Summary of the invention
For solving the problem that prior art exists, the invention provides the piezoelectric ceramics that a kind of sintering temperature is low, piezoelectric property is high.
Another object of the present invention provides the preparation technology of described piezoelectric ceramics.
The present invention is achieved in that
The high efficiency piezoelectric ceramic material that a kind of sintering temperature is low comprises major ingredient and auxiliary composition,
Described major ingredient chemical formula is:
Wherein Me is any one or two kinds of elements among Ba, Ca, the Sr, and 0.97≤a≤1.05,0.03≤b≤0.10,0.05≤c≤0.15,0.05≤d≤0.15,0.35≤e≤0.45,0.35≤f≤0.45, and c+d+e+f=1;
Gross weight with main component is the following auxiliary composition of 100% interpolation:
0.008%~0.1%SiO
2Or 0.008%~0.1%H
3BO
3Or both mixtures;
0.10%~0.60% Sb
2O
5Or Sb
2O
3
0.10%~0.60% Bi
2O
3Or Bi
2O
5
0.03%~0.20%Li
2CO
5Or Na
2CO
3Or both mixtures;
0.08%~0.2%CuO。
The main component of preferred following content and auxiliary composition in the piezoelectric ceramics provided by the invention:
Described major ingredient chemical formula is:
Pb
0.995-0?08Sr
0?05Ba
0?03(Ni
1/3Nb
2/3)
0?08(Zn
1/3Nb
2/3)
0?12Ti
0?40Zr
0?40O
3????(2)
Gross weight with main component is the following auxiliary composition of 100% interpolation:
0.05%SiO
2And 0.05%H
3BO
3Mixture, 0.30% Sb
2O
3, 0.40% Bi
2O
5, 0.15% Li
2CO
3, 0.15% CuO.
A kind of preparation technology who prepares described piezoceramic material comprises the steps:
By the chemical formula batching of main component, in mixed main component, add following ancillary component: CuO, SiO
2Or H
3BO
3Or both mixtures, Sb
2O
5Or Sb
2O
3, Bi
2O
3Or Bi
2O
5, Li
2CO
3Or Na
2CO
3
Above-mentioned ceramic raw material is dropped in the planetary ball mill with deionized water, mix discharging after 6~10 hours, oven dry;
Above-mentioned steps gained mixing raw material 780 ℃~800 ℃ pre-burnings 2~3 hours, is mixed the preburning powder that obtains with deionized water, use planetary ball mill 6~10 hours, up to d
50≤ 0.40 μ M, d
9O≤ 0.60 μ M, oven dry;
To dry powder and add polyvinyl alcohol solution, granulation, dry-pressing formed;
Binder removal, sintering, described sintering temperature is 890 ℃~950 ℃;
With the product face machined flat behind the sintering, carry out silk screen printing silver slurry then, silver ink firing;
Product behind the silver ink firing is polarized, and placed 24 hours the polarization back, promptly obtains described piezoelectric ceramics.
Main component among the present invention
In:
0.97≤a≤1.05, if a<0.97, coking property descends, and sintering temperature rises, simultaneously excessive with the stoichiometric ratio deviation, generate heterogeneously easily, piezoelectric property worsens, if a>1.05, Pb too high levels then, the piezoelectric property of sintered products descends, and environmental pollution is serious;
0.03≤b≤0.10, if b<0.03, the specific inductivity of piezoceramic material and piezoelectric strain constant d33 are on the low side, if b>0.1, the Curie temperature of piezoceramic material descends and sintering character descends;
0.05≤c≤0.15,0.05≤d≤0.15, if c<0.05, d<0.05, the then specific inductivity of piezoceramic material, piezoelectric strain constant d
33Big inadequately, if c>0.15, d>0.15, then the decline of the Curie temperature of piezoceramic material is very big, and if Nb
2O
5Content is big, because Nb
2O
5The price height is so can increase the cost of piezoceramic material;
0.35≤e≤0.45,0.35≤f≤0.45, the composition that keeps piezoelectric ceramics guarantees that piezoelectric ceramics has bigger specific inductivity and higher piezoelectric strain constant near phase interface (MPB).
In main component, add an amount of SiO
2Or H
3BO
3, CuO, Bi
2O
3Or Bi
2O
5, Li
2CO
3Or Na
2CO
3, Sb
2O
5Or Sb
2O
3Main purpose is in order to form eutectic mixture, form liquid phase, the good wetting ceramic particle of liquid phase energy in that sintering forms in earlier stage quickens the process of sintering mass transfer, makes to be diffused rapidly to lattice, reduce sintering temperature from face, in the sintering later stage, described additive enters lattice mostly, thereby improves the piezoelectricity of piezoelectric ceramics.
