CN101429027A - Potassium sodium niobate based leadless piezoelectric ceramic and low-temperature sintering production process - Google Patents
Potassium sodium niobate based leadless piezoelectric ceramic and low-temperature sintering production process Download PDFInfo
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- CN101429027A CN101429027A CNA2008102396281A CN200810239628A CN101429027A CN 101429027 A CN101429027 A CN 101429027A CN A2008102396281 A CNA2008102396281 A CN A2008102396281A CN 200810239628 A CN200810239628 A CN 200810239628A CN 101429027 A CN101429027 A CN 101429027A
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Abstract
The invention discloses potassium-sodium niobate leadless piezoelectric ceramics and a low-temperature sintering preparation method thereof, which belongs to the technical field of functional ceramic materials. The general formula of the potassium-sodium niobate leadless piezoelectric ceramics is (1-x)(Na0.52+yK0.48)NbO3+y/2-xLiNbOS3, wherein x is more than or equal to 0.058 and less than or equal to 0.085, and y is more than or equal to 0.01 and less than or equal to 0.03. The method is as follows: auxiliary materials are weighed, and raw materials are added into a ball grinder for ball grinding, and dried to obtain mixture powder; the mixture powder is subjected to preburning in air and furnace cooling to synthesize alkali metal columbate; the alkali metal columbate powder is subjected to ball grinding, crushing, cold press molding and isostatic cool pressing to obtain an alkali metal columbate preburning blank body; and the preburning blank body after isostatic cool pressing is subjected to pressureless sintering in the air and furnace cooling to obtain the potassium-sodium niobate leadless piezoelectric ceramics. The prepared potassium-sodium niobate leadless piezoelectric ceramics have small fluctuation of chemical compositions, stable performance, superior piezoelectricity and high tightness.
Description
Technical field
The invention belongs to the ceramic material technical field, particularly a kind of potassium niobate sodium-based leadless piezoelectric ceramic and low-temperature melt producing method thereof.
Background technology
Piezoceramic material is a kind of important function stupalith, is widely used in especially information industry field of various industry.But the piezoelectric ceramics of widespread use at present is to be the lead base piezoelectric ceramics of representative with the Pb-based lanthanumdoped zirconate titanates.Though its superior performance, the plumbous oxide content in this class stupalith is up to 70%.And lead is a kind of toxic substance, can cause damage and can be carcinogenic to the brain of human body and neural system; Simultaneously, facial pallor easily gathers and is difficult for the metabolism discharge in vivo.Because plumbous oxide is volatilization easily at high temperature, very easily environment is caused severe contamination so contain lead piezoelectric ceramics in production, use and waste treatment process.The application that present many countries have made laws and forbidden or limit the components and parts of lead-containing materials.China is as production, the big export country of piezoceramic material and device, and the situation that faces is especially severe.Therefore, the lead-free piezoceramic material of research excellent performance has far-reaching social effect and great economic implications.
In recent years, the potassium niobate sodium-based leadless piezoelectric ceramic system is considered to most possible substituting and contains one of system of lead piezoelectric ceramics.Potassium-sodium niobate belongs to the perovskite-type compounds crystal, and its general formula is ABO
3(A is Li, Na, K, and B is Nb, Ta etc.).Compare with lead base piezoelectric ceramics such as Pb-based lanthanumdoped zirconate titanatess, potassium niobate sodium-based leadless piezoelectric ceramic has following characteristics: specific inductivity is little, and frequency constant is big; Density is little; The acoustic velocity height especially is suitable for use on the functional devices such as transverter.Though receiving, potassium niobate report is just arranged in the 1950's, because sintering is not easy densification, the not high (d of performance under the normal pressure as piezoelectric
33=80pC/N), do not cause too big concern.Afterwards, report and adopt hot pressed sintering or discharge plasma sintering, its d
33Can reach 160pC/N.2004, the people such as Saito of Japan write articles on the Nature magazine, claimed it to adopt the potassium sodium niobate piezoelectric ceramics d through doping vario-property of texture method preparation
33Can reach 416pC/N, can match in excellence or beauty, thereby start the research boom of potassium niobate sodium-based leadless piezoelectric ceramic with the lead base piezoelectric ceramics.Wherein, adopt Li, Ta, Sb plasma to carry out doping vario-property and be acknowledged as the effective ways that improve its piezoelectric property, under normal pressure-sintered, d
33Can surpass 300pC/N.Yet, because the volatilization easily under high temperature sintering of alkali metals such as Li, Na, K makes the stoichiometric ratio of pottery be difficult to control, thus the serious performance that reduces pottery.Therefore, reduce sintering temperature, improve preparation technology with the potassium-sodium niobate lead-free piezoelectric ceramics that the obtains stable performance problem that important production practice meaning is arranged to be solved by this invention just.
