is 12 ~ 48h, and dry-pressing formed pressure is 20 ~ 30MPa.
4. the preparation method of KNN-LT-BF leadless piezoelectric ceramics according to claim 1, is characterized in that: the temperature of the plastic removal process in described step 4 is 600 ~ 700 DEG C.
5. the preparation method of KNN-LT-BF leadless piezoelectric ceramics according to claim 1, it is characterized in that: described KNN-LT-BF leadless piezoelectric ceramics also needs to carry out polarization operations, concrete steps are: by KNN-LT-BF leadless piezoelectric ceramics by upper silver electrode, in the silicone oil of 100 ~ 120 DEG C, polarize 30 ~ 60mins under 3 ~ 3.5kV/mm voltage.
6. according to the KNN-LT-BF leadless piezoelectric ceramics that the preparation method of the KNN-LT-BF leadless piezoelectric ceramics in claim 1-5 described in any one obtains, it is characterized in that: its chemical formula is (1-x) (0.46KNbO
3-0.46NaNbO
3-0.08LiTaO
3)-xBiFeO
3, x=0.004 ~ 0.010 is perovskite structure, piezoelectric constant d
33=52 ~ 107pC/N, electromechanical coupling factor K
p=17.1 ~ 23.9%, mechanical quality factor Q
m=23.681 ~ 52.11, Curie temperature T
c=401.1 ~ 468.4 DEG C.
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