Compared with prior art, by the piezoelectric ceramics that prescription of the present invention and preparation technology produce, piezoelectric property significantly improves, and its specific inductivity is 3500-4800, dielectric loss<2%, planar electromechanical coupling factor 〉=65%, piezoelectric strain constant d
33〉=550PV/N, mechanical quality factor Q m is 50-150, in the purpose that keeps above-mentioned high tension performance, sintering temperature is also reduced to 890 ℃-950 ℃, and optimum temperature range is 910 ℃-930 ℃, piezoelectric ceramics provided by the invention, have energy-conserving and environment-protective, cost is low, the performance advantages of higher, be with a wide range of applications, be particularly useful for piezoelectric ceramic loudspeaker and high-power piezoelectricity singing piece.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1:
Pb
0.97-0.10Sr
0.10(Ni
1/3Nb
2/3)
0.05(Zn
1/3Nb
2/3)
0.15Zr
0.35Ti
0.45O
3??(1)
Main component is Pb
3O
4, ZrO
2, TiO
2, SrCO
3, NiCO
3, ZnO, Nb
2O
5, the prescription weighing of pressing chemical formula (1) is 100% with above-mentioned major ingredient gross weight, adds following additive: 0.008%H
3BO
3, 0.60% Sb
2O
5, 0.10% Bi
2O
3, 0.03% Li
2CO
3, 0.2%CuO;
Then, above-mentioned ceramic raw material is dropped in the planetary ball mill with deionized water, mix discharging after 6-10 hour, oven dry, wherein in the planetary ball mill process, compound: ball: water=1: 3.5: 0.7;
With mixing raw material 780 ℃-800 ℃ pre-burning 2-3 hour, the preburning powder that obtains is mixed with deionized water, with planetary ball mill 6-10 hour, up to d
50≤ 0.40 μ m, d
90≤ 0.60 μ m, oven dry;
Weight ratio is 5%~10% with adding in the oven dry powder, concentration is 6%~10% polyvinyl alcohol solution, and granulation is dry-pressing formed;
Binder removal, sintering, the agglomerating temperature range is 890 ℃-950 ℃;
With the product face machined flat behind the sintering, carry out silk screen printing silver slurry then, silver ink firing;
Polarization, the polarization temperature is 100 ℃-150 ℃, polarized electric field is 10-15min for the 2KV-4KV polarization time, places 24 hours.
Place its dielectric properties of test and piezoelectric property after 24 hours, its performance is as follows:
??Kp |
??d
33×10
-12C/N
|
??εr |
??tgδ |
??Q
m |
Optimal sintering temperature |
Porcelain body density |
??0.65 |
??610 |
??4100 |
??1.5% |
??120 |
??920℃ |
??7.75g/cm
3 |
Embodiment 2:
Pb
0.995-0.08Sr
0.05Ba
0.03(Ni
1/3Nb
2/3)
0.08(Zn
1/3Nb
2/3)
0.12Ti
0.40Zr
0.40O
3(2)
Main component is Pb
3O
4, ZrO
2, TiO
2, SrCO
3, BaCO
3, NiCO
3, ZnO, Nb
2O
5, the prescription weighing of pressing chemical formula (2) is 100% with above-mentioned major ingredient gross weight, adds following additive: 0.05% SiO
2And 0.05%H
3BO
3Mixture, 0.30% Sb
2O
3, 0.40% Bi
2O
5, 0.15% Li
2CO
3, 0.15% CuO;
Then, above-mentioned ceramic raw material is dropped in the planetary ball mill with deionized water, mix discharging after 6-10 hour, oven dry, wherein in the planetary ball mill process, compound: ball: water=1: 3.5: 0.9;
With mixing raw material 780 ℃-800 ℃ pre-burning 2-3 hour, the preburning powder that obtains is mixed with deionized water, with planetary ball mill 6-10 hour, up to d
50≤ 0.40 μ m, d
90≤ 0.60 μ m, oven dry;
Weight ratio is 5%~10% with adding in the oven dry powder, concentration is 6%~10% polyvinyl alcohol solution, and granulation is dry-pressing formed;
Binder removal, sintering, the agglomerating temperature range is 890 ℃-950 ℃;
With the product face machined flat behind the sintering, carry out silk screen printing silver slurry then, silver ink firing;
Polarization, the polarization temperature is 100 ℃-150 ℃, polarized electric field is 10-15min for the 2KV-4KV polarization time, places 24 hours.