Summary of the invention
The purpose of this invention is to provide a kind of potassium niobate sodium-based leadless piezoelectric ceramic and low-temperature melt producing method thereof.
A kind of potassium niobate sodium-based leadless piezoelectric ceramic is characterized in that, general formula is: (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, 0.058≤x≤0.085,0.01≤y≤0.03.
A kind of low-temperature melt producing method of potassium niobate sodium-based leadless piezoelectric ceramic is characterized in that, this method steps is as follows,
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning base substrate,
1. the carbonate powder of required Li, K, Na, the oxide powder of Nb are pressed (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3Formula takes by weighing batching, 0.058≤x≤0.085,0.01≤y≤0.03.
2. to join with the dehydrated alcohol be in the ball grinder of medium to confected materials, with ball mill batch mixing 1～48h, obtains the compound powder after the oven dry;
3. with the compound powder in air, 600～900 ℃ of pre-burnings, the insulation 2～10h, furnace cooling, synthetic alkali metal niobate;
4. with the base metal niobate powder after the pre-burning, ball mill pulverizing 1～48h, after the coldmoulding, isostatic cool pressing under 150～200MPa obtains base metal niobate pre-burning base substrate under 50～90MPa;
(2) with the base metal niobate pre-burning base substrate sintering in air after the isostatic cool pressing, temperature is 850～1100 ℃, and soaking time is 2～8h, and furnace cooling makes potassium niobate sodium-based leadless piezoelectric ceramic.
Beneficial effect of the present invention is:
When (1) obtaining the high-compactness piezoelectric ceramics at a lower temperature, keep excellent piezoelectric property, d
33Can be up to 280pC/N;
(2) owing to effectively reduce sintering temperature, the volatilization of alkali metal is effectively controlled, and the chemical component fluctuation of sintered compact is less, stable performance;
(3) though sintering temperature reduces, have liquid phase to exist during owing to sintering, density is very high, makes the electromechanical coupling performance of sintered ceramic body all remain on a higher level in the composition range of a relative broad.
Description of drawings
Fig. 1 is the X ray diffracting spectrum behind the piezoelectric ceramics sintering of heterogeneity;
Fig. 2 is x=0.08, and the density of piezoelectric ceramics is with the variation of sintering temperature during y=0.015;
Fig. 3 is x=0.08, the pattern of the surface of 950 ℃ of sintered piezoelectric ceramics under scanning electronic microscope during y=0.015;
Fig. 4 is x=0.08, the pattern of the section of 950 ℃ of sintered piezoelectric ceramics under scanning electronic microscope during y=0.015.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing:
Embodiment 1
A kind of potassium niobate sodium-based leadless piezoelectric ceramic, general formula is: (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, 0.058≤x≤0.085,0.01≤y≤0.03.