Place its dielectric properties of test and piezoelectric property after 24 hours, its performance is as follows:
??Kp |
??d
33×10
-12C/N
|
??εr |
??tgδ |
??Q
m |
Best sintering |
Porcelain body density |
|
|
|
|
|
Temperature |
|
??0.66 |
??590 |
??3950 |
??1.8% |
??100 |
??930℃ |
??7.70g/cm
3 |
Embodiment 3
Pb
1.05-0.03Ba
0.03(Ni
1/3Nb
2/3)
0.15(Zn
1/3Nb
2/3)
0.05Ti
0.45Zr
0.35O
3????(3)
Main component is Pb
3O
4, ZrO
2, TiO
2, BaCO
3, NiCO
3, ZnO, Nb
2O
5, the prescription weighing of pressing chemical formula (3) is 100% with above-mentioned major ingredient gross weight, adds following additive: 0.1% SiO
2, 0.10% Sb
2O
5, 0.60% Bi
2O
3, 0.2% Na
2CO
3, 0.08% CuO;
Then, above-mentioned ceramic raw material is dropped in the planetary ball mill with deionized water, mix discharging after 6-10 hour, oven dry, wherein in the planetary ball mill process, compound: ball: water=1: 3.5: 0.8;
With mixing raw material 780 ℃-800 ℃ pre-burning 2-3 hour, the preburning powder that obtains is mixed with deionized water, with planetary ball mill 6-10 hour, up to d
50≤ 0.40 μ m, d
90≤ 0.60 μ m, oven dry;
Weight ratio is 5%~10% with adding in the oven dry powder, concentration is 6%~10% polyvinyl alcohol solution, and granulation is dry-pressing formed;
Binder removal, sintering, the agglomerating temperature range is 890 ℃-950 ℃;
With the product face machined flat behind the sintering, carry out silk screen printing silver slurry then, silver ink firing;
Polarization, the polarization temperature is 100 ℃-150 ℃, polarized electric field is 10-15min for the 2KV-4KV polarization time, places 24 hours.
Place its dielectric properties of test and piezoelectric property after 24 hours, its performance is as follows:
??Kp |
??d
33×10
-12C/N
|
??εr |
??tgδ |
??Q
m |
Optimal sintering temperature |
Porcelain body density |
??0.61 |
??550 |
??3400 |
??1.8% |
??60 |
??940℃ |
??7.65??g/cm
3 |
Embodiment 4:
Pb
1.00-0.10Sr
0.06Ca
0.04(Ni
1/3Nb
2/3)
0.10(Zn
1/3Nb
2/3)
0.10Ti
0.38Zr
0.42O
3(4)
Main component is Pb
3O
4, ZrO
2, TiO
2, SrCO
3, CaCO
3, NiCO
3, ZnO, Nb
2O
5, the prescription weighing of pressing chemical formula (4) is 100% with above-mentioned major ingredient gross weight, adds following additive: 0.008% SiO
2, 0.30% Sb
2O
5, 0.40% Bi
2O
5, 0.10% Li
2CO
3With 0.05% Na
2CO
3Mixture, 0.10% CuO;
Then, above-mentioned ceramic raw material is dropped in the planetary ball mill with deionized water, mix discharging after 6-10 hour, oven dry, wherein in the planetary ball mill process, compound: ball: water=1: 3.5: 0.7;
With mixing raw material 780 ℃-800 ℃ pre-burning 2-3 hour, the preburning powder that obtains is mixed with deionized water, with planetary ball mill 6-10 hour, up to d
50≤ 0.40 μ m, d
90≤ 0.60 μ m, oven dry;
Weight ratio is 5%~10% with adding in the oven dry powder, concentration is 6%~10% polyvinyl alcohol solution, and granulation is dry-pressing formed;
Binder removal, sintering, the agglomerating temperature range is 890 ℃-950 ℃;
With the product face machined flat behind the sintering, carry out silk screen printing silver slurry then, silver ink firing;
Polarization, the polarization temperature is 100 ℃-150 ℃, polarized electric field is 10-15min for the 2KV-4KV polarization time, places 24 hours.
Place its dielectric properties of test and piezoelectric property after 24 hours, its performance is as follows:
??Kp |
??d
33×10
-12C/N
|
??εr |
??tgδ |
??Q
m |
Optimal sintering temperature |
Porcelain body density |
??0.62 |
??580 |
??3800 |
??1.9% |
??70 |
??930℃ |
??7.72??g/cm
3 |
More than the technical scheme that the embodiment of the invention provided is described in detail, used specific case herein the principle and the embodiment of the embodiment of the invention are set forth, the explanation of above embodiment only is applicable to the principle that helps to understand the embodiment of the invention; Simultaneously, for one of ordinary skill in the art, according to the embodiment of the invention, the part that on embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.