A kind of low-temperature melt producing method of potassium niobate sodium-based leadless piezoelectric ceramic, this method steps is as follows,
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning base substrate,
1. according to (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, x=0.058 wherein, y=0.01 is with analytically pure Li
2CO
3, Na
2CO
3, K
2CO
3, Nb
2O
5Powder is by the stoichiometric ratio batching;
2. to join with the dehydrated alcohol be in the ball grinder of medium to confected materials, with ball mill batch mixing 2h, obtains the compound powder after the oven dry;
3. with the compound powder in air, 650 ℃ of pre-burnings, the insulation 4h, furnace cooling, synthetic alkali metal niobate powder;
4. with the base metal niobate powder after the pre-burning, ball mill pulverizing 12h, coldmoulding is the round billet sheet of diameter 10mm, thickness 1.5mm under 50MPa, isostatic cool pressing under 150MPa obtains base metal niobate pre-burning base substrate;
(2) with the base metal niobate pre-burning base substrate after the isostatic cool pressing, under air atmosphere, 900 ℃ are carried out pressureless sintering, insulation 2h, and furnace cooling makes potassium niobate sodium-based leadless piezoelectric ceramic.
The X ray diffracting spectrum of the potassium niobate sodium-based leadless piezoelectric ceramic of preparing as shown in Figure 1, as can be seen, the piezoelectric ceramics of gained is single uhligite phase, does not have the existence of other dephasign.
Piezoelectric ceramics polarization and detection: the density of measuring piezoelectric ceramics with Archimedes's method is 4.32g/cm
3Piezoelectric ceramics behind the sintering is coated with roasting silver electrode, polarizes in silicone oil, 80 ℃ of polarizing voltages that apply 4kV/mm, kept 20 minutes, drop to room temperature again, finish polarization, polarization is finished to place and is measured piezoelectric constant d after one day
33The performance of the niobate base lead-free piezoelectric ceramic of preparation is as shown in table 1.
Embodiment 2
A kind of potassium niobate sodium-based leadless piezoelectric ceramic, general formula is: (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, 0.058≤x≤0.085,0.01≤y≤0.03.
A kind of low-temperature melt producing method of potassium niobate sodium-based leadless piezoelectric ceramic, this method steps is as follows,
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning base substrate,
1. according to (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, x=0.065 wherein, y=0.015 is with analytically pure Li
2CO
3, Na
2CO
3, K
2CO
3, Nb
2O
5Powder is by the stoichiometric ratio batching;
2. to join with the dehydrated alcohol be in the ball grinder of medium to confected materials, with ball mill batch mixing 10h, obtains the compound powder after the oven dry;
3. with the compound powder in air, 700 ℃ of pre-burnings, the insulation 6h, furnace cooling, synthetic alkali metal niobate powder;
4. with the base metal niobate powder after the pre-burning, ball mill pulverizing 18h, coldmoulding is the round billet sheet of diameter 10mm thickness 1.5mm under 70MPa, isostatic cool pressing under 170MPa obtains base metal niobate pre-burning base substrate;
(2) with the base metal niobate pre-burning base substrate after the isostatic cool pressing under air atmosphere, 940 ℃ are carried out pressureless sintering, the insulation 4h, furnace cooling makes potassium niobate sodium-based leadless piezoelectric ceramic.
The X ray diffracting spectrum of the potassium niobate sodium-based leadless piezoelectric ceramic of preparing as shown in Figure 1.As can be seen, the piezoelectric ceramics of gained is single uhligite phase, does not have the existence of other dephasign.
Piezoelectric ceramics polarization and detection: the density of measuring piezoelectric ceramics with Archimedes's method is 4.30g/cm
3Piezoelectric ceramics behind the sintering is coated with roasting silver electrode, polarizes in silicone oil, 90 ℃ of polarizing voltages that apply 3kV/mm, kept 40 minutes, drop to room temperature again, finish polarization, polarization is finished to place and is measured piezoelectric constant d after one day
33The performance of the niobate base lead-free piezoelectric ceramic of preparation is as shown in table 1.
Embodiment 3
A kind of potassium niobate sodium-based leadless piezoelectric ceramic, general formula is: (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, 0.058≤x≤0.085,0.01≤y≤0.03.
A kind of low-temperature melt producing method of potassium niobate sodium-based leadless piezoelectric ceramic, this method steps is as follows,
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning base substrate,
1. according to (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, x=0.07 wherein, y=0.02 is with analytically pure Li
2CO
3, Na
2CO
3, K2CO
3, Nb
2O
5Powder is by the stoichiometric ratio batching;
2. to join with the dehydrated alcohol be in the ball grinder of medium to confected materials, with ball mill batch mixing 24h, obtains the compound powder after the oven dry;
3. with the compound powder in air, 750 ℃ of pre-burnings, the insulation 8h, furnace cooling, synthetic alkali metal niobate powder;
4. with the base metal niobate powder after the pre-burning, ball mill pulverizing 4h, coldmoulding is the round billet sheet of diameter 10mm thickness 1.5mm under 80MPa, isostatic cool pressing under 190MPa obtains base metal niobate pre-burning base substrate;
(2) with the base metal niobate pre-burning base substrate after the isostatic cool pressing under air atmosphere, 940 ℃ are carried out pressureless sintering, the insulation 6h, furnace cooling makes potassium niobate sodium-based leadless piezoelectric ceramic.
The X ray diffracting spectrum of the potassium niobate sodium-based leadless piezoelectric ceramic of preparing as shown in Figure 1.As can be seen, the piezoelectric ceramics of gained is single uhligite phase, does not have the existence of other dephasign.
Piezoelectric ceramics polarization and detection: the density of measuring piezoelectric ceramics with Archimedes's method is 4.35g/cm
3Piezoelectric ceramics behind the sintering is coated with roasting silver electrode, polarizes in silicone oil, 100 ℃ of polarizing voltages that apply 3kV/mm, kept 20 minutes, drop to room temperature again, finish polarization, polarization is finished to place and is measured piezoelectric constant d after one day
33The performance of the niobate base lead-free piezoelectric ceramic of preparation is as shown in table 1.
Embodiment 4
A kind of potassium niobate sodium-based leadless piezoelectric ceramic, general formula is: (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, 0.058≤x≤0.085,0.01≤y≤0.03.
A kind of low-temperature melt producing method of potassium niobate sodium-based leadless piezoelectric ceramic, this method steps is as follows,
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning base substrate,
1. according to (1-x) (Na
0.52+ yK
0.48) NbO
3+y/2-xLiNbO
3, x=0.075 wherein, y=0.025 is with analytically pure Li
2CO
3, Na
2CO
3, K
2CO
3, Nb
2O
5Powder is by the stoichiometric ratio batching;
2. to join with the dehydrated alcohol be in the ball grinder of medium to confected materials, with ball mill batch mixing 18h, obtains the compound powder after the oven dry;
3. with the compound powder in air, 800 ℃ of pre-burnings, the insulation 10h, furnace cooling, synthetic alkali metal niobate powder;
4. with the base metal niobate powder after the pre-burning, ball mill pulverizing 10h, coldmoulding is the round billet sheet of diameter 10mm thickness 1.5mm under 75MPa, isostatic cool pressing under 200MPa obtains base metal niobate pre-burning base substrate;
(2) with the base metal niobate pre-burning base substrate after the isostatic cool pressing under air atmosphere, 930 ℃ are carried out pressureless sintering, the insulation 8h, furnace cooling makes potassium niobate sodium-based leadless piezoelectric ceramic.
The X ray diffracting spectrum of the potassium niobate sodium-based leadless piezoelectric ceramic of preparing as shown in Figure 1.As can be seen, the piezoelectric ceramics of gained is single uhligite phase, does not have the existence of other dephasign.
Piezoelectric ceramics polarization and detection: the density of measuring piezoelectric ceramics with Archimedes's method is 4.32g/cm
3Piezoelectric ceramics behind the sintering is coated with roasting silver electrode, polarizes in silicone oil, 110 ℃ of polarizing voltages that apply 4kV/mm, kept 25 minutes, drop to room temperature again, finish polarization, polarization is finished to place and is measured piezoelectric constant d after one day
33The performance of the niobate base lead-free piezoelectric ceramic of preparation is as shown in table 1.
Embodiment 5
A kind of potassium niobate sodium-based leadless piezoelectric ceramic, general formula is: (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, 0.058≤x≤0.085,0.01≤y≤0.03.
A kind of low-temperature melt producing method of potassium niobate sodium-based leadless piezoelectric ceramic, this method steps is as follows,
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning base substrate,
1. according to (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, x=0.08 wherein, y=0.015 is with analytically pure Li
2CO
3, Na
2CO
3, K
2CO
3, Nb
2O
5Powder is by the stoichiometric ratio batching;
2. to join with the dehydrated alcohol be in the ball grinder of medium to confected materials, with ball mill batch mixing 18h, obtains the compound powder after the oven dry;
3. with the compound powder in air, 850 ℃ of pre-burnings, the insulation 2h, furnace cooling, synthetic alkali metal niobate powder;
4. with the base metal niobate powder after the pre-burning, ball mill pulverizing 30h, coldmoulding is the round billet sheet of diameter 10mm thickness 1.5mm under 75MPa, isostatic cool pressing under 190MPa obtains base metal niobate pre-burning base substrate;
(2) with the base metal niobate pre-burning base substrate after the isostatic cool pressing under air atmosphere, under 850,900,930,950,970,1000,1050 and 1100 ℃, carry out pressureless sintering, the insulation 4h, furnace cooling makes potassium niobate sodium-based leadless piezoelectric ceramic.
The variable density of the potassium niobate sodium-based leadless piezoelectric ceramic of preparing under different sintering temperatures as shown in Figure 2.As can be seen, the rising along with sintering temperature when sintering temperature is 850～950 ℃ of the density of piezoelectric ceramics raises, and reduces along with the rising of sintering temperature again reach maximum value in the time of 950 ℃ after.The X ray diffracting spectrum of the potassium niobate sodium-based leadless piezoelectric ceramic of preparing at 950 ℃ of sintering as shown in Figure 1.As can be seen, the piezoelectric ceramics of gained is single uhligite phase, does not have the existence of other dephasign.Distinguish as shown in Figure 3 and Figure 4 in the potassium niobate sodium-based leadless piezoelectric ceramic scanning electron microscope surperficial and section that 950 ℃ of sintering are prepared.As seen from Figure 3, most of crystal grain is thicker in the piezoelectric ceramics, is 20～30 μ m; As seen from Figure 4, the density of piezoelectric ceramics is very high, shown under the yardstick macroscopic hole considerably less.
Piezoelectric ceramics polarization and detection: the density of preparing niobate base lead-free piezoelectric ceramic with 950 ℃ of sintering of Archimedes's method mensuration is 4.36g/cm
3950 ℃ of agglomerating piezoelectric ceramics are coated with roasting silver electrode, polarize in silicone oil, 120 ℃ of polarizing voltages that apply 3kV/mm, kept 40 minutes, drop to room temperature again, finish polarization, polarization is finished to place and is measured piezoelectric constant d after one day
33The performance of the niobate base lead-free piezoelectric ceramic of 950 ℃ of sintering preparations is as shown in table 1.Sintering temperature is 850～950 ℃ a piezoelectric ceramics density height, the piezoelectric property excellence.
Embodiment 6
A kind of potassium niobate sodium-based leadless piezoelectric ceramic, general formula is: (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, 0.058≤x≤0.085,0.01≤y≤0.03.
A kind of low-temperature melt producing method of potassium niobate sodium-based leadless piezoelectric ceramic, this method steps is as follows,
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning base substrate,
1. according to (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, x=0.085 wherein, y=0.02 is with analytically pure Li
2CO
3, Na
2CO
3, K
2CO
3, Nb
2O
5Powder is by the stoichiometric ratio batching;
2. to join with the dehydrated alcohol be in the ball grinder of medium to confected materials, with ball mill batch mixing 48h, obtains the compound powder after the oven dry;
3. with the compound powder in air, 900 ℃ of pre-burnings, the insulation 3h, furnace cooling, synthetic alkali metal niobate powder;
4. with the base metal niobate powder after the pre-burning, ball mill pulverizing 48h, coldmoulding is the round billet sheet of diameter 10mm thickness 1.5mm under 85MPa, isostatic cool pressing under 175MPa obtains base metal niobate pre-burning base substrate;
(2) with the base metal niobate pre-burning base substrate after the isostatic cool pressing under air atmosphere, 930 ℃ are carried out pressureless sintering, the insulation 5h, furnace cooling makes potassium niobate sodium-based leadless piezoelectric ceramic.
The X ray diffracting spectrum of the potassium niobate sodium-based leadless piezoelectric ceramic of preparing as shown in Figure 1.As can be seen, the piezoelectric ceramics of gained is single uhligite phase, does not have the existence of other dephasign.
Piezoelectric ceramics polarization and detection: the density of measuring piezoelectric ceramics with Archimedes's method is 4.11g/cm
3Piezoelectric ceramics behind the sintering is coated with roasting silver electrode, polarizes in silicone oil, 90 ℃ of polarizing voltages that apply 3kV/mm, kept 30 minutes, drop to room temperature again, finish polarization, polarization is finished to place and is measured piezoelectric constant d after one day
33The performance of the niobate base lead-free piezoelectric ceramic of preparation is as shown in table 1.
Table 1
Claims (2)
1, a kind of potassium niobate sodium-based leadless piezoelectric ceramic is characterized in that, general formula is: (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3, 0.058≤x≤0.085,0.01≤y≤0.03.
2, a kind of low-temperature melt producing method of potassium niobate sodium-based leadless piezoelectric ceramic is characterized in that, this method steps is as follows,
(1) preparation base metal niobate based leadless piezoelectric ceramic pre-burning base substrate,
1. the carbonate powder of required Li, K, Na, the oxide powder of Nb are pressed (1-x) (Na
0.52+yK
0.48) NbO
3+y/2-xLiNbO
3Formula takes by weighing batching, 0.058≤x≤0.085,0.01≤y≤0.03.
2. to join with the dehydrated alcohol be in the ball grinder of medium to confected materials, with ball mill batch mixing 1～48h, obtains the compound powder after the oven dry;
3. with the compound powder in air, 600～900 ℃ of pre-burnings, the insulation 2～10h, furnace cooling, synthetic alkali metal niobate;
4. with the base metal niobate powder after the pre-burning, ball mill pulverizing 1～48h, after the coldmoulding, isostatic cool pressing under 150～200MPa obtains base metal niobate pre-burning base substrate under 50～90MPa;
(2) with the base metal niobate pre-burning base substrate sintering in air after the isostatic cool pressing, temperature is 850～1100 ℃, and soaking time is 2～8h, and furnace cooling obtains potassium niobate sodium-based leadless piezoelectric ceramic.
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| CN102910906A (en) * | 2012-10-22 | 2013-02-06 | 天津大学 | High-performance potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof |
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| CN108046801A (en) * | 2017-11-20 | 2018-05-18 | 沧州奥力威智能科技有限公司 | Piezoelectric ceramic composition and preparation method thereof |
| CN109485418A (en) * | 2018-12-14 | 2019-03-19 | 华南理工大学 | A kind of potassium-sodium niobate-based piezoelectric material of high efficiency anti-tumor and the preparation method and application thereof |
| CN109485418B (en) * | 2018-12-14 | 2021-07-20 | 华南理工大学 | Efficient anti-tumor potassium-sodium niobate-based piezoelectric material and preparation method and application thereof |
| CN114276138A (en) * | 2021-12-28 | 2022-04-05 | 清华大学 | Potassium-sodium niobate based leadless piezoelectric ceramic and preparation method thereof |
| CN114276138B (en) * | 2021-12-28 | 2023-01-17 | 清华大学 | Potassium-sodium niobate based leadless piezoelectric ceramic and preparation method thereof |
| CN115321980A (en) * | 2022-07-13 | 2022-11-11 | 北京科技大学 | Preparation method of potassium-sodium niobate (KNN) based lead-free piezoelectric ceramic |
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Application publication date: 20090513 |